TWI309246B - Catalyst for polymerization of polyester - Google Patents

Description

1309246 IX. Description of the Invention: [Technical Field] The present invention relates to a method for producing a polyester polymerization catalyst, a polyester and a polyester; and more particularly, the present invention relates to a filtration which can be used to improve molding. A polyester polymerization catalyst, a polyester, and the like, which are blocked by a device. [Prior Art]

Polyester, in particular polyethylene terephthalate (hereinafter abbreviated as PET), which has excellent mechanical properties and chemical properties and is used in various applications, for example, fibers for use in clothing and industrial materials, Shaped products such as various films or sheets, bottles, and engineering plastics for packaging and magnetic tape. PET is industrially produced by esterification or transesterification of citric acid or dimethyl phthalate with ethylene glycol to produce bis(2-hydroxyethyl) phthalate, and under high temperature, under vacuum, It is obtained by condensation polymerization using a catalyst. As the catalyst used in the polycondensation, antimony trioxide is widely used. Although antimony trioxide is a catalyst having an inexpensive and excellent catalytic activity, it is caused by precipitation of metal ruthenium during polycondensation, which not only causes blackening of PET but also causes problems such as foreign matter. Throughout this, it is often desirable to have a polyester that is completely free of bismuth or that does not contain ruthenium as a main component of the catalyst. Further, the foreign matter in the above polyester causes problems such as the following. (1) In the case of polyester for film, the metal bismuth will become a foreign matter in the polyester', which is a cause of contamination of the mold when it is melted and extruded, and is also a cause of surface defects of the film. In addition, in the case of a raw material such as a hollow molded product, it is difficult to obtain a hollow molded article excellent in transparency. (2) The foreign matter in the polyester for the fiber is a foreign matter which causes deterioration in the strength of the fiber ' 1309246 and is a cause of contamination of the mold and the increase in the filtration pressure of the filter during the spinning. In the production of polyester fibers, in view of operability, it is desired to obtain a polyester polymerization catalyst which does not generate foreign matter. It has been tried to use antimony trioxide as a polycondensation catalyst and to suppress the blackening of PET and the generation of foreign matter. For example, Patent No. 26 66 5 02, by means of.

A compound of antimony trioxide, antimony and selenium is used as a polycondensation catalyst to suppress the formation of black foreign matter in pET. Further, JP-A-H09-291141 discloses the use of antimony trioxide containing an oxide of sodium and iron as a polycondensation catalyst to suppress the formation of metal ruthenium. However, with such a polycondensation catalyst, it is ultimately impossible to achieve a reduction in the amount of antimony. Although it has been proposed to use a titanium compound or a tin compound as a polycondensation catalyst other than a ruthenium compound, the polyester produced by such a film is easily deteriorated by heat during melt forming, and the polyester has a remarkable coloration. The problem point. Therefore, attempts have been made to overcome the problem of using a titanium compound as a polycondensation catalyst; for example, a method of simultaneously using a cobalt salt and a calcium salt of a tetraalkoxy titanate has been proposed by the Japanese Patent Publication No. 55-1 1 6722. Further, according to JP-A No. 8-7358, it is proposed to use a cobalt alkoxide titanate as a polycondensation catalyst and a method of using a fluorescent whitening agent. However, according to these techniques, when tetraalkoxy titanate is used as a polycondensation catalyst, the color of PET cannot be lowered, and the effect of suppressing thermal decomposition of PET cannot be achieved. What is known as aluminum compounds is that the catalyst activity is poor. Among the aluminum compounds, although it has been reported that the use of aluminum chelating compounds has higher catalytic activity than when other aluminum compounds are used as polycondensation catalysts, it cannot be said that it is more than the above. In the case of a ruthenium compound or a titanium compound, the catalyst activity is sufficiently 1309246·; in addition, when an aluminum compound is used as a polycondensation catalyst, it takes a long time to polymerize the polyester, and its thermal stability and thermal oxidation stability are also Will be worse and so on. Moreover, when an aluminum compound is used as a polycondensation catalyst, a large amount of foreign matter insoluble to the polyester is generated, and the filter is clogged by the foreign matter when the polyester is formed; and when the fiber is used, When spinning, it often causes breakage, and when used, it also has problems such as poor film properties.

In view of the disclosure of the Japanese Patent Publication No. 46-41031, it is found that an alkali metal or a compound thereof, when coexisting with a compound of aluminum, has excellent catalytic activity. When the polyester is polymerized according to the method described in the publication, the thermal stability is excellent, but the thermal oxidation stability is still poor. Further, a large amount of foreign matter insoluble to the polyester is formed, and the polyester is formed. When the fiber is used, the yarn is often broken during spinning, and the film properties are deteriorated when used, and thus it is not practical. Although there is also a technique in which an alkaline earth metal compound is added to an aluminum compound to cause a catalyst having a catalytic activity of a sufficient percentage, in order to achieve practical catalyst activity, a large amount of an alkaline earth metal compound must be added. As a result, the thermal stability and thermal oxidation stability of the polyester are deteriorated, so that the color due to heating becomes large, and the amount of insoluble foreign matter generated for the polyester is also increased. Although a ruthenium compound is used as a catalyst, it is possible to impart excellent catalyst activity other than a ruthenium compound, and it is possible to provide a polyester which does not have the above problems, and has been put to practical use, but such a catalyst also has a so-called very expensive problem. Or it has the problem that the concentration of the catalyst 1309246 of the reaction system changes due to the ease of distillation from the reaction system in the polymerization, so that the polymerization becomes difficult to suppress, and there is a problem in that it is used as a main component of the catalyst. . Further, a method of suppressing thermal deterioration of the polyester at the time of melt molding is, for example, a method of removing a catalyst from a polyester. A method of removing a catalyst from a polyester, for example, a method of contacting a polyester with an extracting agent of a supercritical fluid in the presence of an acidic substance is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. However, such a method of using a supercritical fluid is technically difficult, so that the cost of the product is also increased, which is not preferable.

Based on the above various reasons, it is expected that a polymerization catalyst using a main metal component which uses a metal component other than cerium and lanthanum as a catalyst, and excellent catalyst activity, and which can impart heat deterioration without being caused by melt forming A polymerization catalyst for polyesters with excellent thermal stability. The polyester is decomposed by thermal decomposition during melt molding to lower the molecular weight, which is a cause of a decrease in heat resistance and mechanical properties of the melt-forming port, and the quality of the molded article is deteriorated by by-products of thermal decomposition, for example, coloring is increased. A known catalyst or ruthenium catalyst can provide a polyester which is excellent in thermal stability during melt molding as compared with other titanium catalysts; however, thermal deterioration during melt molding cannot be completely prevented. Based on such a problem, a polyester polymerization catalyst capable of imparting a polyester which is extremely inhibited in thermal deterioration during melt molding of a polyester is desired. A technique in which an aluminum compound is used as a polymerization catalyst is proposed in W098/42769 and JP-A-11-507694. The aluminum compound may be, for example, an aluminum chelating compound such as acetonitrile aluminum acetate, an inorganic acid salt such as aluminum chloride or aluminum hydroxide, an aluminum salt of a carboxylic acid, or an aluminum alkoxide. Among them, an aluminum chelating compound such as acetonitrile-9- 1309246 aluminum is generally expensive, and the cost is increased due to a decrease in the content of aluminum in the compound; or it has a solvent such as ethylene glycol. The method of adding low solubility is limited. Aluminum hydroxide or aluminum alkoxide or the like also has a problem that the solubility in the system is lowered and the catalytic activity is lowered, or the amount of insoluble foreign matter generated in the polyester is also increased. The inorganic acid salt containing chlorine such as aluminum chloride has excellent catalyst activity, but also has a problem of high corrosiveness to the device or a large coloration of the obtained polymer.

On the one hand, the aluminum salt of a carboxylic acid such as aluminum acetate, basic aluminum acetate, aluminum lactate or aluminum benzoate is generally cheap, and has low uranium content to the device, but is dissolved by the polyester. It is low in activity and has poor activity on the catalyst. Therefore, not only does the obtained polyester have a problem of turbidity, but it is also problematic when used as a catalyst. For example, JP-A-100-324747 discloses that aluminum acetate used as a catalyst easily forms a foreign matter insoluble to polyester and causes a problem of poor spinnability. SUMMARY OF THE INVENTION An object of the present invention is to provide an improved polyester and a method for producing the same, which are produced by using a polymerization catalyst which is a main metal component of a metal component other than cerium and lanthanum as a catalyst. An ester, and a polyester which improves the clogging of the filter during molding, and a method for producing the same. Another object of the present invention is to provide a method for producing a polyester using a novel polymerization catalyst other than a ruthenium compound and a ruthenium compound, and a polyester produced by the method. Another object of the present invention is to provide a catalyst main component which does not contain a ruthenium compound and a -10 - 1309246 ruthenium compound, which is excellent in catalytic activity and can be imparted when the catalyst is deactivated or not removed. The effect of thermal deterioration at the time of melt molding is suppressed, and the polymerization catalyst of the polyester excellent in thermal stability is obtained. Further, the present invention provides an improvement in thermal stability during melt forming of a hollow molded article, a fiber, an engineering plastic or the like of a film or a bottle by using the above-mentioned catalyst, which occurs when a raw resin is used or when it is reused. The crumb can obtain a polyester of a high quality product; and a method of producing a polyester using the aforementioned polyester polymerization catalyst.

Another object of the present invention is to provide a polyester polymerization catalyst which can provide a polyester which is extremely resistant to thermal deterioration during melt molding, and to form a hollow molded article such as a film or a bottle by using the above-mentioned catalyst. The thermal stability during melt forming of fibers, engineering plastics, etc. is remarkably improved, and polyesters of high quality products can be obtained by using raw resin or by using debris generated during molding; and using the above-mentioned polyester polymerization catalyst The method of making polyester. Another object of the present invention is to provide a catalyst main component which does not contain a ruthenium compound or a ruthenium compound, which is inexpensive, has excellent catalyst activity, less corrosion to a device, and can impart a reduction in polyester insoluble foreign matter. The resulting polymerization catalyst, and a method of manufacturing the same. Further, the present invention also provides a method of producing a polyester using the aforementioned catalyst, and a polyester. The inventors of the present invention have intensively reviewed the results of the above-mentioned problems. As a result, it has been found that the cause of the foreign matter insoluble in polyester produced by polymerization using an alkali metal compound or an alkaline earth metal compound or a catalyst coexisting with an aluminum compound is mainly It is caused by an alkali metal compound or an alkaline earth metal compound, and it is found that by making the content of the alkali metal compound or the alkaline earth metal compound in the polyester, the 111-1309246 and the aluminum compound within a specific range, The present invention has been accomplished in order to produce a problem of suppressing a polyester-insoluble foreign matter and improving the clogging of a filter during molding of the polyester. That is, the present invention provides a polyester which solves the above-mentioned problems, characterized in that the polyester contains at least one selected from the group consisting of alkali metals and compounds thereof, and alkaline earth metals and compounds thereof, and At least one selected from the group consisting of aluminum and its compounds, and the content thereof satisfies the following formulas (1) and (2):

(2) "M" / "A1" $ 20; (In the formulas (1) and (2), "M" represents the total of the alkali metal atom and the alkaline earth metal atom relative to the acid component of the polyester. %: "A1" represents the molar % of aluminum atoms). In addition, the present inventors have conducted an intensive review based on the object of solving the above problems, and as a result, it has been found that an alkali metal compound or an alkaline earth metal compound and a catalyst coexisting with an aluminum compound are formed to be insoluble to polyester at the time of polymerization. The cause of the foreign matter %, and further investigation revealed that the effect of reducing the foreign matter was observed when coexisting with the phosphorus compound, and it was found that when the content of the above metal compound or phosphorus compound in the polyester was within a specific range, The present invention has been achieved in that it has an effect of suppressing the formation of a polyester-insoluble foreign matter and improving the clogging of the filter during the molding of the polyester. That is, the present invention provides a polyester which solves the above-mentioned problems, characterized in that the polyester contains at least one selected from the group consisting of alkali metals and compounds thereof, and alkaline earth metals and compounds thereof, and At least one selected from the group consisting of aluminum and its compound -12-1309246, and at least one selected from the group consisting of phosphorus compounds, and the content thereof satisfies the following formulas (4) to (6) : (4)0.1 ^ [M] ^ 150; (5) [M] / [A1 ] ^ 40 ; (6) [P] / [A1] ^ 0.01 ; (Formula (4) ~ (6), [ M] represents the total amount (ppm) of alkali metal atoms and alkaline earth metal atoms contained in the polyester; [A1] and [P] represent the amount of aluminum thick and phosphorus atoms contained in the polyester, respectively (ppm) )).

In addition, the present inventors have conducted an intensive review based on the object of solving the above problems, and as a result, it has been found that a catalyst which coexists with an alkali metal compound or an alkaline earth metal compound 'and an aluminum compound generates a foreign matter insoluble to the polyester during polymerization. The main causes are alkali metal compounds and alkaline earth metal compounds; further investigation revealed that the use of lithium, sodium, potassium, rubidium, magnesium, calcium and their compounds in alkali metal compounds or alkaline earth metal compounds At least one selected from the group consisting of, and the content of the polyester in the specific range is more than the phosphorus compound, and the effect of reducing foreign matter formation is improved, and the filter is blocked during the molding of the polyester. The problem is achieved by reaching the present invention. The present invention provides a method for solving the above problems, and provides a polyester and a method for producing the same, characterized in that the polyester contains a group consisting of lithium, sodium, potassium, barium, magnesium, calcium and a compound thereof. At least one selected from the group consisting of aluminum and a compound thereof, and at least one selected from the group consisting of phosphorus compounds, and lithium, sodium, potassium, rubidium, magnesium, calcium The total content of the compound and its compound is less than 7.0 moles per 1 gram of the polymer in terms of metal atom. In addition, the inventors of the present invention conducted a review based on the object of solving the above problems, and found that a polyester produced using a catalyst having a main metal component of an aluminum compound contains a self-phosphorus compound. At least one selected from the group consisting of phenolic compounds and at least one selected from the group consisting of phenolic compounds, and the content of phosphorus atoms and aluminum atoms in a specific range is improved in forming. The present invention has been achieved by the problem of filter clogging and thermal oxidation stability. That is, the method for solving the above problems of the present invention provides a polyester and a method for producing the same, characterized in that the polyester contains at least one selected from the group consisting of aluminum and a compound thereof, and self-phosphorus. At least one selected from the group consisting of compounds, and the ratio of the content of the phosphorus atom (ppm) to the content of the aluminum atom (ppm) in the polyester is in the range of 0.01 to 50. In addition, the present inventors have conducted an intensive review based on the object of solving the above problems, and as a result, it has been found that a catalyst made of an aluminum compound generates a foreign substance insoluble in polyester when polymerized, and is mainly an aluminum compound; Further, it was found that the aluminum compound and the phosphorus compound coexist in the polyester, and when the content of the aluminum compound and the phosphorus compound is in a specific ratio, the effect of reducing the foreign matter is improved, and the filter is blocked during the molding of the polyester. The problem is reached and the invention is achieved. In order to solve the above problems, the present invention provides a polyester characterized in that the polyester contains at least one selected from the group consisting of aluminum and a compound thereof, and a group composed of a self-phosphorus compound. At least one selected from the group consisting of at least one selected from the group consisting of phenolic compounds, and the ratio of the content of phosphorus atoms (ppm) in the polyacetate to the content of the atom (ppm) - 14 - 1309246 , 値 is in the range of 0.5 to 20. Further, the present invention provides the above polyester produced by using a catalyst made of the above metal and/or compound, and a method for producing the same. Further, the present inventors have conducted an intensive review based on the object of solving the above problems, and as a result, it has been found that although the catalytic activity of the aluminum compound is inferior, it can be sufficiently obtained by combining it with a phosphorus compound as a catalyst. Activity, thus achieving the present invention. When the polymerization catalyst of the present invention is used, a polyester excellent in quality without using a ruthenium compound can be obtained inexpensively. In the method for solving the above problems, the present invention provides a method for producing a polyester, characterized in that at least one selected from the group consisting of aluminum and a compound thereof is added in the production of a polyester, and The at least one selected from the group consisting of phosphorus compounds, and the ratio of the added phosphorus atom to the aluminum atom is in the range of 0.5 to 20; and a polyester produced by the method is provided. Further, the present invention provides a polymeric polyester catalyst characterized in that the polyester is at least one selected from the group consisting of aluminum and a compound thereof, and at least one selected from the group consisting of phosphorus compounds. One is constituted, and the ratio of the phosphorus atom and the aluminum atom is within the above range; and a polyester produced using the same, and a method for producing the polyester are provided. In addition, the inventors of the present invention have conducted an intensive review based on the object of solving the above problems, and as a result, found that although the catalytic activity of the metal or the metal compound itself is poor, the combination of the phosphorus compound and the phosphorus compound allows polymerization of the polyester which is increased in catalytic activity. The catalyst is used to find a polyester polymerization catalyst made of a metal, a metal compound, and a phosphorus compound, which is excellent in catalytic activity, and is capable of imparting inhibition during melt forming when the catalyst is deactivated or not removed. The present invention has been completed by obtaining a polymerization catalyst of a polyester having excellent heat stability of 15·1309246. That is, the method for solving the above problems of the present invention provides a polyester polymerization catalyst characterized in that the polyester polymerization catalyst is composed of a metal or a metal compound and a phosphorus compound, and the activity parameter (AP) The following formula (1 0 ) is satisfied: (10) AP (minutes) < APX (minutes); (In the above formula, the AP system represents a predetermined amount of catalyst, at a pressure of 275 ° C, 0.1 tory , the polymerization characteristic viscosity is 0. 6 5 d 1 / gram of poly-p-benzene

Time (minutes) required for ethylene dicarboxylate (PET); APX represents the time (minutes) required to polymerize PET in the same amount and under the same conditions as above except for the above metal or metal compound. Further, the present invention provides a polyester polymerization catalyst characterized in that the polyester polymerization catalyst is used for polymerizing polyethylene terephthalate having a thermal stability parameter (TS) satisfying the following formula (9) (PET). The thermal stability during melt molding of a hollow molded article such as a film or a bottle formed of a polyester polymerized by the polyester polymerization catalyst, a fiber, an engineering plastic or the like can be remarkably improved, and a raw resin is used. Or, by using the debris generated during molding, a product having excellent quality can be obtained. (9) TS <0.20; (In the above formula, TS is placed in a test tube with 1 gram of PET having an intrinsic viscosity ([IV],) of 0.64 to 0.66 dl/g, and dried at 130 ° C for 12 hours under vacuum. Thereafter, after maintaining the melting at 300 ° C for 2 hours in a nitrogen atmosphere without flowing, the following formula was used to calculate the characteristic viscosity ([IV ] f ) number); TS = 0.24 5 { [IVjf1·47 - [IV], '1'47} -16- 1309246 PET with a characteristic viscosity of 0.64 ~ 0.66 dl / gram, in fact, can pre-determine the correlation between the stirring torque of the PET polymerization vessel and the characteristic viscosity, The stirring torque for managing the polymerization state is obtained by stopping the polymerization when the stirring torque reaches a predetermined enthalpy. In addition, the present inventors have intensively reviewed the purpose of improving the catalytic activity of the aluminum carboxylate salt, and found that a catalyst prepared by dissolving an aluminum salt of a carboxylic acid in water or an organic solvent in advance is used. The activity of the catalyst will be increased to obtain the proposal of the present invention. In other words, the method for solving the above problems of the present invention provides a polyester polymerization catalyst, characterized in that the polyester polymerization catalyst is selected from at least one selected from the group consisting of aluminum carboxylates. A solution formed by dissolving in water and/or an organic solvent: and providing a method of making the solution. BEST MODE FOR CARRYING OUT THE INVENTION

The polyester of the present invention must be at least one selected from the group consisting of alkali metals and compounds thereof, and alkaline earth metals and compounds thereof; relative to carboxylic acid components of dicarboxylic acids and polycarboxylic acids in polyesters. The molar content of all constituent units, the total content of metal atoms is less than 〇_〇5 mol%. Further, it is preferably at least 0.005 mol%. When the content is 〇_〇5 mol% or more, a large amount of foreign matter insoluble to polyester is generated, and as a result, yarn breakage frequently occurs during spinning, or so-called filter clogging occurs during molding. Further, the problem that the resin is remarkably colored and the appearance of the molded article is broken may also cause a problem that the hydrodegradability of the resin is deteriorated. When the content is less than 〇 00 5 mol %, the problem of lack of thermal stability of the resin will occur. At the same time, in the case of using -17-1309246 as a catalyst, the catalytic activity will be significantly reduced; Not good. The preferred content range is from 0.008% by mole to 0.03 mole%; more preferably in the range of 0.01% by mole to 0.02% by mole. The polyester of the present invention must be at least one selected from the group consisting of at least one selected from the group consisting of alkali metals and their compounds, and alkaline earths. Further, the composition of the phase and the alkaline earth metal and the compound thereof and the composition of the aluminum metal and the compound thereof must have an alkali metal atom and an alkaline earth metal ratio of 20 or less. Further, when it is more preferably 20, a large amount of broken yarn is generated infrequently for the polyester or when it is formed. Moreover, the use of the sensor as a catalyst can be significantly reduced. When the thermal stability of the polyester due to the aluminum compound is deteriorated, it is not preferable. To 10 0. At least one of the compound, the alkaline earth metal, and the like, and the content of aluminum and a compound thereof in the above range, have an inhibitory effect and improve problems such as spinning. The content of the substance is determined by the number of moles of all constituent units of the dicarboxylic acid in the polyester, and the group consisting of metal and its compound from aluminum and its compounds is in the group of alkali metals and their compounds. At least one selected from the group consisting of at least one selected from the group consisting of φ, and the molar amount of the aluminum atom is 0.1 or more. When the specific enthalpy exceeds the solubility of the foreign matter, as a result of the so-called filter clogging during the spinning, the so-called catalyst activity is less than 0.1, a large amount of insoluble foreign matter is generated, and the resin is The preferred range of % 値 is from 0.5 to 4 selected from the group consisting of the group consisting of alkali metals and compounds, and at least the foreign matter insoluble to the polyester is selected. Broken wire, or filter clogging during forming, the aluminum atom of the present invention and its carboxylic acid component and polycarboxylic acid -18- 1309246 aluminum atom content is preferably from 0.001 mol% to 0.05 mol%. When the weight of the Ming atom exceeds 〇·〇5 耳%, the heat of the generated vinegar 'will be worse' and thus is not good. When the aluminum atom content is 0.001 mol% to _, the catalyst activity is significantly lower when used as a catalyst, and thus it is not suitable. A preferred range of content is from 〇·〇〇5mol% to 〇. Moer%; more preferably in the range of 0.01 mol% to 0.03 mol%. The total amount of the alkali atom and the alkaline earth metal atom contained in the polyester of the present invention is preferably 25 ppm or less in view of the reduction of foreign matter. The φ content is preferably below 20 ppm, and more preferably below 15 ppm. Further, in the polyester of the present invention, at least one selected from the group consisting of the above-mentioned metal and its compound, and an alkaline earth metal and a compound thereof must be selected; however, since it contains an alkaline earth metal and a compound thereof The polyester has a relatively poor thermal stability and is colored in a large amount by heating, and the amount of the product is also relatively large. Therefore, in the polyester of the present invention, it is preferred that the alkaline earth metal and its compound are not contained, but an alkali metal is contained. Further, the polyester of the present invention is preferably a compound containing a pity. When the S compound is contained, the effect of suppressing the difference from the alkali metal or alkaline earth metal can be obtained, and the thermal stability of the polyester can be improved. According to the above, the polyester containing aluminum and its compound 'and the alkaline earth metal and the compound tends to have poor thermal stability, and the foreign matter is more likely to be produced; however, the alkaline earth metal contained in the scope of the present invention is further And when it contains a phosphorus compound, it will improve the thermal stability of the polyester and the problem of foreign matter. According to the method of the present invention, when a phosphorus compound is added in the production of a polyester, there is an effect of suppressing generation of a foreign matter insoluble in the polyester, and thus it is preferable to reduce the content of the phosphorus in the base. 19- 1309246. Further, it is preferable to add a phosphorus compound to improve the thermal stability of the polyester and the like. The amount of the phosphorus compound used in the present invention is preferably from 5 X to 10·5 based on the number of moles of all the constituent units of the carboxylic acid component such as the dicarboxylic acid and the polycarboxylic acid in the obtained polyester. The range of % to 1 mol% of the ear; more preferably in the range of from 1 X 10.4 mol% to 0.5 mol%. Further, the additional polyester of the present invention must be at least φ selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds; the total content of metal atoms in the polyester is 0.1 ppm or more and 150 ppm or less. When the content is more than 150 ppm, a large amount of foreign matter insoluble to polyester is generated, and as a result, yarn breakage frequently occurs during spinning, or so-called filter clogging occurs during molding. Further, there is a problem that the color of the resin becomes conspicuous, the appearance of the molded article is deteriorated, and the thermal stability and hydrogenation resistance of the resin are lowered. When the content is less than 1 ppm, the tree will occur.

The problem of lack of heat stability of fat. In the case of use as a catalyst, the problem that the so-called catalyst activity is significantly lowered may occur. The preferred range is from 1 ppm to 100 ppm; more preferably less than 50 ppm above 5 ppra. The polyester of the present invention must be at least one selected from the group consisting of the above-mentioned alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof, which are selected from the group consisting of aluminum and a compound thereof. . Further, the alkali metal is at least one selected from the group consisting of an alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof. Atomic and Soil Testing Gold-20- 1309246

The total amount of atoms (ppm) and the content of aluminum atoms (ppm) must be below 40. Moreover, the ratio is preferably 〇5 or more. When the ratio is more than 40, a large amount of foreign matter insoluble to polyester is generated, and as a result, yarn breakage occurs frequently during spinning, or so-called filter clogging occurs during molding. Further, when it is used as a catalyst, there is a problem that the so-called catalyst activity is remarkably lowered. When the specific enthalpy is less than 0.05, a large amount of foreign matter insoluble to the polyester due to the aluminum compound is generated, and the thermal stability of the resin is deteriorated, which is not preferable. The preferred range of the ratio is 0.1 or more, more preferably 0.5 or more and 10 or less. The polyester of the present invention must be at least one selected from the group consisting of the above-mentioned alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof. And adding at least one selected from the group consisting of phosphorus and a compound thereof. Further, the phosphorus atom is at least one selected from the group consisting of an alkali metal and a compound thereof, and an alkaline earth metal and a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof. The ratio of the content (ppm) to the aluminum atom content (ppm) must be above 〇 〇 〇1. Further, the ratio is preferably less than 30. When the specific enthalpy is less than 〇. 〇 1, a large amount of foreign matter insoluble to the polyester due to the aluminum compound is generated, and the thermal stability of the resin is increased, which is not preferable. When the ratio is more than 30, a large amount of foreign matter insoluble to polyester is generated. Further, when it is used as a catalyst, a problem that the so-called catalyst activity is remarkably lowered may occur. The preferred range of the ratio is 0.1 or more and 20 or less, and more preferably 1 or more and 1 or less. In the polyester of the present invention, by containing an alkali metal and a compound thereof, -21 -

1309246 is selected from the group consisting of alkaline earth metals and their compounds, and from the group consisting of aluminum and its compounds. • Selected from the group consisting of phosphorus and its compounds. _ Inhibition of foreign matter insoluble in polyester. The effect is broken, or the filter is blocked during molding. Further, the range of the aluminum atom contained in the aluminum in the polyester of the present invention and the compound thereof is preferably (the following is the case where the content of the aluminum atom exceeds 500 ppm φ, the foreign matter insoluble to the polyester, the resin is generated. The heat content is not good. When the aluminum atom content is less than 0.5 ppm, the foreign matter of the alkali metal and the alkaline earth metal is used, and the catalytic activity is significantly decreased when used, so it is not suitable to be surrounded by 5 ppm or more and 70 ppm or less; : ί 30 ppm or less. Further, in the phosphorus compound of the present invention, when the amount is preferably in the range of 1 ppm or more and 100 ppm or less and 1 ppm, the thermal stability of the polyester may be insoluble and the thermal stability of the polyester may be changed. Poor, and thus poor. When 100 ppm is used, a large amount of polyester is insoluble. A preferred content range is 1 〇 ppm or more, preferably 20 ppm or more and 100 ppm or less. In the polyester of the present invention, Although it is necessary to contain a group consisting of, and an alkaline earth metal, a compound thereof, and at least one selected from the group consisting of aluminum and a compound thereof, and at least one, and at least one; Spinning In terms of matter, when it is 500 ppm above the polyester t.Sppm, a large amount of qualitative deficiency is generated, and a large amount of cause is used as a catalyst. A relatively good content is a polyester of more than 10 ppm. The content of the phosphorus atom. When the phosphorus atom content is small, the inhibitory effect of the foreign matter, when the content of the phosphorus atom exceeds the foreign matter, it is not suitable for 200 ppm or less; at least one selected from the group consisting of at least one of the alkali metal and the compound thereof, but -22 - 1309246 In terms of reducing the foreign matter in the polyester and reducing the coloration of the polyester, it is preferable to select among the groups consisting of lithium, sodium, potassium, barium, magnesium, calcium and their compounds. At least one of them selected from at least one of the group consisting of lithium, calcium and a compound thereof, preferably having excellent thermal stability of the polyester, and more preferably, according to the reduction of polyester coloration. From the viewpoint of the above, it is preferred to contain at least one selected from the group consisting of calcium and a compound thereof. The present invention relates to a Φ-based medium made of the above metal and/or compound. The ester and the method for producing the same. The amount of the metal and/or compound to be added must be such that the content of the metal atom in the finally obtained polyester is as described above. The polyester obtained by the method is a kind of It is improved in the effect of suppressing the formation of polyester-insoluble foreign matter, the problem of yarn breakage during spinning, or clogging of the filter during molding. Alkali metal and its compound used as a polymerization catalyst in the present invention, and alkaline earth metal And its compounds, preferably from Li, Na, K' Rb, Cs

At least one selected from the group consisting of Be, Mg, Ca, Sr, and Ba; wherein, in the case of using an alkali metal or a compound thereof, since the polyester which is insoluble to the polyester is reduced, the thermal stability of the polyester is also excellent, which is preferable. In the case of using an alkali metal or a compound thereof, it is preferred to use Li, Na, K and a compound thereof. Among these, in order to reduce the foreign matter insoluble to the polyester, it is preferred to use Li and a compound thereof. Further, another polyester of the present invention is characterized in that it contains at least one selected from the group consisting of lithium, sodium, potassium, barium, magnesium, calcium and a compound thereof, and is composed of aluminum and a compound thereof. At least one selected from the group consisting of at least one of 23-13309246, and at least one selected from the group consisting of phosphorus and its compounds; and the total content of lithium, sodium, potassium, rubidium, magnesium, calcium and their compounds is converted The metal atomic number is less than 7.0 moles per 106 grams of polymer. When the content is more than 7.0 mol, a large amount of foreign matter insoluble to polyester is generated, which results in frequent occurrence of yarn breakage during spinning, or causing so-called filter clogging during molding. Further, the resin is remarkably colored, and the problem of the appearance of the molded article is deteriorated, and the problem that the hydrolysis resistance of the resin is deteriorated also occurs. The content is preferably above 〇.〇5 mol; when the content is less than this, the problem of lack of thermal stability of the resin will occur, and when used as a catalyst, the catalytic activity will be significant. The ground is falling. A relatively good content range is 0. 1~4. 0 mole; more suitable is 〇. 2 ~ 2. 5 m; particularly ideal is 〇. 2~1. 2 m. Such a polyester is a problem in which the effect of suppressing the formation of a polyester-insoluble foreign matter is improved, the yarn is broken during spinning, or the filter is clogged during molding. The content of aluminum and its compounds in the polyester of the present invention is reasonable in terms of aluminum atom

I think it is 0.5 ~ 500 ppm. When the content of the aluminum atom exceeds 500 ppm, not only a large amount of the polyester-insoluble foreign matter due to the aluminum atom but also a problem of lack of thermal stability of the resin occurs, which is not preferable. When the aluminum atom content is less than 0.5 ppm, a large amount of foreign matter due to metal and alkaline earth metals is generated, and when used as a catalyst, the catalytic activity is remarkably lowered, which is not preferable. The preferred content range is from 5 to 70 ppm; more preferably from 10 to 40 ppm; particularly preferably from 15 to 25 p p m. The content of phosphorus and its compound in the polyester of the present invention is considered to be 1 to 1 000 ppm based on the phosphorus atom. When the content of the phosphorus atom is less than 1 ppm, not only the effect of suppressing the formation of insoluble foreign matter to the polyester but also the thermal stability of the resin is lowered, which is not preferable. When the content of the phosphorus atom exceeds 1 〇〇〇 ppm, a large amount of insoluble foreign matter due to the aluminum atom is generated, which is not preferable. The preferred content range is from 10 to 200 ppm; more preferably from 20 to 100 ppm. In the polyester of the present invention, at least one selected from the group consisting of lithium, sodium, potassium, rubidium, magnesium, calcium, and a compound thereof must be contained; however, the foreign matter in the polyester is reduced according to φ, and the reduction is performed. From the viewpoint of polyester coloring, it is preferred that at least one selected from the group consisting of lithium, sodium, magnesium, calcium, and a compound thereof. Among them, it is preferred to contain at least one selected from the group consisting of lithium, sodium and a compound thereof. The present invention relates to a method for producing a polyester using a catalyst, wherein the catalyst used contains at least one selected from the group consisting of lithium, sodium, potassium, rubidium, magnesium, calcium, and a compound thereof, and At least one selected from the group consisting of aluminum and its compounds, and the content thereof is in the above range with respect to the polyester obtained in the final S. The polyester obtained by this method is a problem in which the effect of suppressing the formation of a polyester-insoluble foreign matter is improved, the yarn is broken at the time of spinning, or the filter is clogged during molding. Further, another polyester of the present invention contains at least one selected from the group consisting of aluminum and a compound thereof, and at least one selected from the group consisting of phosphorus compounds and from a phenol compound. a polyester selected from at least one of the group; and a ratio of the amount of phosphorus atoms (ppm) contained in the polyester to the amount of aluminum atoms (ppm) (phosphorus atom amount / aluminum atom amount) -25-

1309246 is in the range of 0.01 to 50. When the amount of phosphorus atom (ppm) and the ratio of aluminum (ppm) 値 (amount of phosphorus atom/amount of aluminum atom) are more than 0.1 hour of foreign matter insoluble to polyester, the result is frequent filamentation or formation during spinning. This causes problems such as so-called filter clogging. Further, the coloring is remarkably colored, and the problem of the appearance of the molded article is deteriorated, and the problem that the hydrodecomposition property is deteriorated is also caused. When the ratio exceeds 50, a large amount of foreign matter insoluble to polyester is generated, and as a result, when a yarn is broken at the time of spinning or a so-called filter clogging occurs during molding, the catalyst is used as a catalyst. The activity will be significantly lower in the range of 0.1 to 20; more preferably 0.5 to 10. The content of aluminum and its compounds in the polyester of the present invention is preferably 0.5 to 500 ppm in terms of aluminum. When the content of bromine atoms exceeds 500, not only does it cause a large amount of insoluble aluminum into the polyester, but also the problem of lack of thermal stability of the resin occurs. Therefore, when the content of less than 0.5 ppm is poor, it is used as a catalyst. The activity of the catalyst is significantly reduced and therefore not suitable. Preferably, it is in the range of 5 to 70 ppm; more preferably in the range of 10 to 40 ppm; it is in the range of 15 to 25 ppm. The polyester of the present invention is an effect of improving the catalytic activity of the compound by containing a phosphorus compound, and is capable of suppressing the thermal stability of the polyester and the thermal oxidation stability of the foreign material. Further, the phenol-based compound is contained so that the thermal oxidation stability of the polyester is further improved, and as a result, thermal deterioration and yellowing of the polyester can be suppressed. Further, another polyester of the present invention is characterized in that the amount of atoms thereof is generated, and the resin is generated in the form of a resin, which is frequently generated. Again, it is falling. When comparing sub-meters to ppm, foreign matter, and . In the case of aluminum, the range of the amount is particularly good for the occurrence of aluminization, and is selected by the group of compounds selected from the group consisting of -26-1309246 phosphorus compounds. The total amount of metal atoms contained in the polyester. The polyester is a problem that has been improved to a problem, and it is not suitable for improving the quality of the heat of the atomic mass of more than 100 ppm of the bad polyester. When the total amount is 1 ppm or more, the catalytic activity can be exhibited in the case of φ, which is 3 to 50 ppm; it is more preferably 5, but it is more suitable for self-examination. Phosphorus and its formation in the polyester of the present invention are intended to be 1 to 1 000 ppm. When the phosphorous deficiency is inhibited, the formation of the polyester insoluble property is lowered, which is not preferable. When S, it will not generate a large amount of aluminum origin. A good range of contents is in the range of ~ 100 ppm. Further, on the other hand, in order to make the polyester of the present invention more suitable to contain foreign substances in the group of oligoesters composed of metals and their compounds, and to reduce the aggregation, it is preferable to contain at least lithium, sodium, potassium, and at least A polyester which is at least one of a phenol type; and, in this case, a so-called filter clogging property and thermal oxidation stability when it is in a form of 1 〇〇 ppm with respect to the polyester. When gold is used, the foreign matter in the polyester increases and breaks. It is preferable to use the metal as a catalyst when the metal atom contained in the polyester is used. The total amount of metal atoms is preferably ~ 30 ppm. The metal type does not have a specific content, an alkaline earth metal, and a compound selected from aluminum. When the content of the phosphorus atom is less than 1 ppm, the effect of the foreign matter is not only the effect of the foreign matter, but also when the content of the heat atom of the resin exceeds 1000 ppm. The polyester is insoluble in the polyester, and thus is in the range of 10 to 200 ppm; more preferably, the physical property such as the thermal stability of the 20 ester is increased, and at least one selected from the group consisting of alkali metals and their compounds, and alkaline earths. According to the viewpoint of ester-reducing coloring, at least one of the group consisting of magnesium, calcium and a compound thereof is selected from the group consisting of -27 to 1309246. Among these, at least one selected from the group consisting of lithium, calcium and a compound thereof is preferred because it has excellent polyester heat stability. Further, in view of reducing the coloration of the polyester, _ is preferably at least one selected from the group consisting of calcium and a compound thereof. In the case where the polyester of the present invention contains an alkali metal, an alkaline earth metal, and a compound thereof, the content thereof is preferably from 1 X 10 to 6 or more based on the number of moles of all the polycarboxylic acid units constituting the polyester. To the less than 〇·1 mol%; the preferred φ is 5 X 1 0_6 ~ 0. 05 Moer %; more preferably 1 X 1 0·5 ~ 0 · 03 Mo %%, especially suitable from 1 X 1〇_5 ~ 〇.〇1mol%. When the content of the alkali metal or the alkaline earth metal is small, the thermal stability is deteriorated, the hydrogen decomposition resistance is lowered, and foreign matter or coloring is caused. When the content of the alkali metal, the alkaline earth metal, and the compound thereof is 0.1 mol% or more, the thermal stability is deteriorated, foreign matter is increased, coloring is increased, and hydrostatic decomposition resistance is lowered. When the content is less than 1 X 1 (Τ6 mol%, the effect of the inclusion is not clear.

The present invention relates to a process for producing a polyester as described above using a catalyst made of the above compound. Further, another polyester of the present invention must be at least one selected from the group consisting of aluminum and a compound thereof, and at least one selected from the group consisting of phosphorus and a compound thereof; The ratio of the phosphorus atom content (ppm) to the aluminum atom content (ppm) must be in the range of 〇·5 to 20. When the specific enthalpy is less than 0.5, a large amount of foreign matter insoluble to the polyester is generated, and as a result, the yarn is frequently broken during spinning, or the so-called filter -28-1309246 is blocked during molding. Further, the resin is remarkably colored, and the problem of the appearance of the molded article is deteriorated, and the problem that the hydrodegradability of the resin is deteriorated also occurs. In the case where the ratio exceeds 20, a large amount of foreign matter insoluble to polyester is generated, and as a result, yarn breakage frequently occurs during spinning, or so-called filter clogging occurs during molding. Further, when it is used as a catalyst, there is a problem that the catalytic activity is remarkably lowered. A preferred range is 1 to 15; more preferably 3 to 10.

In the polyester of the present invention, at least one selected from the group consisting of aluminum and a compound thereof, and at least one selected from the group consisting of phosphorus and a compound thereof; Within the range, it has an effect of suppressing generation of foreign matter insoluble in polyester, and can improve problems such as yarn breakage during spinning or clogging of the damper during molding. Further, the content of the aluminum and the compound thereof of the present invention is preferably in the range of from 1 to 100 ppra in terms of the aluminum atom in the polyester. When the content of the aluminum atom exceeds 100 ppm, not only a large amount of insoluble foreign matter due to the aluminum atom but also a problem of lack of thermal stability of the resin occurs, which is not preferable. When the aluminum atom content is less than 1 ppm, when used as a catalyst, a significant decrease in catalytic activity occurs, which is not preferable. Preferably, it is in the range of 5 ppm or more and 70 ppm or less; more preferably in the range of 10 ppm or more and 30 ppm or less. Further, the content of the phosphorus compound of the present invention is preferably in the range of 5 ppm or more and 200 ppm or less in terms of the phosphorus atom in the polyester. When the content of the phosphorus atom is less than 5 ppm, the effect of suppressing the formation of the insoluble foreign matter of the polyester is lacking, and the thermal stability of the polyester is deteriorated, which is not preferable. When the content of the phosphorus atom is -29- 1309246 and exceeds 200 ppm, a large amount of polyester-insoluble foreign matter is generated, which is not preferable. The preferred range is from 10 ppm to 100 ppm; more preferably from 20 ppm to 80 ppm.

The presence of the phosphorus compound in the polyester of the present invention is not particularly limited, but it is preferred to use a phosphonic acid compound, a phosphinic acid compound, or a phosphine oxide system. Any of a compound, a phosphinous acid compound, a phosphinous acid compound, and a phosphine compound. In the case of polymerizing a polyester, the use of a phosphorus compound having such a structure and an aluminum compound coexist, and the effect of increasing the catalytic activity is found. Among these, when a catalyst made of a phosphate-based compound is used, the effect of increasing the activity of the catalyst is increased, which is preferable. Among the phosphate-based compounds, in order to increase the effect of increasing the activity of the catalyst, it is preferred to use a structure having an aromatic ring as a catalyst. Further, on the one hand, in order to increase physical properties such as thermal stability of the polyester, it is preferred that the polyester of the present invention contains at least one selected from the group consisting of alkali metals and compounds thereof, and alkaline earth metals and compounds thereof. One. In view of reducing the foreign matter in the polyester and reducing the coloration of the polyester, it is preferable that at least one selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, and a compound thereof. In the case where the polyester of the present invention contains an alkali metal, an alkaline earth metal, and a compound thereof, the content thereof is preferably from 1 X or more to less than 0.1 mol based on the number of moles of all the polycarboxylic acid units constituting the polyester. Ear %; preferably 5 X 1 (Γ6 ~ 0.05 mole%: more preferably 1 X 10·5 ~ 〇.〇3 莫% -30- 1309246; particularly suitable is from 1 X 105 ~ 0.01 mole %. When the content of alkali metal or alkaline earth metal is small, the thermal stability is deteriorated, the hydrodegradability is lowered, foreign matter, coloration, etc. occur. When the content of alkali metal, alkaline earth metal and its compound is 0. When _1% or more is used, the thermal stability is deteriorated, foreign matter is increased, coloring is increased, and hydrodegradability is deteriorated. When the content is less than 1 X 10_6 mol%, the effect is contained. The present invention relates to a polyester prepared by using the above-mentioned metal and compound catalyst, and a method for producing the same. The amount of metal and/or compound added must be such that the final polymerization is obtained. The content of metal atoms and phosphorus atoms in the ester The method of the present invention is to improve the effect of suppressing the formation of polyester-insoluble foreign matter, the problem of yarn breakage during spinning, or the clogging of the filter during molding. The polyester of the present invention is preferably not a ruthenium compound or a ruthenium compound. It is produced by a polymerization catalyst made of a titanium compound or a tin compound.

Further, in the case where the polymerization catalyst used in the polyester of the present invention is used in combination with a polymerization catalyst such as a ruthenium compound, a ruthenium compound, a titanium compound or a tin compound, the addition amount of the components is added. It is preferable that the problem of the product such as the characteristics, workability, color tone, and the like of the polyester as described above is not caused, the polymerization time is shortened, and the productivity is effectively improved. When the content of the ruthenium atom in the polyester of the present invention is 50 ppra or less with respect to the amount of the polyester, the polyester is not blackened and the occurrence of foreign matter is suppressed, which is preferable. It is preferably below 30 ppm, more preferably below 1 ppm. On the other hand, it is preferred that the polyester of the present invention contains no germanium atoms. Further, the content of germanium atoms in the polyester of the present invention, when measured relative to the amount of polyester -31 -

When 1309246 is below 20 ppra, there will be no cost. Preferably, it is below 1〇ppra, more preferably on the 5th side. In the polyester of the present invention, it is preferred not to contain the content of titanium atoms in the polyester of the present invention. When the phase is less than 5 ppra, the polyester is The heat stability and color tone are preferably 3 ppm or less, more preferably 1 ppm. The polyester of the present invention preferably contains no titanium atom. Further, it is preferred to contain cobalt and a compound thereof from the viewpoint of reducing the color of the polyester. However, the amount of the polyester should preferably be less than 10 ppm and 5 ppm, more preferably less than 3 ppm, relative to the polyester. It is known that when a cobalt compound itself has catalytic activity, when the catalyst effect is fully exerted, the degree of reduction obtained and the thermal stability are deteriorated. The small amount of the cobalt compound described in the present invention is such that the effect of the catalyst is unclear, and the transparency of the obtained polyester polymer is deteriorated, and the effect of coloring is deteriorated. In addition, in the case of the elimination of the system, the period of addition is preferably after the end of the polymerization reaction. On the other hand, in order to make the polyester polymer thermally safe, the polyester of the present invention preferably contains no cobalt atoms, and another polyester polymerization catalyst of the present invention is composed of a group consisting of aluminum and its compounds. The at least one selected from the group consisting of phosphorus compounds is selected, and thus it is preferably at most ppm. The other atom. It is preferred that the amount of the polyester is judged to be excellent. the following. On the other hand, in the polyester of the present invention, the amount of cobalt and its compound is contained. Preferably, it is less than, when the degree of addition makes the transparency of the polyester polymer, by adding the above-mentioned addition amount, reducing, and eliminating the cobalt compound in the thermal invention at the polymerization stage, the qualitative and transparency are improved. The crucible is characterized in that at least one of its constituents is composed of self-species, and the ratio of the phosphorogen-32- 1309246 to the aluminum atom is in the range of 0.5 to 20. The ia method for producing a polyester according to the present invention is characterized in that it is added to at least one selected from the group consisting of the above-mentioned range and its chemical compound, and is composed of a group of self-phosphorus compounds. At least one of the classes selected. When the molar ratio is less than 〇 5, the activity of the catalyst is significantly lowered, and thus it takes more time than the polymerization of the predetermined viscosity. The preferred range of Moerby is 2 to 15; more preferably 3 to 10; and particularly suitable is 4 to 8. In the present invention, the amount of aluminum and its compound added is preferably 0.001 mol% to 0.1 mol% based on the atomic weight of the all-part polycarboxylic acid unit constituting the polyacetate. When the amount added exceeds 0.1 mol%, the thermal stability and thermal oxidation stability of the polyester are deteriorated, and the foreign matter insoluble to the polyester and the increase in coloring are caused. When the content is less than 0_001 mol%, the activity of the catalyst cannot be sufficiently exerted. A preferred addition amount ranges from 0.003 mol% to 0.05 mol%; more preferably 0.005 mol% to 〇.〇2 mol%; particularly preferably from 0.007 mol% to 0.015 mol%. The polymerization catalyst of the present invention in such a small amount of the aluminum component is added in a large amount to exhibit sufficient catalytic activity. As a result, thermal stability and thermal oxidation stability are improved, and foreign matter due to aluminum and coloring are lowered. The amount of the phosphorus compound added in the present invention is preferably 0.005 mol% to 0. 2 mol% based on the phosphorus atom, based on the number of moles of all the polycarboxylic acid units constituting the polyester. When the amount added is less than 〇. 〇〇5 mol%, the additive effect cannot be sufficiently exerted. When the amount added exceeds 0.2 mol%, the opposite is that in the case of a polyester polymerization catalyst, the catalytic activity is lowered. A preferred addition range is from 0.007 mole % to 0.05 mole %; more preferably 0.01 mole -33 - 1309246 % ~ 0 . 0 2 mole %. A technique in which an aluminum compound is mainly used as a catalyst component without using a phosphorus compound, although it is a method for preventing the use of an aluminum compound by reducing the amount of the aluminum compound, and adding an aluminum compound as a catalyst component, the thermal stability is lowered. The technique of coloring, but when the degree of addition is such that the cobalt compound has sufficient catalytic activity, the thermal stability is deteriorated. Therefore, there is a technical difficulty in making both of them both. According to the present invention, by using a specific amount of a phosphorus compound, φ does not cause problems such as a decrease in thermal stability and generation of foreign matter. However, the amount of aluminum containing a metal component is small, but has By using such a polymerization catalyst, it is possible to improve the thermal stability of a hollow molded product such as a polyester film or a bottle, a fiber, or an engineering plastic at the time of melt molding. In the phosphorus compound of the present invention, it is not preferable to add an effect of adding a phosphate such as phosphoric acid or trimethylphosphoric acid. Further, in the range of the amount of the phosphorus compound of the present invention to be added in the present invention, it may be used in combination with a polyester% polymerization catalyst containing a metal such as a ruthenium compound, a titanium compound, a tin compound or a ruthenium compound, but it cannot be confirmed. Promote the effect of melt polymerization. Further, another feature of the present invention is a polyester polymerization catalyst characterized in that the catalyst is used for polymerizing polyethylene terephthalate having a thermal stability parameter (TS) satisfying the following formula (9) Ester (PET); (9) TS <0.20; (However, TS is to put 1 gram of PET with a characteristic viscosity ([IV] i ) of 0 · 64~0 · 66 d 1 /g into the test tube, After drying in vacuum at 130 ° C for 12 hours, 34 - 1309246, after maintaining the melting at 300 ° C for 2 hours in a non-circulating nitrogen atmosphere, the following formula is used to calculate the characteristic viscosity ([IV ] f ).値)); - TS = 0 · 245 { [ IV ] 〆 47 - [ IV ] 丨 · ] 47 } . The so-called "non-circulating nitrogen atmosphere" means that the nitrogen atmosphere does not circulate. For example, the resin sheet is placed in a test tube which is connected to the vacuum line, and the nitrogen gas is depressurized and sealed for 5 times or more, and then sealed with nitrogen gas at 100 Torr to be in a sealed state. By using a catalyst having such a composition, it is possible to obtain a melt heat stability which is imparted to heat and melt during production of a molded article such as a film, a φ bottle or a fiber, and the like, and it is excellent in molecular weight reduction, coloring, or foreign matter. Shaped product. TS is preferably below 0 _ 1 7 , particularly preferably at 〇 . 15 or less.

Conventionally, it has not been known that a polyester polymerization catalyst capable of imparting PET in the above range of TS. According to the present invention, not only PET which can give TS in the above range is found.

A polyester polymerization catalyst; and another feature of the present invention is that a hollow molded article such as a film, a bottle or the like formed of a polymerized polyester using the polyester polymerization catalyst, a fiber engineering plastic, or the like is found. At the time of melt forming, the thermal stability can be remarkably improved, and a product having excellent quality can be obtained even if a resin to be bonded is used or a chip generated during molding is reused. The composition used as the catalyst component is preferably at least one selected from the group consisting of the above-mentioned polyester polymerization catalysts and phosphorus components. Another polyester polymerization catalyst of the present invention is a metal or a metal compound and a phosphorus compound, characterized in that the activity parameter (Ap) satisfies the following formula (10); -35-

1309246 (1 0) AP (minutes) < APX (minutes); (only 'AP' represents the use of a predetermined amount of catalyst, q under the degree of decompression, the polymerization characteristic viscosity is 0.65 diformate (PET) The time (minutes) required for the metal or metal compound, the time (minutes) required to polymerize the PET under the same conditions as above. The measurement method of AP, specifically, the following 1) (BHET production step) uses a mixture of twice as much as 酞' to produce a mixture of bis(2-hydroxyethyl) oligomers having an esterification ratio of 95% (below , referred to as BHET mixing 2) (catalyst addition step) Add a predetermined amount of the contact, in a nitrogen atmosphere, at normal pressure, 245 ° C, 9 to 50 5 minutes to 50 5 t, continue to slow the oligo-pressure Slow underground pressure down to 〇. 1 Toli. 3) (Polycondensation step) at 27 5 ° C, 0.1 Tory, to polymerize until polyethylene terephthalate! 0 . 6 5 d 1 / gram. 4) Polymerization required in the polycondensation step 帛 Here, it is carried out using a batch reactor. 1) (BHET manufacturing step) The method of producing the BHET mixture is carried out. For example, two times the enthalpy is put into a batch autoclave equipped with a stirrer, and the water outside the system is distilled off at 0 24 5 ° C, and then the active parameter AP is in the above range by borrowing, not only E 2 7 5 t, 0.1 1 Tory d 1 / gram of poly-p-phenylene APX represents the only amount, the same description. The molar amount of ethylene glycol to phthalate (BHET) and the substance ” 到 to the above BHET mixed mash for 10 minutes, and then the polycondensation reaction under the reaction of the mixture mixture to achieve a temple viscosity (IV) of 3 is AP (Minutes). It can be made by using ethylene glycol with a male acid molar amount of 25 MPa and by esterification reaction. Thermal stability due to phosphating-36-

1309246 The compound is coexisting and the reaction speed is relatively fast, and the production time of the polycondensation polyester is shortened. AP is preferably at 0.9, more preferably below 0.8 APX, and particularly good at 〇. 7. 2) In the "catalyst addition step", "predetermined amount of catalyst" refers to the effect of changing the amount of catalyst used in response; the amount of catalyst used with high activity is low and the amount of catalyst used is high. In general, phosphorus compounds are known to be used as the stability of polyesters. However, it is known to suppress the thermal deterioration of polyesters; however, it has not been known that the number of APs is within the above range by metals, or metal compounds, A polyester polymerization catalyst formed with the object. In fact, when a polyester polymerization catalyst, that is, a ruthenium compound, a titanium compound, or a ruthenium compound is used as a catalyst to form a polymer polyester, the addition of a phosphorus compound cannot confirm the substantial effect of promoting polymerization. According to the present invention, a polyester polymerization catalyst composed of a metal or a metal compound or a substance having a number AP in the above range is found, characterized in that the catalytic activity is excellent due to the use of the polymerization catalyst. When the catalyst is deactivated or not, it is possible to impart a polymerization catalyst of polyester which is excellent in the property of suppressing the heat deterioration effect at the time of melt molding. Preferably, the above-mentioned polyester polymerization catalyst is further subjected to the thermal stability parameter (TS) of the catalyst polyethylene terephthalate (PET) as the formula (9): (9) TS < 0.20 By using a catalyst composed of such a composition, the catalyst activity is excellent, and thus the poly APX is polymerized by APX, and the active agent, although active phosphatase, is polymerized to have an active phosphatide type polyester. In the case of the polymerization of the film, the bottle, the fiber, and the like, the melting and heat stability of the molded product is excellent, and the formation of the molecular weight is lowered, the coloring, and the foreign matter are less. Polyester. Preferably, TS is below 0.18; particularly preferably less than 0.15. The polyester polymerization catalyst of the present invention is preferably a thermal oxidation stability parameter (T0S) of polyethylene terephthalate (PET) polymerized using the catalyst, which satisfies the following formula (1 1 ): (11) O. 3克的经。 In the above formula, the TOS is a melt-polymerized IV of 0.6-0.66 dl / gram of PET resin sheet, frozen pulverized into a powder below 20 mesh, taking 0.3 grams of After being vacuum-dried for 13 hours in TC, put it into the test tube, dry it under vacuum at 70 ° C for 12 hours, and then heat it at 1300 ° C for 15 minutes in air dried with silicone. The following formula is used to calculate the IV 値; TOS = 0.245 { [ IV ] fr 1 47 - [ IV ] i 1 47} [IV]i & [IV]fl are the IV before the heating test and after the heating test (dl/克)"

An example of a heating method for drying air by means of silicone rubber is, for example, a drying tube of a glued glue which is attached to the upper end of the glass test tube and heated by a dry air. By using the catalyst of the above composition, a film which imparts excellent heat aging resistance, and a molded article such as a bottle can be obtained. TOS is preferably below 0.99; particularly good is below 0.08. In the present invention, the PET resin sheet used for TS and TOS is measured by using the above steps 1) to 3) and then quenched from a molten state. The shape of the resin sheet used herein is, for example, a cylindrical resin sheet having a length of 1309246 of about 3 mm and a diameter of about 2 mm. Further, the polyester polymerization catalyst of the present invention preferably has an activity parameter (AP) of a full-foot type (1 2 ): • (1 2) AP (minute) < 2T (minute) T-system represents relative to The antimony trioxide is used as the acid component in the polyethylene terephthalate produced by the catalyst, and the AP is added in the case where the ruthenium atom is 〇.〇5 mol%. In the present invention, for the purpose of comparative use of antimony trioxide, antimony trioxide having a purity of 99% or more and φ is used. For example, a commercially available ruthenium (m) oxide (manufactured by Adi Ridge Chemical Co., Ltd., purity: 99.999%) is used. In order to shorten the time for producing the polyester by polycondensation, it is preferred to accelerate the reaction rate by setting the activity parameter AP within the above range. AP is preferably below 丨5T, more preferably below 1. 3T, particularly preferably below 1.0T.

The metal component constituting the polyester polymerization catalyst of the present invention is not particularly limited to a substance other than ruthenium, titanium, and ruthenium, but is preferably an alkali metal, an alkaline earth metal, or an aluminum. Or a lanthanide element such as gallium; a group IV element such as sand; various transition metals; and lanthanides and the like. Among them, the group A element of the melon is ideal, and the aluminum is more suitable. The compound of the metal, for example, is not particularly limited, but is preferably a saturated aliphatic carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid or oxalic acid of the metal; acrylic acid, methacrylic acid, etc. An unsaturated aliphatic carboxylic acid; an aromatic carboxylate such as benzoic acid; a halogenated carboxylate such as trichloroacetic acid; a hydroxycarboxylic acid salt of lactic acid, citric acid or salicylic acid; carbonic acid, phosphoric acid, nitric acid-39 - 1309246, inorganic acid salts of phosphoric acid, phosphonic acid, hydrogencarbonate, hydrogen phosphate, phosphine, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrogen bromide, chloric acid, bromic acid, etc.; 1-propanesulfonic acid, 1 - an organic sulfonic acid such as pentane sulfonic acid or naphthalene sulfonic acid; an organic sulphate such as lauryl sulphate; methoxy, ethoxy, η-propoxy, iso-propoxy, η-butoxy, and tri-butoxy Alkoxides; chelating compounds such as acetamidine acetate; hydrides, oxides, hydroxides, and the like.

The preferred use amount of the above metal component in the production of the polyester varies depending on the kind of the metal to be used; but it is preferably in the range of 1 X l from the number of moles of the polycarboxylic acid unit constituting the polyester. (r6 or more and 0.5 mol% or less; more preferably 5 X 10_5 to 0.1 mol%. When the amount added exceeds 0.5 mol%, the quality of the obtained polyester is lowered in thermal stability and color tone. When the amount of addition is less than 1 X 1 〇·6 mol%, the effect of the addition is not clear. The polyester polymerization catalyst of the present invention preferably contains aluminum and its compounds. At least one selected from the group is used as a constituent of the catalyst. In the present invention, the amount of the aluminum compound which is not aluminum is used as a unit of the carboxylic acid component such as a dicarboxylic acid or a polycarboxylic acid in the polyester. The molar number is preferably from 0.001 to 0.05 mol%; more preferably from 0.005 to 0.02 mol%. When the amount used is less than 0.001 mol%, the activity of the catalyst will not be sufficient. Ground play: When the usage rate exceeds 0.05 mil%, due to thermal stability and thermal oxygen The decrease in the stability of the catalyst causes a problem of an increase in coloring due to the foreign matter of aluminum. The addition of such a small amount of the aluminum component is also a significant feature of the catalyst catalyst of the present invention which exhibits sufficient catalytic activity characteristics. The obtained thermal stability and thermal oxidation stability are excellent, and -40-1309246 causes the foreign matter and coloring caused by aluminum to decrease. The amount of the phosphorus compound used in the present invention is relative to all the constituent units of the polycarboxylic acid component in the polyester. The molar number is preferably from 0.000 1 to 0.1 mol%; more preferably 〇 00 5 ～ 0. 05 mol %. When the amount of phosphorus compound is less than 0. 000 1 mol % When the addition amount of the phosphorus compound is more than 0.1 mol%, the catalytic activity of the polyester as a polyester is decreased. In the composition technique, φ is a technique for reducing the amount of the aluminum compound used, and further preventing the coloring by lowering the thermal stability when the aluminum compound is added as the main catalyst of the cobalt compound, but adding a cobalt compound When the degree of sufficient catalyst activity is reached, the thermal stability will be degraded. Therefore, this technology has the difficulty of both.

According to the present invention, it is possible to use a specific amount of a phosphorus compound without causing problems such as a decrease in thermal stability and generation of foreign matter, but it is possible to obtain a small amount of aluminum in a metal-containing component, but has sufficient contact. By using such a polymerization catalyst, it is possible to improve the thermal stability of a hollow molded article such as a polyester film or a bottle, a fiber, or an engineering plastic at the time of melt molding. In the phosphorus compound of the present invention, it is not preferable to add an effect of adding phosphoric acid ester such as phosphoric acid or trimethylphosphoric acid to enhance the catalytic activity. Further, in the range of the amount of the phosphorus compound to be added of the present invention to be added in the present invention, it may be used in combination with a compound containing a ruthenium compound, a titanium compound or a ruthenium compound, but the effect of promoting the melt polymerization reaction cannot be confirmed. The constituent component of the polyester polymerization catalyst of the present invention is preferably at least one selected from the group consisting of aluminum salts of -41 - 1309246 phosphorus compounds. It may be used in combination with an aluminum compound other than the phosphonium salt or a phosphorus compound or the like. The amount of the aluminum salt of the phosphorus compound in the present invention is preferably from 0.0001 to 0.2 mol%, more preferably from 0.005 to 0.1 mol, based on the number of moles of all constituent units of the polycarboxylic acid component in the polyester. ear%. Further, another feature of the present invention is that the aluminum carboxylate salt previously dissolved in water and/or an organic solvent is used as a catalyst.

As the aluminum carboxylate salt of the present invention, for example, specifically, for example, aluminum formate, aluminum acetate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, Aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum sulphate, aluminum tartrate, aluminum sulphate, etc.; but in terms of solubility and activity of the catalyst, it is preferred to have aluminum acetate, base aluminum acetate An aluminum acetate salt structure or an aluminum lactate system. The aluminum salt of a carboxylic acid is used as an example of a polyester polymerization catalyst, and examples thereof include aluminum acetate, aluminum acetate, aluminum lactate, aluminum benzoate, etc., but any one of them is for polyester. Since the solubility is low and the catalytic activity is also poor, there is a problem that foreign matter which is insoluble to the obtained polyester is generated, and there is a problem in using these compounds as a catalyst. According to the present invention, the use of a substance previously dissolved in water and/or an organic solvent as a catalyst will reveal a significant feature of possessing sufficient catalytic activity characteristics. The aluminum carboxylate salt of the present invention is required to be dissolved in water and/or an organic solvent before being added to the polymerization system of the polyester, and then added to the polymerization system. For use as an organic solvent, it is preferably a glycol; in the case of PET, it is preferred to use ethylene glycol. -42- 1309246 may be used as a structure having an aluminum salt of acetic acid, for example, a base of aluminum acetate, aluminum triacetate, an aluminum acetate solution or the like; wherein, according to solubility and stability of the solution, It is preferred to use the base aluminum acetate. It is necessary to dissolve any of the base aluminum acetate in water and/or an organic solvent to use it as a catalyst. By using a catalyst having such a composition, a polyester having excellent catalyst activity and excellent quality can be obtained. As a solvent, it is preferred to use water or glycols; in the case of PET, it is preferred to use water or ethylene glycol. Further, according to the present invention, when an aluminum carboxylate salt stabilized by boric acid or the like is used as a catalyst, it is found that both solubility and stability of the solution are excellent, and the catalytic activity is excellent and the quality is excellent. A major feature of polyester. It can be used as an aluminum salt of a carboxylic acid, preferably a structure having an aluminum salt of acetic acid; and it is preferred to use a base aluminum acetate. It can be used as a stabilizer. In addition to boric acid, for example, urea, thiourea, etc., but boric acid is preferred.

. In the case of using boric acid to stabilize, it is preferable to use a boric acid having a molar amount of less than or equal to the amount of aluminum to be stabilized. In this case, it is preferable to use a boric acid of 1/2 to 1/3 molar amount to stabilize the boric acid. Aluminum compound. From the viewpoint of catalyst activity and quality of the polyester, it is preferred to add a dissolved polymerization system which is previously dissolved in water and/or an organic solvent. As the organic solvent, it is preferred to use a glycol; in the case of PET, it is preferred to use ethylene glycol. In WO 9 8 / 42 7 6 9 , a catalyst in which a basic compound such as aluminum acetate and tetraethylamine hydroxide is mixed in advance is used as a catalyst. Although this method describes a method for suppressing the formation of insoluble foreign matter, according to this technique, it is necessary to use a basic compound;

1309246 The basic compound described in this patent is mixed with the present invention because the basic compound is colored or foreign matter. Therefore, the colored ester can be reduced. In order to produce the solution of the present invention in which the aluminum carboxylate is previously dissolved in a solvent, it is preferred to use a solution of aluminum carboxylate. In the aqueous solution, it is preferred to add a solvent as appropriate. It is preferable to add the aqueous solution to the thermal shock in the original polymerization system. Preferably, the glycol is added to the polymerization system, or the glycol is diluted and the water is distilled off to the polymerization system. in. The solution is diluted with a glycol such as ethylene glycol in an amount ratio of 0.5 to 500 times relative to the volume ratio of water. Further, in order to make it difficult to suppress the formation of the obtained polyester, the aluminum carboxylate dissolved in the polymerization system is 0.01 to 1 mol/liter in terms of aluminum atom. Addition of a stabilizer such as boric acid or an acid such as lemon to a solution obtained by dissolving an aluminum carboxylate salt in water and/or an organic solvent improves the solubility and the solution. The following is an example of preparation of an aqueous solution of aluminum acetate in the solution of the solution used in the present invention in water and/or an organic solvent. > The base aluminum acetate is added to the water in the chamber. Stir the number under temperature. The aluminum compound according to the present invention may be polymerized in water and/or organic glycols dissolved in water, etc., in order to reduce the dilution of the solution: in the case of liquid-liquid extraction of the solution. The preferred concentration of the insoluble foreign matter in the diol to be diluted, preferably in the case of dissolved acid, lactic acid or oxalic acid, and thus a specific example of the base aluminum acetate dissolution method. More than an hour. Stirring -44- 1309246 time is more than 12 hours. Thereafter, the mixture was stirred at 60 ° C or higher for several hours. The temperature in such a case is preferably in the range of 60 to 80 °C. The stirring time is preferably more than 3 hours. The concentration of the aqueous solution is preferably 5 g / liter - 100 g / liter; more preferably 10 g / liter ~ 30 g / liter. <Preparation example of base ethylene glycol solution of ethylene glycol> The opposite ethylene glycol was added to the above aqueous solution. The amount of ethylene glycol added is preferably from 1 to 5 times the volume ratio of the aqueous solution. More preferably 2 to 3 times the amount. The solution was stirred at room temperature for several hours to obtain a uniform φ water/ethylene glycol mixed solution. Thereafter, the solution was heated, and water was distilled off to obtain an ethylene glycol solution. The temperature is preferably above 80 °C and below 120 °C. More preferably, it is stirred at 90 to 110 ° C for several hours to distill off water. The following is exemplified as the aluminum lactate used in the present invention.

Aqueous solution of aluminum lactate is prepared. The modulation system can be carried out at room temperature or under heating, preferably at room temperature. The concentration of the aqueous solution is preferably from 20 g/l to 100 g/l; more preferably from 50 g/l to 80 g/l. Ethylene glycol was added to % of this aqueous solution. The amount of ethylene glycol added is preferably from 1 to 5 times the volume ratio of the aqueous solution. More preferably 2 to 3 times the amount. After the solution was stirred at normal temperature to obtain a uniform water/ethylene glycol mixed solution, the solution was heated and the water was distilled off to obtain an ethylene glycol solution. The temperature is preferably above 80 °c, 120. (: The following is more preferably agitation at 90 to 110 ° C for several hours to distill off water. The aluminum carboxylate salt having the polyester polymerization catalyst of the present invention is dissolved in a solution of water and/or an organic solvent, It is more suitable to add from the phosphorus compound -45-

At least one of the group of 1309246 is selected such that the stability of the solution inhibits the formation of foreign matter. When the aluminum carboxylate salt is dissolved in water; and the agent is used to prepare a solution, it may be composed of a phosphorus compound. At least one of them coexists. The amount of the phosphorus compound added is preferably in the range of 0.1 to 10 with respect to the molar ratio of the phosphorus atom. The addition method may be carried out by adding a phosphorus compound to a pre-modulated aluminization, and the aluminum compound may be dissolved in the previously prepared phosphorus. Alternatively, the two solutions may be mixed to prepare a solution. • Both may be dissolved in a solvent at the same time. As a solvent, water or glycols; in the case of PET, it is more suitable for j or ethylene glycol. When the polyester is produced by the method of the present invention, the molar atom of all the constituent units of the carboxylic acid component such as poly-polycarboxylic acid or the like is preferably 0.01 to 0.05 mol%, more preferably 0.005 %. When the amount of use is less than 〇·〇〇1 mol%, the catalyst is played in a lively manner; when the amount used is more than 〇5〇%, the thermal oxidation stability is lowered, and the cause is caused by aluminum. A problem in which a compound is soluble in foreign matter or an increase in coloration. Having such a small addition amount is also a significant catalyst characteristic of the polymerization catalyst of the present invention. As a result, the thermal stability and the hot oxygen obtained are improved, and the foreign matter and coloring caused by aluminum are lowered. According to the method of the present invention, when at least one selected from the group consisting of the materials is produced in the production of the polyester, the physical properties such as thermal stability of the polymer can be obtained. The compound solution may be added to the solution of the phosphorus compound in the aluminum atomic group, and it is preferred to use the water and the ester in the dicarboxylic acid ear number, aluminum. ~ 0.02 Mo Er is difficult to heat the stability or the stability of the polyester component is characterized by the stability of the characteristics of the self-phosphorization. -46 - 1309246 According to the method of the present invention, in the manufacture of polyester The amount of the phosphorus compound to be used is preferably 0.0001 to 0.1 mol%, more preferably 0.005 to 0.05 mol%, based on the number of moles of all constituent units of the polycarboxylic acid in the polyester. In the case of using a catalyst prepared by adding a phosphorus compound to the aluminum carboxylate having the polyester polymerization catalyst of the present invention, the amount of the catalyst added is preferably such that the amount of the phosphorus compound added is within the above range. . In the case where the catalyst solution of the phosphorus compound is added, the total amount of the phosphorus compound to be added to the polymerization system is preferably within the above range.

By using the phosphorus compound of the present invention for use, it is possible to obtain a catalyst which sufficiently exhibits a catalytic effect in a polyester polymerization catalyst with a small amount of added aluminum. When the amount of the phosphorus compound added is less than 0.001 mol%, it is difficult to sufficiently exhibit the effect of adding a catalyst; and when the amount added exceeds 0.1 mol%, the opposite is caused by a decrease in catalytic activity. In the case, the tendency to decrease varies depending on the amount of use of aluminum or the like. In the case of producing a polyester according to the method of the present invention, it is preferred not to add an alkali metal, an alkaline earth metal or a compound thereof. Further, in one aspect, a preferred embodiment of the present invention is to add at least one selected from the group consisting of a small amount of an alkali metal, an alkaline earth metal, and a compound thereof added to aluminum and a compound thereof. 2 metal components. Further, in the specific embodiment of the polyester polymerization catalyst of the present invention, it is preferred to coexist with the second metal-containing component. Further, at the time of polymerization, at least one selected from the group consisting of a self-test metal, an alkaline earth metal, and a compound thereof may be added to the solution of the polymerized polymerization catalyst of the present invention, and may be added to an alkali metal or an alkaline earth. At least -47 - 1309246 selected from the group consisting of metals and their compounds may also be used in other catalyst solutions. When such a second metal-containing component is added, in addition to the effect of suppressing the formation of diethylene glycol, high catalytic activity can be obtained, and a catalyst component having a relatively high reaction rate can be obtained, and productivity can be effectively improved. .

The addition of an alkali metal compound or an alkaline earth metal compound to an aluminum compound to obtain a catalytically active catalyst is a well-known technique. When such a known catalyst is used, although a polyester excellent in thermal stability can be obtained, a known catalyst for use with an alkali metal compound or an alkaline earth metal compound needs to be added more than a practical catalyst activity. The amount of foreign matter due to the use of alkali metal will increase; the silkiness or silk property used on the fiber, or the film property, transparency, thermal stability, thermal oxidation stability, and resistance when used on a film Hydrodecomposition and the like are all deteriorated. Further, the color tone of the melt-molded article such as a fiber or a film is also deteriorated. Further, when it is used in combination with an alkaline earth metal compound, in order to obtain practical activity, the heat stability and thermal oxidation stability of the obtained polyester are lowered, and coloring by heating increases, and the amount of foreign matter is increased. It will also increase. In the case where an alkali metal, an alkaline earth metal, and a compound thereof are added, the amount thereof is Μ (mol%), and the content thereof is preferably from 1 X 10 based on the number of moles of all the polycarboxylic acid units constituting the polyester. ·6 or more to less than 〇. 1 mol%; more preferably 5 X 10·6 ~ 0.05 mol%; more preferably 1 X 10"~ 〇.〇3 莫%; particularly suitable is from 1 X 10 · 5 ~ 0.01 mol%. When the content of the alkali metal or the alkaline earth metal is small, the thermal stability is deteriorated, the hydrodegradability is lowered, and foreign matter or coloring is caused. When the amount of alkali metal, alkaline earth metal and its compound used is 0.1 mol% or more, '48- 1309246' deteriorates thermal stability, increases foreign matter and color, and reduces hydrocracking resistance. The problem. When the tether is less than 1 X 1 〇 6 mol %, the effect of inclusion is not clear. In the case of producing a polyester according to the method of the present invention, a preferred embodiment is a cobalt compound having a cobalt atom of less than 1 〇 p p ra with respect to the polyester. It is preferably below 5 ppm, and more preferably below 3 ppm. Further, in the polymerization catalyst of the present invention, a compound containing a cobalt compound may be added to the polyester polymerization catalyst of the present invention; additional cobaltation may be added in addition to the catalyst solution.

Compounds are also possible. Further, on the one hand, when the polyester is produced by the method of the present invention, it is preferred not to use a cobalt compound. When a polyester is produced by the method of the present invention, a component of another polymerization catalyst such as a ruthenium compound, a titanium compound, a ruthenium compound or a tin compound is added, and the amount of the co-existing use is preferably such that it does not fall as described above. In the range of problems in products such as polyester properties, workability, color tone, etc., it is also advantageous in shortening the polymerization time and improving productivity. However, the amount of the rhodium compound which can be added is preferably less than 50 ppm with respect to the polyester obtained by polymerization, and the amount of addition is preferably 30 ppm or less. When the addition amount of ruthenium is more than 50 ppm, the precipitation of the metal ruthenium is caused, and the polyester is blackened and foreign matter is generated, which is not preferable. The amount of the titanium compound which can be added is preferably in the range of 10 ppm or less based on the amount of the polyester obtained by polymerization. Preferably, it is below 5 ppra, and it is more preferably less than 2 ppm. When the added content of titanium is higher than iOPPm#, the thermal stability of the obtained resin is remarkably lowered. -49- 1309246 The amount of the ruthenium compound which can be added is 'relative to the polyester on the side obtained by polymerization'. The content of the ruthenium atom is preferably 20 ppm or less. </ RTI> Preferably, the addition amount is 10 ppm or less. When the amount of strontium added is more than 20 ppm, it is not suitable because it is not conducive to cost. When the polyester is produced by the method of the present invention, one or two or more kinds of the ruthenium compound 'titanium compound, ruthenium compound, and tin compound can be used. The alkali metal and the compound thereof, and the alkaline earth metal and the compound thereof can be used in the present invention, and are not particularly limited to a certain substance. For example, for example, formic acid, acetic acid, propionic acid, and butyl of the metal. a saturated aliphatic carboxylic acid such as acid or oxalic acid; an unsaturated aliphatic carboxylic acid such as acrylic acid or methacrylic acid; an aromatic carboxylic acid salt such as benzoic acid; a halogenated carboxylate such as trichloroacetic acid; lactic acid or citric acid; Hydroxycarboxylates such as salicylic acid; carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogencarbonate, hydrogen phosphate, phosphine, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrogen bromide, chloric acid, bromic acid, etc. Inorganic acid salt; organic sulfonic acid of 1-propanesulfonic acid, 1-pentanesulfonic acid, naphthalenesulfonic acid, etc.; organic phosphonate of S such as laurylphosphonic acid; methoxy, ethoxy, η-propoxy, Alkoxides of iso-propoxy, η-butoxy, third-butoxy, etc.; chelating compounds such as acetamidine acetate; hydrides, oxides, hydroxides, and the like. When a strong base such as a hydroxide is used in such a compound, it has a tendency to be dissolved in an organic solvent such as a glycol such as ethylene glycol or ethanol, and thus has to be added to the aqueous solution. The problem with the aggregation process of the polymerization system. Further, in the case of using a strong basic substance such as a hydroxide, the polyester at the time of polymerization is susceptible to a side reaction such as hydrogenation decomposition, so that the polymer of the polymerization of -50-1309246 has a tendency to be easily colored, so that it is resistant. Hydrodecomposition has a tendency to decrease. Therefore, it is suitable as the alkali metal of the present invention and its compound, and the alkaline earth metal and its compound, for example, a saturated fat of the metal, an aliphatic carboxylic acid, an unsaturated aliphatic carboxylic acid, an aromatic carboxylate, Halogen-containing carboxylate, hydroxycarboxylate; selected from sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrogen bromide, chloric acid, bromic acid, etc. Inorganic acid salts; organic phosphonates, organic sulfates, chelating compounds, oxides, and the like. Further, among these, it is preferable to use an organic carboxylate, particularly an acetate, from the viewpoint of easy φ, easy handling, and the like. The aluminum and the compound thereof may be used as the material of the present invention, and are not particularly limited to a certain substance, but in addition to the metal aluminum, for example, aluminum formate, aluminum acetate, aluminum acetate, aluminum propionate may also be used. , aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum tartrate, aluminum citrate, aluminum citrate, etc.; aluminum chloride, hydroxide Inorganic acid salts of aluminum, aluminum hydroxide, polyaluminum chloride, aluminum nitrate, sulfuric acid aluminum, aluminum carbonate, aluminum phosphate, aluminum phosphonate, etc.; aluminum methoxide, aluminum ethoxylate, aluminum η-propyl Aluminide oxides such as oxides, oximes, aluminum η-butoxides, aluminum t-butoxides, aluminum acetonide, aluminum ethyl acetoacetate, aluminum ethyl acetonide, aluminum An aluminum ruthenium compound such as ethyl acetoacetate diiso-propoxide; an organoaluminum compound such as trimethyl aluminum or triethyl aluminum or a partially hydrogenated decomposition product thereof; an alkoxide or aluminum lanthanum from aluminum; a reaction product of a compound and a hydroxycarboxylic acid; alumina, ultrafine alumina, , Aluminum, titanium, and aluminum or silicon, or a pin or the like alkali metal or alkaline earth metal -51-- composite oxide of 1,309,246. Among them, carboxylate, inorganic acid salt and chelating compound are preferably used; more preferably, it is a base of aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide, and aluminum acetate.醯 salt. More preferably, it is stabilized by using an additive such as aluminum acetate. The phosphorus compound of the present invention is not particularly limited, and is, for example, a phosphate such as trimethylphosphoric acid, triethylphosphoric acid or triphenylphosphoric acid; for example, trimethyl Phosphite, triethylphosphorous acid

Acid ester, triphenyl phosphite, tris(2,4-di-tertiary-butylbenzene) phosphite, tetrakis(2,4-di-tertiary-butylbenzene) 4,4'-di A phosphite of a phosphorous acid such as phenyl diphosphoric acid. The phosphorus compound of the present invention is preferably a group of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphinic acid compounds, trivalent phosphonic acid compounds, and phosphine compounds. At least one phosphorus compound is selected. By including such a phosphorus compound, the effect of improving the physical properties of the target polyester of the present invention is improved, and when such a phosphorus compound and the aluminum compound of the present invention are coexisted in the polymerized polyester, an effect of increasing the catalytic activity can be found. Among these, when a phosphonic acid-based compound is used, the effect of increasing the catalytic activity is increased, which is preferable. Among the above phosphorus compounds, when a compound having an aromatic ring structure is used, the effect of improving physical properties and catalytic activity is increased, which is preferable. When the polyester of the present invention is produced, by using such a phosphorus compound, a catalyst which makes the amount of addition of the alkali metal compound or the alkaline earth metal compound small and which sufficiently exerts the catalytic effect is obtained. In the present invention, the phosphonic acid-based compound, the phosphinic acid-based compound, the phosphine oxide-based compound, the phosphinic acid-based compound, the trivalent phosphonic acid-based compound-52-1309246, and the phosphine-based compound have the following For the compound of the formula represented by the formula ((Chem. 1) ~ (Chem. 6)). [化1Ϊ 0

II -0-P-0-[Chemical 2] 〇 -P-0-

I

化II. -P- [.4] t -0-P-0- [5] -P - 1 - 6 - p - 53 1309246 Can be used as the phosphate compound of the present invention For example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, monoethyl phenylphosphonate, diphenyl phenylphosphonate, benzyl Dimethyl phosphonate, diethyl benzylphosphonate, and the like. As the phosphinic acid compound of the present invention, for example, 'diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, Methyl phenylphosphinate, phenyl phenylphosphinate, and the like. The phosphine oxide-based compound of the present invention may, for example, be diphenylphosphine oxide, methyldiphenylphosphine oxide or triphenylphosphine oxide. In the phosphinic acid compound, the phosphine oxide compound, the phosphinic acid compound, the trivalent phosphonic acid compound, and the phosphine compound, the phosphorus compound of the present invention is preferably the following formula ((Chemical 7) ~ 1 2 )) The compound represented. [化7] Q- 〇

II

P-H

I

OH

[化8] ??

Cr^H

[化9] 〇

-54- 1309246

[化1 ο]

[Chem. 1 1] [Chem. 1 2]

[(CHs ) (CH2 ) t ] a P When a compound having an aromatic ring structure is used as the above-mentioned phosphorus compound, the effect of improving physical properties and catalytic activity is increased, which is preferable.

Further, the phosphorus compound of the present invention is particularly suitable for use as a compound represented by the following formula ((Chem. 13) to (Chem. 15)) because the effect of improving physical properties and catalytic activity is increased. -55- 1309246 P (=〇)' R1 (OR2 ) (OR3 [Chemical 1 4] P (=0) R1 R4 (OR2 ) [Chemical 1 5] P (=0) R1 R5 R6 (at In the formula (13), R1, R4, R5 and R6 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and a carbon number having a hydroxyl group or a halogen group or an alkoxy group or an amine group. a hydrocarbon group of 1 to 50. Each of R2 and R3 independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, and a hydrocarbon group having a hydroxyl group or an alkoxy group having 1 to 50 carbon atoms. However, the hydrocarbon group may also contain a cyclohexyl group or the like. An alicyclic structure or an aromatic ring structure such as phenyl or naphthyl.)

In the above formula (Chemical Formula 13) to (Chemical Formula 15), R1, R4, R5 and R6 are preferably compounds having an aromatic ring structure. It can be used as the phosphorus compound of the present invention, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, phenyl. Diphenyl phosphonate, dimethyl benzylphosphonate, diethyl phosphinate, diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenyl Phosphonic acid, phenyl phenylphosphinate, diphenylphosphine oxide, methyl diphenylphosphine oxide, triphenylphosphine oxide, and the like. Among them, dimethyl benzoate and diethyl benzylphosphonate are preferred. Particularly suitable in the above phosphorus compound &apos;in accordance with the present invention is a metal salt compound of phosphating -56-1309246 and phosphorus. The metal salt of a phosphorus compound is not particularly limited as long as it is a metal salt of a phosphorus compound, and the effect of improving the physical properties and catalytic activity of the polyester of the present invention is increased by using a metal salt of a phosphonic acid compound. Therefore, it is more suitable. The metal salt of the phosphorus compound preferably contains a single metal salt, a dimetal salt, a trimetal salt or the like. Further, when the metal portion of the metal salt in the above phosphorus compound is selected from Li, Na, K, Be, Mg, Sr, Ba, Μη, Ni, Cu, Zn or the like, the effect of improving the catalytic activity is changed. Large and therefore more suitable. Among them, it is preferably L i, N a , M g . When at least one selected from the compounds represented by the following formulas (Chemical Formula 16) is used, the phosphorus compound of the present invention is preferred because it can increase the effect of improving physical properties and catalytic activity.

(In the formula (16), R1 represents hydrogen, a hydrocarbon group having a carbon number of U0, a hydrocarbon group having a carbon number of 1 to 50 containing a trans group or a halogen group or an alkoxy group or an amine group, and R2 represents hydrogen and carbon. a hydrocarbon group having a hydrocarbon group of 1 to 50, a hydroxyl group or alkoxy group having a carbon number of 1 to 50. R 3 represents hydrogen, a hydrocarbon group having 1 to 5 carbon atoms, and a carbon having a trans or tertoxy group or a carbonyl group. The number is a hydrocarbon group of 1 to 5 Å. The 1 system represents an integer of 1 or more; m is an integer representing 1 or more; i + m is 4 or less. The lanthanide represents a metal cation of (Ι+m) valence. The hydrocarbon group may have an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a -57- 1309246 naphthyl group; For example, phenyl, anthracenyl-naphthyl, 2-naphthyl, 9-fluorenyl, 4-biphenylyl, 2-biphenyl, and the like. As the above, for example, 'hydrogen, methyl, ethyl, propyl, isopropyl, η-butyl, t-butyl, t-butyl, long-chain aliphatic groups, A phenyl group, a naphthyl group, a substituted phenyl group or a naphthyl group, and a group represented by CH2CH2〇H. It can be used as R3 (for example, a hydroxide ion, an alkylate ion, an acetate ion, or an acetone ion, etc.). Among the compounds represented by the above formula (Chem. 16), It is also preferred to use at least one selected from the compounds represented by the following formula (Chem. 17).

〇 M (R3〇')m

II R CH2 - P - 0' 〇 c2h5 (In the formula (Chem. 17), R1 represents hydrogen, a hydrocarbon group having 1 to 5 carbon atoms, a carbon having a hydroxyl group or a halogen group or an alkoxy group or an amine group. The number is a hydrocarbon group of 1 to 50. R3 represents a hydrogen group and a hydrocarbon group having a carbon number of 1 to 50. A hydrocarbon group having a hydroxyl group or alkoxy group or a carbonyl group having a carbon number of 1 to 50. The 1 system represents an integer of 1 or more; m is Represents 〇 or an integer of 1 or more; Ι+m is below 4. The lanthanide represents a metal cation of (Ι+m) valence. The hydrocarbon group may also contain an alicyclic structure or a branched structure such as a cyclohexyl group or a phenyl or naphthyl group. An aromatic ring structure.) It can be used as the above R1, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, a 4-biphenyl group, a 2-biphenyl group, or the like. . It can be used as R3, for example, hydroxide ion, alkyl ester ion, acetate ion -58-1309246, or acetone ion. Among the above-mentioned phosphorus compounds, when a compound having an aromatic structure is used, the effect of improving physical properties and catalytic activity can be increased, which is preferable. In the above formula (Chem. 17), when the lanthanide system is selected from the group consisting of Li, Na, K, Be, Mg, Sr, Ba, Μη, Ni, Cu, Zn, etc., the physical properties and the catalyst can be improved. The effect of the activity becomes large, and thus it is suitable. Among them, it is more preferable to be L i, N a , M g .

The metal salt compound used as the phosphorus of the present invention is, for example, [(1-naphthyl)methylphosphonic acid ethyl]lithium, [(1-naphthyl)methylphosphonic acid ethyl] Sodium, bis[U-naphthyl)methylphosphonic acid ethyl]magnesium, [(2-naphthyl)methylphosphonic acid ethyl] potassium, bis[(2-naphthyl)methylphosphonic acid ethyl]magnesium , [benzylphosphonate ethyl]lithium, [benzylphosphonate ethyl]sodium, bis[benzylphosphonateethyl]magnesium, bis[benzylphosphonateethyl]indole, bis[benzylphosphonic acid锞, [[benzylphosphonateethyl]manganese, sodium benzylphosphonate, magnesium bis[benzylphosphonate], sodium [(9-fluorenyl)methylphosphonate, bis[(9) - mercapto) methyl phosphonic acid ethyl] magnesium, [4-hydroxybenzylphosphonic acid ethyl] sodium, bis[4-hydroxybenzylphosphonic acid ethyl] magnesium, [4-chlorobenzylphosphonic acid Sodium ethyl], bis[4-chlorobenzylphosphonic acid phenyl] magnesium, [4-aminobenzylphosphonic acid methyl] sodium, bis[4-aminobenzylphosphonic acid methyl]magnesium, benzene Sodium phosphinate, bis [phenylphosphonic acid ethyl] magnesium, bis[phenylphosphonic acid ethyl] zinc, and the like. Among them, it is preferably [(1-naphthyl)methylphosphonic acid ethyl]lithium '[(1-naphthyl)methylphosphonic acid ethyl] sodium, bis[(1-naphthyl)methylphosphonic acid Magnesium, [benzylphosphonate ethyl]lithium, [benzylphosphonate ethyl]sodium, bis[benzylphosphonateethyl]magnesium, phenylphosphonate sodium, bis[phenylphosphonic acid]magnesium. Among the above phosphorus compounds, in the case of the present invention, it is preferred to use phosphorus having at least one Ρ-0Η bond as a phosphorus compound. When -59- 1309246 containing such a phosphorus compound is used, in addition to the effect of improving the physical properties of the target polyester of the present invention, it is found that the aluminum compound of the present invention coexists with the phosphorus compound when it is found to be polymerized in the polymerization of the polyester. , the effect of increasing the activity of the catalyst can be increased. A phosphorus compound having at least one P - OH bond is not particularly limited to a phosphorus compound having at least one P-OH bond in the molecule. Among these phosphorus compounds, when a phosphorus compound having at least one P - 0H bond is used, it is preferable to improve the effect of improving the physical properties and catalytic activity of the polyester. When a compound having an aromatic ring structure is used as the phosphorus compound, the effect of improving physical properties and catalytic activity can be increased by φ, which is also suitable. Further, the phosphorus compound having at least one P-OH bond of the present invention is preferably used when a compound represented by the following formula (Chem. 18) is used, since the effect of improving physical properties and catalytic activity is increased. . [化 18] 〇

R1——〇H OR2

(In the formula (Chem. 18), R1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a carbon atom number of idO containing a trans group or a halogen group or an alkoxy group or an amine group. a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group of 50 or more, and a η group representing an integer of 丨 or more. The hydrocarbon group may also contain an alicyclic structure or a branched structure such as a cyclohexyl group or a phenyl group or An aromatic ring structure such as naphthyl or the like.) It can be used as the above R1, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, a 4-phenylene group, a 2-biphenyl group. Base. It can be used as the above R2, for example, 'hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, first butyl, tert-butyl, long-chain aliphatic, benzene The base, naphthyl group, phenyl or naphthyl group of -60-1309246, represented by ch2ch2〇h. In the above-mentioned phosphorus compound, when a compound having an aromatic ring structure is used, the effect of improving physical properties and catalytic activity is increased, which is also preferable. • It can be used as a phosphorus compound having at least one P-OH bond of the present invention, for example, (1-naphthyl)methylphosphonic acid ethyl ester, (1-naphthyl)methylphosphonic acid, ( Ethyl 2-naphthyl)methylphosphonate; ethyl phosphinate, benzylphosphonic acid, ethyl (9-fluorenyl)methylphosphonate, ethyl 4-hydroxybenzylphosphonate, 2-A Ethyl phosphinate, phenyl 4-benzylphosphonate, methyl 4-aminobenzylphosphonate, 4-methoxybenzyl #ethyl phosphonate, and the like. Among them, ethyl (1-naphthyl)methylphosphonate, ethyl benzylphosphonate and the like are preferred. It can be used as a preferred phosphorus compound of the present invention, for example, a compound represented by a chemical formula (Chemical Formula 9). [Chem. 19] R1 -CH2 -P (=0) (OR2) (OR3)

(In the formula (Chem. 19), R1 represents hydrogen, a hydrocarbon group having 1 to 49 carbon atoms, a hydrocarbon group having a hydroxyl group or a halogen group or an alkoxy group or an amine group having 1 to 49 carbon atoms. R2 and R3 are each Independently representing hydrogen, a light group having a carbon number of 1 to 50, a hydrocarbon group having a hydroxyl group or an alkoxy group having a carbon number of 1 to 50. The hydrocarbon group may also be an alicyclic structure or a branched structure containing a cyclohexyl group or a phenyl group. Or an aromatic ring structure such as a naphthyl group.) Further, it is more preferably a compound having at least one aromatic ring structure among R1, R2 and R3. Specific examples of such a phosphorus compound are as follows. -61 - 1309246 [化2 0] 〇

/=\ II &lt;λ. ^ch2--p-OC2H5 ic2H5

BPADE

[Chem. 2 1]

〇 &lt;C^ch2~p-oc2h5

NMPA

[化2 2]

〇

It ,, CH2-P-OC2H5 OC2H5

2-NMPA -62- 1309246 [Chemical 2 3] Q 〇 V^CH2--P-oc2h5 Q ic2n5

AMPA

[Chem. 2 4]

〇II -p-oc2h5 OC2H5

4PBPADE

[化2 5] 〇

II P-OC2H5 OC2H5

2

2PBPADE Further, the phosphorus compound of the present invention is preferably one which has a large effect of being difficult to distill off a large molecular weight at the time of polymerization. The phosphorus compound used in the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule. Further, the phosphorus compound of the present invention is preferably a compound which is bonded to a phenol-based compound, that is, a phosphorus compound having a phenol moiety in the same molecule. In addition to improving the physical properties of the target polyester of the present invention, the phosphorus compound having a phenol moiety -63 - 1309246 in the same molecule can be used to polymerize the polyester by using a phosphorus compound having a phenol moiety in the same molecule. The effect of improving the activity of the catalyst is increased, and the productivity of the polyester is also excellent. In the case of using a phosphorus compound having a phenol moiety in the same molecule to polymerize a polyester, its content, i.e., the content of aluminum atoms and phosphorus atoms in the polyester, must be within the scope of the present invention. It can be used as a phosphorus compound having a phenol moiety in the same molecule, although

It is not particularly limited to a phosphorus compound having a phenol structure, but it is preferred to use a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphinic acid compound, or a trivalent group having a phenol moiety in the same molecule. The one or more compounds selected from at least one selected from the group consisting of a phosphonic acid compound and a phosphine compound composition group have an effect of improving the physical properties and catalytic activity of the polyester. In particular, when a phosphonic acid-based compound having one or more phenolic moieties in the same molecule is used, the effect of improving the physical properties of the polyester and the catalytic activity is improved, which is preferable. It can be used as the phosphorus compound having a phenol moiety in the same molecule of the present invention, and is preferably a compound represented by the following formula (Chem. 2 6 ) ~ (Chem. 2 8 ). • 64- 1309246 [Chem. 2 6] P (=〇) R1 (OR2 ) (OR3 ) [Chem. 2 7] P (=0) Rl R4 (OR2 ) [Chem. 2 8] P (=〇)R1 R5 R6 ( In the formula (26) to (28), R1 represents a hydrocarbon group having a phenol group of 1 to 50, a substituent having a hydroxyl group or a halogen group or an alkoxy group or an amine group, and a carbon of a phenol moiety. a hydrocarbon group having a number of 1 to 50. R4, R5, and R6 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a substituent having a hydroxyl group or a halogen group or an alkoxy group or an amine group, and the carbon number is 1 a hydrocarbon group of ~50. R2 and R3 each independently represent a hydrogen group, a hydrocarbon group having 1 to 50 carbon atoms, a substituent having a hydroxyl group or an alkoxy group, and a hydrocarbon group having 1 to 50 carbon atoms. However, the hydrocarbon group may also contain An alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group. The ends of R2 and R4 may be bonded to each other.) It may be a phenol moiety in the same molecule of the present invention. For the phosphorus compound, for example, 'P-hydroxyphenylphosphonic acid, dimethyl P-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonic acid Ester, bis(P-hydroxyphenyl)phosphinic acid, (P-hydroxyphenyl) methyl nicotinate, phenyl (P-hydroxyphenyl) phosphinate, P-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate , P-hydroxyphenylphenylphosphinic acid phenyl ester, P-hydroxyphenylphosphinic acid, P-hydroxy-65- 1309246 methyl phenylphosphinate, phenyl P-hydroxyphenylphosphinate, two (P-hydroxyphenyl)phosphine oxide, tris(P-hydroxyphenyl)phosphine oxide, bis(p-hydroxyphenyl)methylphosphinophenyl ester, and the following formula (Chem. 29) ~ (32) The compound represented by the like. Among them, a compound represented by the following formula (Chemical Formula 3) and dimethyl p-hydroxyphenylphosphonate are preferred. [Chem. 2 9]

[化3 0']

-66- 1309246 [Chem. 3 1]

[化3 2]

As a compound represented by the above formula (Chemical Formula 3), SANKO-220 (manufactured by Sanko Co., Ltd.) can be used.

The phosphorus compound having a phenol moiety in the same molecule of the present invention is preferably at least one selected from the group consisting of specific phosphorus metal compounds represented by the following formula (33). / [Chem. 3 3],

(In the formula (33), R'R2 each independently represents hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydroxyl group or alkane-67- 1309246 The carbon number of the oxy group is a hydrocarbon group of 1 to 50. R4 represents a hydrogen group, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group or a carbonyl group having 1 to 50 carbon atoms, and can be used as R4 (T). For example, for example, a hydroxide ion, an alkylate ion, an acetate ion, or an acetone ion, etc., 1 is an integer of 1 or more; 111 is an integer representing 0 or more, and Ι+m is 4 or less. The lanthanide represents a metal cation of (I+m) valence, and the η system represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group. .)

Wherein ' is preferably at least one selected from the group consisting of compounds represented by the following formula (34). [Chem. 3 4]

In the formula (34), 'Μη+ represents a metal cation of η valence, and η represents 1 (in the formula 33) or (34), when lanthanide is used from Li, Na, 、, Be, When it is selected from Mg, Sr, Ba, Μη, Ni, Cu, yttrium, etc., it is preferable because the effect of improving physical properties and catalytic activity is increased. Among them, 'more suitable is Li, Na, Mg. It can be used as a specific phosphorus metal salt of the present invention, for example, [3,5-di-tertiary-butyl-4.hydroxyl; phosphinic acid ethyl]lithium, [3,5_ Sodium di-t-butyl-4-hydroxybenzylphosphonate, sodium [3,5-di-t-butyl-4-68- 1309246 hydroxybenzylphosphonate], [3, 5-di-t-butyl-butyl-4-hydroxybenzylphosphonic acid ethyl]potassium, bis[3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl]magnesium, di[ 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid]magnesium, bis[3,5-di-tris-butyl-4.hydroxyl; phosphinic acid methyl]pyrene, di[ 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid ethyl] saw, bis[3,5-di-t-butyl-butyl-4-hydroxy; phenylphosphonic acid phenyl] hydrazine, Bis[3,5-di-t-butyl-butyl-4-hydroxybenzylphosphonic acid ethyl]manganese, bis[3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl] Nickel, bis[3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl]copper, bis[3,5-di-tris-butyl-4-hydroxy•benzylphosphonic acid Ethyl] zinc and the like. Among them, it is preferably [3,5-di-t-butyl- 4-hydroxybenzylphosphonic acid ethyl]lithium, [3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid Ethyl]copper, bis[3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid ethyl]magnesium. It is also preferred that the phosphorus compound having a phenol moiety in the same molecule of the present invention is at least selected from the specific phosphorus metal compound having at least one Ρ-0Η bond represented by the following formula (35). One. [化3 5]

ΟII(CH2)n~p—〇ΗOR3 (In the formula (35), R1 and R2 each independently represent a hydrogen group and a hydrocarbon group having a carbon number of U3〇. R3 represents hydrogen and has a carbon number of 1 to 5〇. The hydrocarbon group and the hydrocarbon group having a hydroxyl group or an alkoxy group having a carbon number of 1 to 50. The η system represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as a cyclohexyl group or a phenyl group or a naphthyl group. The aromatic ring structure.) Among them, at least one selected from the group consisting of -69 to 1309246 represented by the following formula (Chem. 36) is also preferred. [Chem. 3 6]

(In the formula (36), R3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group having 1 to 50 carbon atoms. The hydrocarbon group may also contain an alicyclic ring such as a cyclohexyl group. A structural or branched structure or an aromatic ring structure such as a phenyl group or a naphthyl group.) As an example of the above R3, for example, hydrogen, methyl, ethyl, propyl, isopropyl, η- Butyl, t-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted phenyl or naphthyl, and represented by CibCH2〇H. It can be used as a specific phosphorus compound having one less P-OH bond of the present invention, for example, ethyl 3,5-di-tris-butyl-4-hydroxybenzylphosphonate, 3,5-di-t-butyl-4-hydroxyl; methyl phosphinate, isopropyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate 3, 5 - 2 - Benzyl-tert-butyl-4-hydroxybenzylphosphonate, octadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, 3,5-di-third-butyl Base-4-hydroxybenzylphosphonic acid and the like. Among them, preferred is ethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tris-butyl-4-hydroxybenzylphosphonate. The phosphorus compound having a phenol moiety in the same molecule of the present invention is preferably a phosphorus compound selected from the group consisting of at least one of -70 to 1309246 selected from the group consisting of the following formula (Chemical Formula 7). [Chem. 3 7],

〇(CH2)nP—〇R4 OR3 (In the formula (37), R1 and R2 each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R3 and R4 each independently represent hydrogen and have a carbon number of a hydrocarbon group of 1 to 50, a hydrocarbon group having a hydroxyl group or an alkoxy group, and a hydrocarbon group having 1 to 50 carbon atoms. n series: an integer of 1 or more. The hydrocarbon group may also contain an alicyclic structure or a branched structure such as a cyclohexyl group or a phenyl group. Or an aromatic ring structure such as a naphthyl group.) In the above formula (37), at least one selected from the group consisting of the compounds represented by the following formula (38) can improve the physical properties of the polyester and The effect of improving the activity of the catalyst is therefore preferred. [化3 8]

(In the formula (38), R3 and R4 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group having 1 to 50 carbon atoms. The hydrocarbon group may also contain a cyclohexyl group. An alicyclic structure or a branched structure or an aromatic ring structure such as a phenyl group or a naphthyl group. The ends of R2 and R4 may be bonded to each other.) Examples of the above R3 and R4 may be, for example, Hydrogen, methyl, ethyl, propyl, isopropyl, η-butyl, t-butyl, t-butyl, long-chain aliphatic, phenyl, naphthyl, substituted phenyl or naphthalene Base, -71 - 1309246 is the base represented by CH2CH2〇H. It can be 'specified as a specific phosphorus compound of the present invention, for example, 3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid diisopropyl ester, 3, 5_di- Tri-butyl 4-hydroxybenzylphosphonic acid di-n-butyl ester, 3,5-di-tris-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, 3,5_di-third - butyl 4-hydroxybenzylphosphonic acid diphenyl ester or the like. Among them, preferred is 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, 3,5-di-tris-butyl-4-hydroxybenzyl ortho-diphenyl ester. The phosphorus compound having a phenol moiety in the same molecule of the present invention is preferably a phosphorus compound selected from at least one of the compounds represented by the following formula (Chemical Formula 3) and (Chemical Formula 40). [化3 9]

The compound shown in the above chemical formula (Chemical Formula 39) can be used as a commercially available Irganox 1222 (manufactured by Ciba Specialty Chemicals Manufacturing Co., Ltd.), and can be represented by the above chemical formula (Chem. 39). For the compound, there is a commercially available Irganox 1425 (manufactured by Ciba Specialty Chemicals Manufacturing Co., Ltd.). It can be used as the phosphorus compound of the present invention, and is preferably at least one selected from the aluminum salts of the phosphorus compound. Further, the aluminized -72-1309246 compound and the phosphorus compound contained in the polyester of the present invention are preferably at least one selected from the aluminum salts of the phosphorus compound. By the aluminum salt containing such a phosphorus compound, in addition to improving the physical properties of the target polyester of the present invention, and the use of the aluminum salt of the phosphorus compound in the polymerization of the polyester, it is found that the activity of the catalyst is increased. Therefore, the productivity of the polyester is also excellent. It may be used in combination with other aluminum compounds, phosphorus compounds or phenol compounds other than the aluminum salt of the phosphorus compound. In the case of using an aluminum salt of a phosphorus compound, the content thereof, i.e., the content of aluminum atoms and phosphorus atoms in the polyester, must be within the scope of the present invention. The aluminum salt of the phosphorus compound is not particularly limited to a phosphorus compound having an aluminum portion; however, it is preferred to use an aluminum salt of a phosphonic acid compound to improve the physical properties of the polyester and the activity of the catalyst. The aluminum salt of the phosphorus compound preferably contains a single aluminum salt, a double aluminum salt, a tri aluminum salt or the like. In the aluminum salt of the above phosphorus compound, it is also preferred to use a compound having an aromatic ring structure to improve the physical properties of the polyester and the activity of the catalyst. It can be used as the aluminum salt of the phosphorus compound of the present invention, and is preferably used as follows

At least one selected from the group consisting of compounds represented by the formula (Chemical Formula 1) is used to improve the physical properties of the polyester and the activity of the catalyst. [North 4 1] , '

Al3+(R3〇-)m (In the formula (41), R1 represents hydrogen, a hydrocarbon group having a carbon number of 1 to 50, a hydroxyl group or a halogen group or an alkoxy group or an amine group having a carbon number of 1 to 50. Hydrocarbyl group. R: represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a hydroxyl group or an alkoxy group - 73 - 1309246 is a hydrocarbon group of 1 to 50. R 3 represents hydrogen and has a carbon number of 1 to 5 Å. a hydrocarbon group, a hydrocarbon group having a hydroxyl group or an alkoxy group or a carbonyl group of 1 to 50. The 1 system represents an integer of 1 or more; m is an integer representing 0 or more; 1 + rn is 3. The η represents 1 or more The hydrocarbon group may also contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group.) The above R1 may be used, for example, a phenyl group or a 1-naphthalene group. Base, 2-naphthyl, 9-fluorenyl, 4-biphenylyl, 2-biphenylyl, and the like. It can be used as the above R2, for example, hydrogen, methyl, ethyl, propyl, isopropyl, η-φ butyl, t-butyl, t-butyl, long-chain aliphatic groups. A phenyl, naphthyl, substituted phenyl or naphthyl group, represented by -CH2CH2〇H. It can be used as R3 (for example, a hydroxide ion, an alkylate ion, an acetate ion, or an acetone ion, etc.).

The aluminum salt used as the phosphorus compound of the present invention is, for example, an aluminum salt of (1-naphthyl)methylphosphonic acid ethyl ester or an aluminum salt of (1-naphthyl)methylphosphonic acid. An aluminum salt of (2-naphthyl)ethylphosphonate, an aluminum salt of ethyl benzylphosphonate, an aluminum salt of benzylphosphonic acid, an aluminum salt of ethyl (9-fluorenyl)methylphosphonate, Aluminum salt of ethyl 4-hydroxybenzylphosphonate, aluminum salt of ethyl 2-methylbenzylphosphonate, aluminum salt of phenyl 4-benzyl phenylphosphonate, 4-aminobenzylphosphonate An aluminum salt of an ester, an aluminum salt of ethyl 4-methoxybenzylphosphonate, an aluminum salt of ethyl phenylphosphonate, and the like. Among them, an aluminum salt of ethyl (1-naphthyl)methylphosphonate or an aluminum salt of ethyl benzyl phosphonate is preferred. It can be used as the aluminum salt of the phosphorus compound of the present invention, and is preferably at least one selected from the aluminum salt of the phosphorus compound having a phenol structure. Further, the aluminum compound, the phosphorus compound and the phenol compound contained in the polyester of the present invention are preferably at least one selected from the aluminum salt of the phosphorus compound having a phenol structure, as compared with -74 to 1309246. By containing the aluminum salt of the phosphorus compound having a phenol structure, in addition to improving the physical properties of the target polyester of the present invention, and coexisting the aluminum salt of the phosphorus compound having a phenol structure in the polymerization polymerization, It can now increase the activity of the catalyst, so that the productivity of the polyester is also excellent. It may be used in combination with other aluminum compounds, phosphorus compounds or phenol compounds other than the aluminum salt of the phosphorus compound having a phenol structure. In the case of using an aluminum salt of a phosphorus compound having a benzene structure, the content thereof, i.e., the content of aluminum Φ and phosphorus atoms in the polyester, must be within the scope of the present invention. As the aluminum salt of the phosphorus compound having a phenol structure of the present invention, it is preferred to use one selected from the compounds represented by the following formula (42). The ester is less phenolic. [Chemical 4 2]

(In the formula (42), R^R2 each independently represents hydrogen and a hydrocarbon group having a carbon number of benzene. R3 represents hydrogen, a hydrocarbon group having a carbon number of 丨~5〇, and a carbon number having a hydroxyl group or an oxy group is The hydrocarbon group of i to 50 represents hydrogen, the number of carbon atoms is 50, the number of carbons having a hydroxyl group or an alkoxy group or a carbonyl group is 丨 ～ "the hydrocarbon group represents an integer of 1 or more; m is an integer representing 1 or more; 1 Μ is 3. The η system represents an integer above 丨. The hydrocarbon group may also contain an alicyclic structure or a branched structure such as a cyclohexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group.) 30 院1的系-75- 1309246 Among them, it is preferred to use at least one selected from the group consisting of compounds represented by the following formula (Chem. 43).

A!3+(R4〇-)m

(In the formula (43), R3 represents hydrogen, a hydrocarbon group having a carbon number of 5 〇, and a hydrocarbon group having a carbon number of 1 to 50 containing a sulfhydryl group or an alkoxy group. R4 represents hydrogen and has a carbon number of 1 a hydrocarbon group of ~50, a hydrocarbon group having a hydroxyl group or an alkoxy group or a carbonyl group, wherein 1 is an integer of 1 or more; m is an integer representing 1 or more; Ι+ra is 3. The hydrocarbon group may also contain a ring. An alicyclic structure or a branched structure of a hexyl group or an aromatic ring structure such as a phenyl group or a naphthyl group.) Examples of the above R3 may, for example, be hydrogen, methyl, ethyl, propyl or iso Propyl, η-butyl, t-butyl, t-butyl, long-chain aliphatic, phenyl, naphthyl, substituted phenyl or naphthyl, represented by -ChCfhOH. It can be used as R4 (for example, a hydroxide ion, an alkylate ion, an acetate ion, or an acetone ion, etc., which can be used as a specific phosphorus compound of the present invention', for example, for example Is an aluminum salt of ethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, an aluminum salt of methyl 3,5-di-t-butyl-4-hydroxybenzyl squarate Aluminum salt of 3,5-di-t-butyl-butyl-hydroxybenzylphosphonic acid isopropyl ester, aluminum salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid phenyl ester , an aluminum salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid, etc. -76- 1309246. Among them, 3,5-di-tert-butyl-4-hydroxybenzyl is preferred. An aluminum salt of ethyl phosphinate, a silver salt of 3,5-di-tert-butyl-4-trans-methylphosphonate. An alkali metal, an alkaline earth metal, or a salt of aluminum is used in the above phosphorus compound. In the case of the addition amount, that is, the content of the aluminum atom and the phosphorus atom in the finally obtained polyester must be within the scope of the patent application of the present invention. By this method, the foreign matter which is insoluble to the polyester can be suppressed. The effect is to improve the problem of spinning or shredding during spinning. For the ruthenium compound to be added to the polymerization catalyst of the present invention, for example, ruthenium trioxide, ruthenium pentoxide, ruthenium acetate, ruthenium glucoside, etc. are used, and ruthenium trioxide is used. As the bismuth compound, for example, it is cerium oxide or cerium tetrachloride. Particularly preferred is cerium oxide. The cerium oxide system can be used in both crystalline and amorphous forms.

Further, other polymerization catalysts such as a titanium compound and a tin compound may be used as the titanium compound, and examples thereof include, for example, tetra-n-propyl titanium, tetraisopropyl titanium, and tetra-n-butyl titanium. Tetraisobutyl titanium, tetra-t-butyl titanium, tetracyclohexyl titanium, tetraphenyl titanium, tetra; base titanium, lithium oxalate titanate, potassium oxalate titanate, manganese oxalate titanate, titanium oxide, titanium and tantalum a composite oxide of chromium, an alkali metal or an alkaline earth metal, a normal ester of titanium or a condensed orthoester, a normal ester of titanium or a reaction product of a condensed orthoester and a hydroxycarboxylic acid, a normal ester of titanium or a condensed orthoester A reaction product formed from a reaction product of a hydroxycarboxylic acid and a phosphorus compound, a normal ester of titanium or a condensed normal ester, and a polyol having at least two hydroxyl groups, and a 2-hydroxycarboxylic acid and a salt group. Among them, a composite oxide of titanium and ruthenium, a composite oxide of titanium and ruthenium, a normal ester of titanium or a condensed orthoester and a reaction product of a hydroxycarboxylic acid and a phosphorus compound are preferable. Further, as a tin compound, for example, -77- 1309246, for example, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, /, ethyltin oxide, triethyltin Nitrogen oxide, monobutyl group-based tin oxide, triisobutyltin oxide, diphenyltin laurate, monobutyltin trichloride, dibutyltin sulfide, dibutylhydroxytin oxide, methylstannic acid , ethyl stannate and the like. A particularly preferred system uses monobutylhydroxytin oxide.

The cobalt compound which may be added in the present invention is not particularly limited to a certain substance, but specific examples thereof are, for example, cobalt acetate, cobalt nitrate, cobalt chloride, ethyl ruthenium acetate, cobalt naphthalate. And its hydrates, etc. Preferably, it is a cobalt acetate tetrahydrate. According to the method of the present invention, in the production of a polyester, it is preferred to add a phenolic compound to increase the thermal stability of the polyester. The phenol compound which can be used in the present invention is not particularly limited to a compound having a phenol structure, for example, 2,6-di-tert-butyl-4-methylphenol, 2,6 -di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-methylphenol, 2,6-di- Third-pentyl-4-methylindole, 2,6-di-t-octyl-4-n-propylindole, 2,6-di-cyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-second-butyl-2-ethyl-6-tri-octyl acid, 2-isobutyl-4- Ethyl tert-hexyl phenol, 2-cyclohexyl 4-n-butyl-6-isopropyl phenol, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,3 - Tris(2-methyl-4-hydroxy-5tris-butylphenyl)ethane, triethylene glycol-tris[3-(3-tri-butyl-5-methyl-4-hydroxyphenyl) Propionate], 1,6-hexanediol-bis[3-(3,5-di-tris-butyl-4-transphenyl)propionate], 2,2-sulfonate Ethyl 2-[3-(3,5-di-tris-butyl-4,4-hydroxyphenyl)propionate], N,N'-hexamethylenedi(3, 5-di. No. -78-1309246 Tri-butyl-4-hydroxy-hydrocinnamate, 1,3,5-tri ( 2,6-Dimethyl-3-hydroxy-4-tri-butylbenzyl)isocyanate, 1,3,5-tris(3,5-di-tris-butyl-4-hydroxyphenyl)isocyanate, 1 ,3,5-tris[3,5-di-t-butyl-4-hydroxyphenyl)propenyloxyethyl]isocyanate, tris(4-tri-butyl-2,6-dimethyl Isocyanate, 2,4-di(η-octylthio)-6-(4-hydroxy-3,5-di-tris-butylanilino)isocyanate, 1,3 5-trimole, tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]amine, bis[3,3-di(3-tri-butyl-) 4-hydroxyphenyl)butyric acid diol]ether, anthracene, fluorene-φ bis[3-(3,5-di-tris-butyl-4-hydroxyphenyl)propanyl] well, 2,2 '-oxazolamide II [ethyl-3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], bis[2-tris-butyl-4-methyl -6-(3-tris-butyl-5-methyl-2hydroxy; hydroxy)phenyl]p-nonanoate, 1,3,5-trimethyl-2,4,6-tris (3 ,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-{々-(3-tri-butyl-4-hydroxyl) -5-methylphenyl)propionyloxy}ethyl]-2,4,8, 10-tetradecyl[5,5]undecane, 2,2 -di[4-(2- (3,5-di-t-butyl- 4-hydroxypropylanilinyloxy))ethoxyphenyl]propane, /3 - (3,5-di-tertiary-butyl%-4-hydroxybenzene Alkyl propionate, tetrakis-[methyl-3-(3',5'-di-tris-butyl-4-hydroxyphenyl)propionate]methane, octadecyl-3-(3) ,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tri-butylphenyl)butane, Thiodiethylene-bis[3-(3,5-di-tris-butyl-4-hydroxyphenyl)propionate], ethylidene di(oxyethyl)di[3-(3) ,5-di-t-butyl-4-hydroxyphenyl)propionate, trihexaol-di-[3-(3'-tris-butyl-5-methylphenyl)propionic acid Ester, l,l,3-tris(2-methyl-4-[3-(3,5-di-tris-butyl-4-hydroxyphenyl)propanyloxy]-5-third- Butyl phenyl) butane and the like. In this *•79- 1309246, it is also possible to use both at the same time. Among them, 1,3,5-trimethyl-2,4,6·tris(3,5-di-tri-butyl-4-hydroxybenzyl)benzene and tetra-[methyl-3 are preferred. -(3',5-di-tris-butyl-4-hydroxyphenyl)propionate]methane, thiodiethylene-bis[3-(3,5-di-tertiary-butyl 4-hydroxyphenyl)propionate]. The phenol compound of the present invention is preferably a hindered phenol structure. The amount of the phenolic compound to be used in the present invention is preferably from 5 X 10·5 based on the number of moles of all constituent units of the carboxylic acid component such as a dicarboxylic acid or a polycarboxylic acid in the obtained polyester. Mohr % to 1 mol%; more preferably φ is in the range from 1 X 1 (Γ4 mol% to 0.5 mol%. When the polyester is produced according to the present invention, a method known per se can be used. For example, when PET is produced, a method of esterifying and then re-condensing citric acid and ethylene glycol, or an alkyl ester of citric acid such as dimethyl phthalate, and The method of performing the esterification exchange reaction between the diols and then performing the heavy condensation may be carried out by any one of the methods. Further, the polymerization apparatus may be a batch type or a continuous type. The catalyst used in the polyester is not only % has a catalytic activity for the esterification reaction of the polycondensation reaction, but also has a catalytic activity for the esterification exchange. For the dicarboxylic acid such as dimethyl phthalate The esterification exchange reaction between the alkyl ester and ethylene glycol, usually in zinc, etc. In the presence of an ester exchange catalyst, the catalyst of the present invention may be used in place of or in combination with the catalyst. Further, in the polymerization of the polyester according to the method of the present invention, The catalyst may be used for melt polymerization, and has catalytic activity for either solid phase polymerization or solution polymerization, and the polyester may be produced by any method. -80 - 1309246 When polymerizing polyester according to the method of the present invention The catalyst to be used may be added to the reaction system at any stage of the polymerization reaction. For example, it may be at any stage before the start of the esterification reaction or the esterification exchange reaction and in the middle of the reaction, or in the case of the polycondensation reaction. Adding to the reaction system before starting and at any stage in the middle of the reaction. In particular, it is preferred to add the compound containing no aluminum just before the start of the polycondensation reaction. The touch used in polymerizing the polyester according to the method of the present invention The method of adding the medium or other compound may be a slurry or a solution of a solvent such as a powder or a kneaded form, or a solvent such as ethylene glycol, or a solution, and is not particularly limited. The catalyst component and other compounds may be added in advance, and may be added separately. Alternatively, a mixture of the catalyst solution of the aluminum compound of the present invention and a mixture of other compounds may be added and added separately. The catalyst component and other compounds may be added to the side polymerization system at the same time, and the individual components may be added separately. Further, the catalyst and other compounds may be added at once, and may be added in plurals.

The term "polyester" as used in the present invention means at least one selected from the group consisting of ester-forming derivatives of dicarboxylic acids and polycarboxylic acids, and at least one selected from the group consisting of glycol-containing polyols. Or two or more of the resulting substances; or a product derived from a hydroxycarboxylic acid and an ester-forming derivative thereof; or a product formed from a cyclic ester. It can be used as a dicarboxylic acid, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and ten base two. Carboxylic acid, dodecyldicarboxylic acid 'tetradecyl dicarboxylic acid, hexadecyl dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,2- Saturation of cyclohexyl-81 - 1309246 alkanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, iota, 4-cyclohexanedicarboxylic acid, 2,5-n-decene dicarboxylic acid, dimer acid, etc. An aliphatic dicarboxylic acid or an ester-forming derivative thereof; an unsaturated aliphatic dicarboxylic acid exemplified as fumaric acid, maleic acid or itaconic acid or an ester-forming derivative thereof; o-decanoic acid or isophthalic acid , citric acid, 5-(alkali metal) thioisophthalic acid, diphenyl acid, 1,3-naphthalene dicarboxylic acid, iota, naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6 -naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4·-diphenyldicarboxylic acid, 4,4'-diphenylthiodicarboxylic acid, 4,4'-diphenyl ether dicarboxylate An aromatic dicarboxylic acid or an ester thereof exemplified by an acid, 1,2, bis(phenol oxy)ethane-p,p|-dicarboxylic acid, palmitic acid, 蒽φ dicarboxylic acid or the like. Among these dicarboxylic acids, preferred are citric acid, naphthalene dicarboxylic acid, and 2,6 naphthalene dicarboxylic acid. For example, it is ethane tricarboxylic acid, propane tricarboxylic acid, butane tricarboxylic acid, pyromellitic acid, trimellitic acid, trihydroxyl. Formic acid, 3,4,3,4,-biphenyl-nonanoic acid' and its ester-forming derivatives.

It can be used as a diol, for example, 'e.g., ethylene glycol, hydrazine, 2. propylene glycol, 1,3-propanediol, diethylene glycol, triethylene glycol, I,2-butanol, 1, 3_ butanediol, 2,3-butanediol, hydrazine, 4·butanediol, I,5·pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol 1,3_cyclohexanol, hydrazine, 4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, hydrazine, 4-cyclohexanedimethanol, 1,4- Aliphatic exemplified by cyclohexanediethanol, hydrazine, 10-trimethylene glycol, 1,12-dodecyl diol, polyethylene glycol, polytrimethylene glycol, polytrimethylene glycol, etc. Alcohol; hydroquinone, 4,4'-hydroxydiphenol, 1,4-bis(no-hydroxyethoxy)benzene, 1,4·bis(col-ethoxyethylphenyl)pyrene, double (p_xiang Phenyl)ether-82- 1309246, bis(p-phenyl)anthracene, bis(p-phenyl)carbene, 1,2-bis(p-phenyl)ethane, biphenol A, An aromatic diol exemplified by phenol C, 2,5-naphthyl glycol, a diol to which ethylene oxide is added to the diol, and the like, and ethylene glycol and 1, among these diols. 4-butanediol is idealThe polyol other than the diol may, for example, be trimethylolethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol or hexanetriol. It can be used as a hydroxycarboxylic acid, for example, lactic acid, niacin, apple φ acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzene. Formic acid, 4-hydroxycyclohexanecarboxylic acid, or an ester-forming derivative thereof. The cyclic ester may, for example, be ε-caprolactone, propiolactone, /3·methyl-wan-propiolactone, valerolactone, glycolate, lactide or the like. Further, in the polyester of the present invention, a known phosphorus compound may be included as a copolymerization component. The phosphorus compound is preferably a difunctional phosphorus compound, and examples thereof include, for example, dimethyl phenylphosphonate, diphenyl phenyl phosphonate, and (2-carboxyethyl)methylphosphinic acid. (2-carboxyethyl)phenylphosphinic acid, methyl (2-methoxycarboxyethyl)phenylphosphinate, methyl (4-methoxycarboxyethyl)phenylphosphinate, [2- (/3-Hydroxyethoxycarbonyl)ethyl]methylphosphinic acid ethylene glycol ester, (1,2-dicarboxyethyl)methylphosphine oxide, 9,10-dihydro-10-oxygen- (2,3-Carboxypropyl)-10-phosphine-exetylene-10-oxide. By making the copolymerization component containing these phosphorus compounds, the flame retardancy and the like of the obtained polyester can be increased. As an ester-forming derivative of a polyvalent carboxylic acid or a hydroxycarboxylic acid, for example, -83-1309246 is described as, for example, an alkyl ester, an acid chloride, an acid anhydride or the like. In the polyester used in the present invention, it is preferred to use a main acid component as a phthalic acid or an ester-forming derivative thereof, or a naphthalene dicarboxylic acid or an ester-forming derivative thereof; the main alcohol component is a stretched alkane Alcohol polyester. Preferably, the polyester is based on the total acid component of citric acid or an ester-forming derivative thereof, or the entire acid component of the naphthalene dicarboxylic acid or an ester-forming derivative thereof, preferably containing citric acid. Or a polyester-forming derivative thereof and a polyester having a total amount of naphthalene dicarboxylic acid or an ester-forming derivative thereof of 70 mol% or more, more preferably a polyester of 80 mol% or more, most preferably More than 90% polyester. The main alcohol component is a polyester of alkylene glycol, preferably more than 70 mol% of the total amount of alkylene glycol, more preferably 80 mol%, based on the total diol component. The polyester above % is most preferably a polyester of more than 90 mol%. The alkylene glycol as referred to herein may also be a structure having a substituent or an alicyclic structure in the molecular chain.

As the naphthalene dicarboxylic acid or its ester-forming derivative used in the present invention, for example, it is preferably 1,3 -naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1, A naphthalene dicarboxylic acid such as 5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid or 2,7-naphthalene dicarboxylic acid or an ester-forming derivative thereof. The alkylene glycol which can be used in the present invention is ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, diethylene glycol, triethylene glycol, 1,2-butanediol. , 1,3-butanediol, 2,3-butanediol, iota, butanediol, 1,5-pentanediol, neopentyl glycol, 1,6·hexanediol, 1,2- Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, hydrazine, 3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, iota, 10-decethylene glycol, ^2-84- 1309246, dodecyl glycol, and the like. It is also possible to use two or more of these at the same time. In the polyester of the present invention, 'the oxalic acid, malonic acid, succinic acid can be used as the acid component other than the phthalic acid or its ester-forming derivative, or the naphthalene dicarboxylic acid or its ester-forming derivative. , glutaric acid, adipic acid, pimelic acid 'suberic acid, azelaic acid, sebacic acid, decahydrodicarboxylic acid, dodecyl dicarboxylic acid, tetradecyl dicarboxylic acid, hexadecyl dicarboxyl Acid, 1,3·cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4- Saturated fat of cyclohexanedicarboxylic acid, 2,5-n-decene dicarboxylic acid, dimer acid, etc. #Adicarboxylic acid or an ester-forming derivative thereof, fumaric acid, maleic acid, itacon An unsaturated aliphatic dicarboxylic acid or an ester-forming derivative thereof exemplified by an acid or the like; o-decanoic acid, isophthalic acid, p-citric acid, 5-(alkali metal) sulfur isophthalic acid, diphenyl acid, 4, 4 '-Diphenyldicarboxylic acid, 4,4'-diphenylthiodicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 1,2-bis(phenoloxy)ethane-P, P, Forming derivatization of an aromatic dicarboxylic acid or an ester thereof exemplified by a dicarboxylic acid, palmitic acid, stilbene dicarboxylic acid or the like; ethane tricarboxylic acid, propane Tricarboxylic acid, butane tricarboxylic acid, pyromellitic acid, trimellitic acid, trihydroxycarboxylic acid, 3,4,3 ', 4 1 -biphenylparaben, and ester-forming derivatives thereof; lactic acid, Citric acid, malic acid, tartaric acid, glycolic acid, 3-hydroxybutyric acid, P-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or ester-forming derivative thereof Things and so on. Further, it may contain a cyclic ester exemplified by ε-caprolactone, ιδ-propiolactone '泠-methyl-/3-propiolactone, 5-valerolactone, glycolate, lactide, and the like. . In the polyester of the present invention, it can be used as a diol component other than an alkylene glycol, for example, containing diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene glycol, polytetrazol. An aliphatic diol exemplified by methyl glycol or the like; hydroquinone, 4,4·-85- 1309246 hydroxydiphenol, 1,4-bis(no-hydroxyethoxy)benzene, 1,4-bis (/ 3-hydroxyethoxyphenyl)anthracene, bis(P-hydroxyphenyl)ether, bis(p-hydroxyphenyl) maple, bis(p-hydroxyphenyl)methane, 1,2-bis(p-hydroxybenzene) An aromatic diol exemplified by ethane, biphenol A, biphenol C, 2,5-naphthalene diol, diol having ethylene oxide added thereto, etc.; trimethylolethane, The polyol exemplified as trimethylolethane, trimethylolpropane, pentaerythritol, glycerin or hexanetriol is a copolymerization component. Further, in the polyester of the present invention, a known phosphorus compound φ may be included as a copolymerization component. The phosphorus compound is preferably a difunctional phosphorus compound, and examples thereof include, for example, dimethyl phenylphosphonate, diphenyl phenylphosphonate, (2-carboxyethyl)methylphosphinic acid, ( 2-carboxyethyl)phenylphosphinic acid, methyl (2-methoxycarboxyethyl)phenylphosphinate, methyl (4-methoxycarboxyethyl)phenylphosphinate, [2-( Ethylene glycol ester of stone-hydroxyethoxycarbonyl)ethyl]methylphosphinic acid, (1,2-dicarboxyethyl)methylphosphine oxide, 9, 10-dihydro-10-oxo- (2 , 3-carboxypropyl)-1〇-phosphine, phenethylamino-10 oxide, and the like. By making the copolymerization component containing these phosphorus-based compounds, the flame retardancy and the like of the obtained polyester can be increased by %. It can be used as the polyester of the present invention, preferably polyethylene terephthalate, propylene terephthalate, poly U,4-cyclohexanemethylene terephthalate, polynaphthalene Ethylene glycol ester, polybutylene naphthalate, propylene glycol naphthalate and copolymers thereof; among them, polyethylene terephthalate and copolymers thereof are particularly preferred. In order to improve the dyeability in the case of using as the ester fiber, a preferred embodiment is a copolymerized component of a polycarboxylic acid having a calcium sulfate metal salt group as a constituent of the polyester of the present invention. . -86 - 1309246 A metal-containing sulfate group used as a copolymerized monomer' is not particularly limited to a substance, for example, {sodium thioisophthalate, 2-sodium sulphate citrate 5 - lithium thioisophthalic acid sulfur bismuth citrate, 5-potassium thioisodecanoate, 2-potassium sulphate citrate alkyl ester derivative, and the like. In the present invention, it is particularly preferable to use a 5-sodium isothioate-forming derivative. The amount of the copolymerization of the metal sulfate-containing compound is preferably from 0.3 to 10.0 mol%, more preferably from 0.80 to φ%, based on the acid component. When the amount of copolymerization is too small, when the dyeability of the salt-based dye is deteriorated, in the case of forming a fiber, not only the yarn-forming property but also the viscosity is increased, so that the obtained fiber strength is insufficient. 2.0 mol% or more of a metal sulfate-containing compound to impart a modified polyester fiber having a normal pressure dyeability. Further, the easy-dyeing monomer can appropriately reduce the amount of metal sulfate-containing used. It can be used as an easily dyeable monomer, and is not particularly limited. For example, it is a long-chain diol compound of polyethylene glycol, polytetramethylene%, or adipic acid or sebacic acid. An aliphatic dicarboxylic acid. After the polyester is polymerized according to the method of the present invention, the polymerization can be made higher by the addition of the phosphorus compound to deactivate the catalyst. In the polyester of the present invention, it may include a phenol-based or aromatic oxidation preventing agent, and for example, one or the like may be included to make the thermal stability of the polyester higher. The compound is, for example, 5-salt, 2-lithium, or its lower bismuth or 5.0 mils of polyester, when too much is poor. Further, when polymerizing, a suitable base compound is selected as a diol or a thermal anion amine such as a catalyst or an ester, and more than -87 to 1309246 are used in the polyester of the present invention. It may include a blue agent, an organic system, an inorganic system, or an organometallic dye, a pigment, a fluorescent whitening agent, etc.; if one or more of these may be contained, the yellow color of the polyester may be inhibited. Wait for the color. The polyester of the present invention may also include other polymers or stabilizers, oxidation inhibitors, electricity generators, antifoaming agents, dyeability improvers, dyes, pigments, deodorants, and other additives. Such an additive may be added at the time of polymerizing the polyester or after the polymerization, or at any stage of the formation of the poly- φ ester; the appropriate stage may be due to the properties of the polymer or the performance requirements of the polyester formed body. Different. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited thereto. The evaluation method used in the embodiment of the present invention is as follows. (1) The content of metals and phosphorus in the polymer. The contents of phosphorus, cerium and lanthanum are determined by a fluorescent X-ray method. The test sample % polyester was placed in a 5 mm, 40 mm diameter non-steel ring placed on a photographic iron plate. It was melted by heating at 300 ° C for 10 minutes in an oven. After taking it out and cooling it, the sample formed by the loop was taken out, and the smooth side was measured. In addition, the other method is a chemical analysis method in which a plurality of points of a predetermined polyester are formed by the above method, and the intensity of the fluorescent X-rays is measured to obtain enthalpy and fluorescent X-rays obtained by a chemical analysis method. Check line. The content of phosphorus, bismuth, and antimony in each sample was calculated based on the calibration curve obtained by measuring the fluorescence X-ray intensity data of the sample polyester. -88- 1309246 Other metal contents were determined by the following methods. Weigh 1.0 kg of polyester, ash it in a platinum carbide furnace at 550 ° C in a platinum crucible, and cool to room temperature with 6N hydrochloric acid (in the case of titanium, it is hydrofluoric acid / The hydrochloric acid mixture was dissolved, and the mixture was evaporated to dryness, and then dissolved in 1.2 N hydrochloric acid to be supplied to a high-frequency plasma luminescence analysis (ICPS-2000, manufactured by Shimadzu Corporation) and atomic absorption analysis (manufactured by Shimadzu Corporation, AA). - 640 - 1 2) The sample on it. Further, in another method, a commercially available standard solution for atomic absorption is used to prepare a calibration line φ solution for each metal to be measured in a concentration range of 0.1 to 30 mg/liter to a high frequency. Plasma luminescence analysis (Al, Ca, Mg, Co) and atomic absorption analysis (Na, Li, K) are performed to make a calibration curve, based on the calibration curve, and the analysis data of each sample is used. The metal content in the polyester was calculated. (2) Viscosity of polyester (IV) Dissolve 0.1 g of polyester in a mixed solvent of 25 ml of phenol/1,1,2,2-tetrachloroethane in a weight ratio of 6/4. Uberalda viscosity meter, measured at a temperature of 30 °C.

The polyester was freeze-pulverized and dried under vacuum at 130 ° C for 12 hours or more. A 0.1 g sample was placed in the test, and 10 ml of benzyl alcohol was added to dissolve it. After dissolution, it was allowed to cool in a water bath. 10 ml of chloroform, phenolphthalein indicator was added and titrated with a 0.1 N NaOH methanol/kilo alcohol = 1/9 solution to obtain an acid hydrazine. (4) Diethylene glycol content (DEG) 0.11 g of polycondensed in 2 ml of methanol, after 25 (TC heating decomposition -89- 1309246, by gas chromatography (using Shimadzu Corporation) GC - 1 4B ) Quantitatively determined. The column was analyzed using a column of PEG-HT 迪 迪 迪 迪 5 (5) Differential Scanning Thermal Analysis (DSC) using the DSC2920 manufactured by ΤΑ Instruments 1. About 10.0 mg of the polyester was sealed in a special aluminum basin for the autosampler manufactured by ΤΑ Instruments Co., Ltd., and heated to 280 ° C at a heating rate of 50 ° C/min, and reached at 280 ° C for 1 minute. Thereafter, the mixture was quenched with liquid nitrogen, and then heated from room temperature to φ at a temperature increase rate of 20 ° C /min to 300 ° C to obtain a crystallization temperature Tc 1 at a temperature rise and a melting point Tm. After reaching 30 (the TC is kept for 2 minutes, the temperature is lowered at 10 ° C / min to obtain the crystallization temperature Tc2 at the time of cooling. The maximum part of each peak is used as the temperature of Tel, Tro, Tc2 respectively ( 6) The hue is measured by a color difference meter (manufactured by Tosei Electric Co., Ltd., TC-1500MC-88) to determine the characteristics of the Hunter , a値, b値. In the case where the measurement sample is a poly% ester resin sheet, a sheet having a diameter of about 2 mm and a length of about 3 mm is obtained by the method described in the examples, and air-dried on the filter paper at room temperature. After a day and night, use it to determine the color. (7) Evaluation of the pressure rise during spinning and the breaking of the yarn during stretching. The PET resin sheet obtained by melt polymerization is dried and then supplied to the melt extruder. Using a 20 micron filter, spit out from a spinning port of 290 ° C with a hole diameter of 0.14 mm Φ, and cool it by the usual method. After refueling, 1 7 20 Take the meter/min. Continue to take the lead, use -90- 1309246 to preheat 80C light, set the temperature to 150 ° C, stretch 2 127 times, and get 47 dt ex, 1 08 filament polyester stretch In addition, the evaluation of Examples 1 to 5 was carried out using different spinning machines. According to the degree of increase in the furnace pressure during the knotting, the following evaluation was carried out. 〇: It is true that there is no increase in filtration pressure. △: The filter pressure rise is recognized; X: The filter pressure rises remarkably. According to the broken wire frequency during stretching, it is evaluated according to the following φ 〇: does not cause broken wire; △: causes broken wire; X: multiple broken wire occurs. (8) Thermal stability parameter (TS) The IV of melt polymerization of 1 gram is 0.64 ~ 0.66 dl / gram (melting Before the test: the PET resin sheet of [IV] i) was placed in a glass test tube with an inner diameter of about 14 mm, and after 13 hours of vacuum drying for TC, the glass test tube on the vacuum line was decompressed, and After the nitrogen gas was sealed and repeatedly operated for 5 times or more, the nitrogen gas was sealed with 100 torr and the tube was sealed. The test tube was immersed in a salt bath at 300 ° C, and after being kept in a molten state for 2 hours, the sample was taken out, freeze-pulverized, and vacuum dried, and then measured IV (before melting test: [IV ] f ) ° using the following calculation From the [IV]f, the TS is obtained. This type is cited (Shangshan La: Japan Rubber Association, Vol. 63, No. 8, p. 497, 1990). TS = 0.245 { [IV]r -1·47 - [IV]i 147 } (9) Thermal oxidation stability parameter (TOS) The melt polymerization IV is 0.64~0.66dl/g (UIV before melting test)1) -91 - 1309246

The PET resin sheet of the correction sheet is freeze-pulverized into a powder of 20 mesh or less by a usual method. 0.3 g of 1 3 (TC vacuum drying the powder for 12 hours) was placed in a glass test tube having an inner diameter of about 8 mm and a length of 140 mm. After vacuum drying at 70 ° C for 12 hours. The drying tube which is poured into the silicone rubber is connected to the upper portion of the test tube, and is immersed in a salt bath at 230 ° C for 15 minutes under dry air. The following calculation formula is used in the same manner as the above TS, from the heating After the test, the IV of PET was obtained from TS. However, it refers to [IV], and [IV] fi before the heating test and after the heating test IV (d 1 /g). The frozen crushing system uses a honing machine (American Spey) Co., Ltd. made of Model 6750). After loading about 2 grams of resin sheet and special impactor into the special cell, set the cell to the device and fill it with liquid nitrogen for about 10 minutes. The pulverization was carried out for about 5 minutes at a rate of 10 (after about 20 seconds for the impactor). T0S = 0.245 { [ IV] fi'1'47 - [ IV] i (1 0 ) Thermal stability of the film ( i) Film formation of film

The PET sheets obtained by melt polymerization in the examples and comparative examples described later were vacuum dried at 135 ° C for 6 hours. Thereafter, the film was supplied to an extruder, melted at a sheet temperature of 280 ° C, and solidified by a metal roll having a surface temperature of 20 ° C to obtain a cast film having a thickness of 1,400 μm. Then, the cast film was heated by a heating roll group and an ultraviolet heater at 1 ° C, and then a roll set having a circumferential speed difference was used, and the set direction in the longitudinal direction was 3.4 times stretched to obtain a single axis. Oriented PET film. Then' continue to be gentle at 120. (:, set in the width direction 値 is 4 · 0 times stretched in 'the width is -92-

1309246 In a fixed state, at 60 ° C, the infrared heater was used to heat the crucible. 5 seconds One step was subjected to 3% relaxation treatment at 200 ° C for 23 seconds to obtain a 1 μ micro-biaxially oriented PET film. (ii) a film obtained by recovering nine films to obtain a film, and the PET film obtained by the method described in the above (i) is cut into a short vacuum-dried and then placed in an extruder, and the resin is melted at a temperature of 280 ° C. After being extruded from a nozzle having a diameter of 5 mm, it was cooled with water to be cut to obtain nine pieces. The PET resin sheet obtained by melt polymerization and the above-mentioned recovered particles were mixed at a weight ratio of 50:50 at 135. (When it is vacuum dried, it is then supplied to an extruder, melted at a temperature of 280 ° C, melted in a sheet, and solidified on a metal roll having a surface temperature of 20 ° C to obtain a cast film having a thickness of micron. Next, After the casting was heated by a heating roll set and an ultraviolet heater at 100 ° C, a uniaxially oriented PET film was obtained by using a roll set having a peripheral speed difference and a set 値 of 3 in the longitudinal direction to obtain a uniaxially oriented PET film. Miltly stretched at a concentration of 4.0 in the width direction at a ratio of 4.0 in the width direction to obtain a microscopic biaxially oriented PET film. The obtained film was again cut into a short grid shape, and recovered in the same manner as described above. The film is formed into a film. The operation is carried out five times in reverse (iii) The thermal stability of the film is measured. The obtained film is cut into a length of 8 cm and a width of 4 cm, and the obtained film is slowly obtained. The film is stretched in the direction of the length of the film, and melted in the grid of the rice, which is less than the surface of the 1400 film, 5 times 120 100. The above test evaluation -93- 1309246 is easy to cut. 〇: good; : Poor. (11) The heat aging resistance of the film will be utilized. The film obtained by the method of (10)(i) was cut into a test piece having a length of 10 cm and a width of 5 cm, and the test piece was treated at 200 ° C using a gear type hot air dryer. After 0 hours, the length direction of the obtained film was slowly stretched to evaluate the heat aging resistance of the film. ◦: good; X: poor. (12) 1H-NMR measurement of synthetic phosphorus compound φ The compound was dissolved in CDC13 or d6-DMSO and assayed at room temperature using a Fahrenheit GEMINI-200. (1 3) Determination of the melting point of the synthetic phosphorus compound The compound was coated on glass using a Younger Micro melting point apparatus. The temperature is measured at a temperature of 1 ° C / min. (1 4 ) Elemental analysis of synthetic phosphorus compounds Phosphorus analysis is carried out by wet decomposition of PET flakes, followed by molybdenum blue-colorimetry. After the acid/acid dissolution, it is carried out by high-step rate plasma % luminescence analysis and atomic absorption analysis. (Example 1-1) (Synthesis Example of Phosphorus Compound) Phosphorus compound represented by the following formula (Chem. 44) Synthesis of Compound a) [Chemical 4 4]

-94- 1309246 Amendment page 17 years? Lunar New Year. Japanese repair (history) is replacing 1 sodium (oxy-ethyl 3,5-di-tri-butyl-4-hydroxyphenylphosphonate) synthesis at 6.5 g (84 mmol) 50% 5 g (14 mmol) of diethyl (3,5-di-t-butyl-4-hydroxybenzyl)phosphonate (I) was added to a mixed solution of sodium hydroxide and 6.1 ml of methanol (I) A methanol solution of ragnoxl 222 (available from Ciba Specialty Chemicals Co., Ltd.) was heated under reflux for 24 hours under a nitrogen atmosphere. After the reaction, while cooling the reaction mixture, 7.33 g (70 mmol) of concentrated hydrochloric acid was added, and the precipitate was taken out and washed with isopropyl alcohol, and then the filtrate was evaporated under reduced pressure. The obtained residue was dissolved in hot isopropanol, and the insoluble matter was taken out, and the isopropyl alcohol was distilled off under reduced pressure, and then the residue was washed with hot heptane and dried to give 3.4 g (69%) of sodium (oxygen-B). 3,5-di-t-butyl-4-hydroxybenzylphosphonate). Shape: White powder: Melting point: 294~302 °C (decomposition) 'H-NMRCde-DMSO. ό): l.〇78(3H.t, J=7Hz), 1.354 (18H, s). 2.71K2H. d 3,724 (2H.m. J=7Hz). 6.626(1H, s), 6.9665(2H. s)

Elemental analysis (theoretical 括 in brackets): Na: 6 · 36% ( 6 . 56%), P : 9.18% (8.84%) Oxy-ethyl 3,5-di-tert-butyl-4-hydroxyl Synthesis of benzylphosphonic acid (phosphorus A) with 1 gram (2.8 mmol) of sodium (oxy-ethyl 3, 5-di-tertiary-butyl·4) in 20 ml with stirring at room temperature To the aqueous solution of the hydroxybenzylphosphonate, 1.5 g of concentrated hydrochloric acid was added and stirred for a few hours. 150 ml of water was added to the reaction mixture, which was filtered, washed with water and dried to give 826 mg (8 8%) of oxy-ethyl 3, 5-di-tri-butyl-4. - Hydroxybenzylphosphonic acid. Shape: plate crystal; -95- Ϊ309246

Melting point: 1 2 6 ~ 1 2 7 °C • H-NMR (CDC'la, δ): 1.207 (3 Η, t, J = 7 Hz), 1.436 (18H, s), , 3.013 (2H, d), 3.88 8 (2H. in. J=7Hz). 7.088(2H. s). 7.679-8.275(IH. br). (Polyester polymerization example)

Using a 2 liter stainless steel autoclave with a stirrer, a mixture of bis(2-hydroxyethyl)p-phthalate and oligomer produced from high purity p-citric acid and ethylene glycol according to a conventional method, Adding 2.5 g/L of an ethylene glycol solution of aluminum triacetate, and 20 g/L of the above ethylene compound solution of the phosphorus compound A, and 50 g/L of sodium acetate in ethylene glycol solution Polycondensation catalyst. The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 1. The amount of the metal component added to the catalyst is at least the same as that obtained according to the analysis result of the vaporization during the polymerization, but the added phosphorus component is more than the analysis during the polymerization and the volatilization during the formation. result. Further, the amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, the mixture was stirred under a nitrogen atmosphere at normal pressure at 245 ° C for 10 minutes. Subsequently, the temperature was raised to 27 5 ° C for 50 minutes, and the reaction system pressure was gradually lowered to 0.1 Torr, and the polycondensation reaction was further carried out at 27 5 ° C and 0.1 Torr. The polymerization time required for the polyethylene terephthalate to reach 0.65 d 1 /g is shown in Table 1. Further, polyethylene terephthalate having an IV of 0.65 dl / gram obtained by the above polycondensation was exfoliated according to a usual method. That is, when the melt polymerization reaches a predetermined stirring torque, nitrogen gas is introduced into the autoclave, returned to normal pressure, the polycondensation reaction is stopped, and the discharge nozzle is continuously discharged under the pressure of about 0.1 mg. The molten polymer was extruded into a bundle, quenched in cold water, and cut into a cylindrical sheet having a diameter of about 3 - 96 - 1309246 mm and a diameter of about 2 mm by a cutter. The hold time in cold water is about 20 seconds. The sheet was used to determine the physical properties of PET. The results were 'IV of 0.65 dl/g, acid bismuth of 2 eq/ton, DEG of 2_1 mol%' Tm of 256.6 °C, Tel of 166. (TC, Tc2 was 188_6 ° C. Further, L 値 was 66.0, a 値 is -1.8, and b 値 is 3.6. The evaluation of the filtration pressure at the time of spinning and the breaking of the yarn during the drawing using the PET resin sheet are shown in Table 1. Example 1 - 2 to 1 - 3, Comparative Example 1 - 1 ) φ The polyester was polymerized in the same manner as in Example 1-1 except that the catalyst was changed. In each of the examples and the comparative examples, it was used as The catalyst compounds are shown in Table 1. The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 1. Polymerization of each of Examples and Comparative Examples The results, the evaluation of the filtration pressure at the time of spinning, and the evaluation results of the broken yarn at the time of stretching are shown in Table 1. I rag η ο X 1 4 2 5 is a product manufactured by Ciba Specialty Chemicals Co., Ltd. And the phosphorus compound was synthesized using the same method as in Example 1-1. [Table 1] It can be understood from the above examples and comparative examples: When the content of the metal in the polyester is within the scope of the patent application of the present invention, both the spinning and the stretching workability are excellent; in contrast, outside the scope of the patent application of the present invention, the result is when spinning The filtration pressure is remarkably increased, and the yarn breakage often occurs during stretching, and the workability is poor. (Example 2 - 1 ) A double produced from high purity p-citric acid and ethylene glycol according to a conventional method. (2 - -97- 1309246

a mixture of hydroxyethyl) phthalate and an oligomer, added with 2.5 g/L of an ethylene glycol solution of aluminum triacetate, and 50 g/L of a solution of lithium acetate dihydrate in ethylene glycol. A polycondensation catalyst. The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 2. However, the content is expressed by mol% relative to the metal atom of the acid component in the polymer. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, the mixture was stirred under a nitrogen atmosphere at normal pressure at 245 ° C for 10 minutes. Then, the temperature was raised to 27 5 ° C for 50 minutes, and the pressure of the reaction system was gradually lowered to 0.1 tol, and the polycondensation reaction was further carried out at 27 5 ° C and 0.1 tol. The polymerization time required for the polyethylene terephthalate to reach 0.65 dl / gram is shown in Table 2. Further, polyethylene terephthalate having an IV of 0.65 dl / gram obtained by the above polycondensation was exfoliated according to a usual method. This PET resin sheet was used to carry out the evaluation of the filtration pressure at the time of spinning and the breaking of the yarn at the time of stretching. The results of the evaluation are shown in Table 2. (Example 2 - 2 to 2 - 6, Comparative Example 2 - 1 to 2 - 2) A polyester was polymerized in the same manner as in Example 2-1 except that the catalyst was changed. The results are shown in Table 2. In Examples 2 to 6, magnesium acetate and aluminum acetate were added as a polycondensation catalyst, and dimethyl phenylsulfonate was added in an amount of 0.01 mol% based on the acid component in the polymer. [Table 2] From the above examples and comparative examples, it is understood that when the content of the metal in the polyester is within the scope of the present invention, both the spinning and the stretching work are excellent; Outside the scope of the patent application of the present invention, when -98- 1309246 is the year of the bamboo. The bow repair (laugh) is replacing the correction sheet. When the spinning is performed, the rolling pressure is remarkably increased, and the yarn is often broken during stretching, which is inferior in workability. (Example 3-1) A mixture of bis(2-hydroxyethyl)-p- phthalate and an oligomer produced by high-purity citric acid and ethylene glycol according to a conventional method was added in an amount of 2.5 g/liter. A polycondensation catalyst made of an ethylene glycol solution of aluminum triacetate and an ethylene glycol solution of 10 g/liter of Iragnox 1425 (manufactured by Ciba Specialty Chemicals Co., Ltd.). The content of each metal atom and phosphorous φ in the polymer finally obtained from the compound was added in an amount shown in Table 3. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, the mixture was stirred under a nitrogen atmosphere at normal pressure at 24 ° C for 10 minutes. Then, the temperature was raised to 27 5 ° C for 50 minutes, and the pressure of the reaction system was gradually lowered to 0.1 tol, and further, a polycondensation reaction was carried out at 275 ° C and 0.1 tol. The polymerization time required for the IV of the polyethylene terephthalate to reach 〇.65 dl/g is shown in Table 3. Further, polyethylene terephthalate having an IV of 0.65 dl / gram obtained in the above polycondensation was subjected to sheet nitration according to a usual method. The sheet was used to determine the physical properties of PET. The results 'IV is 〇·65 dl / gram, acid equivalent is 6 equivalents/ton, DEG is 2.1 mol for 256.3 °C, and Tc2 is 186_2 °C. Further, L 値 is 68.9' a 値 is - 2.56, and b 値 is 5.49. The PET resin sheet was used to carry out the evaluation of the filtration pressure at the time of spinning and the breaking of the yarn during the stretching. The evaluation results are shown in Table 3. Φ ° (Examples 3 - 2 to 3 - 9, Comparative Examples 3 - 1 to 3 - 3 ) Polymerization was carried out in the same manner as in Example 3-1 except that the catalyst was changed. -99- 1309246 Ester. In each of the examples and comparative examples, the compounds used as the catalyst were shown in Table 3, respectively. The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 3. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. In Examples 3 - 9, ruthenium trioxide was used as a catalyst. Antimony trioxide is added in accordance with the content of germanium atoms in the finally obtained polymer. The results of the polymerization of each of the examples and the comparative examples, the filtration pressure during spinning, and the evaluation results of the broken yarn at the time of stretching are shown in Table 3. Iragnox φ 1 42 5 is a product made by Ciba Specialty Chemicals Co., Ltd., and phosphorus compound A is a product synthesized by the above method. [Table 3] It can be understood from the above examples and comparative examples that when the content of the metal in the polyester is within the scope of the present invention, both the spinning and the stretching workability are excellent; In addition to the scope of the patent application of the present invention, as a result, the filtration pressure is remarkably increased during spinning, and the yarn breakage often occurs during stretching, and the workability is poor.

Adding 13 g/L of aluminum trichloride to a mixture of bis(2-hydroxyethyl)p-phthalate and oligomer obtained from high-purity citric acid and ethylene glycol according to a conventional method. The alcohol solution and the acid component of the polyester are 〇. 〇1 4 mol%, and 10 g/l of Iragnox 1 42 5 (made by Ciba Specialty Chemicals Co., Ltd.) in ethylene glycol solution, relative The polycondensation catalyst made of 0.02 2 mol% of the acid component of the polyester was Iragnox 1425, and the mixture was stirred for 10 minutes under a nitrogen atmosphere at normal pressure at 245 t. Then, the temperature was raised to 275 ° C for -100 - 1309246 for 50 minutes, and the pressure of the reaction system was gradually lowered to 0.1 tol, and the polycondensation reaction was further carried out at 27 5 ° C and 0 · 1 torr. The polymerization time required for the polyethylene terephthalate to reach 〇 65 d 1 /g is shown in Table 4. The PET resin sheet contains 45 ppm of calcium atoms, so that the total content of metal atoms is 65 ppm. Such a PET resin sheet was used to carry out the evaluation of the filtration pressure at the time of spinning and the breaking of the yarn at the time of stretching. The results of the evaluation are shown in Table 4. (Example 4 - 2) (Synthesis Example of Phosphorus Compound) 8.13 g (50 mmol) of triethyl phosphite was synthesized under a nitrogen gas atmosphere of a phosphorus compound (NMPA) represented by the following formula (21). A gas (C2H5C1) was produced with a mixture of 8.83 g (50 mmol) of methyl chloride. The mixture was heated at 200 ° C (external temperature) for about 30 minutes. After cooling to room temperature, 10.8 g (yield: 75%) of a colorless oily liquid was obtained. 'H-NMR (CDC13, 5): 1.151 (6H, t). 3.64K2H. d), 3.948 (4H.m). 7.381-7.579 (4H, m&gt;, 7.749-7.867(2H.m). 8.088 -8.133 (1H. m) (Polyester polymerization example)

The polyester was polymerized in the same manner as in Example 4-1 except that the catalyst was changed. In the present embodiment, 2.5 g/L of an ethylene glycol solution of aluminum triacetate was used, and the aluminum atom was 0.014 mol% based on the acid component of the polyester, and 0.014 based on the acid component of the polyester. 50 g/L of the above-mentioned hydrazine ethylene glycol solution and 0. 02 mol% of ethylene glycol converted to 0.1% by weight of Iragnox 1330 (made by Ciba Specialty Chemicals Co., Ltd.) A solution, 50 g/liter of an ethylene glycol solution of lithium acetate dihydrate, and a compound having a lithium atom of 0.01 mol% based on the acid component of the polyester was used as a polycondensation catalyst. -101 - 1309246 The polymerization time required for the polyethylene terephthalate to reach 0.65 dl/g, and the amount of aluminum atoms and the amount of phosphorus atoms contained in the obtained PET resin sheet were measured.

The results, as well as the aluminum atomic ratio with respect to the phosphorus atom, are shown in Table 4. The amount of lithium atoms contained in the PET resin sheet is 4 ppm, so that the total content of metal atoms is 24 ppm. Such a PET resin sheet was used to carry out the evaluation of the rolling pressure at the time of spinning and the breaking of the yarn at the time of stretching. The evaluation results are shown in Table 4 〇 (Comparative Example 4 - 1 ) φ The polyester was polymerized in the same manner as in Example 4-1 except that the catalyst was changed. Using an ethylene glycol solution of 13 g/L of aluminum chloride, an ethylene glycol solution of 0.055 mol% of aluminum ion relative to the acid component of the polyester, and 50 g/l of lithium acetate dihydrate, relative to The acid component of the polyester is a compound having a lithium atom of 0.06 mol% as a polycondensation catalyst. The polymerization time required for the polyethylene terephthalate to reach 0.65 dl / gram is shown in Table 4. This PET resin sheet was used to carry out the evaluation of the filtration pressure during spinning and the breaking of the yarn during stretching. The results of the evaluation are shown in Table 4. Lu [Table 4] It is understood from the above examples and comparative examples that a polyester polymerized with an aluminum compound, a phosphorus compound, and a phenol compound is used, and the content of the metal in the polyester is within the scope of the present patent application. At the time, the spinning and stretching workability are excellent. On the other hand, in the case where a phosphorus compound or a phenol compound is not used, the thermal oxidation stability is deteriorated, and the filtration pressure is remarkably increased at the time of spinning. The yarn breakage often occurs during stretching, and the workability is poor. (Example 5 - 1 ) -102- 1309246 To a mixture of bis(2-hydroxyethyl)p-phthalate and oligomer obtained by high-purity citric acid and ethylene glycol according to a conventional method, 2 to 5 g was added. a polycondensation catalyst made of an ethylene glycol solution of aluminum triacetate and 10 g/liter of a solution of the above-mentioned phosphorus compound A in ethanol. The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 5. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, it was stirred for 10 minutes under nitrogen atmosphere at normal pressure at 245 °C. Next, the temperature was raised to 27.5 ° C for 50 minutes, and the pressure of the reaction system was gradually lowered to 托 1 Tory, and the polycondensation reaction was further carried out at 275 ° C and 0.1 Torr. The polymerization time required for the polyethylene terephthalate to reach 0.65 dl/g is shown in Table 1. Further, polyethylene terephthalate having an IV of 0.65 dl / gram obtained by the above polycondensation was exfoliated according to a usual method. This sheet was used to determine the physical properties of PET. The results of the evaluation are shown in Table 5. (Example 5 - 2) A mixture of bis(2-% hydroxyethyl)-p- phthalate and an oligomer obtained by high-purity p-citric acid and ethylene glycol was added in an amount of 2.5 g/liter. A polycondensation catalyst made of an ethylene glycol solution of aluminum triacetate and an ethylene glycol solution of 10 g/liter of Iragnox 1425 (manufactured by Ciba Specialty Chemicals Co., Ltd.). The content of each metal atom and phosphorus atom in the polymer finally obtained from the compound was added in an amount shown in Table 5. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. After the above solution was added, it was stirred for 1 Torr in a nitrogen atmosphere at normal pressure at 245 °C. Then, the temperature was raised to 275 t in 50 minutes, and the pressure of the reaction -103 - 1309246 was gradually decreased to 0.1 torr, and further, a polycondensation reaction was carried out at 275 ° C and 0.1 torr. The polymerization time required for the polyethylene terephthalate to reach 0.65 dl / gram is shown in Table 1. Further, polyethylene terephthalate having an IV of 0.65 dl / gram obtained by the above polycondensation was exfoliated according to a usual method. This sheet was used to carry out the evaluation of the filtration pressure at the time of spinning and the breaking of the yarn at the time of stretching. The results of the evaluation are shown in Table 5. (Comparative Example 5 - 1 to 5 - 2 ) A poly φ ester was polymerized in the same manner as in Example 5-1 except that the catalyst was changed. In each of the examples and comparative examples, the compounds used as the catalyst were shown in Table 5, respectively. The content of each of the metal atoms and phosphorus atoms in the polymer finally obtained from the compound was added in an amount shown in Table 5. The amount of addition is appropriately selected depending on the characteristics of the reactor used in the polymerization and the polymerization conditions. The results of the polymerization and the evaluation of the increase in the filtration pressure at the time of spinning and the breaking at the time of stretching are shown in Table 5. [Table 5] From the above examples and comparative examples, it is understood that when the content of the metal in the polyester is K within the scope of the present invention, both the spinning and the stretching workability are excellent; In addition to the scope of the patent application of the present invention, the filtration pressure is remarkably increased during spinning, and the yarn breakage often occurs during stretching, and workability is a poor result. (Example 6 - 1 ) (Polyester polymerization example) High-purity citric acid and 2 times the amount of ethylene glycol were put into a 2 liter stainless steel tube with a stirrer, and the acid component was added. The esterification reaction was carried out for 120 minutes, and the esterification reaction was carried out for 1 to 20 minutes while distilling off the water outside the system at 245 ° C under the pressure of 0.25 Mpa. a mixture of hydroxyethyl) p-phthalate and oligomer. To the mixture, 2.5 g/liter of an ethylene glycol solution of aluminum triacetate, an aluminum atom of 〇.07 mol% based on the acid component, and 10 g/liter of the ethylene compound of the above phosphorus compound A were added. The solution and a polycondensation catalyst made of a phosphorus atom of 0. 2 mol% based on the acid component were stirred under a nitrogen atmosphere at a normal pressure of 245 ° C for 10 minutes. Then, the temperature was raised to 27 5 ° C for 50 minutes, and the pressure of the reaction system was gradually reduced to φ 0·1 tol, and the polycondensation reaction was further carried out at 27 5 ° C and 0.1 tol. The polymerization time required for the polyethylene terephthalate to reach 0.65 dl / gram is shown in Table 6. (Examples 6-2 to 6-3, Comparative Examples 6-1 to 6-3) Polyester was polymerized in the same manner as in Example 6-1 except that the catalyst was changed. In each of the examples and comparative examples, the compounds used as the catalyst were shown in Table 6, respectively. The amount added is expressed by the amount of the aluminum atom and the phosphorus atom based on the acid component. The polymerization results are shown in Table 6. Phosphorus compound A is used in the above-mentioned article', and Iragnox 1425 is made from Ciba Specialty Chemicals. In Comparative Example 6-3, although the polymerization was carried out for 120 minutes or more, the predetermined viscosity was not obtained. (Examples 6 - 4) Triethylene acetoacetate and Iragnox 1425 were preliminarily mixed in ethylene glycol to prepare a solution to be used as a polycondensation catalyst. The polyester was polymerized in the same manner as in Example 6-1 except that the solution was added as a catalyst. The IV of the polyethylene terephthalate reached between -105 and 1309246 during the polymerization required for 65.65 dl / gram, and the same results as in Example 6-1. [Table 6] From the above examples and comparative examples, it is understood that when the amount of the aluminum compound and the phosphorus compound added is within the scope of the present invention, the catalyst activity is excellent, and the productivity of the polyester is also Excellent; in contrast, outside the scope of the patent application of the present invention, the catalytic activity is poor and the productivity of the polyester is also deteriorated. (Example 7 - 1 ) _ (Polyester polymerization example) High-purity citric acid and 2 times the amount of ethylene glycol were placed in 2 liters of a stainless steel autoclave equipped with a stirrer, and the addition was based on the acid component. 0.3 mol% of triethylamine, which was subjected to an esterification reaction for 120 minutes while distilling off water outside the system under a pressure of 0.25 Mpa at 245 ° C to obtain bis(2-hydroxyethyl)-p-citric acid. a mixture of esters and oligomers. To the mixture, 2.5 g/liter of an ethylene glycol solution of aluminum triacetate, an aluminum atom of 0.014 mol% based on the acid component, and 1 g/l of the ethylene compound of the above phosphorus compound A were added. The solution, the phosphorus atom of 〇.3 mol% relative to the acid component, and the ethylene glycol solution of 50 g/liter of lithium acetate dihydrate, and the lithium atom of 0.01 mol% based on the acid component The resulting polycondensation catalyst was stirred in a nitrogen atmosphere at a normal pressure of 245 ° C for 1 minute. Subsequently, the temperature was raised to 275 ° C for 50 minutes, and the pressure of the reaction system was gradually lowered to 托 1 Tory, and further, a polycondensation reaction was carried out at 275 ° C, 托 1 tol. The polymerization time UP required to obtain polyethylene terephthalate to 0.65 dl / gram is shown in Table 7. Further, polyethylene terephthalate having an IV of 0.65 - 106 to 1309246 d 1 /g obtained in the above polycondensation was exfoliated according to a usual method. The pet resin sheet was used to obtain a thermal stability parameter (TS) and a thermal oxidation stability parameter (T0S). The results are shown in Table 7. Further, the above-mentioned PET resin sheet was used to form a film to form a recovered pellet, and a film was formed by recovering nine particles. The results of the evaluation of the thermal stability and heat aging of the film are shown in Table 7. The catalyst of the present invention has high catalytic activity, and the film made of PET obtained by using it has excellent thermal stability and heat aging resistance. (Example 7 - 2) (Synthesis Example of Phosphorus Compound) Synthesis of a phosphorus compound (phosphorus compound B) represented by the following formula (Chem. 45) [Chem. 4 5]

1. Synthesis of diethyl (1-naphthyl)methylphosphonate under nitrogen atmosphere, 8.31 g (50 mmol) of triethyl phosphite and 8.83 g (50 m) at 2001 (external temperature) A mixture of 1-chloromethylnaphthalene is heated to 'produce a gas (EtCl) until about 30 minutes. After cooling to room temperature, a colorless oily liquid of 10.8 g (yield: 75%) of diethyl (1-naphthyl)methylphosphonic acid was obtained. 'H-NMR (CDC13, δ): 1.15K6H, t), 3.64K2H, d). 3.948(4H, m). 7.381-7.579(4H, m), 7.749-7.867(2H, m). 8.088- 8.133(1H.m) -107- 1309246 Γ&quot;--% of January f.曰修(粟) replacement page correction page 2. Sodium [oxyethyl (1-naphthyl)) synthesis in a mixture of 6.5 g (84 mmol) 50% sodium hydroxide and 6.1 ml methanol 6.1 ml of a methanol solution containing 5 g (18 mmol) of (p-naphthyl)methylphosphonic acid diethyl ester was added, and the mixture was heated under reflux for 24 hours under a nitrogen atmosphere. After the reaction, while cooling the reaction mixture, 6.59 g (63 mmol) of concentrated hydrochloric acid was added, and the precipitate was taken out and washed with isopropyl alcohol, and then the filtrate was evaporated under reduced pressure. The obtained residue was dissolved in hot isopropanol, and the insoluble matter was taken out, and the isopropyl alcohol was distilled off under reduced pressure. The residue was washed with hot η-heptane and dried to dryness to give 3.8 g (78%) of sodium. [Oxyethyl (1-naphthyl)methylphosphonate] ° Shape: needle crystal; melting point: 277~281 ° C (decomposition) ^-NMR (DMS0-d6, δ): 0.961 (3H, t J=7Hz), 3.223(2H, d), 3.589(2H, m), 7.3 65-7.468(4H, m, J=7Hz), 7.651-8.314C3H, m). 3. Oxygen-ethyl (1 Synthesis of -naphthyl)methylphosphonic acid (phosphorus compound B) containing 1 g (3.7 mmol) of sodium [oxy-^ethyl(1-naphthyl)methyl) in 10 ml with stirring at room temperature To the aqueous solution of the phosphonate], 1.9 g of concentrated hydrochloric acid was added to stir for 1 hour. After extracting the reaction mixture, washing the toluene phase with water, and distilling off toluene under reduced pressure, 497 mg (54%) of oxy-ethyl(1-naphthyl)methylphosphonic acid was obtained. Shape: colorless oily liquid; ^-NMR (CDC13 &gt; 5): L085 (3H.t. J = 7 Hz). 3.450 (2H.d). 3.719 (2H, m, 7 Hz), 7. 369-7.532 (4H , m), 7. 727-8.043 (3H, m). 10.939 (1H, s) (Polyester polymerization example) Polymerization was carried out in the same manner as in Example 7-1 except that the catalyst was changed. . The compounds used as the contact and the media, and the amounts added are shown in Table 7. The amount of the aluminum compound to be added is expressed by the amount of the aluminum atom added to the acid component, and the amount of the phosphorus compound B added is the amount of the phosphorus atom added to the acid component. The polymerization time (AP) required for the IV of the polyethylene terephthalate to reach 0.65 dl / gram is shown in Table 7. Further, the polyethylene phthalate obtained by the above polycondensation in the above polycondensation was 〇 6 5 dl / gram of polyethylene terephthalate. The PET resin sheet was used to obtain a thermal stability parameter (TS) and a thermal oxidation stability parameter (t〇S). The results are shown in Table 7. Further, a film was formed by using the above-mentioned PET resin sheet to form a film, and nine pieces were recovered, and nine films were collected to form a film. The results of the evaluation of the thermal stability and heat aging of the film are shown in Table 7. The catalyst of the present invention has high catalytic activity, and the film made of PET obtained by using it is excellent in both heat stability and heat aging resistance. (Comparative Example 7 - 1) In addition to the use of antimony trioxide (the amount of which is added in an amount of 〇_〇5 mol% based on the acid component of PET), -1 The same operation method is used. As the antimony trioxide, a commercially available ruthenium (m) oxide (manufactured by Aldrich Vapor Chemicals Co., Ltd., purity of 99.99 %) was used. The antimony trioxide used was stirred for about 1 hour to dissolve it in 15 g of ethylene glycol to form a solution having a concentration of about 10 g/l. The polymerization time (AP) required for the IV of the polyethylene terephthalate to reach 0.65 dl / gram is shown in Table 7. Further, polyethylene terephthalate having an IV of 0.65 d 1 /g obtained by the above polycondensation was exfoliated according to a usual method. The PET resin sheet -109-1309246 was used to determine the thermal stability parameter (TS) and the thermal oxidation stability parameter (TOS). The results are shown in Table 7. Further, a film was formed by using the above-mentioned PET resin sheet to obtain a recovered film, and nine films were recovered to form a film. The results of the evaluation of the thermal stability and heat aging of the film are shown in Table 7. Although the catalyst of the present invention has excellent catalytic activity, the film made of PET obtained by using it has poor thermal stability than the contents of the examples. φ (Comparative Example 7 - 2) Except that the catalyst of Comparative Example 7-1 was further added with a phosphorus compound A (the amount of addition was 0.03 mol% based on the phosphorus atom of the acid component in PET) This was carried out in the same manner as in Example 7-1. As the antimony trioxide, a commercially available ruthenium (m) oxide (manufactured by Aldrich Vapor Chemicals Co., Ltd., purity of 99.99%) was used. The antimony trioxide used was mixed and dissolved in ethylene glycol at 150 ° C to obtain a solution having a concentration of about 1 g/l. The polymerization time (AP) required for the IV of the polyethylene terephthalate to reach 〇 65 dl / gram is shown in Table 7. The change in the catalytic activity of the antimony trioxide was not confirmed by the use of the phosphorus compound A. (Comparative Example 7 - 3) The same procedure as in Example 7-1 except that chromium dioxide (the amount of addition is 0.03 mol% based on the acid atom of the PET component) was used as the catalyst. The way of operation is carried out. The polymerization time (AP) required for the IV of the polyethylene terephthalate to reach 0.65 dl / gram is shown in Table 7. Further, polyethylene terephthalate having an IV of 0.65 - 110 to 1309246 d 1 /g obtained in the above polycondensation was subjected to flaking according to a usual method. The PET resin sheet was used to determine the thermal stability parameter (TS) and the thermal oxidation stability parameter (T0S). The results are shown in Table 7. Further, a film was formed by using the above-mentioned PET resin sheet to obtain a film, and nine particles were collected, and nine films were collected to form a film. The results of the evaluation of the thermal stability and heat aging of the film are shown in Table 7.

Although the catalyst of the present invention has excellent catalytic activity, the film made of PET obtained by using it has poor thermal stability and heat aging resistance than those in the examples. (Comparative Example 7 - 4) Except for the use of acetonitrile aluminum (the amount of which is added in an amount of 0.14 mol% based on the acid component of PET) as a catalyst, Example 7-1 was carried out in the same manner. Although heating was carried out for more than 150 minutes, the IV of polyethylene terephthalate could not reach 0.65 dl / gram. (Comparative Example 7 - 5) Except that lithium acetate dihydrate (the amount of addition is 0.01 mol% based on the acid atom of the PET component) was used as a catalyst, and Example 7 - 1 The same operation method is used. Although the heating was carried out for more than 15 minutes, the IV of the polyethylene terephthalate could not reach 0.65 dl / gram. [Table 7] It can be understood from the above examples and comparative examples that when the thermal stability parameter of the PET resin sheet is within the scope of the patent application of the present invention, the thermal stability of the film becomes excellent, and the film is The quality will also be excellent; and the quality of the recycled film is also excellent. On the one hand, in the case of the patent application No. -111 - 1309246 of the present invention, the thermal stability of the film is deteriorated, and the quality of reuse of the chip film is also poor. Further, although the catalytic activity of the original aluminum compound and the lithium compound is not good, the activity of the catalyst of the present invention which coexists with the phosphorus compound is excellent, and the obtained polyester is also excellent in thermal stability. On the one hand, when the phosphorus compound is used in combination with the ruthenium compound, the catalytic activity of the ruthenium compound is not affected (Example 8 - 1)

(Preparation Example of Aqueous Solution of Aluminium Acetate Aluminate) Add 1 gram of basic aluminum acetate (hydroxyaluminum diacetate; Aldrich) to deionized water at a ratio of 50 ml, and stir at room temperature. 12 hours. Thereafter, the liquid temperature was gradually increased while continuing to stir. When the liquid temperature reached about 60 ° C, the mixture was kept stirring at this temperature for about 2 hours to further increase the liquid temperature and continue to stir. When the liquid temperature reached about 75 ° C, the temperature was maintained at this temperature for about 2 hours or more to obtain a transparent aqueous solution. (Polyester polymerization example) A mixture of bis(2-hydroxyethyl)p-phthalate and an oligomer obtained by a high-purity citric acid and a 2-fold molar amount of ethylene glycol according to a conventional method is added. The above-mentioned alkali-based aluminum acetate aqueous solution having an aluminum atom content of 0.035 mol% based on the acid component in the polyester, and the relative acid component of 10 g/liter Irganox 1425 (manufactured by Ciba Specialty Chemicals Co., Ltd.) The polycondensation catalyst 'made of 乙二醇·〇2 mol% of ethylene glycol solution was stirred for 15 minutes under nitrogen atmosphere at normal pressure at 24 °C. Then, after heating for 5 5 minutes to 275 °C, the pressure of the reaction system was slowly decreased to 66.5 bar (0.5 ton), further at -112-1309246 2 7 5 °C, 6 6 . The bar was subjected to a polycondensation reaction for 90 minutes. The obtained IV and Tm are shown in Table 8. (Example 8 - 2) (Preparation of a solution of a salt-based aluminum acetate in ethylene glycol) Acryl aluminum acetate (CH3COOAl (OHh· 1/3Η3Β〇3; manufactured by Ald) was stirred in ethylene glycol For about 12 hours or more, an ethylene glycol solution having a concentration of about liter is obtained. (Polyester polymerization example) The above-mentioned basicity is exemplified by the aluminum atom relative to the acid component in the polyester. A solution of aluminum acetate in ethylene glycol and 10 g/L of hydrazine; 1 425 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a polycondensation catalyst based on a molar amount of ethylene glycol solution The operation was carried out in the same manner as in the actual 8.1. The IV of the obtained PET was as shown in Table 8. (Comparative Example 8 - 1) except that the aluminum atom was calculated relative to the acid component in the polyester. a solution of 0. 035 of a basic aluminum acetate (hydroxyaluminum diacetate) of about 10 g / liter: solution, and 10 g / liter of Irganox 1425 (Ciba specialization; system) relative to acid The composition was calculated to be 0.02 mol% of the ethylene glycol solution: the polycondensation catalyst, and the same procedure as in Example 8-1 was carried out. The IV and Tm of the obtained PET were shown in (Example 8 - 3) (Preparation of a solution of a salt-based aluminum acetate in ethylene glycol) 1 g of a salt which is stabilized with boric acid of about 1/16 molar amount

PET Lee 5g /

Moer % ganox 0.02 : Example Tm shows Mo % % ; diol 〖 ΐ ΐ 【 【 行 行 113 113 - 113 - 1309246 · Aluminium silicate to 50 ml ratio of deionized water, stirred at room temperature about 1 2 hours. Thereafter, the mixture was stirred at about 70 ° C for about 2 hours to obtain a transparent aqueous solution. Ethylene glycol having a capacity ratio of 2 times was added to the aqueous solution, and stirred at room temperature for several hours. Thereafter, the solution was stirred at 1 ° C for several hours while removing water from the system to obtain an ethylene glycol solution. (Polyvine polymerization example)

A mixture of bis(2-hydroxyethyl)-p- phthalate and an oligomer produced by high-purity citric acid and ethylene glycol according to a conventional method, and an aluminum atom is added relative to the acid component in the polyester. 0. 0 1 4 mol% of the above-mentioned salt-based aluminum acetate glycol solution, and 10 g / liter of Irganox 1425 (Ciba Specialty Chemicals Co., Ltd.) relative to the acid component is 〇. 0 The polycondensation catalyst prepared by the 2 mol% ethylene glycol solution was stirred for 1 minute in a nitrogen atmosphere at normal pressure at 245 °C. Then, the temperature was raised to 275 1 in 45 minutes, and the pressure of the reaction system was gradually lowered to 66 /5 bar (〇·5 Torr), and the polycondensation reaction was further carried out at 275 ° C and 66.5 bar for 20 minutes to obtain iv of 0.38. Dl/gram of PET

(Example 8 - 4) (Preparation of a salt-based aluminum acetate water/ethylene glycol mixed solution) 1 g of a salt-based aluminum acetate (hydroxyaluminum diacetate; Aldrich) 5 50 ml The ratio was added to deionized water and stirred at room temperature for about 12 hours. Thereafter, the mixture was stirred at about 70 ° C for about 6 hours to obtain a transparent aqueous solution. Ethylene glycol was added to the aqueous solution in an amount of 3 times (capacity ratio) with respect to the aqueous solution, and the mixture was stirred at room temperature for 6 hours to obtain a catalyst solution. (Polyester polymerization example) -114- 1309246 High-purity citric acid and 2 times the amount of ethylene glycol were put into 2 liters of a thermocycling stainless steel autoclave equipped with a stirrer. 0.3 mol% of triethylamine, which is subjected to an esterification reaction for 5 minutes while distilling off the water outside the system under a pressure of 0.25 Mpa at 250 ° C to obtain an esterified to 95% or more. Hydroxyethyl) phthalate (BHET) and oligo

A mixture of polymers (hereinafter, referred to as a BHET mixture). To the BHET mixture, a water/glycol mixed solution of the above-mentioned basic aluminum acetate having an aluminum atom of 0.014 mol% based on the acid component in the polyester, and Irganox 1 425 (1 g/liter) were added. a gas-concentrated catalyst made of an ethylene glycol solution of 0.02% by mole based on the acid component, in a nitrogen atmosphere, at a normal pressure, at 250 ° C, Stir for 15 minutes. Then, the temperature was raised to 275 ° C for 60 minutes, and the pressure of the reaction system was gradually lowered to 66.5 bar (0.5 torr), and the polycondensation reaction was further carried out at 275 ° C and 66.5 bar for 132 minutes to obtain an IV of 0.61 dl. / gram of PET, the present invention is a substance having practical catalyst activity. The obtained PET physical properties are shown in Table 9. (Example 8 - 5) (Preparation of a solution of a salt-based aluminum acetate solution in ethylene glycol) The above-mentioned salt-based aluminum acetate water/ethylene glycol solution was stirred at 90 to 110 ° C for several hours. Distill water from the system. As a result, an ethylene glycol solution having a concentration of about 6.5 g/liter was obtained. (Polyester polymerization example) An ethylene glycol solution of the above-mentioned base-based acetic acid was added in an amount of 0.014 mol% based on the acid component in the polyester, and 1 g/liter of Irganox 1 4 2 5 (Ciba-Special Chemicals Co., Ltd.) is a polycondensation catalyst made of an ethylene glycol solution of 〇·〇1 -115-1309246 mol% based on the acid component, and is in the same manner as in Example 8 - 4 The same approach to polymerize polyester. The polymerization time was 133 minutes, and PET with an IV of 0.66 cil / gram was obtained. The obtained PET physical properties are shown in Table 9. (Examples 8 - 6) (Preparation of a solution of a salt-based aluminum acetate in ethylene glycol solution)

Base aluminum acetate (CH3COOAl(OH)2· 1/3Η3Β〇3; Aldrich) was stirred in ethylene glycol at about 70 ° C for 5 hours to give a concentration of about 5 g / liter. Ethylene glycol solution. (Polyester polymerization example) A mixture of bis(2-hydroxyethyl)-p-phthalate and an oligomer produced by high-purity p-citric acid and ethylene glycol according to a conventional method is added to the polyester. The acid component is an ethylene glycol solution having an aluminum atom of 0.014 mol% of the above-mentioned basic aluminum acetate in an amount of 5 g/liter, and 10 g/liter of Irganox 1 42 5 (manufactured by Ciba Specialty Chemicals Co., Ltd.). The polycondensation catalyst made of an ethylene glycol solution of 0.01 mol% based on the acid component was stirred for 10 minutes under a nitrogen atmosphere at normal pressure at 24 °C. Then, after raising the temperature to 27 5 ° C for 50 minutes, the pressure of the reaction system was gradually lowered to 13.3 bar (0.1 torr), and the polycondensation reaction was further carried out at 275 ° C and 13.3 bar for 90 minutes to obtain IV. 0.65 dl / gram of PET. The PET of the obtained PET was 2 equivalent/ton, Tm was 256 ° C, L値 was 68.9, a値 was -2.3, and b値 was 4.2. (Example 8 · 7) (Preparation example of ethylene glycol solution of aluminum lactate) Aluminum lactate was prepared into an aqueous solution of about 67 g/liter. Thereafter, ethylene glycol -116 - 1309246 &quot; was added and heated at about 100 ° C to distill off water to obtain a solution of about 29 g / liter of ethylene glycol. (Polyester polymerization example) An ethylene glycol solution of the above aluminum lactate having an aluminum atom of 0.014 mol% based on the acid component in the polyester, and Irgoxl 425 (100 g/liter) manufactured by Ciba Specialty Chemicals Co., Ltd. The polyester was polymerized in the same manner as in Example 8-4 except that the polycondensation catalyst made of an ethylene glycol solution having an acid component of 0.01% by mole was used. The polymerization time was 1 24 minutes, and PET having φ I V of 0.6 d 1 /g was obtained. The obtained PET physical properties are shown in Table 9. (Comparative Example 8-2) An ethylene glycol solution of about 5 g/liter of aluminum lactate in an amount of 0.014 mol% based on the acid component in the polyester, and Irgox 1 425 (100 g/liter) were added. The polyester was polymerized in the same manner as in Example 8-4 except that the polycondensation catalyst made of a glycol solution of 0.01 mol% based on the acid component was produced by Ciba Specialty Chemicals Co., Ltd. . The polymerization time was 1 68 minutes, and the PET having an I V of 0.61 d 1 /g was obtained, and the catalyst was not active. $ (Evaluation result) It can be understood from the above examples and comparative examples that when a solution in which aluminum carboxylate is dissolved is used as a catalyst, the polymerization activity is excellent in any case, and the obtained polyester is also excellent. It is a good quality; in contrast, when a solution in which aluminum carboxylate is not dissolved is used as a catalyst, a result of poor polymerization activity will be obtained. [Table 8] [Table 9] -117- 1309246 * [Field of Industrial Applicability] The possible application range of the polyester of the present invention, for example, the interior represented by the fabric, the curtain, the carpet, the bedding, etc. Fiber for sleeping materials; fiber for industrial materials represented by tire cords and ropes; fibers for various fabrics, various knitted fabrics, short-fiber non-woven fabrics, long-fiber non-woven fabrics, packaging films, industrial films, and optical films , film for tape, film for photographic film, film for layering, film for condensation, film for heat shrinking, film for air barrier, white film, easy-cut film, non-heat-resistant stretch bottle, heat-resistant stretch bottle, straight φ bottle Various molded articles such as a hollow molded body such as a gas barrier bottle, a pressure resistant bottle, and a heat-resistant pressure bottle, a mat for A-PET or C-PET, a glass fiber reinforced polyester, and a single plastic. , as well as paints or adhesives. -118- 1309246

1) The tree 1° hangs the 龉 龉 龉 睁 钿屮 WI ^ M. 2) _1° 神濑龉丑露除||钿屮苕鄹:±1睁_钿屮N·灵ni&gt;M. Comparative Example 1-1 Example 1-3 Example 1-2 1 ! _1 Example 1-1 Sodium acetate triacetate acetonitrile aluminum phosphate 絜丨 11 蹑咏隳皤豸 (eight) 11 ^ m ^ sodium acetate aluminum chloride Irganox 1425 S I'll M 泠IN隳 隳鄯^ m Compound 7.8 L/1 NJ t—» 0.7 Alkali metal content (mole) u 1 1 1 0.5 1 Alkaline earth metal content (mole) υ Λ (-Λ to i 1 1 2.0 | o -o Μ (mole) 2) g to to to aluminum content (ppm) 〇\ to ON OJ LO phosphorus content (ppm) σν α\ ON L&gt;0 0〇polymerization time/minute X &gt; 〇〇Filter pressure rise X t&gt; 〇〇断丝 [姗1] -119- 1309246

1) 翎龉 戆咏 戆咏 » 屮苕翳 屮苕翳: ±: 鏰睁 1 | 钿屮 ^ | | _ 剌 ( (5 鹡 鹡 粬 粬 & & & & & & & & & & & & & & & & & & & & 2) 骚 丑 露 露 ^ ^ ^ ^ ^ ^ ^ 咏翮 ί ί ί ί ί 雾 雾 雾 雾 雾 雾 雾 雾 雾 雾 雾Comparative Example 2-2 Comparative Example 2-1 Example 2-6 Example 2-5 Example 2-4 Example 2-3 ... J Example 2-2 Example 2-1 Sodium Acetate Aluminum Chloride Acetate Acetate Acetate Aluminum Acetate Magnesium Acetate Aluminum Acetate Sodium Acetate Acetate Acetate Aluminum Acetate Lithium Chloride Aluminum Acetate Acetate Acetate Aluminum | Sodium Acetate Chlorinated Lithium Acetate Acetate Acetate Aluminum Compound 0.04 0.0015 0.05 0.02 0.015 1 ! 0.01 0,025 0.06 0.04 0.015 0.025 | 0.02 1 0.02 0.02 i 0.01 0.015 Content / Molar % 26.7 1 1 2.5 1_-_ &gt;—* 〇to -0 1—k tO 1—* 〇Μ / A1 ratio 値u 0〇s'. OJ 〇ί—* s〇to metal amount / ppm2) (—1 g LT\ U\ oo 〇\ Ό g 〇\ 0〇polymerization time/minute XX [&gt;D&gt;D&gt; 〇〇〇Filter pressure rise XX &gt ; &gt;t&gt; 〇〇〇断丝 [m2] -120- 1309246, 1) Polyester 1 2) Polyester Μ 3) Polyester 1 4) Polyester bow Comparative Example 3-3 Comparative Example 3-2 Comparative Example 3-1 Embodiment 3-9 Embodiment 3-8 Embodiment 3-7 Embodiment 3-6 Embodiment 3-5 Embodiment 3-4 Embodiment 3-3 Embodiment 3-2 Embodiment 3-1 r \ l The total amount (ppm) of alkali metal atoms and alkaline earth metal atoms. What is the ratio of the total amount (ppm) of the alkali metal atom and the earth-like metal atom to the silver content (ppm)? The ratio of the phosphorus atom content (ppm) to the aluminum content (ppm). => The chain atom content is 50 ppm. Sodium acetate aluminum chloride phosphorus compound A mnm An IN鄹菡[N &gt;黩§δ Sodium acetate triacetate acetonitrile aluminum phosphate aluminum acetate Irganox 1425 three gasification 锑4&gt; 1 potassium acetate aluminum chloride! Phosphorus compound A 黧(1)躅鄹IN婼隳® [Nil Μ in S Μ g露^ Μ 7 Lancome yer fS ·&gt; no Mum left (N隳nvwm 漤mh &gt; 谞 盘 :Tii丨躅5 [N隳g隳鄯^(N κ盘:r in 蹦SM婼g mm M II 7顬关漥g 111 1 ^ 二隳S (N ^ stamped ss compound gg 1 1 H—*—» H— o 碱 alkali metal content (ppm ) 1 1 1 g 1 1 1—* 〇1 1 g ON LA Alkaline earth metal content (ppm) f—» ο LO ω gggog U3 o Aluminum content (ppm)_ ι~&gt; ~Α to U\ ls&gt; g ( --►—» LO «-Λ LA «-Λ w TO Phosphorus content, (P training)__: S *—· gg ι~ι g I—1 Ο «_Λ CA ω On &lt;-Λ Is ο 〇\ Os t—» LO Ο 4^- to o 1_Λ 〇u&gt; Ι-Λ t^n Οι to to Μ / A1 ratio &2&gt; ο ο ~λ μ·* as -j 〇&lt;-Λ -J 00 OJ Ο ts) to ί-η oo Ul h&gt;- Ln to -〇P / Α13) ί〇LA s Η-1 Ο &lt;-η Ux U\ TO a 00 Vi 〇\ &lt;ν Polymerization time/minute XXX 0 0 &gt; 0 0 o 〇0 0 Filter pressure rise XXX I&gt;D&gt; 〇o 〇o 〇o Broken wire i _1 • 121- 1309246 Comparative Example 4-1 Example 4-2 Example 4 -1 Lithium aluminum chloride dihydrate 蹑二 I Π 隳 it g [N 蹯g W 1 [ ^ (8) ^ LO 淳 淳 I I Irganox 1425 compound! Aluminium content (ppm) 1 〇〇 Phosphorus content (ppm ) 1 〇〇〇to &gt; Η—* •—1 〇\ to polymerization time/minus 0.01 0.01 or less thermal oxidation stability (T0S) X 〇〇 filtration pressure rise X 〇〇 broken wire [姗4] -122- 1309246

1) 龉 龉 - &amp; - float 1 | 屮 _ (? 1 &gt; 5 苕盩 屮 屮 (ppm) (^trrpf. Comparative Example 5-2 Comparative Example 5-1 Example 5-2 Example 5 - 1 黎ϋί [N nl> 隳豸CN &gt; 颜鹡繁Hi夫 IN n&gt; m Μ (Ν &gt; mms μ g 隳= 尔 NJ ΰ ΰ t t t cold IN 卟隳豸IN &gt; said DC compound g LO Aluminium content (ppm) &gt;—* Η-* CT\ h—* LO o Phosphorus content (ppm) to Ο LO OJ LO UJ &gt; to to ο Η—» Ο 1~1 1—* o Aggregation time/minute XX 〇〇 Filtration pressure rise XX 〇〇 Broken wire [姗5] -123 - 1309246 ► • € 1) 屮 屮 屮 faig 屮 屮 NM-Wtt. Comparative Example 6-3 Comparative Example 6-2 Comparative Example 6-1 Implementation Example 6-3 Example 6-2 1 Example 6-1 Ethylene acetate aluminum S Hi ^ (N 卟隳漤 N &gt; m 鹡. S [11 fv [N 卟礴豸 (N &gt; mm [11] 1 ® § [N Er Er tvj ^tt&gt; ^ m S III She (N 豸M &gt; er mm III ^ [N 卟隳豸M &gt; 园 m compound 〇〇〇〇. 〇LO CT\ 0.014 0.3 0.012 ! 0.04 0.014 0.1 1 O ° ^ s Addition amount / mole % 1 Ο tS3 1—» 〇〇t—» Ni Ό Adding ratio n 120 or more 1 i 117 110 oo On O O polymerization time / min 5 6] -124- 1309246

Comparative Example 7-5 Comparative Example 7-4 Comparative Example 7-3 Comparative Example 7-2 Comparative Example 7-1 Example 7-2 Example 7-1 Lithium acetate dihydrate triacetic acid acetonitrile aluminum chromium dioxide i three Yttrium oxide phosphide compound A 1 antimony trioxide HI 舍 (N Πί> 隳» 圏sm in 泠隳 (N # 11 Μ · &gt; 圔 π> 酩遂 compound 0.01 0.014 〇S Ο 〇Ο 〇I 0.05 i 0.014 0.03 0.05 0.014 0.01 0.03 Addition amount/mol% 150 or more 150 or more 〇\ 00 1—k 〇\ —^ I - 1 〇1 〇to L〇〇0.16 1 1 〇to 1 0.01 or less 0.04 0.01 or less T0S 1 1 X Thermal oxidation stability of 1 X 〇〇 film 1 1 X 1 耐热 film heat aging resistance

-125- 1309246 Comparative Example 8-7 Example 8-5 Example 8-4 ! j _i Aluminum lactate Irganox 1425 7颙sm § wz ^ K) ^H&gt; Ui ΠΠ OWN uz ^ to «H&gt; On nc component touch Medium glycol solution ethylene glycol solution water/ethylene glycol solution shape 0.014 0.01 0.014 0.01 0.014 0.01 Addition amount (mole%) μ-» h-i LO LO 〇〇$咏0.60 0.60 0.61 IV (dl/g) m 龉豸U3 A Λ AV (equivalent/ton) 66.5 66.6 64.9 pf 1 K) Η—» to bo 1 h—&gt; Ο ▲ 〇LO --0 PF ^ t# to OS to ON Κ5 L/&gt; ON ·&gt;-&quot;S 〇° 33 ►—* -UW One H-* 〇〇la t~~» 〇〇&gt;—1 00 ts) 3. # w [姗9] Comparative Example 8-1 Example 8-2 1 Example 8-1 7阄sm 〇F# ^ m 二隳κ m 口· ® ^ mm §隳F# ^ 蹑= 隳^ m 7鼹's m § s μ蹑* ira m to LLn ΠΠ Ingredients Catalyst Ethylene Glycol Ethylene glycol solution Aqueous solution shape 0.035 0.02 0.035 0.02 | 0.035 0.02 Addition amount (mol%) Polymerization time (minutes) 1 0.22 1 1 0.49 _1 s 0.47 IV (dl/克) Excited to 〇\ 257 /—S 〇° 33 mo: 漤f# [Xie 8] -126- 1309246 [Simple description of the diagram] No [Main component symbol description] None

Claims (1)

/σ日修(4)止'4ί No. 94105784 "Polyester polymerization catalyst" patent case (amended on September 10, 2008) X. Patent application scope: 1. A polyester polymerization catalyst characterized by: constituents The invention comprises a phosphorus compound and a metal or metal compound; wherein the phosphorus compound is derived from a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, or a phosphonic acid system. At least one selected from the group consisting of a compound, a phosphinous acid compound, and a phosphine compound; wherein the content of the phosphorus atom is 0.005 to the acid component constituting the polyester. 0.2 mol%; wherein the metal component is at least one selected from the group consisting of alkali metals, alkaline earth metals, group IIIA elements, group IVA elements, transition metals and lanthanides; wherein the content of the metal or metal compound is relatively The acid component constituting the polyester is 1&gt;&lt; 106 to 0.5 mol%: the polyester polymerization catalyst is used for polymerization having a thermal stability parameter (TS) satisfying the following (9) Polyethylene terephthalate (PET); (9) TS &lt; 0 · 20 ; (In the above formula, TS is a characteristic viscosity of 1 gram ([ΐν]〇 is 0.64 to 0.66 dl / gram) The PET was placed in a glass test tube and dried under vacuum at 130 ° C for 12 hours. After maintaining the melting at 300 ° C for 2 hours in a non-circulating nitrogen atmosphere, the characteristic viscosity was calculated by the following formula ([IV ] f The number of 値); TS = 〇. 245 ([ IV] f'1 47 - [ IV] i1'47) 2. The polyester polymerization catalyst of claim I, in which the metal or metal 1309246 compound Other than 锑, 钦, 锗. 3. A polyester polymerization catalyst, characterized in that the polyester polymerization catalyst is composed of a metal or a metal compound and a phosphorus compound, wherein the phosphorus compound is derived from phosphine. At least one selected from the group consisting of an acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphinic acid compound, a trivalent phosphonic acid compound, and a phosphine compound; wherein the content of the phosphorus atom is relative to The acid component constituting the polyester is '0.005 to 0. 2 mol%; wherein the metal or metal compound And at least one selected from the group consisting of alkali metal 'alkaline earth metals, lanthanum elements, IV lanthanum elements, transition metals, and lanthanide metals and compounds thereof; wherein the content of the metal or metal compound is relative to the composition The acid composition of the polyester is 1x1 6·6~〇.5 mol%; and the activity parameter (AP) satisfies the following formula (10); (10) AP (minute) &lt; APX (minute); In the above formula (10), the AP system represents a polyethylene terephthalate (PET) having a polymerization characteristic viscosity of 0.65 dl / gram at a pressure of 275 ° C and a pressure of 0.1 Toli using a predetermined amount of a catalyst. The time (minutes) required; APX represents the time (minutes) required to polymerize PET under the same conditions when the metal or metal compound in the above catalyst is the same amount as described above. 4. The polyester polymerization catalyst according to claim 3, wherein the metal or metal compound is at least one selected from the group consisting of metals other than cerium, titanium, and cerium, and a compound thereof. 5. The polyester polymerization catalyst of claim 3, wherein the metal or metal compound is at least one selected from the group consisting of aluminum and a compound thereof. 6. The polyester polymerization catalyst according to item 3 of the patent application, wherein the polyester polymerization catalyst is further used for polymerizing polyethylene terephthalate having the thermal stability parameter (TS) satisfying the following formula (9) 1309246 Diester (PET); (9) TS &lt; 0.20. 7. The polyester polymerization catalyst according to any one of claims 1 to 6, wherein the polyester polymerization catalyst is further used for polymerization having a thermal oxidation stability parameter (TOS) satisfying the following formula (11) Polyethylene terephthalate (PET); (11) TOS &lt;0.10; (In the above formula (11), TOS means that the PET resin sheet having a melt polymerization IV of 0.64 to 0.66 dl / gram is frozen. The powder is pulverized into 20 mesh or less. 'After 0.3 g, it is vacuum dried at 130 ° C for 12 hours and placed in a glass test tube. After vacuum drying at 70 ° C for 12 hours, it is 230 ° in air dried with silicone. After heating for 15 minutes, the IV 値 is calculated by the following formula; TOS = 0.245 ( [IV]» · ' 47 - [IV]i.丨.47) [IV]i and [IV]fl are respectively before the heating test Iv (dl / gram) after the heat test. 8. The polyester polymerization catalyst according to any one of claims 1 to 6, wherein the activity parameter (AP) further satisfies the following formula (12); (12) AP (minutes) &lt; 2T (minutes) (In the above formula (12), the AP system represents a polyethylene terephthalate having a polymerization characteristic viscosity of 0.65 dl / gram at a pressure of 275 ° C and a Toli pressure of 275 ° C using a predetermined amount of catalyst. The time (minutes) required for the ester (PET); the T system represents the addition of 0.05 mole% of the cesium atom relative to the acid component in the polyethylene terephthalate formed by using ruthenium trioxide as a catalyst. In the case of AP). A polyester polymerization catalyst which is prepared by dissolving at least one selected from the group consisting of aluminum carboxylates and at least one selected from the group consisting of phosphorus compounds in water and/or A solution formed in an organic solvent, wherein the phosphorus compound is a phosphonic acid compound, a phosphinic acid compound, an oxygen 1309246 I, a phosphine compound, a phosphinic acid compound, a trivalent phosphonic acid compound, or a phosphine compound. At least one selected from the group consisting of at least one selected from the group class. 1 . The polyester polymerization catalyst according to claim 9 of the patent application, wherein the content of the aluminum atom in the obtained polyester is 0.001 to 0.05 mol% based on the acid component constituting the polyester. The polyester polymerization catalyst of claim 9, wherein the organic solvent is a glycol. g 1 2. The polyester polymerization catalyst of claim 9, wherein the organic solvent is ethylene glycol. 1 3. The ratio of the organic solvent/water in the polyester polymerization catalyst of claim 9 is 0.5 to 50 in terms of a capacity ratio. -4-