TWI227246B - Catalyst for polyester production and process for producing polyester with the same - Google Patents

Abstract

A polyester having a good color tone (a high L value and a low b value) and a low acetaldehyde content is obtained by using a catalyst containing a reaction product of (A) a titanium compound (1) represented by the general formula (I) and/or a titanium compound (2) obtained by reacting the titanium compound (1) of the general formula (I) with an aromatic polyhydric carboxylic acid represented by the general formula (II) or an anhydride thereof, with (B) a phosphorus compound (3) represented by the general formula (III), [wherein R1, R2, R3, R4 and R5 is a C2-C10 alkyl group, k is 1 to 3, m is 2 to 4, and R6 is a substituted or non-substituted C6-C20 aryl group or a C6-C20 alkyl group].

Description

1227246 A7 B7 The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed strict and inventive instructions (Q metallurgy field) The present invention relates to a catalyst for manufacturing polyester and a method for manufacturing polyester using the same. More specifically, the present invention relates to Catalyst for manufacturing polyester containing specific titanium compound and phosphorus compound, and method for manufacturing polyester using cobalt compound which can have good hue (b 値) _ 'without adding color adjustment. Background Art Because of the polyester, In particular, polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polybutylene terephthalate 'have excellent mechanical, physical, and chemical properties. Therefore, it is widely used in fibers, films, or other shaped articles. Known methods for manufacturing polyethylene terephthalate, such as generally, direct esterification of terephthalic acid and ethylene glycol, or The lower alkyl ester of terephthalic acid, such as dimethyl phthalate, and ethylene glycol are transesterified 'or the terephthalic acid is reacted with ethylene oxide to obtain the terephthalic acid-containing ethylene glycol ester and / Or Polymer reaction product, and then in the presence of a polymerization catalyst, the method of 'heating to a certain degree of polymerization under reduced pressure to perform a polycondensation reaction.' Also, the production of polyethylene naphthalate, polytrimethylene terephthalate The method of polybutylene terephthalate can be the same as the aforementioned method. It is known that the catalyst used in the above polycondensation reaction has a great influence on the reaction speed and the quality of the obtained polyester. Moreover, the most widely used method The polycondensation catalyst of polyethylene terephthalate is an antimony compound. The reason is that the antimony compound catalyst has excellent polycondensation catalyst performance, and the resulting polyester has good 3g. 5 paper standards are applicable to Chinese national standards (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

1T contention. -J—. • 1.4 ί 1 —- 1---4-1227246 A7 B7 V. Description of the invention (2) Color tone. (Please read the precautions on the back before filling this page.) However, when antimony compounds are used as polycondensation catalysts, when the obtained polyester is continuously melt-spun for a long time, foreign matter will accumulate around the nozzle holes for melt-spinning ( Hereafter referred to as nozzle foreign matter), the molten polymer stream discharged from the nozzle will be bent, which will cause problems such as fluffing and / or thread breakage in the fiber yarn obtained in the spinning step and / or the stretching step. It has also been proposed to use titanium compounds such as titanium tetrabutoxide as polycondensation catalysts other than antimony compounds. Although this titanium compound can solve the problem caused by the accumulation of foreign matter in the nozzle, the obtained polyester has new problems such as yellow coloring itself and poor thermal stability. Generally, in order to solve the coloring problem, a cobalt compound for a color tone adjuster is added to polyester to suppress yellowing. It is true that the addition of cobalt compounds can improve the color tone (b 値) of polyesters, but the addition of cobalt compounds can reduce the thermal stability of the polyester melt, and easily cause the problem of polymer decomposition. Other titanium compounds printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, as disclosed in Japanese Patent No. 4 8-2 2 2 9, using titanium hydroxide as a catalyst for polyester manufacturing, Japanese Patent No. 4 7-2 6 5 9 7 The publication discloses that α-titanic acid is used as a catalyst for polyester production. However, in the former method, it is difficult to powder titanium hydroxide, and in the latter method, α-titanic acid is easily deteriorated and difficult to store and handle. Therefore, none of the aforementioned catalysts is industrially applicable, and it is difficult to obtain a polymer having a good hue (b) using it. In addition, Japanese Patent Publication No. 5 9-4 6 2 5 8 describes that a product obtained by reacting a titanium compound with trimellitic acid as a catalyst for polyester production is disclosed in Japanese Patent Application Laid-Open No. 5 8-3 8 7 2 It has been revealed that 'Titanium compounds and phosphorous ^ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 1227246 A7 B7 5 4 Description of the invention (3) (Please read the notes on the back before filling (This page) The product obtained by the acid ester reaction is used as a catalyst for polyester production. It is true that this method can improve the melt heat stability of polyester to a certain extent, but the obtained polyester has insufficient hue. Therefore, it is expected to further improve the color tone of polyester. In addition, Japanese Patent Application Laid-Open No. 7-1 3 8 3 5 4 has proposed that a complex compound of titanium compound and phosphorus compound as a catalyst for polyester production can not only improve the heat stability of the melt to some extent, but also Insufficient hue of polymer The invention discloses that an object of the present invention is to provide a polyester catalyst having a good hue (b 値), little foreign matter, and excellent thermal stability when melted, and a method for producing a polyester using the same. The above-mentioned object can be achieved by the catalyst for manufacturing polyester of the present invention and the method for manufacturing polyester using the same. The catalyst for manufacturing polyester of the present invention contains (A) a titanium compound (1) represented by the following general formula (I): (OR2) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (R1.)-(Η -〇) k —R4 (i) (OR3) [In the formula (I), R1, R2, R3 and R4 are each independently an alkyl group having 2 to 10 carbons, 'k is an integer of 1 to 3, and When k is 2 to 3, 2 or 3 R 2 bases and R 3 bases may be the same or different.] This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -6- 1227246 Intellectual Property of the Ministry of Economic Affairs A7 ______B7___ printed by the Bureau's Consumer Cooperatives. 5. Description of the Invention (5) 1) It is preferably selected from the group consisting of 'titanium tetraalkoxides, octaalkyltrititanates and hexaalkyldititanates. Among the catalysts for producing polyesters of the present invention, the aromatic polycarboxylic acid or its anhydride of formula (Π) is preferably phthalic acid, trimellitic acid, pyromellitic acid, pyromellitic acid or its anhydride. Elected. In the catalyst for manufacturing polyester of the present invention, the titanium compound (2) is preferably a titanium compound (1) of formula (I) and an aromatic polycarboxylic acid of formula (Π) or a molar ratio of reaction thereof is: 2 ·· 1 to 2: 5 reaction products. In the catalyst for manufacturing polyester of the present invention, the phosphorus compound (3) of the formula (III) is preferably a monomethyl phosphate, a monoethyl phosphate, a monotrimethyl phosphate, or a mono-η-butyl group. Phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, monolauryl phosphate, monoolenyl Phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4-ethylpropyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotolyl phosphate, monoxylyl phosphate, Selected among monobiphenyl phosphate, mononaphthyl phosphate, and monoanthracene phosphate. In the catalyst for manufacturing polyester of the present invention, the reaction product is preferably a titanium compound component (A) composed of at least one titanium compound of formula (I) (but k is 1), and the formula (m A reaction product of a phosphorus compound component (B) composed of at least one of the phosphorus compounds (3). In the catalyst for manufacturing polyester of the present invention, the formula (1) (but k is 1) (Please read the precautions on the back before filling this page)

、 1T line The size of this paper is applicable to Chinese National Standard (CNS) Α4 specification (UOxMVLf) 1227246 A7 B7 5. Description of the invention (

The reaction product of the titanium compound component (A) composed of at least one titanium compound in 6J and the phosphorus compound component (B) composed of at least one phosphorus compound (3) in formula (ΠΓ) preferably contains the following Compound represented by formula (IV):, 0, 0, R 6-Ο-

Ji

10 — R 0 (IV) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [In formula (IV), R6 and R7 are each independently an alkyl group having 2 to 1 atoms, or an alkyl group having 6 to 12 carbon atoms Aryl〕. In the catalyst for manufacturing polyester of the present invention, the reaction product of the titanium compound component and the phosphorus compound component (B) is produced at a reaction temperature of 50 to 50 ° C. The method for producing a polyester according to the present invention comprises polycondensing an ester of an aromatic dicarboxylic acid and an alkanediol and a polymerization starting material composed of at least one selected thereof in the presence of the ester catalyst of the present invention. In the method of ester, the total amount of millimolars of the aromatic dicarboxylic acid component of the polymerization starting material is preferably 2 to 40% of the amount of titanium moles contained in the catalyst. In the method for manufacturing a polyester according to the present invention, the aromatic dicarboxylic acid is more than phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylate, diphenylmethanedicarboxylic acid, and diphenyl. In the method for producing a polyester of the present invention selected from ether dicarboxyoxyethanedicarboxylic acid and / 5-hydroxyethoxybenzoic acid, terephthalic acid may be 0 carbon atoms (A) and 200. . The manufacture of poly oligomers reacts. The aromatic atoms contained in the compound are preferably p-acid, dibenzoic acid, and dibenzene. , Will gather together τ; --- 衣 — (Please read the notes on the back before filling in this page} Ψ. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 9 1227246 A7 B7 Ministry of Economic Affairs wisdom Printed by the Consumer Cooperative of the Property Bureau V. Description of the invention (7) The product obtained by hydrolyzing the dimethyl terephthalate after depolymerization of alkyl phthalate. In the method for producing polyester of the present invention, · The polyalkylene terephthalate used for the depolymerization may be the waste polyalkylene terephthalate formed article and / or the product recovered in the step of manufacturing the polyalkylene terephthalate Polymer shavings. In the method for producing polyester of the present invention, alkanediol is preferably selected from ethylene glycol, trimethyl glycol, tetramethyl glycol, neopentyl glycol, and hexamethyl glycol. The polyester produced by the present invention In the method, the temperature at which the polycondensation reaction is performed is preferably 230 to 320 ° C. The polyester of the present invention is produced by the production method of the present invention. The polyester produced by the method of the present invention is preferably Condensation reactants have an inherent viscosity of 0.70 to 0.90, aromatic dicarboxylic acids and alkanes The cyclic trimer content of the ester of alcohol is 0.5 to 50% by mass, and the content of acetaldehyde is 5 ppm or less. The polyester produced by the method of the present invention preferably has a content of 1 to the mass of the polyester. At least one type of hindered phenol compound by mass% or less. The polyester obtained by the method of the present invention is suitable for manufacturing a molded article. The molded article of the polyester obtained by the method of the present invention includes a bottle, a sheet, and a heat. A molded container and an injection molded product. The molded product includes a polyester fiber obtained by melting the resin raw material containing the polyester produced by the method of the present invention, and extruding the molten product into a fibrous form, and curing the obtained polyester fiber. The product contains and will contain the polyester ir prepared by the method of the present invention. (Please read the precautions on the back before filling out this page) -Packing-, 11-line-This paper size applies to China National Standard (CNS) A4 specifications ( 2! 〇X 297 mm) -10- 1227246 A7 B7 V. Description of the invention (8) After the resin raw material is melted, the melt is extruded into a sheet shape, and the resulting unstretched film is biaxially stretched after curing. The obtained polyester film. (Please read first Please fill in this page again before filling in this page) The best form of implementing the invention The catalyst for producing polyester of the present invention is a reaction product containing the titanium compound component (A) and the phosphonium compound component (B) described in detail below. The titanium compound component (A) used in the catalyst of the invention is a titanium compound (1) represented by the general formula (I), and a titanium compound (1) represented by the general formula (I) and an aromatic polybasic compound represented by the general formula (Π). At least one selected from the titanium compounds (2) obtained by the reaction of a carboxylic acid or its anhydride. In the formula (I), R 1, R 2, R 3, and R 4 are each the same or different and have 2 to 10 alkyl groups, preferably 2 to 6 carbon atoms, k is an integer from 1 to 3, more preferably 1, when k is 2 or 3, 2 or 3 R 2 and R 3 may be the same Or different. In formula (Π), m is an integer of 2 to 4, and 2 or 3 is more preferable. The phosphorus compound component (B) used in the catalyst of the present invention is a compound composed of at least one of the phosphorus compounds (3) represented by the general formula (m). In the printed version (ΠΙ) of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, R 5 is an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, and preferably 6 to 12 carbon atoms, or 1 to 20 alkyl groups, preferably 1 to 12 carbon atoms. In the reaction product of the titanium compound component (A) and the phosphorus compound component (B) used in the production of the polyester catalyst of the present invention, the titanium atom component (A) has a molar equivalent (m τ :) Molar ratio m τ, / mp is better in response to the molar amount (mp) of the phosphorus atom of the compound component (B) -11-Wood paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 1227246 A7 B7 V. Description of the invention (9) is 1: 1 to 1: 3, more preferably 1 ·· 1 to 1: 2. The molar amount of titanium atom equivalent of the titanium compound component (A) refers to the total of the product of the molar amount of each titanium compound contained in the titanium compound component (A) and the number of titanium atoms contained in one molecule of the titanium compound.又, In addition, the molar amount in terms of phosphorus atom in terms of the phosphorus compound (B) refers to the molar amount of each phosphorus compound contained in the phosphorus compound component (B) and the number of phosphorus atoms contained in one molecule of the phosphorus compound. The sum of the product of the numbers. However, since the phosphorus compound of the formula (m) is a compound containing 1 phosphorus atom per molecule, the molar amount of the phosphorus atom in the phosphorus compound is equal to the molar amount of the phosphorus compound. When the reaction molar ratio m τ i / mp is greater than 1: 1, when the amount of the titanium compound component (A) is too large, the color tone of the polyester obtained using the obtained catalyst will be poor (b 値 is too high), and Reduces heat resistance. When the reaction molar ratio m τ i / mp is less than 1: 3, that is, when the amount of the Chin compound component (A) is too small, the catalyst activity will be insufficient for the polyester-forming reaction using the obtained catalyst. . The titanium compound (1) represented by the general formula (I) used for the titanium compound component (A) is, for example, titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, and titanium tetraethoxide. Alkoxides; alkyl titanates such as octyl trititanates, hexaalkyl dititanates, etc. Among them, titanium tetranes having good reactivity with the phosphorus compound components used in the present invention Oxides are preferred, and titanium tetrabutoxide is particularly preferred. The titanium compound (2) used in the titanium compound component (A) is obtained by reacting a titanium compound (1) of general formula (I) with an aromatic polycarboxylic acid of general formula (Π) and its anhydride. The size of the aromatic polycarboxyl paper of general formula (Π) applies the Chinese National Standard (CNS) Ad specification (210X297 mm) --------- 1 ^ II (Please read the notes on the back before filling in this Page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1227246 A7 B7 Printed by the Employees’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Trimellitic acid, pyromellitic acid, and anhydrides thereof. Particularly preferred is trimellitic anhydride, which has good reactivity with the titanium compound (1) and has high affinity with the polyester of the obtained polycondensation catalyst. Titanium compound (1 ) And the aromatic polycarboxylic acid or its anhydride of general formula (π) are reacted by mixing the aromatic polybasic residual acid or its anhydride in a catalyst, dissolving part or all of it in a solvent, and then dissolving the titanium compound ( 1) Dropwise mixing of the mixture at 0 ° C to 200 ° C for more than 30 minutes, and heating at 30 to 150 ° C for 40 to 90 minutes is preferred. At this time, the reaction pressure is not particularly limited 'Atmospheric pressure is sufficient. The catalyst can be dissolved, and the dissolvable part must be all The amount of the compound of the formula (Π) or its anhydride is appropriately selected, and is preferably selected from ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene, etc. The titanium compound (1) and the formula ( The reaction molar ratio of the compound of Π) or its anhydride is not limited. However, when the ratio of the titanium compound (1) is too high, the hue of the obtained polyester is deteriorated and the softening point is lowered. Furthermore, the titanium compound (1) When the ratio is too low, the polycondensation reaction will be difficult. Therefore, the reaction of the titanium compound (1) with the compound of the formula (Π) or its anhydride is preferably controlled from 2/1 to 2/5. The reaction product can be directly supplied to the phosphorus compound (3) for reaction, or it can be recrystallized using a solvent formed from acetone, methanol, and / or ethyl acetate, etc., and reacted with the phosphorus compound (3) after purification. (B) In the phosphorus compound (3) represented by the general formula (III) used, C6 to C2 are represented by R5. Aryl or (: 1 to 02. Alkyl ----------- Installation-(Please read the precautions on the back before filling in this page) Binding paper size suitable for China National Standard (CNS) A4格 （21GX297mm） -13-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 1227246 A7 ___B7_ V. Description of the invention ("May be unsubstituted or substituted by more than one substituent. The substituents such as carboxyl, alkyl, Hydroxyl and amine groups, etc. Phenolic compounds (3) of the general formula (m), such as monomethyl sauce, monoethyl phosphate, monopropyl phosphate, single η ~ butyl phosphate, monohexyl phosphate , Monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, monolauryl phosphate, monoolenylated phosphate, monotetradecane Monophosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4-ethylphenyl) ) Phosphate ester, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotolyl phosphate, monoxylyl phosphate, monobiphenyl phosphate, Monoalkyl phosphates and monoaryl phosphates such as mononaphthyl phosphate and mono anthracenyl phosphate, and They may be used singly or in combination of two or more kinds, for example, a mixture of a monoalkyl phosphate and a monoaryl phosphate. However, when a mixture of two or more phosphorus compounds is used, the ratio of the monoalkyl phosphate is preferably 50% or more, more preferably 90% or more, and particularly preferably 100%. A method for preparing a catalyst from a titanium compound component (A) and a phosphorus compound component (B) is, for example, mixing a component (B) composed of at least one phosphorus compound (3) and a solvent in formula (n) to partially or completely After the phosphorus compound component (B) is dissolved in the solvent, the titanium compound component (A) is dripped into the mixed solution, and thereafter it is generally at 50 ° C to 200 ° C, and again at 70 to 150 ° C. The reaction system is heated at a preferred temperature for 1 to 4 minutes, and preferably 30 minutes to 2 hours. The reaction pressure of the reaction is not particularly limited, and may be under pressure (0.1 to 0.5 MPa), under normal pressure or under reduced pressure (this paper size is applicable. National Standard (CNS) A4 size (210X 297 mm)) (Please read the notes on the back before filling this page)

-14-1227246 A7 _B7_ 5. Explanation of the invention (^ 0 · 001 to 0.1MPa), and it is generally carried out under normal pressure. (Please read the precautions on the back before filling this page) The solvent for the phosphorus compound component (B) shown in the formula (m) for the above-mentioned catalyst preparation reaction can be one that dissolves at least part of the phosphorus compound component (B), and there is no It is particularly limited, and at least one selected from the group consisting of ethanol, ethylene glycol, trimethyl glycol, tetramethyl glycol, benzene, and xylene is preferred. It is particularly preferable to use a compound having the same diol component as the polyester of the final object. In this catalyst preparation reaction, the addition ratio of the titanium compound component (A) and the phosphorus compound component (B) in the reaction system is set to be the ratio of the titanium compound component (A) and the phosphorus compound component (B) contained in the obtained catalyst. In the reaction product, the reaction molar ratio m τ i / mp of the titanium atom equivalent molar amount (mTi) of the titanium compound component (A) to the phosphorus atom equivalent molar amount (mP) of the phosphorus compound component (B) is 1 ·· 1 to 1: 3, and more preferably 1: 1 to 1: 2. After printing the reaction product of titanium compound component (A) and phosphorus compound component (B) by centrifugal precipitation treatment or filtration, etc., printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, it can be directly used as a catalyst for manufacturing polyester without purification. Or, a recrystallization agent such as propanol, methanol, and / or water is used to recrystallize and refine the reaction product obtained from the separation, and then use the obtained refined product as a catalyst. In addition, the reaction mixture containing the reaction product can be directly used as the catalyst-containing mixture without separating the reaction product from the reaction system. In one aspect of the catalyst for manufacturing polyesters of the present invention, at least one titanium compound (1) of formula (I) (but k is 1), that is, a titanium compound component (A) composed of titanium tetraalkoxide , And the reaction product of the phosphorus compound component (B) composed of at least one phosphorus compound in formula (m) as the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -15- A7 1227246 _____B7 5 Description of the invention (^ Catalyst. (Please read the precautions on the back before filling out this page) In this catalyst, the titanium compound component composed of at least one titanium compound in formula (1) (but k = 1), And a reaction product of a phosphorus compound component composed of at least one phosphorus compound in formula (III), which contains a compound represented by formula (IV). However, in formula (IV), R6 and R7 are each independently and derived from titanium At least one of R 1, R 2, R 3 and R 4 of the compound (1) has an alkyl group having 2 to 10 carbon atoms, or the R 5 group derived from the phosphorus compound (3) has 6 to 1 2 Alkyl group of one carbon atom. The catalyst containing the titanium / phosphorus compound represented by formula (iv) has high catalyst activity, and The polyester obtained has good color tone (low b 値) and practically very low cyclic terpolymer of acetaldehyde, residual metal, aromatic dicarboxylic acid and alkanediol ester, and has practically sufficient Polymer properties. In the catalyst for manufacturing polyesters of the present invention, the content of the ammonium / phosphorus compound represented by the general formula (IV) is preferably 50% by mass or more, more preferably 70% by mass or more. Wisdom of the Ministry of Economic Affairs The method for manufacturing the polyester of the present invention printed by the employee's consumer cooperative of the property bureau is to polycondensate a polymerization starting material composed of at least one selected from the group consisting of an alkylene glycol ester of an aromatic dicarboxylic acid and its oligomer in the presence of the above catalyst. At this time, for the total millimoles of the aromatic dicarboxylic acid component contained in the polymerization starting material, the millimoles equivalent of the titanium atom used for the catalyst is preferably set to 2 to 40%, more It is preferably 5 to 35%. Especially good is 10 to 30%. When the amount of the catalyst is less than 2%, the catalyst promotion effect on the polycondensation reaction of the polymerization starting material will be insufficient, resulting in insufficient production efficiency of polyester. Therefore, it is not possible to obtain a polyester having a desired degree of polymerization. When it exceeds 40%, the color tone (b 値) of the obtained polyester will be less than the paper size. The Chinese National Standard (CNS) A4 specification (210X297 mm) will be applied. -16- 1227246 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (^ However, it has a yellow taste, so it will reduce practicality. In the method for producing a polyester of the present invention, among the alkylene glycol esters of aromatic dicarboxylic acids used as raw materials for polymerization, Preferably, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonic acid, diphenylmethanedicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl Oxygenated dibasic acid and fluorene-hydroxyethoxybenzoic acid are selected from terephthalic acid and naphthalenedicarboxylic acid. The alkanediol is preferably selected from the group consisting of ethylene glycol, trimethyl glycol, tetramethyl glycol, neopentyl glycol, and hexamethyl glycol. The method for producing the alkanediol ester of the aromatic dicarboxylic acid and / or its oligomer is not limited. Generally, the aromatic dicarboxylic acid or its ester-forming derivative 'and the alkanediol or its ester are used. Formable derivatives are obtained by heating. For example, polyethylene terephthalate and / or its oligomer used as a raw material of polyethylene terephthalate can be subjected to direct esterification reaction of terephthalic acid and ethylene glycol, or The lower alkyl ester of phthalic acid and ethylene glycol are transesterified, or the terephthalic acid is subjected to an addition reaction of ethylene oxide. In addition, monomethyl alcohol vinegar and / or its oligomer of terephthalic acid used as a raw material of polytrimethylene terephthalate may be subjected to a direct esterification reaction of terephthalic acid and dimethyl alcohol, or The lower alkyl ester of terephthalic acid and trimethyl glycol are transesterified, or the terephthalic acid is subjected to the addition reaction of oxetanoxy. In addition, without substantially impairing the effect of the method of the present invention, the above-mentioned alkanediol esters of aromatic dicarboxylic acids and / or their oligomers may be contained. Specifically, based on the total amount of g love ingredients, the addition amount is 10 Less than mol%, and then 5%. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297mm). „'Ll (Please read the precautions on the back before filling this page) -17- 1227246 A7 B7 V. Description of the invention (1f or less is a preferred additional component copolymerizable with other dicarboxylic acid esters. The copolymerizable additional component is preferably, for example, adipic acid, sebacic acid, 1,4-cyclohexanedi Aliphatic acids such as carboxylic acids, and alicyclic dicarboxylic acids, hydroxycarboxylic acids such as / 9 monoethoxyethoxybenzoic acid, and P-oxybenzoic acid, and one or more acid components, for example, with two or more carbon atoms One or more of aliphatic, alicyclic, aromatic diol compounds such as alkanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, bisphenol A, and bisphenol S, and polyoxyalkylene glycol The ester of the diol component or its anhydride is selected. The additional component ester may be used alone or in combination of two or more. The polymerization amount is preferably within the above range. It can be used when terephthalic acid and / or dimethyl terephthalate are used as starting materials. Based on the mass of all the acid components constituting the polyester, it will be 70 mass or more. Recovered terephthalic acid diester obtained by depolymerizing polyalkylene terephthalate or hydrolyzed recovered terephthalic acid. At this time, the target polyalkylene terephthalate is more It is preferably polyethylene terephthalate, and from the viewpoint of effective utilization of resources, the original source of polyester used for manufacturing polyester is particularly preferably recycled PET bottles, fiber products and polyester film products, and the Polymer shavings produced during the product manufacturing process, etc. The method for depolymerizing the recovered polyalkylene terephthalate to obtain a terephthalic acid diester is not particularly limited, and any method currently known can be used. For example, using After the ethylene glycol depolymerizes the recovered polyalkylene terephthalate, the depolymerized product is supplied to a transesterification reaction using a lower alcohol, such as methanol, and the reaction mixture is refined to recover the lower alkyl ester of terephthalic acid. Transesterification reaction Then, the obtained phthalic acid / alkanediol ester is polycondensed to obtain a polyester. In addition, the paper size of the terephthalic acid recovered from the recovered terephthalic acid diester is applicable. National National Standard (CNS) A4 specifications · (2) 〇χ 297 公 楚) I Zhuangyi-(Please read the notes on the back before filling this page) Order printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 1227246 A7 ____ B7_ V. Description of the invention ((please first Read the notes on the reverse side and fill in this page) The method is not particularly limited, and any current method can be used. For example, recrystallization and / or distillation can be used to recover dimethyl terephthalate from the reaction mixture obtained by transesterification. After that, it is heated with water under high temperature and pressure for hydrolysis, and terephthalic acid can be recovered. In the impurities contained in the terephthalic acid obtained by this method, the total content of 4-hydroxybenzaldehyde, p-toluic acid, benzoic acid, and hydroxyterephthalic acid diester is preferably 1 ρ ρ ηι or less. The content of monomethyl terephthalate is preferably from 1 to 5000 p pm. After terephthalic acid and alkanediol recovered by this method are directly esterified, the obtained ester is polycondensed to obtain a polyester. In the method for producing a polyester of the present invention, the period of time during which the polymerization starting material is added as a catalyst may be any period of time when the polycondensation reaction of the aromatic dicarboxylic acid alkylene glycol ester and / or its oligomer is started. The method is unconstrained. For example, after preparing an aromatic dicarboxylic acid alkylene glycol ester, add a catalyst solution or slurry to the reaction system to start the polycondensation reaction, or when preparing an aromatic dicarboxylic acid alkylene glycol ester, together with the starting materials or after Add the catalyst solution or slurry to the reaction system. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The reaction conditions for the production of polyester by the method of the present invention are not particularly limited. In general, the polycondensation reaction is preferably performed at 230 to 320 ° C under normal pressure or reduced pressure (0 · IPa to 0 · IMPa), or a combination of these conditions, for 15 to 300 minutes. Polycondensation. In the method of the present invention, a reaction stabilizer such as trimethyl phosphate can be added to the reaction system at any stage of manufacturing the polyester, if necessary, and an antioxidant, an ultraviolet absorber, a flame retardant, and a fluorescent agent can be added to the reaction system when necessary. One or more of a light whitening agent, a delustering agent, a tinting agent, a wave suppressant and other additives. This paper is in accordance with Chinese national standard (〇) ^) 6 specifications (210 mm 297 mm) '~ 1227246 kl ____ B7 V. Description of the invention (〇 (Please read the precautions on the back before filling this page) The polyester contains an antioxidant containing at least one type of hindered aniline compound, and its content is preferably 1% by mass or less based on the mass of the polyester. When the content exceeds 1% by mass, the heat of the antioxidant itself deteriorates, causing the The quality of the obtained product is deteriorated, so it is not suitable. The hindered phenol compound for antioxidant used in the polyester of the present invention may be pentaerythritol tetrakis [3-(3, 5-di-tert-butyl-4-hydroxyphenyl ) Propionate], 3,9 bis (2--[3- — (3-tert —butyl-4 —Ethyl-5—methylphenyl) propionyloxy] -1,1,1-dimethyl Ethyl 丨 -2,4 '8,1 0-tetra-n-oxaspiro [5,5] 11,1,1,3-tris (2-methyl-4 4-hydroxy-5-tert-butylbenzene Group) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,2,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzene) isophthalic acid, triethylene glycol-bis [3-(3-ter t-butyl -5-methyl-4 monohydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4 monohydroxyphenyl) propionic acid Ester], 2, 2-thio-diethylene-diethyl-bis [3- (3, printed by 5-indot-butyl-4-hydroxyphenyl) propionic acid Esters], octadecyl-1 [3- (3,5-di-tert-4 triphenylphenyl) propionate], etc. It is also preferable to use the hindered phenol-based antioxidant and The sulfide-based secondary antioxidant. There is no particular limitation on the method for adding the hindered phenol-based antioxidant to the polyester. 'It is preferably any time between the completion of the transesterification reaction or the esterification reaction and the completion of the polymerization reaction. U Paper size Applicable to the Chinese national standard "⑽ 丨 from specifications ^ training / mm) -20- 1227246 A7 ________B7___ V. Description of the invention (^ (Read the precautions on the back before filling (This page) In addition, in order to fine-tune the color tone of the obtained polyester, in the process of manufacturing polyester, organic cyan pigments such as azo-based, triphenylmethane-based, quinoline-based, anthraquinone-based, and phthalocyanine-based, and Inorganic cyan pigments contain at least one type of color stabilizer. Of course, in the production method of the present invention, it is not necessary to use inorganic cyan pigments such as cobalt for color stabilizers that reduce the melt heat stability of polyester. Therefore ', substantially, the polyester obtained by the method of the present invention is free of cobalt. Generally, the polyester obtained by the method of the present invention has an L 値 measured by a Hunter-type color difference meter of 8 0 · 0 or more, and a b 値 of 2.0 to 5 · 0. When the L 値 of the polyester is less than 80 · 0, the whiteness of the obtained polyester is reduced, and a practically high-whiteness molded article cannot be obtained. In addition, when b 値 is lower than −2.0, the yellow taste of the obtained polyester is reduced and the green taste is increased. When b 値 exceeds 5.0, the yellow taste of the obtained polyester is strengthened, and it is impossible to supply a practical molded article. use. The L 値 of the polyester obtained by the method of the present invention is preferably 8 2 or more, particularly preferably 8 3 or more, b 値 is preferably -1 · 0 to 4 · 5, and particularly preferably 0 · 0 to 4 · 0. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The L 値 and b 値 of the polyester obtained by the method of the present invention were measured by the following methods. That is, at 90 ° C under vacuum, the polyester sample was melted for 10 minutes, and then formed on a name plate into a sheet shape having a thickness of 3.0 ± 1.0 mm, and the sheet-like polyester test piece was immediately put into operation. It is rapidly cooled in ice water, and then the sheet test piece is dried for 1 hour at i 6 0 t for crystallization treatment. Then, the sheet test piece is placed on a white standard for color difference meter adjustment, and a color difference meter such as Minoda is used. The Hunter-type color difference meter CR-200 manufactured by the company measures the surface tone of a sheet test piece on a standard sheet. The inherent viscosity of the polyester of the present invention is not particularly limited, and it is preferred to use the Chinese national standard (CNS) A4 size (210 X 297 mm) of this paper size '-21-1227246 A7 B7 V. Description of the invention (^ (please Read the precautions on the back before filling in this page) 0. 55 to 1 · 0. Because of the inherent viscosity range, it is easy to melt-mold and the resulting molded product has higher strength. The inherent viscosity is more preferably 0.6 to 〇 to 〇 · 90 'Niu inch is preferably 62 · Q to 80. The inherent viscosity of the polyester is determined by dissolving the polyester for trial in o-chlorophenol at 35 ° C. Most of the polyesters obtained by solid phase polycondensation 5 wt Because it is used in bottles, etc., the polyester needs to have an inherent viscosity of 0.70 to 0.90. Therefore, the content of the cyclic trimer of the aromatic dibasic acid and the ester of the glycol is preferably 0.5 wt. % Or less' and the acetaldehyde content is preferably 5 ppm or less. The cyclic trimer includes alkyl terephthalate, such as ethylene terephthalate, propylene terephthalate, terephthalate Butanediol esters, hexanediol terephthalate, and the like, and alkylnaphthalene dicarboxylates such as naphthalenedicarboxylic acid Ethylene glycol, propylene naphthalate, butyl glycol naphthalate, hexanediol naphthalate, etc. Example Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs However, the present invention is not limited to this example. In addition, the measurement methods of the examples are shown below. (1) Intrinsic viscosity (IV) The intrinsic viscosity (IV) of the polyester polymer is that the polyester sample is dissolved at 35 ° C in The viscosity 値 measured after the o-chlorophenol solution. (2) Hue (L 値 and b 値) 290 t, the polyester sample was melted under vacuum for 10 minutes, and then formed on the aluminum plate to a thickness of 3.0 ± 1 · Sheets with a thickness of 0 mm, and then put in ice immediately. 324 The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) ^ -22-1227246 A7 V. Description of the invention (^ (Please read the precautions on the back first) Fill in this page again) Cool in water, then dry and crystallize the obtained sheet test piece at 160 ° C for 1 hour, then place it on the white standard for color difference adjustment, and use a Hunter type color difference meter made by Minoda. CR-2 0 0 Hunter L 値b 値. Among them, L 値 represents the brightness, the larger L 値 means the test piece is brighter, and the larger b 表示 means the test piece has a higher yellow tone. (3) The film color tone (L 値 and b 値) will be Five biaxially stretched polyester films were overlapped to obtain a test piece, and the test piece was stored in a 160 t dryer for 90 minutes, and then crystallized by heat treatment, and then used CM-7 manufactured by Color Machine Corporation. Measured with a type 500 color machine. (4) The concentration of titanium and phosphorus atoms of the catalyst obtained by metal concentration analysis is determined by fixing the dried catalyst sample to a scanning electron microscope (Hitachi measuring instrument Sabis Co., Ltd. S 570), the connected energy dispersive X-ray microanalyzer (XMA, EMAX-7 0 0 0 manufactured by Horiba, Ltd.) was used to determine the catalyst's titanium and phosphorus atom concentrations. The method for printing and measuring the concentration of residual catalyst metal in polyester by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is to heat and melt a granular polyester sample on an aluminum plate, and then use a compression laminator to make a test shaped article with a flat surface. 'The concentration of the metal in the test molded article was determined using a fluorescent X-ray measuring device 3 2 7 0 E manufactured by Rigaku Denki Co., Ltd. (5) The fiber elongation was measured in accordance with the method described in J S L 10; (6) Turbidity (bottle waist)] This paper size applies to Chinese National Standard (CNS) A4 size (210x 297 mm) -23- 1227246 A7 B7 V. Description of the invention ((Please read the notes on the back before filling (This page) After the pre-molding of the pre-form for bottle molding is started, any one after the fifth mold is used as a sample, and then the central part of the pre-molded product is taken at the central part of the waist. Then Nippon Denshoku Industries Co., Ltd. The turbidity meter (HD-1 01 DP) manufactured by the company measures the turbidity of the sample. (7) Haze (unstretched film) The granulated polymer sample is heat treated with a dryer at 150 ° C for 6 hours. After drying, it is melt-extruded into a sheet using a melt-extrusion machine at 2900 ° C, and then quenched and solidified to obtain an unstretched film (sheet) with a thickness of 50 0 // m. The surface of the extension sheet was sampled without any damage, and then the turbidity (HD-100 1 D) manufactured by Nippon Denshoku Industries Co., Ltd. was used to determine the turbidity of the sample. (8) Acetaldehyde content The polyester sample was frozen After drying, put it into a vial and keep it at 60 ° C for 60 minutes. After using Hitachi Instrument AG gas chromatography measurement sample was prepared in the content of acetic acid. (9) an amount of a cyclic trimer economic Intellectual Property Office employee printed consumer cooperatives

After crushing the polyester sample with a pulverizer, take a certain amount, dissolve it in a small amount of hexafluoroisoacetone / chloroform mixed solution, and then dilute the solution to a certain concentration (50 g / L) with chloroform. The obtained sample solution was supplied to a gel permeation chromatograph (GPC, ALC / GPC 2 2 4 type manufactured by Waters Corporation) to separate a low molecular weight field and detect peaks thereof, and then used a standard sample of a cyclic trimer to detect The content line is used as a reference to determine the cyclic trimer content in the sample. (1 〇) film thermal stability This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -24- 1227246 A7 B7 V. Description of the invention (d (Please read the precautions on the back before filling this page) Measure the intrinsic viscosity 値 (A) of the biaxially stretched film and the inherent viscosity 値 (B) of the granular polymer used to make the biaxially stretched film, and then calculate the 値 of (B)-(A). The 値 (( When B)-(A)) is from 0 to 0.05, the thermal stability is particularly excellent, and when it exceeds 0.05 to 0.1, the thermal stability is slightly worse, and when it exceeds 0.1, the thermal stability Very poor. (1 1) The attached layer generated from the spinning nozzle melted the polyester sheet at 290 ° C, and then spewed out from the spinning nozzle with a hole diameter of 0.1 mm and a hole number of 12 After spinning at a speed of 60 m / min for 2 consecutive days, the height of the attachment layer generated at the outer edge of the nozzle discharge port was measured. The higher the attachment layer, the more polyester monofilament flow that is discharged is more likely to bend. Decrease the moldability of polyester. That is, the height of the adherent layer generated by the spinning nozzle is an index of the moldability of the polyester. [Example 1] Titanation Compound: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Put 9 1 9 g of ethylene glycol and 10 g of acetic acid into a 2-liter three-necked flask with equipment for mixing and stirring the contents. Slowly add the mixture while stirring the mixture. 71 g of titanium tetrabutoxide was obtained as a transparent ethylene glycol solution of titanium compound. This solution is hereinafter referred to as a "TB solution". The titanium concentration of the solution measured by fluorescent X-rays was 1.02%. : Put 6 5 6 g of ethylene glycol into a 2-liter three-necked flask equipped with a device for heating and mixing the contents, and heat it to 1000 while stirring. This paper size applies the Chinese National Standard (CNS) A4 specification ( 210X297 mm) -25- 1227246 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (after d C, add 3 4 · 5 g of monolauryl phosphate, heat and stir the mixture, and dissolve to obtain Transparent solution. The solution is hereinafter referred to as "p 1 solution" 〇§ weekly catalyst: When stirring the above P 1 solution (about 690 g), control the temperature to 100 ° C and slowly add the above TB solution 3 10 g, followed by stirring at 100 C It should be 1 hour to end the reaction between the Chin compound and the phosphorus compound. At this time, the addition ratio of the P 1 solution to the TB solution is to adjust the molar ratio of the phosphorus atom to titanium atom to 2. · Because the obtained reaction product is insoluble In ethylene glycol, there are fine precipitates, and the mixture is cloudy. The catalyst dispersion is hereinafter referred to as "TP 1-2 · 〇 catalyst". To analyze the reaction precipitates in TP 1-2 · 0 catalyst, Filter a part of the sample through a filter with a pore size of 5 // m, and capture the solid precipitated reactants, and then wash with water and then dry. The obtained precipitated reactant was subjected to X ΜΑ analysis to analyze the element concentration. As a result, the titanium contained was 12 · 0%, the phosphorus was 16.4%, and the molar ratio to the phosphorus atom of the titanium atom was 2.1. Further, this was subjected to solid-state NMR analysis, and the results are shown below. C— 1 3 CP / MAS (cycle number 7 5. 5 Η z) measurement method confirmed that the peaks of chemical shifts of 14 ppm, 20 ppm, and 36 ppm of titanium tetrabutoxide from butoxide disappeared, and that P — 3 1 DD / The MAS (cycle number 1 2 1 · 5 H z) assay confirmed the presence of a novel chemical shift peak that is not present in monolauryl phosphate 2 2 ppm. From this analysis, it was confirmed that the reaction precipitate obtained in this example contains the novel compound produced by the reaction between the titanium compound and the phosphorus compound. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) I ---: --.----% —— 一-, —— 1T ----- | Dance (Please read the back first Please note this page before filling in this page) -26- 1227246 A7 _ B7 _ V. Description of the invention (2 meanings [Example 2] (Please read the precautions on the back before filling this page) Same as in Example 1 with T i / p-catalyst. However, the monolauryl phosphate for the phosphorus compound was replaced with a monobutyl phosphate, and 28.3 g of the monobutyl phosphate was dissolved in 537 g of ethylene glycol under heating (P2 solution). Then add 4 3 5 g of TB solution to the resulting solution for reaction. At this time, the addition ratio of the P 2 solution to the TB solution is to adjust the molar concentration ratio of phosphorus atom to titanium atom to 2.0. The resulting reaction mixture is hereinafter It is called "TP2-2 · 0 catalyst". The heating temperature of this reaction is 7CTC, and the reaction time is 1 hour. In order to analyze the reaction precipitates, the obtained reaction solution sample is filtered with a filter with a pore size of 5 // m, and captured. After the solid reaction precipitates were collected, they were washed with water and then dried. The element concentrations of the reaction precipitates obtained were analyzed in the same manner as in Example 1. The concentration of titanium is 17.0%, the concentration of phosphorus is 21.2%, and the molar ratio of phosphorus atom to moles of titanium atom is 1. 9 [Example 3] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as in Example 1 However, the composition of the TP 1 solution and the amount of the TB solution were changed as follows. That is, 3 1 · 3 g of monolauryl phosphate was dissolved in 5 9 4 g of ethylene glycol under heating to obtain a p 3 solution. 7.5 g of TB solution was added to the reaction to obtain a reaction mixture. At this time, the addition ratio of the P 3 solution to the TB solution was to adjust the molar concentration ratio of phosphorus atom to titanium atom to 1.5. This reaction is hereinafter referred to as the reaction. The mixed solution is "TP3 -1 · 5 catalyst". This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -27- 1227246 A7 B7 V. Description of the invention ([Example 4] (read first read Note on the back page, please fill in this page again.) The catalyst was prepared in the same way as in Example 2. However, the composition of the τ p 2 solution and the amount of butyl B solution were changed as follows. That is, the monobutyl phosphate 3 3 · 〇g was heated. Dissolved in 6 2 7 g of ethylene glycol to obtain a p 4 solution, then add 3 4 0 g of TB solution to it. The reaction yields a reaction mixture. At this time, the addition ratio of the p 4 solution to the TB solution is such that the molar concentration of phosphorus is adjusted to 3.0 for titanium atoms. The reaction mixture is hereinafter referred to as "τρ4_ 3 · 0 catalyst" [Example 5] Stirring 2 2 5 g of ethylene glycol-terephthalic acid oligomer remaining in the reactor, while maintaining 2 5 5 t in a nitrogen stream, under normal pressure, supply at a certain rate A slurry obtained by mixing 179 g of high-purity terephthalic acid and 95 g of ethylene glycol, and while agitating the reaction mixture in the reactor, 'the esterification of the two and the formation of the oligomerization reaction The water and glycol tank were left out of the system, and after 4 hours the two compounds were esterified and the reaction ended. At this time, the printing rate of the employee cooperative of the Intellectual Property Bureau of the Ministry of Ester Economy is over 98%, and the degree of polymerization of the resulting ester oligomer is about 5 to 7 ° The ester oligomer obtained by the esterification reaction 2 2 5 After putting the polycondensation reaction Fengcao 'mixed polycondensation catalyst, the titanium / phosphorus reaction compound (TP 1-2.0) solution obtained in Example 1 was 0.82 g. Stir the reaction system with a stirring wing, while gradually increasing the reaction temperature from 2 55 ° C to 280 ° C, and depressurizing the reaction pressure from normal pressure to 60 P a stepwise. Applicable to Chinese national standard ((: milk) 8 4 specifications (210/297 mm) -28- 1227246 A7 ___ _ B7 V. Description of the invention (^ Also, water and ethylene produced by the condensation reaction of oligomers) The polycondensation reaction of the oligomer is carried out outside the alcohol distillation system. At this time, the polycondensation reaction time is 110 minutes. In addition, the progress of the polycondensation reaction is checked by monitoring the load of the stirring wings in the reaction system. When the polyester reaches the desired degree of polymerization, the reaction is ended. After that, the reaction mixture in the system is continuously extruded or monofilament-shaped by the discharge section, cooled and solidified, and cut to obtain particles with a diameter of about 3 mm. As a result, the reaction mixture The IV 値 of polyethylene terephthalate is 0.52, the content of diethylene glycol (DEG) is 1.3% by mass, and L 値 in the color tone is 81 ′ b 値 is 1 · 〇. The catalyst metal concentration is titanium; [3 ppm and phosphorus 16 ppm. Among them, the DEG content is based on the use of hydration After the sample was decomposed, the decomposition product was supplied to a gas chromatograph (manufactured by Hitachi, Ltd., a model "2 6 3-7 0") for measurement. The measurement results are shown in Table 1. [Example 6] Same as in Example 5 Preparation of polyethylene terephthalate. However, in the example --- τ-: ---- ^ 衣 ---- Ί--1T ------ (Please read the back Please fill in this page again.) The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the polycoated card, which is shown as anti-IV%. The amount of gold is 1% of the liquid ester. · Contains fruit ο, the result of acetone 1. The acid is determined as 2, and the amount of benzene is 8. Measure the content of benzene. 2 3} om P 9 Poly G is P T5 to get E 値 P (• The D b 5 substance ο 〇C, 1 combined with benzyl alcohol, 1 phosphatization amount divided into 2 8 and 5 should be added. 2 B is 1T1 reverse investment. 2 値 P and 1—I, LP \, which is 2 in 2 and titanium. · The color titanium alloy is ο, 2 is time-delayed, and the time is doubled. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -29- 1227246 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs , Explanation (y [Example 7] Polyethylene terephthalate was produced in the same manner as in Example 5. However, the solution of the acetic acid / phosphonium compound (TPH. 5) obtained in Example 3 was used as a polycondensation catalyst and the amount of the catalyst was added.) It was changed to 0.4 and 3 g, and the polycondensation reaction time was changed to 5 minutes. The obtained polyethylene terephthalate was 0.52, the DEG content was χ. 2 mass%, and l 値 in the color tone was 8 1, and b 値 was i. 8, the catalyst metal contained The concentration is 8 PP m of titanium and 7 ppm of phosphorus. The measurement results are shown in Table χ. [Example 8] A polyethylene terephthalate was produced in the same manner as in Example 5. However, a solution of the it / phosphorus reaction compound (τ P 4-3 · 〇) obtained in Example 4 was used as a polycondensation catalyst, and the input amount was changed to 2.27 7 g. The polycondensation reaction time was changed to 120 minutes. The IV 値 of the obtained polyethylene terephthalate was 0.52, the DEG content was 1.3% by mass, and L 値 in the color tone was 8 1 'b 値 was 0.7, and the concentration of the catalyst metal contained It is 38 ppm of titanium and 65 ppm of phosphorus. [Comparative Example 1] A polyethylene terephthalate was produced in the same manner as in Example 5. However, an ethylene glycol solution with a concentration of 1.3% of antimony dioxide was used as a polycondensation catalyst, and the input amount was 4.83g. In addition, a stabilizing agent is added to the reaction mixture with a trimethyl phosphonate 25% concentration of an ethylene glycol solution of 0 · 1 2 1 g, and the polycondensation is reversed. The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297). Mm) • j Z: '· I ---------- ΜΎ ---- Ί--, 玎 -----— φ. (Please read the notes on the back before filling this page ) -30- 1227246 A7 B7 V. Description of the invention (The time required for the 2 reaction is 110 minutes. The obtained polyethylene terephthalate! V 値 is 0.52, and the deg content is 1.0.5% by mass. In the color tone, L78 is 78 ′ b3 is 3 · 5, and the concentration of the catalyst metal contained is antimony 250 ρ P m and phosphorus 2 6 ρ pm. The measurement results are shown in Table _. [Comparative Example 2] Same as the example 2 Polyethylene terephthalate was produced. However, the TB B valley liquid used in Example 1 was used as a polycondensation catalyst, and the input amount was 0.258 g. The polycondensation reaction time was changed. It is 95 minutes. The obtained poly (p-phenylene terephthalate) IV is 0.52, the DEG content is 13% by transient, the L is 8 1 in the hue, and the b is 6 · Q. The catalyst metal concentration is titanium 1 3 ρ pm. The measurement results are shown in Table 1. [Comparative Example 3] Polyethylene terephthalate was produced in the same manner as in Example 5. However, the τ B solution obtained in Example 1 which was separately introduced without reacting with each other was a τ B solution of 0.28 g and a Pi solution of 0. 574 g was used as a polycondensation catalyst, and the polycondensation reaction time was 110 minutes. The w 値 of the obtained polyethylene terephthalate was 0. 52 'DEG with a star content of 1. 3% by mass. l 値 is 8 1, b 値 is 3.5, and the catalyst metal concentration is 13 ppm of titanium and 1 4 ρ ρ m. The measurement results are shown in Table 1. [Comparative Example 4] Manufactured in the same manner as in Example 6. Polyethylene terephthalate g purpose. However, the Chinese National Standard (CNS) A4 specification (210X 297 mm) applies to unprinted paper standards ---: --.----%-( Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau's Consumer Cooperatives of the Ministry of Economic Affairs -31-1227246 Μ Β7 V. Description of the invention (2? (Please read the notes on the back before filling this page) Response Methods: The TB solution obtained in Example 1 of the reaction system, 0.258 g and 0.25 g of the p2 solution, were respectively charged as a polycondensation catalyst, and the polycondensation reaction time was changed. It was further 1 12 minutes. The IV 値 of the obtained polyethylene terephthalate was 0.52, the DEG content was 1.3% by mass, L 値 in the color tone was 8 1, and b 値 was 3.0 ·, so The concentration of the catalyst metal was 1 3 p P m of titanium and 13 ppm of phosphorus. The measurement results are shown in Table 1. [Comparative Example 5] Preparation catalyst: A catalyst was produced in the same manner as in Example 1. However, mono-n-lauryl phosphate for phosphorous compounds was replaced with di-n-butyl phosphate, and the addition amount and reaction conditions of the compounds used were changed as follows. Under the printing and heating of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 38.6 g of di-n-butyl phosphate was dissolved in 5 3 7 g of ethylene glycol (p 5 solution), and 4 3 5 g of TB solution was added to obtain Reaction product. At this time, the heating temperature was 70 t, the reaction time was 1 hour, and the addition ratio of the P 2 solution to the T B solution was such that the molar ratio of the phosphorus atom to the titanium atom was adjusted to 2.0. The obtained reaction mixture is hereinafter referred to as "TP5 — 2.0 catalyst". In order to analyze the reaction precipitates in the reaction mixture, a sample of the reaction solution was filtered through a filter with a pore size of 5 // m, and the reaction precipitates were collected, washed with water, and then dried. The element concentration of the obtained reaction precipitate was analyzed by the above method. As a result, titanium was 16.9%, phosphorus was 21.0%, and the molar ratio of phosphorus atom to titanium atom was 1.9. This paper size applies Chinese National Standard (CNS) A4 specification U! 〇X29 < 7 mm) 1227246 A7 B7 V. Description of the invention (& 1 made of polyester: (Please read the precautions on the back before filling this page) Same Example 5 produced polyethylene terephthalate. However, using the TP 5-2 · ○ catalyst solution obtained above 5.9 g as a polycondensation catalyst, the water condensation reaction time was 100%. Min. The rv 値 of the obtained ethylene terephthalate was 0.52, the DEG content was i · 3, the L 値 in the color p week was 7 8 'b 値 was 5 · 4, and the catalyst gold contained The M concentration was 13 ppm of titanium and 16 pm of phosphorus. The measurement results are shown in Table i. [Comparative Example 6] Preparation of catalyst: The catalyst was produced in the same manner as in Example 1. Since trimethyl drone vinegar was used instead of the dish compound The purpose of m laurel * phosphate ... Change the amount of compounds used and the reaction conditions as follows. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperative, and dissolving trimethyl phosphate 2 5 · 7 g in ethylene glycol 5 3 7 g (p 6 solution), then add τ B solution 4 3 5 g, heating temperature: 70 t, reaction time: i hour The reaction results in a reaction mixture. At this time, the addition ratio of the p 2 solution to the TB solution is to adjust the molar ratio of the phosphorous atom to titanium atoms to 2.0. The resulting reaction mixture is hereinafter referred to as "TP6-2.0 catalyst". In order to analyze the reaction precipitates in the obtained TP 6-2 · 0 catalyst, a sample of the reaction solution was filtered with a filter having a pore size of 5 // m, and the solid reaction precipitates were collected, washed with water, and then dried. The obtained method was analyzed by the above method. The result of the concentration of the element in the reaction precipitate is 16. 9%, and the tolerance is 20 -9%. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -33-1227246 Α7 Β7 V. Description of the invention (3 |, the molar ratio of phosphorus atom to titanium atom is 1.9. Production of polyester: Polyethylene terephthalate was produced in the same manner as in Example 5. However, the above was obtained. TP 6-2 · 0 The catalyst solution of 0.5 · 9 1 g was used as a polycondensation catalyst, and the polycondensation reaction time was 92 minutes. The IV 値 of the obtained ethylene terephthalate was 0.5 2 and the DEG content was 1.3. Mass%, L 値 in the color tone is 7 7, b · is 5 · 9, and the concentration of the catalyst metal is titanium 1 3 ρ ρ m and 1 6 pm. The measurement results are shown in Table 1. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Table 1 Catalyst Polymer Quality Catalyst Type Catalyst Content IV DEG Content hue Ti / P (ppm) Mass (%) L 値 b 値 Lb 値 Example 5 TP1-2.0 13/16 0.52 1.3 81 1.0 80.0 Example 6 TP2-2.0 12/15 0.52 1.3 81 0.8 80.2 Example 7 TP3 -1.5 8/7 0.52 1.2 81 1.8 79.2 Example 8 TP4-3.0 38/65 0.52 1.3 81 0.7 80.3 Comparative example 1 Sb2 03 250 (Sb) 0.52 1.0 78 3.5 74.5 Comparative example 2 TB solution 13A 0.52 1.3 81 6.0 75.0 Comparative example 3 TB + P1 solution 13/14 0.52 1.3 81 3.5 77.5 Comparative example 4 TB + P2 solution 13/13 0.52 1.3 81 3.0 76.0 Comparative example 5 TP5-2.0 13/16 0.52 1.3 78 5.4 72.6 Comparative example 6 TP6 · 2.0 13/16 0.52 1.3 77 5.9 71.1 This paper size applies to the Chinese National Standard (CNS) A4 specifications (210 × 297 mm) 1227246 A7 ____B7 _ V. Description of the invention (d (Please read the precautions on the back before filling this page) ) From Table 1, it is known that the catalysts of the titanium / phosphorus reaction compounds obtained in Examples 1 to 4 of the present invention are true. Examples 5 to 8 show the superiority of the polycondensation reaction, and can produce polyester in a smaller amount than the current antimony compound catalysts, and compare the catalysts formed by antimony catalysts or simple mixtures of titanium compounds and phosphorus compounds This system can greatly improve the hue of the obtained polyester. [Example 9] After drying the polyethylene terephthalate having 0.64 IV 値 prepared in the same manner as in Example 5, the pellets were supplied for melt spinning to obtain 3 3 3 dte X / 3 6 The unstretched filament of fi 1 was then stretched at a stretching ratio of 4 · 0 times to obtain a composite filament stretched yarn of 83 · 25dtex / 36f i 1. The quality of the obtained polymer and yarn is shown in Table 2. [Examples 10 to 12] Examples 10 to 12 each produced polyethylene terephthalate filaments in the same manner as in Example 9. However, the polyethylene terephthalate particles used were those obtained in Examples 6 to 8, respectively. The quality of the obtained polymer and yarn is shown in Table 2 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. [Comparative Examples 7 to 10] Comparative Examples 7 to 10 each produced polyethylene terephthalate filaments in the same manner as in Example 9. However, the polyethylene terephthalate particles obtained in Comparative Examples 1 to 4 were respectively used. The quality of the obtained yarn is shown in Table 2. This paper size applies to China National Standard (CNS) A4 (210X297 mm) — ~ — -35- 1227246

AB V. Description of the invention (4 Intellectual Property Bureau of the Ministry of Economic Affairs g (Industrial and Consumer Cooperatives Printed Silk Quality Nozzle Surface Height (// m) Inch Bu On ON Elongation g CNl CO CSJ un CN | CNl Strength (cN / dtex) oo oo cn oo cn c-5 Polymer-quality hue Lb 値 80.0 80.2 79.2 on g 74.5 75.0 77.5 76.0 p oo oo ο 53 5S 5〇53 oo 5S 5S oo DEG content rate (% by mass) CO CO CNj CO ρ CO CO CO > 0.64 0.64 0.64 _! 1 0.64 0.64 0.64 0.64 Polymer manufacturing conditions | Example 5 Example 6 Example 7 Example 8 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 9 Example 10 Senna m 1 Example 12 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 ---- > -I: ---- Φ ------, w ------ Φ (Please Please read the notes on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -36-A7 B7 Ϊ227246 V. Description of the invention ([Example 1 3] (Please read first Note on the back, please fill out this page again.) 1 8 0 t will be 0.6 4 IV of the polyethylene terephthalate prepared in Example 5 After the pellets were dried for 3 hours, they were supplied to a single-shaft compounding extruder (with an inner diameter of 65 mm and a passage length of 100 mm and a residence time of 10 minutes). The temperature near the inlet of the extruder was controlled to 2 80 ° C, and set the vicinity of the discharge port to 300 ° C, slowly polymerize the polymer to heat and melt, and then extrude the film with a discharge die to form an unstretched film. Extend at 9 ° C After stretching the lengthwise direction of the unstretched film (uniaxially stretched film) at a magnification of 3.5 times, the widthwise direction (biaxially stretched film) was stretched at a stretching ratio of 4.0 times, and then heat-fixed at 200 ° C to obtain a thickness of 15 / / m of polyester biaxially stretched film. The properties of the obtained polyester and film are shown in Table 3. [Examples 14 and 15] Examples 14 and 15 were the same as those in Example 13 to produce polyterephthalic acid. Ethylene glycol film. However, the polyethylene terephthalate particles obtained in Examples 6 and 7 were used. The properties of the obtained polymer and film are shown in Table 3. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [ Comparative Examples 1 to 1 3] Comparative Examples 1 to 1 3 were produced in the same manner as in Example 13 to produce polyethylene terephthalate films. However, each of the polyethylene terephthalate particles obtained in Comparative Examples 1 to 3 was used. The properties of the obtained film are shown in Table 3. This paper size applies Chinese National Standard (CNS) A4 specification (21 OX29? Mm) -37- 1227246 A7 B7 V. Invention Description (4 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

—--- ^ --.------ (Please read the notes on the back before filling out this page) The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) -38- 1227246 A7 _____ B7 _ _ 5. Description of the invention ([Example 1 6] (Please read the precautions on the back before filling out this page) 1 6 0 ° C using a high-speed stirring flow crystallization machine to polymerize the obtained in Example 5 After the ethylene terephthalate particles were treated for 10 minutes, the polymer was semi-crystallized, and then treated at 160 ° C for 4 hours under a nitrogen flow to crystallize and dry. The obtained particles were transferred to a packed tower In a solid-phase polymerization tower, a solid-phase polycondensation step is performed at 2 15 ° C for 2 to 25 hours under nitrogen flow. At this time, the reaction time is adjusted so that the IV of polyethylene terephthalate is 0 7 60 0. The quality of the obtained polyethylene terephthalate is shown in Table 4. The obtained polyethylene terephthalate particles were formed into a pre-molded body in the following method. Using a disc dryer Dry the polyethylene terephthalate at a temperature of 160 ° C, atmospheric pressure and nitrogen flow for more than 10 hours. Then, the dried polyethylene terephthalate was supplied to an injection molding machine ("M-100D Μ" manufactured by SEIKI Co., Ltd.), and then the cylinder temperature was 27 5 C, and the number of spiral revolutions was 1 60. Conditions for r pm, primary pressing time 3.0 seconds, mold cooling temperature 10 ° C, cycle time 30 seconds. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, injection molding, with an outer diameter of about 28 mm and an inner diameter of about A cylindrical pre-model of 19 mm, length 1 36 mm, waist thickness 4 mm, and weight about 56 g.

Sampling was performed on the central part of the waist of the obtained pre-molded body, and the IV, turbidity, acetaldehyde concentration, and cyclic trimer content were measured. The results are shown in Table 4. [Example 17] JJS This paper size is in use. National National Standard (CNS) A4 specification (210X297 mm) -39- 1227246 A7 B7 V. Description of the invention ((Please read the back first (Notes for filling in this page, please fill in this page again)) In the same manner as in Example 16, a polyethylene terephthalate pre-molded body was produced. However, the polyethylene terephthalate particles obtained in Example 6 were used. The measurement results are shown in the table. Shown in 4. [Comparative Examples 1 to 16] Comparative Examples 1 to 16 each produced a polyethylene terephthalate preform molded body in the same manner as in Example 16. However, Comparative Examples 1 to 3 were used respectively. The obtained polyethylene terephthalate particles. The measurement results are shown in Table 4. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs _y 3 3 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X29? (Mm) -40- 1227246 A7 B7 V. Description of the invention (4 Quality cyclic trimer content (mass%) printed by the pre-model of the molded body of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs CO 0 0.34 0.37 0.45 0.37 Acetaldehyde content (ppm) 〇τ—Η ^ Γ) Γ < 1 Haze (%) uo p CNj > 0.70 0.69 0.70 0.68 0.69 Cyclic terpolymer content (mass%) of polymer quality after solid phase polymerization 0.32 1_ 0.32!] 0.35 0.30 0.32 Acetaldehyde content (ppm) P cs O Hue Lb 値 mg 80.8 76.0 1 75.0 78.5 § csj p § wo CO oo CO oo oo CO oo > 0.76 0.76 0.76 0.76 0.76 Polymer Manufacturing Conditions Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 16 Example 17 Comparative Example 14 Comparative Example 15 Comparative Example 16 (Please read the notes on the back before filling this page)

1. The paper size of the 1T line wins the Chinese national standard (CNS) A4 specification (210X297 mm) -41 Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1227246 a7 _ B7 V. Description of the invention (y [Example 1 8] Same Example 6 produced polyethylene terephthalate particles. However, after the esterification reaction was completed, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid was prepared. Esters] ("Iruka 1 0 1 0" manufactured by Gibbs Corporation) 〇. 4 1 g was added to the oligomer. The IV of the obtained polyethylene terephthalate particles was 0 · 63, hue The medium L 値 is 81, b1 is 1.9, and the concentration of the catalyst metal is 12 PP m of titanium and 15 ppm of phosphorus. The obtained polyethylene terephthalate particles are supplied to the fiber produced in Example 9 Step. The IV of the obtained polyester fiber is 0 · 62, the tensile strength is 3 · 7cN / dt ex, the elongation is 23%, and the height of the foreign matter on the nozzle surface is 5 // m. [Example 1 9] Manufacturing and recycling Dimethyl phthalate: Put 200 g of ethylene glycol into a 500 ml separable flask, then put 1.5 g of carbonated soda, crushed PET bottles, etc. 50 g of the polyethylene terephthalate crumbs were formed, and the mixture was heated to 185 ° C under stirring. After being stored for 4 hours in this state, the polyethylene terephthalate crumbs were dissolved. The depolymerization reaction was completed. The obtained depolymer was distilled under reduced pressure, and 150 g of the ethylene glycol fraction was recovered after concentration. The concentrated liquid was used as a transesterification reaction catalyst, and 0.5 g of carbonated soda was mixed, and then methanol 100 was added. g, the reaction mixture was stirred at atmospheric pressure and liquid temperature at 7 5 ° C for 1 hour, and the transesterification reaction was ended. After cooling the obtained reaction mixture to 40 ° C, the glass filter was used for 34t. (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

-42- 1227246 A7 B7 V. Description of the invention ((Please read the precautions on the back before filling out this page} filter. Then put the crude dimethyl terephthalate trapped on the filter into 100 g of methanol After heating, stirring at 40 ° C, washing, and then filtering again with a glass filter, the washing and filtering steps are repeated twice. The crude dimethyl terephthalate captured on the filter is put into distillation The inside of the device was subjected to reduced-pressure distillation under the conditions of a pressure of 6.65 kPa and a reflux ratio of 0.5, and then the distillate dimethyl terephthalate was collected. As a result, the collected fraction was 47 g, and the residue was distilled. The amount of dimethyl terephthalate measured in the sample was 2 g, and the recovery rate of dimethyl terephthalate was 93% by mass based on the mass of the polyester as input. In addition, the recovered refined The concentration of dimethyl terephthalate detected in dimethyl phthalate was 0.5 ppm. The purity of the recovered dimethyl terephthalate after purification was 99.9% by mass or more. Vehicle: 3 · 5 g of mono-η-butyl phosphate was mixed into 1 3 1 g of ethylene glycol, and the mixture was heated at 120 ° C for 1 〇. After dissolving, add 40 g of ethylene glycol to the resulting ethylene glycol solution 1 3 4 · 5 g, and then dissolve 3. 8 g of titanium tetrabutoxide. The reaction system obtained at 120 ° C The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed and stirred for 60 minutes to react the titanium compound with mono-η-butyl phosphate to obtain a white slurry for the catalyst containing the reaction product. The titanium content of the obtained catalyst slurry It is 0.3% by mass, and the molar ratio (m τ i / m ρ) of the titanium atom content to the phosphorus atom content is 2.0. Manufacture of polyester and fiber = dimethyl terephthalate recovered as described above 1 A mixture of 〇〇g and 70 g of ethylene glycol, and the above-mentioned titanium / phosphorus catalyst 1, 6 4 g input device. 2. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -43 -Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1227246 A7 B7__ V. Description of the invention (4: | In a reactor equipped with a stirrer, rectification tower and methanol distillation condenser, the reaction mixture is heated from 140 ° C to 2 40 ° C to carry out the transesterification reaction. Thereafter, the mixed solution containing the reaction product is transferred into a polycondensation reaction. In the container, the temperature was raised to 285 ° C, and then the polycondensation reaction was performed at a high vacuum of 26.67 Pa or less. The IV of the obtained polyester was 0.63 and the DEG content was 0.7 mass%. The obtained polyester was pelletized and dried. Then, the dried polyester particles are supplied to the melt-spinning step to obtain 3 3 3 dte X / 3 6 fi 1 unstretched yarns, and then stretched at 4.0 times to obtain 8 3 · 2 5 dte X / 3 6 Fii's composite yarn extends the silk thread. The measurement results are shown in Table 5. [Example 20] Production and recovery of dimethyl terephthalate: The same method as in Example 19 was used to produce and recover dimethyl terephthalate. Modulation catalyst: 0.8 g of trimellitic anhydride was dissolved in 2.5 g of ethylene glycol, and then 0.7 g of titanium tetrabutoxide was added dropwise (the molar amount of trimellitic anhydride used in the production of polyester described later is 0 under the reference. 5mo1), and the reaction system is kept in the air at 80 ° C under normal pressure for 60 minutes under reaction conditions to react titanium tetrabutoxide with trimellitic acid and mature the reaction product. After that, the reaction system was cooled to normal temperature, 15 g of acetone was added, and the reaction precipitate was filtered through No. 5 filter paper, and the collected material was dried at 100 ° C for 2 hours. The titanium content of the obtained reaction product was 11.2% by mass. Next, a single η-butyl phosphate 3 · 5 g is mixed into the ethylene glycol. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ---; --.---- Φ ---- Γ-^ ------ (Please read the precautions on the back before filling this page) -44- 1227246 A7 B7 V. Description of the invention (1 3 1 g, heat the mixture at 1 2 0 ° C 1 〇 Zhong, after dissolving, add 40 g of ethylene glycol to the ethylene glycol solution 1 3 4 · 5 g, and then add 駄 ---; —, ---- MW—— (Please read the precautions on the back first Fill in this page again) 5.0 g of the compound is dissolved therein. The reaction system is stirred at 120 ° C for 60 minutes, and the titanium compound is reacted with the mono-η-butyl phosphate to obtain a catalyst containing a reaction product. White slurry. The titanium content of the obtained catalyst slurry was 0.3% by mass, and the molar ratio of titanium atom content to phosphorus atom content (mTi / m ρ) was 2.0. Manufacture of polyester and fiber: The above titanium / Phosphorus catalyst 1, 6 4 g is mixed into a reactor equipped with a stirrer, a rectification tower and a methanol distillation condenser, and a mixture of 100 g of recovered dimethyl terephthalate and 70 g of ethylene glycol is obtained. After The reaction system is transesterified by increasing the temperature from 1 40 ° C to 240 ° C. Thereafter, the reaction product is transferred into a polycondensation reaction vessel, and the temperature is raised to 2 8 5 ° C, and then a high vacuum of 2 6 · 6 7 P a or less Polycondensation is carried out at the degree of reaction! The reaction yields a polyester having an IV of 0.63 and a DEG content of 0.8% by mass. The obtained polyester is pelletized and dried, and the dried pellets are then supplied to the melt spinning step to obtain 3 3 3 The unstretched yarn of dte X / 3 6 fi 1 was printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at a stretching rate of 4.0 times, and a composite yarn of 8 3 · 2 5 dtex / 3 6 fi 1 was obtained. The test results are shown in Table 5. [Example 2 1] Manufacture of recovered terephthalic acid: Recovered dimethyl terephthalate was produced in the same manner as in Example 19. Next, dimethyl terephthalate was recovered. 1 0 0 g mixed with water 2 0 〇344 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -45- 1227246 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (5 g The mixture was stirred at 180 ° C and supplied to a hydrolysis reaction. Device. The temperature of the liquid in the hydrolysis reaction device is raised to 250 ° C, and the dimethyl terephthalate is hydrolyzed with stirring, and the methanol produced by the reaction is distilled off with water. In the obtained terephthalic acid / water slurry The terephthalic acid / water mass ratio is about 1/1 '. In the obtained slurry, the total content of terephthalic acid was 4 p-carboxybenzaldehyde, p-toluic acid, benzoic acid, and dimethyl 2-hydroxyterephthalate were 1 P P m or less. Subsequently, 166 g of the obtained terephthalic acid / water slurry and 41 50 g of ethylene glycol were put into a centrifuge and mixed. The mass ratio of terephthalic acid / water / ethylene glycol is 1: 1: 50. The terephthalic acid water / glycol slurry was treated with a centrifugal separator 'to capture a terephthalic acid cake. In this terephthalic acid cake, the mass ratio of terephthalic acid / water / ethylene glycol is about 83: 0. 4: 14.3. Ethylene glycol was added to the slurry and mixed to adjust the terephthalic acid / ethylene glycol mass ratio of the terephthalic acid / ethylene glycol slurry to 6 6: 3 4. Preparation of a catalyst 3.5 g of a single η-butyl phosphate was mixed with 131 g of ethylene glycol, and the mixture was heated at 120 ° C for 10 minutes to obtain a solution. 40 g of ethylene glycol was added to 134.5 g of the ethylene glycol solution, and 3.8 g of titanium tetrabutoxide was dissolved therein. The resulting reaction system was stirred at 120 ° C for 60 minutes. The titanium compound was reacted with mono-?-Butyl phosphate to obtain a white slurry for a catalyst containing a reaction product. The catalyst slurry has a titanium content of 0.3% by mass. The molar ratio of the titanium atom content to the phostom content (niTi / mP) is 2.0. The size of this paper is applicable. National Standard (CNS) A4 Specification (2) 0X297 mm -46-(Please read the precautions on the back before filling this page)

1227246 A7 B7 5. Description of the invention (4 Manufacturing of polyester and fiber: (Please read the precautions on the back before filling this page) Put the 200 g of terephthalic acid / ethylene glycol slurry obtained above into a mixer, In the reactor of the rectification column and the methanol distillation condenser, an esterification reaction was carried out at 270 ° C and a pressure of 0.3 MPa for 240 minutes. After removing half of the obtained reaction mixture, the remaining half was kept as At 250 ° C, 100 g of the above-recovered terephthalic acid / ethylene glycol slurry was added at 150 minutes under normal pressure, and then the resulting reaction mixture was subjected to an esterification reaction, and then heated at normal pressure for 90 minutes. In addition, during this reaction, the temperature in the reaction system was maintained at 250 ° C. After removing half of the obtained reaction mixture, 100 g of the recovered terephthalic acid / ethylene glycol slurry was supplied in the same manner as above. The remaining half is subjected to an esterification reaction, and the foregoing steps are repeated until the diethylene glycol content of the reactant is stabilized. After the DEG content of the reaction mixture is stabilized, the reaction mixture obtained by the half of the esterification reaction is transferred into a polycondensation reaction device, and the above-mentioned titanium is added. / Phosphorus Catalyst 1 · 2 7 g. The obtained reaction system was heated to 2 8 5 ° C, and the polycondensation reaction was performed at a high vacuum degree below 2 6 · 7 7 Pa. The obtained IV printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was 0.63, DEG content It is 1.0% by mass. The obtained polyester flakes are dried, and then the dried flakes are subjected to a melt spinning step to obtain 3 3 dte X / 3 6 fi 1 unstretched yarns at a stretching ratio of 4.0 times. After the unstretched yarn was drawn, a composite yarn of 8 3 · 2 5 dtex / 3 6 fi 1 was obtained. The measurement results are shown in Table 5. [Example 2 2] Production and recovery of terephthalate: g Paper Zhang scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -47- 1227246 A7 _____B7 V. Description of the invention (The same method as in Example 21 is used to make recycled terephthalic acid. Modulation catalyst: (Please read first Note on the back page, please fill in this page again) Dissolve 0.8 g of trimellitic anhydride in 2.5 g of ethylene glycol, and then drop 0.7 g of titanium tetrabutoxide (the molar amount of trimellitic anhydride used for polyester production described later) 0 ～ 5 m 〇1), and then keep the reaction system in air At normal pressure and 80 ° C for 60 minutes, the titanium tetrabutoxide and trimellitic anhydride were reacted and the reaction product was matured. After the reaction system was cooled to normal temperature, 15 g of acetone was added and filtered with N 0.5 filter paper. The reaction product was collected. After drying at 100 ° C for 2 hours, the titanium content of the obtained reaction product was 1 · 2% by mass. Next, a single amount of η-butyl phosphate 3.5g was mixed with ethylene glycol Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in 13 1 g, 12 0 t: heating for 10 minutes, dissolving, and adding 40 g of ethylene glycol to the 1 4 4.5 g of ethylene glycol solution. 5.0 g of the above-mentioned titanium compound was dissolved therein. The obtained reaction system was stirred at 120 t for 60 minutes, and the titanium compound was reacted with mono-η-butyl phosphate to obtain a white slurry containing a catalyst for the reaction product. The titanium content of the catalyst slurry was 0.3% by mass, and the molar ratio (mTi / mp) of the titanium atom content to the phosphorus atom content was 2.0. Zhihao polyester and fiber: Put 200 g of the terephthalic acid / ethylene glycol slurry obtained above into a reactor equipped with a stirrer, a refiner 1 retention tower, and a methanol distillation condenser at 270 ° C. The esterification reaction was performed by heating at 0. 3 MPa under pressure for 240 minutes. After removing half of the obtained reaction mixture, keep the remaining half at 250 ° C, and mix it into the above terephthalic acid paper at 150 minutes under normal pressure. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm). ） -48- 1227246 A7 ___ B7 V. Description of the invention (/ ethylene glycol slurry 100g, and then esterification reaction under normal pressure for 90 minutes. During this time, the temperature in the reaction system was maintained at 2 50 ° C. After removing half of the resulting reaction, 100 g of a terephthalic acid / ethylene glycol slurry was mixed with the above to perform an esterification reaction, and then this step was repeated until the DEG content of the reactant was stable. After the DEG content in the medium is stabilized, the reaction mixture obtained by half of the esterification reaction is transferred to a polycondensation reaction device, and the above-mentioned titanium / phosphorus catalyst 1.27 g is added. After heating to 285 t, the polycondensation is performed at a high vacuum of 26.67Pa or less. Reaction. The IV of the obtained polyester was 0 · 63, and the DEG content was 1.0% by mass. The obtained polyester was pelletized and dried, and the dried particles were then supplied to the melt spinning step to obtain 3 3 3 dte X / 3 6 unstretched filaments of fi 1, followed by a draw ratio of 4 · 0 times extension to obtain 8 3. 2 5 dte X / 3 6 fi 1 composite yarn extension yarn. The measurement results are shown in Table 5. (Please read the precautions on the back before filling out this page) Intellectual Property Bureau of the Ministry of Economic Affairs The paper size printed by the employee consumer cooperative is applicable to the Chinese National Standard (CNS) a4 size (2IOX 297 mm) -49- 1227246 A7 B7 V. Description of the invention Height of surface foreign matter (βτη) csi cn C ^ l CO Elongation g CNl un Csl Strength ί (cN / dtex) oo \ o cn Polymer quality hue Lb 値 76.7 76.9 1 ί 77.0 77.1 § CNl C-; ON CN Mouth 1 ® ㈡ oo r—H g 79.9 80.2 DEG content (% by mass) oo oo p > CO VD 〇CO Ό o 1 0.63: 0.63 Example 19 Example 20 Surface Example 21 Example 22 ------- ^ ----— (Please read the notes on the back before filling in this page), 11 Φ, —., W This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 × 297mm) -j ή ', .τ -50-

Claims (1)

1227246 Α8 Β8 C8 D8 VI. Application for Patent Scope 1 Patent Application No. 91 Π 5 724 Amendment of Chinese Patent Application Scope (Please read the precautions on the back before filling this page) Amendment 1 August 11, 1993 A catalyst for producing polyesters, which comprises (A) an ammonium compound (1) selected from the group consisting of titanium tetraalkoxides, octaalkyltrititanates and hexaalkyldititanates, and, The titanium compound (1) of the amidine compound (1) of general formula (I) and an aromatic polycarboxylic acid selected from phthalic acid, trimellitic acid, biphenyltricarboxylic acid, pyromellitic acid or its anhydride, and a titanium compound (2) Select at least one of the obtained titanium compound components; and (B) a phosphorus compound (3) represented by the following general formula (Π): 0 II (R50) — P-OH (m) I OH [However, the formula (HI ), R 5 is an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.] It is at least one of the employees' cooperative printing of the Intellectual Property Bureau of the Ministry of Economic Affairs. Reaction products of phosphorus compounds. 2. The catalyst for manufacturing polyester according to item 1 of the scope of patent application, wherein the titanium compound component (A) has a titanium atom conversion equivalent in the reaction product of the titanium compound component (A) and the phosphorus compound component (B). The molar ratio (m τ, / m P) of the molar amount (m τ) of the molar amount (MP) of the phosphorus atom component (B) to the phosphorus atom component (B) of the phosphorus compound component (B) is 1: 1 to 1: 3. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 1227246 A8 B8 C8 D8 VI. Application for patent scope 2 3. For the polyester catalyst used in item 1 of patent scope, where the titanium compound (2) It is a reaction product obtained by titanium compound (1) and aromatic polycarboxylic acid (please read the precautions on the back before filling in this page) to react with a molar ratio of 2: 1 to 2: 5. 4. The catalyst for manufacturing polyesters according to item 1 of the scope of patent application, wherein the phosphorus compound (3) of formula (III) is composed of monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, mono -η-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, monolauryl phosphate Monool. Alkenyl phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylbenzene) Base) phosphate, mono (4-ethylpropyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotolyl phosphate, mono Selected among xylyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate, and monoanthryl phosphate. 5. The catalyst for manufacturing polyester according to item 1 of the scope of patent application, wherein the reaction product of the titanium compound component (A) obtained from the titanium compound and the phosphorus compound component (B) contains a compound represented by the following formula (IV) : Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs jU (iv) 〇 \ 〇 / 〇 [In the formula (IV), R6 and R7 are each independently an alkyl group having 2 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms]. 6. As for the catalyst for manufacturing polyester in item 1 of the scope of patent application, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)-2-1227246 Α8 Β8 C8 D8 6. Scope of patent application 'titanium The reaction product of the compound component (A) and the phosphorus compound component (B) is a product having a reaction temperature of 50 to 200 ° C. (Please read the precautions on the back before filling out this page} 7 · — A method for manufacturing polyester, which exists in the presence of a catalyst for manufacturing polyester as described in any one of the claims 1 to 6, Among the esters of aromatic dicarboxylic acids and alkanediols and their oligomers, at least one of the polymerization starting materials selected is subjected to a polycondensation reaction. 8 · The manufacturing method according to item 7 of the patent application, wherein The total millimolar amount of the aromatic diresidual acid component contained in the raw materials is started, and the millimolar amount of the titanium atom contained in the catalyst is 2 to 40%. 9 · For the manufacturing method of the seventh item in the scope of patent application, Among them, the aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyl ground dicarboxylic acid, diphenylmethanedicarboxylic acid, and diphenyl The acid is selected from the group consisting of 5 ^, monobenzylacetic acid, and / 3-heteroethoxybenzoic acid. 1 0 · The manufacturing method of item 9 in the scope of patent application, wherein Formic acid is a product obtained by depolymerizing polyalkylene terephthalate and hydrolyzing the obtained dimethyl terephthalate. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 1 If the manufacturing method of item 7 of the patent application scope, wherein the ester of aromatic dicarboxylic acid and alkanediol is the ester of terephthalic acid and alkanediol, and 'It is a product obtained by depolymerizing a polyalkylene terephthalate and transesterifying the obtained dimethyl terephthalate and an alkanediol. 1 2 As described in the patent application No. 10 or 11. The manufacturing method of item 1, wherein the polyalkylene terephthalate used for depolymerization can be discarded polyterephthalate® female 丨 τΕ monoethanol vinegar molded article and / or manufacturing polyterephthalate Steps of alcohol and vinegar This paper scale applies the Chinese National Standard (CNS) A4 specification (210 × 297 meals) 1227246 A8 B8 C8 D8 4 6. Polymer scraps recovered in the scope of patent application 1 3. As in item 7 of the scope of patent application A manufacturing method in which the alkanediol is selected from ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and hexanediol. 14. The manufacturing method according to item 7 of the scope of patent application, wherein the polycondensation reaction Performed at 2 3 0 to 3 2 0 ° C. (Please read the note on the back first Please fill in this page for the matters needing attention.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm).