JPH1121337A - Crystallization control type polyester - Google Patents

Abstract

(57) [Problem] To obtain PET in which crystallization is suppressed while using an inexpensive Sb-based catalyst as a catalyst. SOLUTION: Terephthalic acid is added to 95 parts of the total acid component.
A polyester containing at least 95 mol% of an acid component and ethylene glycol at 95 mol% or more of the total glycol component;
The amount of the element is 60 ppm to 38 with respect to the total amount of the polyester.
A crystallization-suppressing polyester, wherein the polyester satisfies the following formulas (1) and (2) in terms of thermal properties, and the polyester satisfies the following formula (3) in terms of intrinsic viscosity. 24.6 / [η] + 130.0 ≦ Tcd ≦ 24.6 / [η] +142.0 (1) 34.5 × [η] + 130.0 ≦ Tci ≦ 34.5 × [η] +142.0 (2) [Tcd is crystallization at the time of cooling by DSC The exothermic peak temperature (° C.), and Tci is the crystallization exothermic peak temperature (° C.) when the temperature was raised by DSC. 0.50 ≦ [η] ≦ 1.10 (3) [[η] represents intrinsic viscosity, [η] is phenol / tetrachloroethane
It is a value calculated from the solution viscosity measured at 35 ° C. using a solvent of (= 3/2 component ratio). ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyethylene terephthalate (hereinafter sometimes abbreviated as PET) with controlled crystallinity, which can suppress whitening and clouding of molded articles and improve spinnability. More specifically, isophthalic acid (hereinafter may be abbreviated as IA),
A PET substantially free of a copolymer component such as cyclohexane dimethanol (hereinafter sometimes abbreviated as CHDM) and obtained using an inexpensive Sb-based compound as a catalyst. It relates to PET that can be produced by production equipment.

[0002]

2. Description of the Related Art Polyesters represented by polyethylene terephthalate have excellent mechanical properties, heat resistance, weather resistance, electrical insulation resistance, and chemical resistance, and are widely used as fibers, bottles, films and other molded products.

[0003] The properties required of such polyesters differ depending on the application. For use in fibers and films, there is a demand for a polyester which is oriented and crystallized, has high strength, and is excellent in thread formability and film formability.

[0004] For use in packaging films and bottles, there is a strong demand for polyesters which are not cloudy and have excellent transparency.

[0005] It is generally considered that a molded article molded from a resin is required to improve strength. One of the causes of difficulty in improving the strength is that the resin is crystallized before sufficient molecular orientation occurs during stretch molding.

[0006] One of the causes of fogging of films and bottles is that polyester is crystallized during molding, and it is important to control the polymer so as to suppress crystallization.

[0007] For example, as for polyester for bottles, it is difficult to form crystal nuclei in the polyester and GeO having good transparency is used.
It is common in Japan to use _two catalysts.

[0008] However, in the recent market, there is an increasing tendency to demand a material of higher quality and lower cost, and the use of expensive GeO ₂ causes a decrease in the international competitiveness of the polymer. There is a demand for a method of using an inexpensive metal compound as a polymerization catalyst.

In addition to Ge catalysts, for example, Sb, Ti and Sn catalysts are known as metals having a polymerization activity of polyester.

[0010] Sb2O3 is often used as a polymerization catalyst, but is reduced during polymerization to form Sb metal, which gives the polyester a dark color, makes it easier to crystallize the resin, lowers the strength, and generates fogging. Bring.

Although Ti- and Sn-based catalysts generally have high polymerization activity, on the other hand, the generation rate of side reaction products is high and coloring of the polymer occurs. For this reason, it is difficult to use it for applications that require particularly good transparency and hue.

Japanese Patent Application Laid-Open No. 61-78828,
JP-A-576692 discloses an unfogged bottle polyester obtained by using a Sb compound as a polymerization catalyst and adding a predetermined amount of an Mg or Mn compound and an alkali compound. However, according to studies by the inventors, this polyester hardly has the effect of imparting low fogging properties or suppressing crystallization.

One of the methods for imparting low haze to polyester and suppressing crystallization using an Sb-based catalyst is isophthalic acid (IA), cyclohexane dimethanol (C
A method of copolymerizing HDM), an alkyldicarboxylic acid and an excess of diethylene glycol (hereinafter sometimes abbreviated as DEG) is known. According to this method, there is certainly an effect of imparting low haze and suppressing crystallization. However, there is a problem in applications that require strength, in that the molecular orientation is disturbed by the presence of the copolymer component and the strength is reduced.

Further, when such a copolymerized PET is used, the odor and the flavor may be greatly changed depending on the filler, and there is a problem in bottles and food packaging films.

[0015]

An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to obtain PET with suppressed crystallization characteristics while using an inexpensive Sb-based catalyst as a catalyst. It is. More specifically, it is an object of the present invention to obtain PET having substantially no fogging and whitening and having suppressed crystallization characteristics without substantially containing a copolymer component other than DEG. Here, suppressing the crystallization characteristics means suppressing the crystallization speed to a low value. Another object of the present invention is to obtain PET having less whitening when formed into a preform for a bottle and less fogging when formed into a bottle and having suppressed crystallization characteristics.

[0016]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that PET, which is preferable as a packaging material, for example, a bottle material, has low fogging properties and low whitening properties and has suppressed crystallization properties, An exothermic peak (hereinafter may be referred to as Tci) detected when a polymer rises from an amorphous state in a measurement by a differential scanning calorimeter (hereinafter may be abbreviated as DSC) and a temperature decrease from a molten state. It has been found that the value of the exothermic peak (sometimes referred to as tcd hereinafter) sometimes detected is PET satisfying specific conditions.

According to the findings of the present inventors, the polyester of the present invention can be obtained by polymerizing PET using a predetermined amount of a polycondensation catalyst compound prepared from Sb2O3 by a specific preparation method.

The present invention relates to a polyester comprising terephthalic acid as an acid component in an amount of 95 mol% or more based on the total acid component, and ethylene glycol as a glycol component in an amount of 95 mol% or more based on the total glycol component. The amount of the Sb element present is 60 pp to the total amount of the polyester.
m-380 ppm, the polyester satisfies the following formulas (1) and (2) in terms of its thermal properties, and the polyester satisfies the following formula (3) in terms of intrinsic viscosity. Polyester. 24.6 / [η] + 130.0 ≦ Tcd ≦ 24.6 / [η] +142.0 (1) 34.5 × [η] + 130.0 ≦ Tci ≦ 34.5 × [η] +142.0 (2) [Tcd is crystallization at the time of cooling by DSC The exothermic peak temperature (° C.), and Tci is the crystallization exothermic peak temperature (° C.) when the temperature was raised by DSC. 0.50 ≦ [η] ≦ 1.10 (3) [[η] represents intrinsic viscosity, [η] is phenol / tetrachloroethane
It is a value calculated from the solution viscosity measured at 35 ° C. using a solvent of (= 3/2 component ratio). Hereinafter, the present invention will be described in detail.

[Polyester] The polyester of the present invention contains terephthalic acid in an amount of 95 mol% or more, preferably 97 mol% or more, more preferably 99 mol%, based on the total acid components.
More preferably, the acid component is 99.5 mol% or more, and ethylene glycol is added in an amount of 9 to the total glycol component.
PET having a glycol component of 5 mol% or more, preferably 96 mol% or more.

As the third component, components other than terephthalic acid, ethylene glycol and diethylene glycol can be contained in an amount of 3 mol% or less, preferably 1 mol% or less, more preferably 0.5 mol% or less. The content needs to be within a range that does not impair the purpose of the present invention. It is particularly preferred that the third component other than diethylene glycol is not copolymerized.

Other components other than diethylene glycol include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and diphenylether dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and fatty acid dicarboxylic acids such as adipic acid and sebacic acid. Aliphatic diols such as triethylene glycol, tetramethylene glycol, hexamethylene glycol; alicyclic diols such as cyclohexanediol and cyclohexane dimethanol; aromatic diols such as naphthalene diol, bisphenol A, resorcinol;
-Oxybenzoic acid, m-oxybenzoic acid, salicylic acid,
Examples include oxycarboxylic acids such as mandelic acid, hydroacrylic acid, glycolic acid, 3-oxypropionic acid, asiatic acid, and quinovanic acid.

In the range where the polyester is substantially linear, trifunctional or higher polyfunctional compounds such as glycerin, trimethylolpropane, pentaerythritol,
Components such as trimellitic acid, trimesic acid, pyromellitic acid, tricarballylic acid, and gallic acid may be copolymerized, and if necessary, a monofunctional compound such as o-benzoylbenzoic acid, a small proportion of naphthoic acid, For example, 1 mol%
It may be contained as a copolymer component in the following ratio.

[Sb Element Amount] In the present invention, an Sb-based catalyst, preferably Sb 2 O 3, is used as a polyester polymerization catalyst.
Is used.

The amount of the Sb element present in the polyester of the present invention is from 60 ppm to 380 with respect to the total amount of the polyester.
ppm, preferably 90 ppm to 300 ppm.
If the amount of the Sb element is less than 60 ppm, the polymerization activity is small,
Melt polymerization takes too much time, and practical productivity cannot be obtained. If the amount of the Sb element exceeds 380 ppm, not only does the hue of the polymer deteriorate, but also with the use of the Sb-based polymerization catalyst prepared by the method disclosed in the present invention, it becomes impossible to control Tci and Tcd, and only the polymer that is rapidly crystallized can be used. No longer available.

[Tcd, Tci] The polyester of the present invention satisfies the following formulas (1) and (2) for its thermal properties. 24.6 / [η] + 130.0 ≦ Tcd ≦ 24.6 / [η] +142.0 (1) 34.5 × [η] + 130.0 ≦ Tci ≦ 34.5 × [η] +142.0 (2) However, Tcd is measured by DSC when the temperature falls. Is the crystallization exothermic peak temperature (° C.), and Tci is the crystallization exothermic peak temperature (° C.) at the time of temperature increase in DSC measurement.

PET having a Tcd higher than the range of the present invention is likely to crystallize at the stage of cooling the molten PET, causing rapid crystallization at the time of molding, and it is difficult to suppress oriented crystallization and haze. Become. Haze suppression is particularly important in bottle and film applications.

PET with a Tcd lower than the range of the present invention is too amorphous and becomes an excessively flexible PET, and is not suitable for use in bottles, films and industrial fibers.

PET having a Tci higher than the range of the present invention hardly crystallizes at the stage of stretching. In order to impart an appropriate crystalline state to a molded product, it is necessary to perform stretching under a high temperature atmosphere in accordance with the crystallization temperature, but the stretching process is generally performed in the presence of air. Therefore, stretching at a high temperature causes deterioration of PET.

PET having a Tci lower than the range of the present invention undergoes crystallization in the stretching step, and it is difficult to suppress crystallization and control fogging, so that PET with little fogging cannot be obtained.

The PET of the present invention is a PET having crystallinity expressed by Tcd and Tci while using an Sb-based catalyst. Even with conventional PET, the amount is 2.
By copolymerizing more than 5% by weight of diethylene glycol (DEG), the same numerical value as that of the present invention can be achieved for Tci and Tcd. In the copolymerized PET, the high elongation, shrinkage, fragrance retention, and gas barrier properties decrease.

[Intrinsic Viscosity Number] There is an optimum range for the intrinsic viscosity depending on each application.
With a polymer of 5 or less, the strength of the molded product is insufficient even for film and filament applications, and it is not acceptable to users as a product. If the limiting viscosity number is 1.10 or more, the viscosity in the molding step becomes high, which not only puts a load on the equipment, but also generates a large amount of heat generated by shearing, and the deterioration of the polymer becomes conspicuous, causing quality problems.

The polyester of the present invention is preferably used as a filament for clothing. In this case, the preferred intrinsic viscosity is 0.55 to 0.68. If the limiting viscosity number is lower than this, the strength is insufficient, and if the limiting viscosity number is higher, the wearing comfort of the garment becomes poor.

The polyester of the present invention is preferably used as an industrial fiber for tire cords. In this case, the preferred intrinsic viscosity is 0.90 to 1.10. If the limiting viscosity number is lower than this, the strength is insufficient, and if it is higher, it is difficult to spin stably.

The polyester of the present invention is preferably used as a beverage bottle. In this case, the preferred intrinsic viscosity is 0.65 to 0.90. If the limiting viscosity number is lower than this, the strength is insufficient, and if the limiting viscosity number is higher, the moldability decreases.

The polyester of the present invention is preferably used as a film. In this case, the preferred intrinsic viscosity is 0.55 to 0.68. If the limiting viscosity number is lower than this, the strength is insufficient, and if the limiting viscosity number is higher, the moldability decreases.

[DEG] In the present invention, the amount of the diethylene glycol (DEG) component in the polyester is 2.5% by weight or less based on the total amount of the polymer. When the amount of the DEG component exceeds 2.5% by weight, the physical properties such as the strength and elongation and shrinkage of the polyester molded article are greatly changed, and the strength and elongation, shrinkage, fragrance retention and gas barrier properties are reduced. Particularly in packaging applications, there is a concern that the odor and flavor of the filler may change, or the gas barrier properties may decrease, resulting in adverse effects.

[Catalyst] In the present invention, a divalent metal element and / or an alkaline earth metal element is present in the polyester.
The condition of the following formula (5) is satisfied as the molar ratio to the element b. 0.05 ≦ M / Sb ≦ 5.0 (5) [M represents a divalent metal and / or an alkaline earth metal. ]

If the molar ratio is less than 0.05, a polymer having Tci or Tcd within the range of the present invention cannot be obtained. If the molar ratio exceeds 5.0, the heat resistance is reduced and at the same time the amount of foreign matters in the polymer is increased. Excessive addition results in impairing the physical properties of PET.

The polyester of the present invention contains a divalent metal element and / or an alkaline earth metal element, preferably an alkaline earth metal element, satisfying the above conditions.

The alkaline earth metals are Be, Mg, Ca, S
r, Ba, and Ra. Mg is particularly preferable among the alkaline earth metals.

Among the divalent metals, metals belonging to Groups 3A to 1B of the third or fourth period in the periodic table are preferred, that is, Ca, Sc, Ti, V, Cr, Mn, F
e, Co, Ni, and Cu are preferable, and Mn is particularly preferable.

The divalent metal element and / or alkaline earth metal element is derived from a catalyst, and the catalyst is preferably an organic acid salt. Acetate is particularly preferred as the organic acid salt of the catalyst.

[Production Method] The polyester of the present invention is obtained by directly esterifying terephthalic acid and ethylene glycol, and then preparing an Sb-based polycondensation catalyst and a salt of a divalent metal and / or an alkaline earth metal salt. Add the resulting catalyst solution,
Subsequently, it can be obtained by melt polycondensation.

In the present invention, preparation of this catalyst solution is important, and preparation of the catalyst solution is performed as follows.

The Sb-based polymerization catalyst is previously uniformly dissolved in ethylene glycol, and a salt of a divalent metal and / or an alkaline earth metal salt is added as a powder or a uniform ethylene glycol solution. To 140C, preferably 60C to 120C, particularly preferably 70C to 10C.
At 0 ° C., for 20 minutes to 24 hours, preferably 30 minutes to 1 hour
The mixture is heated and stirred for 2 hours, particularly preferably 1 hour to 6 hours, to obtain a catalyst solution. If the temperature of the heating and stirring is lower than 60 ° C., the Tcd of the obtained PET cannot be reduced to within the range of the present invention, and the crystallization of PET cannot be suppressed.
If the temperature of the heating and stirring is 140 ° C. or higher, the stability of the catalyst solution is lowered when a precipitated compound is formed at the bottom of the reaction system or when a suspended matter is formed on the solution surface, which may shorten the life of the filter provided in the preparation process. is there.

The Sb-based polymerization catalyst and the salt of the divalent metal and / or the alkaline earth metal salt are prepared together as described above and simultaneously added to the reaction system. If they are prepared together and not added at the same time, Tcd cannot be reduced to the range of the present invention, and crystallization of PET cannot be suppressed.

[Additives] In the case of melt polycondensation, it is preferable to add a phosphorus compound as a stabilizer. Since the specific addition amount varies depending on the reaction apparatus, it should be appropriately adjusted.

If necessary, other additives such as a tinting agent,
Colorants, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, and the like may be added.

After completion of the melt polycondensation, the mixture is melt-extruded, cooled in a suitable cooling medium, for example, water, and cut into a suitable size to form chips. The tip may be a rectangular parallelepiped, a cylinder, a die, or a sphere.

The PET of the present invention can be subjected to solid-state polymerization after melt polycondensation to obtain PET having a desired intrinsic viscosity.

[0051]

The present invention will be described below in detail with reference to examples. In the examples, “parts” means parts by weight. The method for measuring the characteristics used in the examples is shown below.

1) Intrinsic viscosity number [η]: Calculated from the solution viscosity measured at 35 ° C. using a mixed solvent of phenol / tetrachloroethane (weight ratio 60/40).

2) Diethylene glycol (DEG) copolymerization ratio: 200 g of polymer and 10 ml of hydrazine hydrate (hydrazine monohydrate) were mixed, and the polymer was completely decomposed at 150 ° C. for 10 minutes. The solution was analyzed by gas chromatography, and the proportion of diethylene glycol copolymerized in the polymer was determined from the detected concentration.
Gas chromatography 2 manufactured by Hitachi, Ltd.
Type 63 was used.

3) Thermal characteristics: DSC (differential scanning calorimeter) analysis Thermal analysis 2200 manufactured by TA Instruments
The measurement was performed using a type differential scanning calorimeter. Put 10.0mg of polymer chip sample in aluminum pan and add 20mg
Heat to 300 ° C at a heating rate of
After reaching 0 ° C. and holding for 2 minutes, it was quickly quenched in a test tube immersed in an ice bath without direct contact with water. Thereafter, the temperature was raised again at 20 ° C./min to determine the crystallization temperature Tci and the melting point Tm. When the temperature reached 300 ° C., the temperature was maintained for 2 minutes, and then the temperature was lowered at 10 ° C./min. At that time, the crystallization peak at the time of temperature decrease was defined as Tcd. T
As for ci, Tm, and Tcd, the maximum points of the peaks were read.

4) Hue: The polymer was heat-treated at 140 ° C. for 60 minutes in a drier and dried. The polymer was measured using a color machine CM-7500 type color machine.

5) Metal content measurement: The metal content (unit: ppm) in the polymer was measured by a predetermined method using fluorescent X-rays (X-ray fluorescent 3270 manufactured by Rigaku Denki Kogyo Co., Ltd.).

6) Film Forming and Quality Evaluation: The polymer was dried at 160 ° C., melt-extruded at 280 ° C., and quenched and solidified on a castin pellet maintained at 40 ° C. to obtain an unstretched film. This unstretched film was sequentially biaxially stretched under the conditions of a longitudinal stretching ratio of 3.5 times and a transverse stretching ratio of 4.0 times, and further subjected to a heat treatment temperature of 215.
A biaxially oriented film having a thickness of 25 μm was obtained at a temperature of ° C.

7) Bottle molding and quality evaluation: After drying the polymer at 160 ° C. for 5 hours, a preform of 50 g was molded at a cylinder temperature of 285 ° C. using an injection molding machine Dynamelter M-100DM manufactured by Meiki Seisakusho. Then, it is blow-stretched to obtain an axial stretching ratio of about 3 times and an internal volume of 1.5.
1 liter, a bottle having a body thickness of 0.3 mm.

The blow molding machine uses Milacron manufactured by Cincinnati Co., Ltd. The heating conditions are as follows: the heating heater scale is 1 to 9; 1: 50%, 2 to 4: 45%, 5 to 8: 48%, 9:70. %
, And a heating time was selected so as to minimize the haze, and blow molding was performed.

For the evaluation of the transparency, the straight body was cut off, and the haze of the bottle body was measured with a haze meter to determine the haze of the bottle. Color and color difference metal model 1 manufactured by Nippon Denshoku Industries Co., Ltd.
The 001DP type was used.

The pressure resistance indicates the pressure value when water is fed into the bottle using a hydraulic pump, the pressure is increased at 10 kg / min, and the bottle bursts.

The buckling strength was measured using an autograph (manufactured by Shimadzu Corporation).
(AG-100B) 500m with the bottle upright in the pros head
At a speed of m / min, the width of the pros head was reduced to load the bottle. At that time, the value of the maximum load measured until the bottle is greatly deformed is shown.

The molding width is defined as the difference between the longest heating time and the shortest heating time when the haze of the molded bottle body is 1% or less when the dial is blow-molded under the above heating conditions (unit). : Seconds). It can be said that the longer the molding width is, the more suppressed the whitening is for a bottle polymer.

8) Spinning and quality evaluation: 160
After drying at 5 ° C for 5 hours, the spinning temperature is 300 ° C, the cooling air velocity is 15m / min (26 ° C, relative humidity 70%) and the take-up speed is 3000m /
A 75 denier, 36 filament yarn was spun per minute. At this time, the number of yarn breaks per 1 T of the polymer was observed. This number of yarns reflects the effect of improving the spinnability by suppressing crystallization.
Under this spinning condition, only the take-up speed was accelerated at a rate of 200 m / min, and the take-off speed when the yarn was completely broken was recorded as the total breaking take-up speed.

9) Spinning property: Spinning property is a spinning hole 3 having a diameter of 0.3 mm.
The height of foreign matter containing Sb metal around the outside of the spinning hole when melt spinning at a discharge rate of 80 g / min, a discharge temperature of 285 ° C. and a take-up speed of 1200 m / min for 7 days using a spinneret having 0 pieces, Then, the state of generation of a bent was observed during the period, and the spinning property of the polymer was evaluated. The lower the height of the foreign matter on the base, the better the spinning property, and the lower the occurrence of pending, the better the spinning property.

Example 1 0.01 mol of antimony trioxide and 0.01 mol of magnesium acetate tetrahydrate were present in 326 g of ethylene glycol, and heated and mixed at 80 ° C. for 2 hours to obtain a transparent catalyst solution. Was prepared.

Next, was slurried with 3600 parts of terephthalic acid and ethylene glycol 2100 parts at room temperature, charged into an autoclave fitted with a stirrer, pressure 2 of 3 kg / cm ²
The reaction was performed at 70 ° C. When the amount of distilled water reached 600 parts, the pressure was released, and the reaction was further performed at 270 ° C. under normal pressure. Further, when the amount of distilled water becomes 740 parts or more, 0.2 g of normal phosphoric acid is added.
One part was added and 10 minutes later, a previously prepared clear catalyst solution was added.

Subsequently, a polycondensation reaction was carried out at 285 ° C. under a reduced pressure of 0.1 mmHg for 2.5 hours to obtain an intrinsic viscosity of 0.1.
641 polyethylene terephthalate was obtained. The quality of this polymer was as shown in Table 1, the thermal characteristics (measured by DSC) and the hue were as shown in Table 2, and the physical properties as a film were as shown in Table 3.

Comparative Example 1 0.01 mol of antimony trioxide was added to 221 g of ethylene glycol.
The mixture was heated and mixed for 2 hours to prepare a transparent catalyst solution. Polyethylene terephthalate was obtained in the same manner as in Example 1 except that this catalyst solution was used instead of the mixed catalyst solution of antimony trioxide and magnesium acetate tetrahydrate of Example 1.
The quality of this polymer was as shown in Table 1, the thermal characteristics (measured by DSC) and the hue were as shown in Table 2, and the physical properties as a film were as shown in Table 3.

Example 2 A transparent catalyst solution was prepared in the same manner as in Example 1. Next, 3600 parts of terephthalic acid and 2100 parts of ethylene glycol were slurried at room temperature, charged into an autoclave equipped with a stirrer, and reacted at 270 ° C. under a pressure of 3 kg / cm ² . When the amount of distilled water reached 600 parts, the pressure was released, and the reaction was further performed at 270 ° C. under normal pressure.
Further, when the amount of distilled water became 740 parts or more, 0.21 part of orthophosphoric acid and DEG were added so as to have the amounts shown in Table 1, and 10 minutes later, the transparent liquid prepared earlier was further added. A fresh catalyst solution was added.

Subsequently, a polycondensation reaction was carried out at 285 ° C. under a reduced pressure of 0.1 mmHg for about 1.8 hours to obtain an intrinsic viscosity.
About 0.56 polyethylene terephthalate was obtained. The polymer was further treated under N ₂ atmosphere of 0.5 mmHg for 21
Solid-state polymerization at 0 ° C reduces the limiting viscosity number of the polymer to about 0.86.
Up.

Table 1 shows the quality of the polymer after the solid phase polymerization. Table 2 shows the thermal characteristics (measured by DSC) and the hues.
Table 4 shows the quality of bottles formed using this polymer.

Example 3 0.01 mol of antimony trioxide and 0.005 mol of magnesium acetate tetrahydrate (molar ratio 1: 0.5) were added to 274 g of ethylene glycol, and the mixture was heated at 80 ° C. for 2 hours. By heating and mixing, a clear catalyst solution was prepared.

An intrinsic viscosity of about 0 was obtained in the same manner as in Example 2 except that this catalyst solution was used in place of a catalyst solution obtained by dissolving equimolar amounts of antimony trioxide and magnesium acetate tetrahydrate into ethylene glycol. .86 was obtained. Table 1 shows the quality of the polymer after the solid phase polymerization. Thermal properties
Table 2 shows (measured by DSC) and hue. Table 4 shows the quality of bottles formed using this polymer.

Example 4 0.01 mol of antimony trioxide and 0.01 mol of calcium acetate hydrate were present in 307 g of ethylene glycol, and heated and mixed at 80 ° C. for 2 hours to prepare a transparent catalyst solution. did. A polymer having an intrinsic viscosity of about 0.86 was prepared in the same manner as in Example 2 except that this catalyst solution was used in place of a catalyst solution in which equimolar amounts of antimony trioxide and magnesium acetate tetrahydrate were dissolved in ethylene glycol. Obtained. Table 1 shows the physical properties of this polymer. Table 2 shows the thermal characteristics (measured by DSC) and the hue. Table 4 shows the quality of bottles formed using this polymer.

Comparative Example 2 A transparent catalyst solution was prepared in the same manner as in Comparative Example 1. Polyethylene terephthalate was obtained in the same manner as in Example 2, except that this catalyst solution was used instead of a mixed catalyst solution of antimony trioxide and magnesium acetate tetrahydrate. Table 1 shows the physical properties of this polymer. Table 2 shows the thermal characteristics (measured by DSC) and the hue of this polymer. Table 4 shows the quality of bottles molded using this polymer.
Shown in

Comparative Example 3 0.01 mol of antimony trioxide and 0.10 mol of magnesium acetate tetrahydrate were present in a molar ratio of 1:10 in 1272 g of ethylene glycol and heated at 80 ° C. for 2 hours. A clear catalyst solution was prepared by mixing. A polyethylene terephthalate was obtained in the same manner as in Example 2 except that this catalyst solution was used. Table 1 shows the physical properties of this polymer. Table 2 shows the thermal characteristics (measured by DSC) and the hue of this polymer. Table 4 shows the quality of bottles formed using this polymer.

Comparative Example 4 A transparent catalyst solution was prepared in the same manner as in Example 1. A polyethylene terephthalate was obtained in the same manner as in Example 2 except that this catalyst solution was used instead of the catalyst solution of Example 2. Table 1 shows the physical properties of this polymer. Table 2 shows the thermal characteristics (measured by DSC) and the hue of this polymer. Table 4 shows the quality of bottles formed using this polymer.

Comparative Example 5 A transparent catalyst solution was prepared in the same manner as in Example 1. A polyethylene terephthalate was obtained in the same manner as in Example 2, except that 0.201 part of potassium acetate was added to the reaction system as a 5% ethylene glycol solution immediately before adding the catalyst solution. Table 1 shows the physical properties of this polymer. Table 2 shows the thermal characteristics (measured by DSC) and the hue of this polymer. Table 4 shows the quality of bottles formed using this polymer.

Comparative Example 6 0.01 mol of antimony trioxide was dissolved in 221 g of ethylene glycol.
The mixture was heated and mixed for 2 hours to prepare a catalyst solution. 0.01 mol of magnesium acetate tetrahydrate is added to ethylene glycol 107
g and heated and mixed at 35 ° C. for 2 hours to prepare a catalyst solution.

Next, was slurried with 3600 parts of terephthalic acid and ethylene glycol 2100 parts at normal temperature, when charged into an autoclave fitted with a stirrer, were added an ethylene glycol solution of magnesium acetate, 3 kg / cm ² under pressure 2
The reaction was performed at 70 ° C. When the amount of distilled water reached 600 parts, the pressure was released, and the reaction was further performed at 270 ° C. under normal pressure. Further, when the amount of distilled water becomes 740 parts or more, 0.2 g of normal phosphoric acid is added.
1 part and DEG were added to the amounts shown in Table 1,
Ten minutes later, a catalyst solution which was previously prepared and was ethylene glycol of antimony trioxide was added. This addition was performed so that the amounts of magnesium and antimony to be added were as shown in Table 1.

Subsequently, a polycondensation reaction was carried out at 285 ° C. under a reduced pressure of 0.1 mmHg for 1.8 hours to obtain polyethylene terephthalate having an intrinsic viscosity of about 0.56. The polymer was further placed under a 0.5 mm Hg N ₂ atmosphere at 210 mm Hg.
The polymer was subjected to solid-phase polymerization to increase the intrinsic viscosity of the polymer to about 0.86.

Table 1 shows the quality of the polymer after the solid phase polymerization. Table 2 shows the thermal characteristics (measured by DSC) and the hues.
Table 4 shows the quality of bottles formed using this polymer.

Example 5 A transparent catalyst solution was prepared in the same manner as in Example 1. Next, 3600 parts of terephthalic acid and 2100 parts of ethylene glycol were slurried at room temperature, charged into an autoclave equipped with a stirrer, and reacted at 270 ° C. under a pressure of 3 kg / cm ² . When the amount of distilled water reached 600 parts, the pressure was released, and the reaction was further performed at 270 ° C. under normal pressure.
Further, at the time when the amount of distilled water became 740 parts or more, 0.21 part of orthophosphoric acid and DEG were added so as to have the amounts shown in Table 1, and 10 minutes later, the transparent liquid prepared earlier was further added. The catalyst solution was added. 0.1 mmHg at 285 ° C
The polycondensation reaction was carried out under reduced pressure for about 2.5 hours to obtain polyethylene terephthalate having an intrinsic viscosity of about 0.64.
This polymer was further added under a 0.5 mmHg N ₂ atmosphere,
The polymer was subjected to solid-state polymerization at 210 ° C. to reduce the intrinsic viscosity of the polymer to about 0.1.
Increased to 99.

Table 1 shows the quality of the polymer after the solid phase polymerization. Table 2 shows the thermal characteristics (measured by DSC) and the hues.
Table 5 shows the quality and spinnability of fibers spun using this polymer.

Example 6 A transparent catalyst solution was prepared in the same manner as in Example 4. Example 5 Example 5 was repeated except that this catalyst solution was used in place of the catalyst solution in which equimolar amounts of antimony trioxide and magnesium acetate tetrahydrate were dissolved in ethylene glycol.
In the same manner as in the above, a polymer having an intrinsic viscosity of about 0.99 was obtained.

Table 1 shows the quality of the polymer after the solid phase polymerization. Table 2 shows the thermal characteristics (measured by DSC) and the hues.
Table 5 shows the quality and spinnability of fibers spun using this polymer.

Comparative Example 7 A catalyst solution was prepared in the same manner as in Comparative Example 1. Polyethylene terephthalate was obtained in the same manner as in Example 5, except that this catalyst solution was used instead of a mixed catalyst solution of antimony trioxide and magnesium acetate tetrahydrate. Table 1 shows the physical properties of this polymer.

Table 1 shows the physical properties of the polymer after the solid phase polymerization. Table 2 shows the thermal characteristics (measured by DSC) and the hues.
Table 5 shows the quality and spinnability of fibers spun using this polymer.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

Example 7 A solution of 0.01 mol of antimony trioxide and 0.01 mol of manganese acetate tetrahydrate in 311 g of ethylene glycol was heated and mixed at 80 ° C. for 2 hours to produce a purple transparent catalyst solution. Was prepared.

[0096] Then, was slurried with 3600 parts of terephthalic acid and ethylene glycol 2100 parts at room temperature, charged into an autoclave fitted with a stirrer, pressure 2 of 3 kg / cm ²
The reaction was performed at 70 ° C. When the amount of distilled water reached 600 parts, the pressure was released, and the reaction was further performed at 270 ° C. under normal pressure. Further, when the amount of distilled water becomes 740 parts or more, 0.2 g of normal phosphoric acid is added.
One part was added, and 10 minutes later, a clear catalyst solution previously prepared so as to have the amounts of antimony and manganese shown in Table 6 was added. 0.1 mm at 285 ° C
The polycondensation reaction was carried out under a reduced pressure of Hg for 2.5 hours to obtain polyethylene terephthalate having an intrinsic viscosity of 0.645.

Table 6 shows the quality of this polymer.
Table 7 shows the hue and the hue. Table 8 shows the physical properties of the film.

Example 8 326 g of 0.01 mol of antimony trioxide and 0.01 mol of magnesium acetate tetrahydrate
In ethylene glycol, and heated and mixed at 80 ° C. for 2 hours to prepare a transparent catalyst solution. This transparent catalyst solution was used in the same manner as in Example 7 except that an equimolar amount of antimony trioxide and manganese acetate tetrahydrate was dissolved in ethylene glycol, and the limiting viscosity number was 0.641. Of polyethylene terephthalate was obtained. Table 6 shows the quality of this polymer, and Table 7 shows its thermal characteristics (measured by DSC) and its hue. Table 8 shows the physical properties of the film.

Example 9 0.01 mol of antimony trioxide, 0.005 mol of manganese acetate tetrahydrate and 0.005 mol of magnesium acetate tetrahydrate were present in 318 g of ethylene glycol. The mixture was heated and mixed at 80 ° C. for 2 hours to prepare a pale purple transparent catalyst solution.

Example 7 was repeated except that this transparent catalyst solution was used in place of the catalyst solution obtained by dissolving equimolar amounts of antimony trioxide and manganese acetate tetrahydrate in ethylene glycol.
In the same manner as in the above, polyethylene terephthalate having an intrinsic viscosity of 0.640 was obtained.

Thermal properties of this polymer (measured by DSC)
And hue are shown in Table 7. Table 8 shows the physical properties of the film.

Comparative Example 8 0.01 mol of antimony trioxide was added to 221 g of ethylene glycol, and heated and mixed at 155 ° C. for 2 hours to prepare a transparent solution.

A polyethylene terephthalate was obtained in the same manner as in Example 7, except that this catalyst solution was used in place of the mixed solution of antimony trioxide and manganese acetate tetrahydrate of Example 7. Table 6 shows the physical properties of the polymer. Table 7 shows the thermal characteristics (measured by DSC) and the hue of this polymer. Table 8 shows the physical properties of the film.

Example 10 A violet transparent catalyst solution was prepared in the same manner as in Example 7. Next, 3600 parts of terephthalic acid and 2100 parts of ethylene glycol were slurried at room temperature, charged into an autoclave with a stirrer, and charged to 3 kg / cm ^2.
Under a pressure of 270 ° C. When the amount of distilled water reached 600 parts, the pressure was released, and the reaction was further performed at 270 ° C. under normal pressure. Further, when the amount of distilled water became 740 parts or more, 0.21 part of orthophosphoric acid and DEG were added so as to have the amounts shown in Table 6, and 10 minutes later, the amount of antimony and manganese shown in Table 6 were further added. The clear catalyst solution previously prepared to make up the volume was added. 0.1 mmH at 285 ° C
The polycondensation reaction was carried out under a reduced pressure of about 1.8 hours for about 1.8 hours to obtain polyethylene terephthalate having an intrinsic viscosity of about 0.56. This polymer was further subjected to solid-state polymerization at 210 ° C. under an N ₂ atmosphere of 0.5 mmHg to increase the intrinsic viscosity of the polymer to about 0.86.

Table 6 shows the quality of the polymer after the solid phase polymerization. Table 7 shows the thermal characteristics (measured by DSC) and the hues.
Table 9 shows the quality of bottles formed using this polymer.

Example 11 A transparent catalyst solution was prepared in the same manner as in Example 8. The same experiment as in Example 10 was carried out except that this transparent catalyst solution was used in place of the catalyst solution in which an equimolar amount of antimony trioxide and manganese acetate tetrahydrate was dissolved in ethylene glycol, and the intrinsic viscosity was reduced to about 10%. 0.86 polymer was obtained.

Table 6 shows the quality of this polymer. Thermal properties
Table 7 shows (measured by DSC) and hue. Table 9 shows the quality of bottles formed using this polymer.

Example 12 Antimony trioxide 0.01
Mol and 0.005 mol of manganese acetate tetrahydrate were present in 266 g of ethylene glycol, and heated and mixed at 80 ° C. for 2 hours to prepare a pale purple transparent catalyst solution.

Except that this catalyst solution was used in place of the catalyst solution obtained by dissolving equimolar amounts of antimony trioxide and manganese acetate tetrahydrate in ethylene glycol, the limiting viscosity number was reduced to about 0 in the same manner as in Example 10. .86 was obtained.

Table 6 shows the quality of this polymer.
C) and hue are as shown in Table 7, and Table 9 shows the quality of bottles formed using this polymer.

Example 13 Antimony Trioxide 0.01
Mol, 0.005 mol of manganese acetate tetrahydrate and 0.005 mol of magnesium acetate tetrahydrate are present in 318 g of ethylene glycol, and mixed by heating at 80 ° C. for 2 hours to give a pale purple transparent catalyst solution. Was adjusted.

The same procedure as in Example 10 was repeated except that this catalyst solution was used in place of a catalyst solution obtained by dissolving equimolar amounts of antimony trioxide and manganese acetate tetrahydrate in ethylene glycol. 86 polymers were obtained.

Table 6 shows the quality of this polymer.
C) and hue are as shown in Table 7, and Table 9 shows the quality of bottles formed using this polymer.

Comparative Example 9 A catalyst solution was prepared in the same manner as in Comparative Example 8. Polyethylene terephthalate was obtained in the same manner as in Example 10 except that this catalyst solution was used instead of a mixed catalyst solution of antimony trioxide and manganese acetate tetrahydrate. The quality is shown in Table 6. Thermal properties of this polymer (DSC
And the hue are shown in Table 7. Table 9 shows the quality of bottles formed using this polymer.

Comparative Example 10 Antimony Trioxide 0.01
Mol and 0.10 mol of manganese acetate tetrahydrate were present in 1122 g of ethylene glycol, and heated and mixed at 80 ° C. for 2 hours to obtain a dark purple opaque catalyst solution.

A polyethylene terephthalate was obtained in the same manner as in Example 10 except that this solution was used as the catalyst solution. Table 6 shows the polymer quality. Table 7 shows the thermal characteristics (measured by DSC) and the hue of this polymer. Table 9 shows the quality of bottles formed using this polymer.

[Comparative Example 11] A purple transparent catalyst solution was prepared in the same manner as in Example 7. A polyethylene terephthalate was obtained in the same manner as in Example 10 except that this solution was used as the catalyst solution. Table 6 shows the polymer quality. Table 7 shows the thermal characteristics (measured by DSC) and the hue of this polymer.
Table 9 shows the quality of bottles formed using this polymer.

Comparative Example 12 Except that 0.201 part of potassium acetate was added to the reaction system as a 5% ethylene glycol solution immediately before adding the catalyst solution obtained from antimony trioxide and manganese acetate tetrahydrate. In the same manner as in Example 10, polyethylene terephthalate was obtained. Table 6 shows the polymer quality of this polymer. Thermal properties of this polymer (DS
C) and the hue are shown in Table 7. Table 9 shows the quality of bottles formed using this polymer.

[Comparative Example 13] Antimony trioxide 0.01
Mol at 155 ° C.
And a catalyst solution prepared by heating and mixing for 2 hours, and 0.01 mol of manganese acetate tetrahydrate was added to 90 g of ethylene glycol, and heated and mixed at 80 ° C. for 2 hours to separately prepare catalyst solutions.

Next, when 3600 parts of terephthalic acid and 2100 parts of ethylene glycol were slurried at room temperature and charged in an autoclave equipped with a stirrer, a catalyst solution which was a previously prepared manganese acetate ethylene glycol solution was added. The reaction was performed at 270 ° C. under a pressure of 3 kg / cm ² .
When the amount of distilled water reached 600 parts, the pressure was released, and the reaction was further performed at 270 ° C. under normal pressure. Further, when the amount of distilled water became 740 parts or more, 0.21 part of orthophosphoric acid and DEG were added so as to have the amounts shown in Table 6, and 10 minutes later, trioxide prepared in advance was further added. A solution of antimony in ethylene glycol was added as a polycondensation catalyst. The amounts of manganese and antimony to be added were as shown in Table 6.

Subsequently, a polycondensation reaction was carried out at 285 ° C. under a reduced pressure of 0.1 mmHg for about 1.8 hours to obtain an intrinsic viscosity.
About 0.56 polyethylene terephthalate was obtained. The polymer was further treated under N ₂ atmosphere of 0.5 mmHg for 21
Solid-state polymerization at 0 ° C reduces the limiting viscosity number of the polymer to about 0.86.
Up.

Table 6 shows the quality of the polymer after the solid phase polymerization. Table 7 shows the thermal characteristics (measured by DSC) and the hues.
Table 9 shows the quality of bottles formed using this polymer.

Example 14 A violet transparent catalyst solution was prepared in the same manner as in Example 7. Next, 3600 parts of terephthalic acid and 2100 parts of ethylene glycol were slurried at room temperature, charged into an autoclave with a stirrer, and charged to 3 kg / cm ^2.
Under a pressure of 270 ° C. When the amount of distilled water reached 600 parts, the pressure was released, and the reaction was further performed at 270 ° C. under normal pressure. Further, when the amount of distilled water became 740 parts or more, 0.21 part of orthophosphoric acid and DEG were added so as to have the amounts shown in Table 1, and 10 minutes later, the amount of antimony and manganese shown in Table 6 were further added. A clear catalyst solution, previously prepared in a volume, was added. 0.1 mmH at 285 ° C
The polycondensation reaction was carried out under a reduced pressure of about 2.5 hours to obtain polyethylene terephthalate having an intrinsic viscosity of about 0.64. This polymer was further subjected to solid-state polymerization at 210 ° C. under an N ₂ atmosphere of 0.5 mmHg to increase the intrinsic viscosity of the polymer to about 0.99.

Table 6 shows the quality of the polymer after the solid phase polymerization. Table 7 shows the thermal characteristics (measured by DSC) and the hues.
Table 10 shows the quality and spinnability of fibers spun using this polymer.

Example 15 A transparent catalyst solution was prepared in the same manner as in Example 8. Example 14 except that this catalyst solution was used in place of the catalyst solution in which equimolar amounts of antimony trioxide and manganese acetate tetrahydrate were dissolved in ethylene glycol.
In the same manner as in the above, a polymer having an intrinsic viscosity of about 0.99 was obtained.

Table 6 shows the quality of the polymer after the solid phase polymerization. Table 7 shows the thermal characteristics (measured by DSC) and the hues.
Table 10 shows the quality and spinnability of fibers spun using this polymer.

[Comparative Example 14] Antimony trioxide 0.01
Moles to 221 g of ethylene glycol,
For 2 hours to prepare a catalyst solution. Polyethylene terephthalate having an intrinsic viscosity of about 0.99 was obtained in the same manner as in Example 14, except that this catalyst solution was used in place of the mixed solution of antimony trioxide and manganese acetate tetrahydrate.

Table 6 shows the quality of the polymer after the solid phase polymerization. Table 7 shows the thermal characteristics (measured by DSC) and the hues.
Table 14 shows the quality and spinnability of fibers spun using this polymer.

[0129]

[Table 6]

[0130]

[Table 7]

[0131]

[Table 8]

[0132]

[Table 9]

[0133]

[Table 10]

[0134]

According to the present invention, inexpensive Sb is used as a catalyst.
It is possible to obtain PET in which crystallization is suppressed while using a system catalyst, without substantially containing a copolymer component,
PET with little clouding and whitening and with suppressed crystallization can be obtained.

Claims (13)

[Claims] 1. The method according to claim 1, wherein terephthalic acid is added in an amount of 95 to the total acid component.
A polyester containing at least 95 mol% of an acid component and ethylene glycol at 95 mol% or more of the total glycol component;
The amount of the element is 60 ppm to 38 with respect to the total amount of the polyester.
A crystallization-suppressing polyester, wherein the polyester satisfies the following formulas (1) and (2) in terms of thermal properties, and the polyester satisfies the following formula (3) in terms of intrinsic viscosity. 24.6 / [η] + 130.0 ≦ Tcd ≦ 24.6 / [η] +142.0 (1) 34.5 × [η] + 130.0 ≦ Tci ≦ 34.5 × [η] +142.0 (2) [Tcd is crystallization at the time of cooling by DSC The exothermic peak temperature (° C.), and Tci is the crystallization exothermic peak temperature (° C.) when the temperature was raised by DSC. 0.50 ≦ [η] ≦ 1.10 (3) [[η] represents intrinsic viscosity, [η] is phenol / tetrachloroethane
It is a value calculated from the solution viscosity measured at 35 ° C. using a solvent of (= 3/2 component ratio). ] 2. The polyester according to claim 1, wherein the diethylene glycol component as a constituent component of the polyester satisfies the following formula (4). DEG ≦ 2.50 wt% (4) [where DEG represents a diethylene glycol component, and the numerical values are based on the total amount of the polymer. ] 3. The polyester according to claim 1, wherein the Sb element is derived from an Sb compound used as a polyester polymerization catalyst. 4. A polyester containing a divalent metal element and / or
The polyester according to claim 1, wherein an alkaline earth metal element is present, and the amount of the alkaline earth metal element satisfies the condition of the following formula (5) as a molar ratio to the Sb element present in the polyester. 0.05 ≦ M / Sb ≦ 5.0 (5) [M represents a divalent metal and / or an alkaline earth metal. ] 5. The polyester according to claim 4, wherein the divalent metal and / or the alkaline earth metal is an alkaline earth metal. 6. The bivalent metal is a metal belonging to Group 3A to Group 1B in the third or fourth period of the periodic table.
Polyester according to the above. 7. The polyester according to claim 6, wherein the divalent metal is Mn. 8. The diol component constituting the polyester is ethylene glycol and diethylene glycol,
3. The polyester according to claim 2, wherein ethylene glycol and diethylene glycol are at least 99.5 mol% based on all diol components constituting the polyester. 9. The polyester has an intrinsic viscosity number [η] of 0.55.
A filament for apparel comprising the polyester according to claim 1, which has a thickness of from 0.68 to 0.68. 10. The polyester having an intrinsic viscosity number [η] of 0.1.
An industrial fiber for tire cords comprising the polyester according to claim 1, which has a molecular weight of 90 to 1.10. 11. A polyester having an intrinsic viscosity number [η] of 0.1.
A bottle comprising the polyester according to claim 1, which is 65 to 0.90. 12. The polyester having an intrinsic viscosity number [η] of 0.1.
The film comprising the polyester according to claim 1, which has a thickness of from 55 to 0.68. 13. The polyester according to claim 1, which is obtained by further performing solid phase polymerization after melt polymerization.