TW505668B - Aromatic polyester and transparent container made therefrom - Google Patents

Abstract

An aromatic polyester comprises terephthalic acid in an amount of at least 95 mol% and ethylene glycol in an amount of at least 95 mol%, and contains antimony and a divalent metal element a special relationship between their amounts. The aromatic polyester further has a special relationship between intrinsic viscosity and crystallization temperature. The polyester is excellent in transparency.

Description

Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 505668 kl B7 V. Description of the Invention (1) The present invention relates to an aromatic polyester and a transparent container made of the same. More specifically, it relates to an aromatic polyester which contains a controlled amount of antimony and a divalent metal element and whose crystallinity is suppressed; and to a transparent container made therefrom. The polyester represented by polyethylene terephthalate is superior in mechanical properties, heat resistance, weather resistance, electrical insulation resistance, and chemical resistance and is widely used to form fibers, bottles, films, and other molds. Articles (molded products). The requirements for such polyesters vary according to their application. For applications such as fibers and films, there is a need for a polyester whose orientation and crystallization are suppressed and which have high strength and superior yarn-making and film-forming properties. 0 For applications such as packaging films and bottles, it is superior Transparency, non-turbid polyesters are strongly desired. Resin molding is often desired to improve its strength. One of the factors that makes it difficult to improve the strength is that during stretch molding, the resin has crystallized before sufficient molecular orientation occurs. One of the factors that cause haze in films or bottles is that the polyester crystallizes during stretch molding. Therefore, it is important to control the polymer to suppress its crystallinity. For example, a polyester with almost no crystal nucleus in a polyester and having high transparency is used for bottle making, which is very common in Japan. However, recent trends in the market have shown that there is a growing need for high-quality, less expensive materials, and the use of expensive Ge02 has caused a decrease in the international competitiveness of polymers. Therefore, a method of using inexpensive metal compounds as a polymerization catalyst is desired. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) _ 4 · (Please read the precautions on the back before filling this page)

505668

Attachment 2: Amendment to the Chinese specification of Patent Application No. 87107058. Republic of China V. Invention Description) In addition to catalysts mainly based on Ge, SS η-based catalysts are known to have Polymerization active metal. (Please read the notes on the back before filling in this page) Although S b 2 03 is widely used as a polymerization catalyst, it is reduced during polymerization to produce a metal S b that will make the polyester black, and again , Its role is a nucleating agent to cause the resin to crystallize, thereby reducing the strength and producing turbidity. Although T i-and S η-based catalysts generally have high polymerization activity, in many cases they generate side reaction products and thus the polymer is colored. Therefore, it is difficult to use them in such applications where high transparency and good color are particularly required. ΓΡ — Α48 — 30794 ('JP — used in this article, printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, meaning Α 〃 means > Unexamined Announcement Japanese Patent Application) discloses a method for producing polyester. By adding catalyst amount of antimony compound and one mole amount of zinc compound from 0.5 to 1 times of chain compound to a difunctional carboxylic acid ester or its oligomer (including terephthalic acid as the main acid component) ) And diols (including ethylene glycol as the main diol component) to perform the polycondensation reaction. The above examples show that dimethyl terephthalate and ethylene glycol are subjected to transesterification in the presence of transesterification catalysts such as calcium acetate, manganese acetate or cobalt acetate. A zinc compound of a diol to a reaction product to perform polycondensation. This announcement makes no mention of the relationship between the crystallization temperature and the intrinsic viscosity of the resulting polyester. JP — A 49 — 55795 discloses a method for producing polyester, which is a product obtained by polycondensation by esterification or transesterification of a dibasic acid or its derivative and a diol in the presence of an antimony catalyst, in which manganese or zinc ( X atom Mohr-5- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 505668 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention θ)%), trivalent phosphorus ( y atomic mole%) and alkaline earth metal (ζ atomic mole%) are present in the polymerization step, and their amounts satisfy the following expression: -0. 〇2 ^ zy + x ^ 〇. 〇7 The conditions are X, y and z has the following about and atomic mole% is based on the acid component of the polyester O.Ol ^ z ^ O.5 〇 ^ yx ^ 〇. 2 0 < ζ 〇 This announcement also does not mention the crystallization temperature of the resulting polyester And intrinsic viscosity. JP-A 6 1 — 78828 also discloses a method for producing polyester, which uses (a) a catalytic amount of an antimony compound, (b) a manganese compound and / or a manganese compound soluble in a diol, and (c) a base Metal compounds and (d) phosphorus compounds, in which the amount of component (b) and component (c) satisfies the following expression: Μ ^ 5 0 Α ^ 6 0 A / Μ ^ 0-7 3 where M is the amount of component (c) (Halo mole%) and A is the amount of component (b) (millimolar%). This announcement also makes no mention of the crystallization temperature and intrinsic viscosity of the obtained polyester. As one of the methods to provide low turbidity to a polyester and use Sb as the main catalyst to inhibit its crystallization, a copolymerization Phthalic acid (IA) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -6-(Please read the precautions on the back before filling this page)

'31505668 A7 B7

V. Invention Description 4)

Method for nr, cyclohexanedimethanol (CHDM), alkylene dicarboxylic acid or too much ethylene glycol (hereinafter may be abbreviated as DEG). Of course, this method has the effect of providing low turbidity and suppressing crystallization. However, because the strength of the obtained polyester is reduced due to the disorder of molecular orientation (this is caused by the presence of copolymer components), this method will involve problems in applications requiring strength. When the packaging film according to the content is used, the production chain and the production system of the present invention are used, even if it has almost no turbidity. The production product of the present invention is made of polycondensation polyester of the present invention. Family polyesters achieve acidity. And, when it contains an antimony ethylene glycol copolymer, the content odor or aroma is significantly changed. Therefore, there are issues such as bottles and food. This kind of terephthalic acid will become clear in use. The purpose of the invention is to provide an aromatic polyester which contains a divalent metal element and its crystallization is suppressed. Another object is to provide an aromatic polyester whose crystals are suppressed to substantially contain no copolymer component other than diethylene glycol, and which may be whitened. Another object is to provide an aromatic polyester which can be produced using existing, antimony-based compound catalysts which are inexpensive and readily available, and whose crystallization is suppressed. Another object is to provide other objects of the aromatic transparent container provided by the present invention. First of all, its advantages including the amount of all and divalent gold and its advantages will become apparent from the following description. 'The above objects and advantages of the present invention are based on an ethylene glycol element with an aromatic content of at least 95 mol% of all the acid components and at least 95 mol% of the glycol component. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page) 刈 5668 A7 V. Invention Description 6) Π: Μ

I \ ...------------------- 1) and (2): δΟ ^ Μ '^ βδΟ (1) where M1 is contained in the aromatic polyester The amount of element S b (P Pm) 0.01 01 M2 / Sb ^ 10. 0 (2) where M 2 is the atomic mole% of the divalent metal element contained in the aromatic polyester and 3 b is aromatic The atomic mole% of the element antimony contained in the polyester has a relationship between the intrinsic viscosity and the crystallization temperature satisfying the following expressions (3) to (5): 0 · 50 ^ [τ?] $ 1 · 10 ( 3) where [7?] Is the intrinsic viscosity of the aromatic polyester, measured in a mixture solution of phenol and tetrachloroethane (3/1 weight ratio) at 3 5 t; 130. 〇 ^ Tcd- 24. 6 / [η) ^ 142. 〇 (4) where [7?] Is as defined above, T cd is measured by DSC. When the temperature decreases, the peak temperature (t) of the crystalline exothermic peak of the aromatic polyester, 130.〇 $ Tci— 34 · 5χ [τ?] $ 14 2.0 (5) where [7?] Is the same as above, and T ci is measured by DSC. When the temperature rises, the crystallization of the aromatic polyester is exothermic. Peak-to-peak temperature (° C). The aromatic polyester of the present invention includes terephthalic acid in an amount of at least 95 mol% of all acid components and ethylene glycol in an amount of at least 95 mol% of all diol components. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) ~ ^-(Please read the notes on the back before filling out this page) Ordered by the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives 505668 Printed by the Consumer Cooperative of the Bureau A7 B7 V. Description of Invention) --------.. ______. One • A pair of ugly acid content accounts for at least 97 mole% of all the acid components. At least 99 mol%, particularly advantageously at least 99.5% mol%. All glycol components are advantageously composed of at least 95 mole% ethylene glycol and other glycols below 5 mole%, including diethylene glycol. The molding of aromatic polyesters containing more than 5 mol% of other diols will change drastically in its physical properties such as strength-elongation and shrinkage, and its strength-elongation, shrinkage, fragrance retention and gas The shielding will decrease. In particular, in the case of packaging applications, there are undesired effects such as a change in odor or flavor of the content and a reduction in air-shielding property. The total amount of ethylene glycol and diethylene glycol accounts for all diol components, advantageously at least 99.5% mole. The non-terephthalic acid content of 5 mol% or less includes, for example, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and diphenyl ether dicarboxylic acid; alicyclic dicarboxylic acid Acids such as cyclohexanedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; and oxycarboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, salicylic acid, mandelic acid, hydrogen acrylic acid Glycolic acid, 3-oxypropionic acid and quinolic acid. Non-ethylene glycol other diols containing less than 5 mole% of all diols include aliphatic diols such as triethylene glycol, tetraethylene glycol, and hexanediol (except diethylene glycol); Cycloaliphatic diols such as cyclohexanediol and cyclohexanedimethanol; and aromatic diols such as naphthalenediol, bisphenol A and resorcinol. The content of other diols other than diethylene glycol is favorably 3 mol% or less, more favorably 1 mol% or less' and particularly favorably 0.5 mol% or less. However, it is particularly desirable that diols other than diethylene glycol are not contained. (Please read the notes on the back before filling this page)

-1T

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 505668 A7 __B7 V. Description of the invention f) ^ Multifunctional compounds with at least trifunctional groups such as glycerol, trimethylolpropane, pentaerythritol, trimellitic acid, trimesic acid, benzene, etc Tetraacid, glyceric acid or osmic acid can be copolymerized in an amount that makes the aromatic polyester substantially linear. In short, a monofunctional compound such as phthalic acid or naphthoic acid may be contained in a small amount such as 1 mol% or less as a copolymer component. The aromatic polyester of the present invention contains elemental antimony, and its amount satisfies the above expression (1), that is, an amount of 60 to 380 ppm. The above amounts of elements are essentially derived from an antimony compound as a polycondensation catalyst for an aromatic polyester, advantageously Sb203. When the amount of elemental antimony is less than 60 p p m, its polymerization activity is small and its melt polymerization amount is too long, so that it cannot achieve actual productivity. When the amount of the element chain exceeds 380 p p m, not only the color of the obtained polymer becomes poor, but also crystallization inhibition cannot be achieved, which is a feature of the aromatic polyester of the present invention. The amount of elemental antimony is advantageously in the range of 90 to 300 p pm. The aromatic polyester of the present invention contains a divalent metal element, and its amount satisfies the following expression (2): 0. 〇l ^ M2 / Sb ^ l0. 〇 (2) wherein M2 is the second one contained in the aromatic polyester The atomic mole% of the valence metal element and 3b is the mole% of all the elements antimony in the aromatic polyester. When the above ratio (M 2 / S b) is less than 0.001, crystallization inhibition cannot be achieved, which is a characteristic of the aromatic polyester of the present invention. When the ratio is more than 5.0, the heat resistance of the aromatic polyester decreases and the amount of foreign substances contained in the polymer increases. Therefore, the addition of an excessive amount of the divalent metal element deteriorates the physical properties of the aromatic polyester. This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) -10- (Please read the notes on the back before filling this page) Order 505668 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Invention Explanation @) The ratio of M 2 / S b advantageously satisfies the following expression (2) — 1: 〇.〇5 ^ M2 / Sb ^ 5.〇 (2) -1 where M2 and Sb are as defined in the above expression (2). The divalent metal element, whose amount satisfies the above expression (2) or (2) -i, is substantially derived from an esterification catalyst or a polycondensation catalyst used in a reaction for producing an aromatic polyester. Examples of useful divalent metal elements include Mg, Ca, Sr, Ba, Ra'Sc, Ti, V, Cr.Mn'Fe'Co, Ni, Cu or Zn. They can be used alone or in combination. Among these, 'C a' M g and M η are particularly advantageous. These divalent metal elements advantageously exhibit catalytic functions in the form of their organic acid salts. Of the organic acid salts, the 'acetate salt is particularly advantageous. The intrinsic viscosity of the aromatic polyester of the present invention is measured in a solvent mixture of phenol and tetrachloroethane (weight ratio of 3/2), which is one of those satisfying the above expression (3), that is, from 0. 50 to 1 · 10 in the range. When the intrinsic viscosity is lower than 0.5, sufficient strength cannot be obtained for the molding of most of the aromatic polyester, but when the intrinsic viscosity is higher than 1.1, the viscosity of the aromatic polyester is being molded. The step becomes too high, resulting in a large load on the equipment and a large amount of shear heat is generated, thus significantly destroying the polymer. Therefore, quality problems are caused. The aromatic polyester of the present invention can be formed into different moldings. In order to obtain a typical molding of the aromatic polyester of the present invention, the advantageous intrinsic viscosity is as follows. When the polyester of the present invention is used as a filament of clothes, an advantageous intrinsic viscosity is from 0.55 to 0.58. Below this range, the strength of the filaments is not suitable for this paper. The Chinese standard (CNS) Α4 specification (210X297 mm) -11-(Please read the precautions on the back before filling this page)

VT order 505668 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of invention $) is sufficient, and above this range, clothing made of filaments is not comfortable to wear. When the polyester of the present invention is used as an industrial fiber for a tire tendon, an advantageous intrinsic viscosity is 0.90 to 1.10. Below this range, the strength is insufficient 'and above this range, it is difficult to spin stably. When the polyester of the present invention is used as a transparent container such as a spout bottle, the advantageous intrinsic viscosity is 0. 65 to 0. 9 0. Below this range, the strength is insufficient and above this range, and the moldability is reduced. When the polyester of the present invention is used as a film, an advantageous intrinsic viscosity is from 0. 55 to 0. 68. Below this range, the strength is insufficient, and above this range, moldability is reduced. The aromatic polyester of the present invention has a crystallization temperature that satisfies the following expressions (4) and (5) related to its intrinsic viscosity [β]: 13〇.〇 ^ Tcd-24.6 / (77) ^ 124.0 (4) Where [7?] Is as defined in the above expression (3) and TC d is the peak temperature (° C) of the crystalline exothermic peak of the square-group polyacetate measured by DSC when the temperature drops, 130.0. Tci-34.5 x [/?] ^ 142.〇 (5) where [7?] is as defined above and TC i is the peak temperature of the crystalline exothermic peak of the aromatic polyester measured by DSC when the temperature rises. Its Ted-24 · Aromatic polyesters with a 値 of 0 / [/?] Greater than the upper limit of (4) are easy to crystallize when cooled from the molten state, and intense crystallization occurs during the production of Fengmo, making it difficult to suppress the directional crystallization and This paper size is applicable to Chinese National Standard (CNS) A4 gauge (210X297mm) ~ 12 I (Please read the precautions on the back before filling this page)

505668 A7 ____ 一 ^ 5. Description of the invention (10) Especially when aromatic polyester is used for applications such as bottles and films, the suppression of turbidity is important. (Please read the precautions on the back before filling this page) On the other hand, the aromatic polyester whose T cd — 24 · 6 / [7 /] is less than the lower limit of (4) is too amorphous and too Flexible and therefore unsuitable for applications such as bottles, films and industrial fibers. The relationship between T cd and [7?] Is advantageously represented by the following expression (4) -1: 132.0STcd — 24 · 6 / [τ?] ^ 142 · 0 (4) -1 where T cd and [7? ] As defined above, it is more advantageous to have the following expression (4) — 2: 135.0STcd — 24 · 6 / [τ?] ^ 142 · 0 (4) -2 where Ted and [7?] Are as defined above. The aromatic polyester having the above relationship (4) -1 or (4) -2 is economically advantageous because it is relatively easy to produce. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Aromatic polyesters with Tc i 34 · 5x [7?] 値 greater than the upper limit indicated by (5) are difficult to crystallize when stretched. In order to provide a suitable crystalline state to a molding, stretching must be performed in an atmosphere having a temperature higher than the crystallization temperature of the aromatic polyester. Because stretching is usually carried out in the presence of air, stretching at too high a temperature will destroy the aromatic polyester. On the other hand, an aromatic polyester having T c i-3 4 · 5 X [7?] 値 smaller than the lower limit of the expression (5) will crystallize during the stretching step and it is difficult to suppress crystallization and control turbidity. Therefore, an aromatic polyester having low turbidity cannot be obtained. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -13- 505668 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The relationship between the invention description (M) τ ci and [7?] Advantageously, it is represented by the following expression (5) -1: 13〇.〇 ^ Tci-34.5x [7?] ^ 14〇.〇 (5) ^ 1 where Tci and [7?] Are as defined above, more advantageous The ground is the following expression (5)-2: 130.〇 ^ Tci-34 · 5χ [τ?] ^ 138 · 0 (5) -2 where T ci and [77] are as defined above. Aromatic polyesters having a relationship of (5) — 1 or (5)-2 are economically advantageous because they are easier to produce. In the conventionally known aromatic polyesters, it contains diethylene glycol in an amount of more than 5 mole% of all diol components, which meets the above expressions (4) and (5) in terms of strength-elongation and shrinkage characteristics, It is inferior to the aromatic polyester of the present invention in terms of flavor retention and air-shielding property. The aromatic polyester of the present invention is advantageously produced using a catalyst, which is prepared according to the following special method discovered by the inventor of the present invention. The aromatic polyester of the present invention can be obtained by the following method: · For the esterification of phthalic acid and ethylene glycol, a catalyst solution prepared from a polycondensation catalyst mainly composed of S b and a divalent metal element is added, and melt polycondensation is performed. The catalyst solution was prepared as follows. The polymerization catalyst based on Sb is uniformly dissolved in ethylene glycol, and a powder or a divalent metal salt of a uniform ethylene glycol solution type is added to this solution. Result This paper size is in accordance with Chinese National Standard (CNS) A4 (210x297 mm) -14 «(Please read the precautions on the back before filling this page)

505668 A7 B7 V. Description of the invention (12) The mixture is heated and stirred at 60 to 140 ° C, 60 to 120 ° C, particularly advantageously 70 to 100 ° C. Minutes to 24 hours' advantageously 30 minutes to 12 hours, particularly advantageously 1 to 6 hours to obtain a catalyst solution. When the heating and stirring temperature is below 60. (:, The T cd of the obtained aromatic polyester cannot be reduced to the specific range of the present invention and the crystallization of the aromatic polyester cannot be suppressed. When the heating and stirring temperature is higher than 14 0 t, Compounds or floating substances on the surface of the solution reduce the stability of the catalyst solution. As a result, the service life of the filter provided in the preparation step may be shortened. Sb-based polymer catalysts and divalent metal salts are required Prepared together and added simultaneously to the reaction system as described above. Otherwise, T cd cannot be reduced to the scope of the present invention and the crystallization of the resulting aromatic polyester cannot be suppressed. Phosphorus compounds are advantageously added during stabilization of the melt polycondensation as stability Because the amount of phosphorus compound varies depending on the reactor used, it should be prepared appropriately. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Aromatic polyester visible Need to contain other additives such as color control agents, pigments, antioxidants, UV absorbers, antistatic agents, flame retardants and the like. After the melt-condensation is completed, the obtained aromatic polyester is, for example, melt-extruded, cooled in a suitable solvent such as water and cut into appropriate sizes to produce small pieces. The small pieces may be rectangular parallelepipeds, cylinders, Cubes or spheres. The aromatic polyester of the present invention can be polymerized in the solid state to achieve the desired intrinsic viscosity after melt polycondensation. This paper size applies to China National Standard (CNS) A4 (210X297 mm) _ 15-505668 kl ____ B7 V. Description of the invention (13) (Please read the notes on the back before filling out this page) The following examples are given to further illustrate the invention. In the following examples, "parts" means "parts by weight". Used in the examples The measuring method of its properties is described below. 1) Intrinsic viscosity [7?]: This is a mixture of phenol and tetrachloroethane (weight ratio of 60/40) at 35 ° C. The viscosity of the solution measured in. 2) Proportion of copolymerized diethylene glycol (D E G) Mix 200 g of polymer and 10 ml of hydrazine hydrate (hydrazine monohydrate) to completely decompose this polymer within 10 minutes at 150 ° C. This solution was analyzed by gas chromatography, and the proportion of diethylene glycol copolymerized in the polymer was obtained from the measured concentration. G.C. 2 6 3 of Hitachi, Ltd. was used for gas chromatography. Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 505668 A7 B7 V. Description of the invention (14), this temperature is maintained for 2 minutes' and then 'at a rate of 10 ° C / minute. The crystalline peak as the temperature decreases is regarded as T c d. Tci, Tm and Ted are read from the maximum points of the respective peaks. 4) Color: The polymer dried by heating in a desiccator at -140 ° C for 60 minutes was measured by a Model CM-7500 of Color Machine Co., Ltd. 5) Measurement of the amount of metal: The amount of metal (unit: P pm) contained in the polymer is measured according to a predetermined method using fluorescent X-rays (Rigaku Denki Kogyo, Co., Ltd. Model 3270). 6) Evaluation of molding and film quality Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The polymer is dried at 160 ° C and at 28 ° C Melt-extruded and quenched at a temperature of 40 ° C per minute and solidified to obtain a non-oriented film. This non-oriented film was sequentially stretched 3 to 5 times in the long axis direction. It was stretched by 4 · 0 times in the transverse direction, and further heat-fixed at 2 1 5 ° C to obtain a biaxially oriented film with a thickness of 2 5 // m. 7) Evaluation of molding and bottle quality Dry at 0 ° C for 5 hours and at a cylinder temperature of 285 ° C using a Dynamelter M-100DM injection molding machine from Meiki Seisakusho Co., Ltd. to mold 50 grams of preplastic. This preplastic applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -17-505668 on the paper size of the paper. A7 B7 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention 5) V / 1 It was blown three times to obtain a bottle having an internal volume of 1.5 liters and a cylinder thickness of 0.3 mm. A Miracron blow molding machine from Cincinnati Co., Ltd was used. The scale of the heater is set at 1 (50%) '2 to 4 (45%), 5 to 8 (48%) and 9 (70%)' and the heating time is selected to minimize turbidity. Blow molding is performed under the above conditions. By measuring the side wall of the bottle with a turbidity meter, the turbidity of the strips was evaluated for transparency. Nippon Denshoku Kohyo K.K.'s The Color and Color Difference Metal Model 1001DP was used as the turbidity §10. The compressive strength indicates the pressure when the bottle is filled with water through a hydraulic pump and the pressure is increased at a rate of 10 kg / min to rupture the bottle. The flexural strength was measured as follows. The bottle was placed vertically in the cross-head of an automatic plotter (AG—100B of Shimadzu Corp.), and then the width of the crosshead was narrowed at a rate of 500 mm / min. The bottle is subjected to a load. The bending strength indicates the maximum load measured until the bottle is greatly deformed. The width of the heating time is the difference between the longest heating time and the shortest heating time when the bottle is heated by the fixed heater above. Here During the molding process, the turbidity of the "side wall" of the bottle fell below 1%. It can be explained that the greater the width of the heating time, the more inhibited the whitening of the polymer as a bottle. 8) Spinning and quality evaluation After drying at 160 ° C for 5 hours, 36 denier filaments were spun at 300 ° C at a spinning temperature of 15 m / min. Cooling air lines This paper is sized to Chinese National Standard (CNS) A4 specifications ( 210 X 297 mm) -18- s -I! Order-I ^ #. (Please read the notes on the back before filling out this page) 505668 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description ( 16) Sexual speed (26 ° C, 70% relative humidity) and 3,000 Spinned at a take-up speed of 0 m / min. The number of broken yarns per 106 grams of polymer was calculated. The number of broken yarns reflects the effect of improving the drawability obtained by suppressing crystallization. When the yarn is completely broken by increasing the winding speed at a rate of 2000 m / min under the above conditions, this winding speed is recorded as the maximum breaking winding speed. 9) Yarn-making property The polymer's yarn-making property was evaluated by observing the height of the foreign material containing metal Sb around the spinneret and the state of occurrence of bending. Melt spinning at a discharge rate of 80 g / min, a discharge temperature of 285 ° C and a take-up speed of 1,200 m / min, using a spinning orifice with 30 0 · 3 mm diameter orifices Spinning plates were implemented for 7 days. The smaller the height of the foreign matter on the surface of the spinneret, the better the yarn-making property of the polymer and the less the occurrence of bending, the better the yarn-making property. Example 1 A 0.01 mol antimony trioxide and 0.01 mol magnesium acetate tetrahydrate were present in 326 g of ethylene glycol, heated at 80 ° C and mixed for 2 hours to prepare a transparent Catalyst solution. After that, a slurry of 3,600 parts of terephthalic acid and 2,100 parts of ethylene glycol was prepared at room temperature and poured into an autoclave equipped with a stirrer at a temperature of 2700 ° C. The reaction was carried out under an increased pressure of 3 kg / cm2. The pressure decreases when the amount of distilled water becomes 600 parts. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -19-(Please read the precautions on the back before filling this page)

τ, 1T ii 505668 A7 ΒΊ 5. Description of the invention (17), and the reaction is further carried out at 27 ° C under normal pressure. Further, when the amount of distilled water exceeds 700 parts, 0.2 parts of orthophosphoric acid is added and a transparent catalyst solution prepared in advance is added after 10 minutes. Subsequently, polycondensation was performed at a temperature of 285 ° C under a reduced pressure of 0.1 mm m Hg for 2.5 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of 0.64 1. The quality of this polymer is shown in Table 1, its thermal characteristics (measured by DSC) and its color are shown in Table 2, and the physical properties of the film made by him are shown in Table 3. Comparative Example 10 · 01 Molar antimony trioxide was added to 221 grams of ethylene glycol, heated at 15 5 ° C and mixed for 2 hours to prepare a transparent catalyst solution. Poly (ethylene 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. The quality of this polymer is shown in Table 1, its thermal characteristics (measured by DSC) and its color are shown in Table 2, and the physical properties of the film made by him are not shown in Table 3. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Example 2 Prepare a transparent catalyst solution in the same manner as in Example 1. After that, a slurry of 3,600 parts of terephthalic acid and 2,100 parts of ethylene glycol was prepared at room temperature and poured into an autoclave equipped with a stirrer at a temperature of 2700 ° C. The reaction was carried out under an increased pressure of 3 kg / cm2. When the amount of distilled water becomes 600 parts, the pressure is reduced. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 2〇- 505668 A7 B7 5. The invention description (18) is low, and the reaction is further 270 ° C, under normal pressure. In addition, when the amount of distilled water exceeds 740 parts, 0.21 parts of orthophosphoric acid and DEG (the amounts of which are shown in Table 1) are added, and a transparent catalyst solution prepared in advance is added after 10 minutes. Subsequently, a polycondensation reaction was performed at a reduced pressure of 0.1 mm H g at a temperature of 2 8 ° C for about 1.8 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of about 0.56. ester. The polymer was further solid-state polymerized at 210 ° C in an N2 atmosphere with 0.5 mmHg t to increase the intrinsic viscosity of the polymer to about 0.86. The properties of the polymer after this solid state polymerization are shown in Table 1, and its thermal characteristics (measured by DSC) and color are shown in Table 2. The properties of the bottles molded from this polymer are shown in Table 4. Example 3 0,01 mole of antimony trioxide and 0.005 mole (1: 0 · 5 mole ratio) of magnesium acetate tetrahydrate were present in 274 g of ethylene glycol at 80 ° C. Heat and mix for 2 hours to prepare a transparent catalyst solution. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). A polymer with an intrinsic viscosity of about 0.86 was obtained in the same manner as in Example 2, except that this catalyst was used. The solution replaces the catalyst solution of equal molar amounts of antimony trioxide and magnesium acetate tetrahydrate dissolved in ethylene glycol. The properties of this polymer after this solid state polymerization are shown in Table 1, and its thermal characteristics (measured by DSC) and color are shown in Table 2. The properties of the bottles molded from this polymer are shown in Table 4. This paper size applies the Chinese National Standard (CMS) A4 specification (210X297 mm) -21-505668 kl B7 V. Description of the invention (l9) Example 4 Use 0 · 0 1 mol antimony trioxide and 〇 〇1 mol acetic acid Calcium hydrate is present in 307 g of ethylene glycol, heated and mixed at 80 t for 2 hours to prepare a transparent catalyst solution. A polymer having an intrinsic viscosity of about 0.86 was obtained in the same manner as in Example 2, except that this catalyst solution was used instead of the equivalent molar amounts of antimony trioxide and magnesium acetate tetrahydrate dissolved in ethylene glycol. Catalyst solution. The physical properties of this polymer are shown in Table 1, and its thermal characteristics (measured by DSC) and color are shown in Table 2. The properties of the bottles molded from this polymer are shown in Table 4. Comparative Example 2 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (Please read the precautions on the back before filling this page) i. Prepare a transparent catalyst solution 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 the catalyst solution of a mixture of antimony trioxide and magnesium acetate tetrahydrate. The physical properties of this polymer are shown in Table 1, And its thermal characteristics (measured by DSC) and colors are shown in Table 2. The properties of the bottle molded from this polymer are not shown in Table 4. Comparative Example 3 0. 01 Molar of antimony dioxide was dissolved in 21 g of ethylene glycol, and heated and mixed at 15 5 ° C for 2 hours to prepare a catalyst solution. 0 · 0 1 Mol of magnesium acetate tetrahydrate dissolved in 107 g of ethylene glycol. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 22 _ 505668 A7 B7 5. Invented) Medium 'was heated at 35 ° C and mixed for 2 hours to prepare a catalyst solution. After that, a slurry of 3,600 parts of terephthalic acid and 100 parts of ethylene glycol was prepared at room temperature, and poured into an autoclave equipped with a stirrer, while adding ethyl acetate of magnesium acetate. The diol solution was reacted at a temperature of 27000c under an increased pressure of 3 kg / cm2. When the amount of distilled water became 600 parts, the pressure decreased, and the reaction was further carried out at 27 ° C and normal pressure. Furthermore, when the amount of distilled water exceeds 740 parts, 0.2 parts by weight of orthophosphoric acid and DEG (the amounts of which are shown in Table 1) are added, and after 10 minutes, three of the previously prepared dissolved in ethylene glycol are added. Antimony oxide catalyst dissolves' liquid. This addition was performed to ensure that the amounts of magnesium and antimony added were as shown in Table 1. Subsequently, a polycondensation reaction was performed at a temperature of 285 ° C under a reduced pressure of 0.1 mmHg for about 1.8 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of about 0.56. The polymer was further solid-state polymerized at 210 ° C in an N2 atmosphere having a pressure of 0.5 mmHg to increase the intrinsic viscosity of the polymer to about 0.86. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The properties of this polymer after solid state polymerization are shown in Table 1, and its thermal characteristics (measured by DSC) And colors are shown in Table 2. The properties of the bottles molded from this polymer are shown in Table 4. Example 5 A transparent catalyst solution was prepared in the same manner as in Example 1. After that, a slurry of 3,600 parts of terephthalic acid and 2,100 parts of ethylene glycol was prepared at room temperature, and poured into a press equipped with a stirrer. The paper size was adapted to Chinese National Standard (CNS) A4. Specification (210X297 mm) -23- 505668 A7 B7 V. Description of the invention θ) A reaction is carried out in a heater at a temperature of 270 ° C and a pressure of 3 kg / cm2. When the amount of distilled water became 600 parts, the pressure was reduced, and the reaction was further performed at 27 ° C and normal pressure. Furthermore, when the amount of distilled water exceeds 740 parts, 0.21 parts of orthophosphoric acid and DEG (the amounts thereof are shown in Table 1) are added and a transparent catalyst solution prepared in advance is added after 10 minutes. Subsequently, a polycondensation contract was carried out at a temperature of 285 ° C under a reduced pressure of 0.1 mm H g for 2.5 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of about 0.64. . This polymer was further solid-state polymerized at 210 ° C in an N2 atmosphere having a pressure of 0.5 mmHg to increase the intrinsic viscosity of the polymer to about 0.99. The properties of the polymer after solid-state polymerization are shown in Table 1, and its thermal properties (measured by DSC) and color are shown in Table 2. Table 5 shows the properties and drawability of fibers spun using this polymer. Example 6 A transparent catalyst solution was prepared in the same manner as in Example 4. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). A polymer with an intrinsic viscosity of about 0.99 was obtained in the same manner as in Example 5, except that this catalyst solution was used. To replace the equivalent molar amounts of antimony trioxide and magnesium acetate tetrahydrate in the catalyst solution. The properties of this polymer after solid state polymerization are shown in Table 1, and its thermal characteristics (from DSC (Measured) and color are shown in Table 2. The properties and drawability of fibers spun using this polymer are shown in Table 5. Comparative Example 4 This paper size is in accordance with the Chinese Standard (CNS) A4 specification (210 ^ 297 mm 1 to 24-505668 kl _____ B7 V. Description of the Invention 綍) 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 replaces the catalyst solution of a mixture of antimony trioxide and magnesium acetate tetrahydrate. The physical properties of this polymer after solid state polymerization are shown in Table 1, and its thermal characteristics (measured by DSC) and color are shown. In Table 2. Use this polymer The properties and drawability of the spun fibers are shown in Table 5. (Please read the precautions on the back before filling this page)

τ, 1T

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -25- This paper size is applicable to Zhongguanjiazhuan (CNS) (21 () > < 297gongchu) 505668

7 7 AB V. Description of the invention 钤) Table 1 Polymer properties IV Metals contained in polymers: ppm (ppm) M / Sb DEG dl / g Sb Mg Ca Molar ratio wt% Ex.l 0.0641 278 30 0 0.547 1.15 C.Ex.l 0.0642 268 0 0 0 1.06 Ex. 2 0.863 141 15 0 0.539 1.81 Ex. 3 0.861 141 8 0 0.288 1.79 Ex. 4 0.859 136 0 24 0.541 1.8 C.Ex. 2 0.863 144 0 0 0 0 1.81 C.Ex.3 0.861 146 16 0 0.556 1.8 Ex.5 0.998 184 21 0 0.579 1.21 Ex.6 0.993 188 0 31 0.506 1.24 C.Ex. 4 0.995 194 0 0 0 1.25 (Please read the notes on the back before filling (This page) M: Total amount of Mg and Ca Ex .: Examples; C. Ex .: Comparative examples Printed on the paper by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) _ 26-505668

7 B Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention θ) Table 2 Thermal properties and colors of polymers Tci Tm Ted Col ° C ° C ° CL b Ex. 1 155 253 177 76 1.8 C.Ex. 1 153 254 189 77 2.2 Ex. 2 163 251 165 80 0.3 Ex. 3 162 252 165 81 -0.1 Ex. 4 164 250 167 81 -0.4 C · Ex · 2 159 252 177 81 0.2 C. Ex. 3 159 250 175 79 0.4 Ex.5 166 254 163 78 1.1 Ex. 6 166 253 164 79 0.8 C · Ex · 4 162 254 170 78 1.5 (Please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS ) A4 specification (210X297 mm) -27 505668 Μ B7 V. Description of the invention 鲊) Table 3 Evaluation results of the membrane IV turbidity dl / g% Ex. 1 0.587 0.6 C. Ex. 1 0.585 0.9 Ex .: Examples; C.Ex .: Comparative example (please read the notes on the back before filling out this page) The paper size printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -28- 505668 A7 B7 Instructions 5

MaM Inch Skirt Printed Heating Time Width (Transparent Bottle) by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy GO CN ο T < Inch Bending Strength 47.2 47.9 47.6 48.0 48.6 Compressive Strength kg / cm2 CO wn y—i 15.4 t 1 H wS oo VO 15.6 Turbidity inchvn OO Side wall thickness mm 0.344 0.342 0.339 0.345 0.342 Volume 1481.3 1481.5 1480.8 1481.9 1480.2 Axial tensile ratio 3.02 3.04 3.05 3.02 3.04 Preplastic IV 0.794 0.801 0.792 0.795 0.796 Ex.2 Ex .3 Ex.4 C.Ex.2 C.Ex.3 (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -29 _ 505668

AB V. Description of the invention (> "?) Table 5 Physical properties of the yarn IV Number of broken yarns Maximum breakage Winding yarn speed dl / g Times / polymer 106 m / min Bending on the surface of the spinning board g Height of Foreign Matter (//) Ex.5 0.954 0.6 7400 13 Not seen Ex.6 0.961 0.7 7200 13 Not seen C.Ex.4 0.957 2.2 6650 13 Seen (Please read the notes on the back before filling in this page)

Ex .: Examples; C.Ex .: Comparative Examples Printed paper rule vl printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economy Applicable to China National Standard (CNS) A4 (210X 297 mm) Fee 505 668 kl ___ B7 V. Invention Explanation and) Example 7: 0. 0,1 mol of antimony trioxide and 0. 0,1 mol of manganese acetate tetrahydrate were present in 3,1 g of ethylene glycol, heated at 80 ° C and mixed for 2 hours to Prepare a clear catalyst solution. After that, a slurry of 3,600 parts of terephthalic acid and 2'100 parts of ethylene glycol was prepared at room temperature and poured into an autoclave equipped with a stirrer at 270 ° C. The reaction was carried out at an increased pressure of 3 kg / cm2 at a temperature. When the amount of distilled water became 600 parts, the pressure was reduced 'and the reaction was further carried out at 27 ° C under normal pressure. Further, when the amount of distilled water exceeds 740 parts, 0.21 parts of orthophosphoric acid is added and a transparent catalyst solution prepared in advance is added after 10 minutes to ensure that the amounts of antimony and calcium are shown in Table 6. Subsequently, the polycondensation contract was carried out at a temperature of 2 8 5 ° C under a reduced pressure of 0.1 mm H g for 2 · 5 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of 0 · 6 4 5 . The quality of this polymer is shown in Table 6, and its thermal characteristics (measured by DSC) and color are shown in Table 7. The physical properties of the film made by him are shown in Table 8. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Example 8 Make 0.01 mol of antimony trioxide and 0.01 mol magnesium acetate tetrahydrate exist In 6 grams of ethylene glycol, heat and mix at 80 ° C for 2 hours to prepare a transparent catalyst solution. A polyethylene terephthalate having an intrinsic viscosity of about 0.64 1 was obtained in the same manner as in Example 7, except that this catalyst solution was used instead of the solvent paper and the Chinese national standard (CNS) A4 specification was applied ( 210X297 mm) 31 505668 A7 B7 V. Description of the invention Note) An equivalent molar amount of antimony trioxide and manganese acetate tetrahydrate catalyst solution in ethylene glycol. The physical properties of this polymer are shown in Table 6, and its thermal characteristics (measured by DSC) and color are shown in Table 7. The physical properties of the film made of this polymer are shown in Table 8 < Example 9: 0.01 moles of antimony trioxide and 0.005 moles of manganese acetate tetrahydrate and 0.05 moles of magnesium acetate tetrahydrate were present in 318 g of ethylene glycol. Heat and mix at 0 ° C for 2 hours to prepare a pale purple transparent catalyst solution. A poly (ethylene terephthalate) having an intrinsic viscosity of about 0.64 0 was obtained in the same manner as in Example 7, except that this catalyst solution was used in place of an equivalent amount of trioxide dissolved in terephthalic acid. Catalyst solution of antimony and manganese acetate tetrahydrate. The thermal properties (measured by DSC) and color of this polymer are shown in Table 7. The physical properties of the film are shown in Table 4. Comparative Example 5 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 0 · 0 1 Moore antimony trioxide is added to 2 2 1 g of ethylene glycol, at 1 5 5 Heat and mix at ° C for 2 hours to prepare a transparent catalyst solution. Polyethylene terephthalate was obtained in the same manner as in Example 7, except that this catalyst solution was used instead of a mixed solution of antimony trioxide and manganese acetate tetrahydrate. The physical properties of this polymer are shown in Table 6, and its thermal characteristics (measured by DSC) and color are shown in Table 7. The physical properties of the film made by him are based on the Chinese National Standard (CNS) A4 specification (210X297). Mm) 32-505668 ____ 5. Description of the invention 00) is shown in Table 8. (Please read the precautions on the back before filling out this page) Example 1 0 A purple transparent catalyst solution was prepared in the same manner as in Example 7. After that, a slurry of 3,600 parts of terephthalic acid and 2'100 parts of ethylene glycol was prepared at room temperature and poured into an autoclave equipped with a stirrer at a temperature of 2700 ° C. The reaction was carried out under an increased pressure of 3 kg / cm2. When the amount of distilled water becomes 600 parts, the pressure decreases, and the reaction proceeds further at 270 ° C and under normal pressure. Furthermore, when the amount of distilled water exceeds 740 parts, 0.21 parts of orthophosphoric acid and D EG (the amounts of which are shown in Table 6) are added and a transparent catalyst solution prepared in advance is added after 10 minutes. To ensure that the amounts of antimony and manganese are as shown in Table 6. Subsequently, the polycondensation reaction was performed at a temperature of 2 5 ° C under a reduced pressure of 0.1 mm H g for about 1.8 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of about 0.56. ester. The polymer was further polymerized in a solid state in an N2 atmosphere having 0.5 mmHg t at 210 ° C to increase the intrinsic viscosity of the polymer to about 0.8. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economics The polymer properties after solid state polymerization are shown in Table 6, and its thermal characteristics (measured by DSC) and colors are shown in Table 7. The properties of the bottles molded from this polymer are shown in Table 4. Example 11 A transparent catalyst solution was prepared in the same manner as in Example 8. In the same way as in Example 10, a paper with a size of about 0.86 ^ applicable to China National Standard (CNS) A4 specifications (210X297 mm 1 ~: 33-printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 505668 kl 5. Description of the invention 01) Polymers of inherent viscosity except for using this transparent catalyst solution to replace the equivalent molar amounts of antimony trioxide and manganese acetate tetrahydrate catalyst solutions in terephthalic acid. The properties of the polymer after this solid state polymerization are shown in Table 6, and its thermal characteristics (measured by DSC) and color are shown in Table 7. The properties of the bottles molded from this polymer are shown in Table 9. Example 1 2 0. 01 mol of antimony trioxide and 0. 005 mol of manganese acetate tetrahydrate were present in 266 g of ethylene glycol, heated at 80 ° C and mixed for 2 hours to prepare a light solution. Purple transparent catalyst solution. A polymer having an intrinsic viscosity of about 0.86 was obtained in the same manner as in Example 10, except that this transparent catalyst solution was used instead of the equivalent molar amounts of antimony trioxide and manganese acetate dissolved in terephthalic acid. Catalyst solution of tetrahydrate. The properties of this polymer are shown in Table 6, and its thermal characteristics (measured by DSC) and color are shown in Table 7. The properties of bottles molded from this polymer are shown in Table 9. Example 13 3 0.018 mol of antimony trioxide 0. 005 mol manganese acetate tetrahydrate and 0.05 mol of magnesium acetate tetrahydrate were present in 318 g of ethylene glycol. Heat and mix at 80 ° C for 2 hours to prepare a pale purple transparent catalyst solution. This paper size applies to China National Standard (CNS) A4 (210X297 mm) _ 34-(Please read the precautions on the back before filling this page)

1T 505668 A7 B7 V. Description of the invention and) A polymer having an intrinsic viscosity of about 0.86 was obtained in the same manner as in Example 10, except that this catalyst solution was used instead of the one dissolved in ethylene glycol, etc. Molar amount of catalyst solution of antimony trioxide and manganese acetate tetrahydrate. The properties of this polymer are shown in Table 6, and its thermal characteristics (measured by DSC) and color are shown in Table 7. The properties of bottles molded from this polymer are shown in Table 9. Comparative Example 6 A catalyst solution was prepared in the same manner as in Comparative Example 5. Poly (ethylene terephthalate) was obtained in the same manner as in Example 10, except that this catalyst solution was used instead of a catalyst solution of a mixture of antimony trioxide and manganese acetate tetrahydrate. The properties of this polymer are shown in Table 6, its thermal properties (measured by DSC) and its color are shown in Table 7, and the physical properties of this polymer molded film are shown in Table 9. A purple transparent catalyst solution was prepared in the same manner as in Example 7. After that, 3,600 parts of terephthalic acid and 2,100 parts of ethylene glycol 'were heated and mixed at 80 ° C for 2 hours at room temperature to prepare a transparent catalyst solution. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) 4 After that, prepare 3,600 parts of terephthalic acid and 2,100 parts of ethylene at room temperature. The alcohol slurry was poured into an autoclave equipped with a stirrer to carry out the reaction at a temperature of 270 ° C and an increased pressure of 3 kg / cm2. When the amount of distilled water becomes 600 parts, the pressure decreases, and the reaction is further performed at 27 ° C and normal pressure. Further, when the amount of distilled water exceeds 740 parts, 0.2 parts of orthophosphoric acid is added and the Chinese National Standard (CNS) A4 specification (210X 297 mm) is applied at the paper scale—35-505668 B7. 5. Description of the invention 03) After 10 minutes, the transparent catalyst solution prepared in advance is added. To ensure that the amounts of antimony and manganese are as shown in Table 6. Subsequently, the polycondensation reaction was performed at a reduced pressure of 0. 1 mm H g at a temperature of 2 8 5 t for about 2.5 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of 0.64. . This polymer was further solid-state polymerized at 210 ° C in an N 2 atmosphere having a pressure of 0.5 m m H g to increase the polymer's intrinsic viscosity to about 0.99. After this solid state polymerization, the properties of this polymer are shown in Table 6, and its thermal characteristics (measured by DSC) and its color are shown in Table 7. The properties and drawability of the fibers spun using this polymer are shown in Table 10. Example 15 A transparent catalyst solution was prepared in the same manner as in Example 8. A polymer 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 an equivalent amount of antimony trioxide and manganese acetate dissolved in ethylene glycol. Catalyst solution of hydrate. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) The properties of this polymer after solid state polymerization are shown in Table 6 and its thermal characteristics (measured by DSC) And the colors are shown in Table 7. The properties and fiber drawing properties of the fibers spun using this polymer are shown in Table 10. Comparative Example 7 0.01 mol of antimony trioxide was added to 221 g of ethylene glycol, heated and mixed at 15 5 ° C for 2 hours to prepare a transparent catalyst solution. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 36 — ~ 505668 A7 ____B7 V. Description of the invention ") !, ^ is obtained in the same manner as in Example 14 and has a value of about 0.9 9 _ & amp Polyethylene terephthalate of viscosity, except for using this catalyst solution to take a catalyst solution of a mixture of # = _ antimony and manganese acetate tetrahydrate. The quality of this polymer is shown in Table 6, Its thermal characteristics (measured by DSC) and color are shown in Table 7. The properties and drawability of the yarns spun from this polymer are shown in Table 10. The paper size printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Applicable to China National Standard (CNS) A4 specification (2i0x297mm) _ 37-505668 7 Β V. Description of the invention (long Π Table 6 Polymer properties IV Polymer metal content M / Sb DEG dl / g Sb Μη Mg Moire wt% Εχ.7 0.645 275 68 0 0.553 1.13 Ex. 8 0.641 278 0 30 0.547 1.15 Ex. 9 0.64 270 34 15 0.564 1.13 C.Ex. 5 0.641 269 0 0 0 1.06 Ex. 10 0.865 139 34 0 0.548 1.79 Ex. 11 0.863 141 0 15 0.539 1.81 Ex. 12 0.859 144 18 0 0.2 8 1.82 Ex. 13 0.856 138 17 7 0.533 1.77 C.Ex. 6 0.861 144 0 0 0 1.81 Ex_14 0.989 189 48 0 0.569 1.19 Ex. 15 0.998 184 0 21 0.579 1.21 C.Ex. 7 0.992 191 0 0 0 1.18 ( Please read the notes on the back before filling in this page) Μ: The total amount of Μ η and M g elements Ex .: Examples; C.Ex .: Comparative Examples China National Standard (CNS) A4 Specification (210X 297mm) -ί?-505668 V. Description of Invention (^) Table 7 Thermal Characteristics of Polymers Printed by Cooperatives of Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs) ¢ 1 Color Tci Tm Ted Col ° C ° C ° CL b Ex. 7 156 253 178 77 1.7 Ex · 8 155 253 177 76 1.8 Ex. 9 155 253 178 77 1.7 C. Ex. 5 153 254 190 76 2 Ex. 10 162 251 166 81- 0.1 Ex.l 1 163 251 165 80 0.3 Ex. 12 163 252 165 80 0 Ex. 13 162 251 165 80 0.1 CEx. 6 159 252 178 81 0.3 Ex. 14 165 254 164 79 0.9 Ex. 15 166 254 163 78 1.1 C.Ex. 7 162 254 171 78 1.5 (Please read the notes on the back before filling this page)

、 1T This paper size applies Chinese National Standard (CNS) A4 specification (210X 297mm) A dozen-505668 Printed by A7 B7, Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention U)) Table 8 Evaluation results of film IV Turbidity dl / g% Ex. 7 0.584 0.5 Ex. 8 0.587 0.6 Ex. 9 0.585 0.6 C · Ex · 5 0.586 0.9 Ex .: Examples; C.Ex .: Comparative Examples (Please read the precautions on the back before (Fill in this page). 4.

、 1T 4 This paper size applies to Chinese National Standard (CNS) Α4 specification (210X 297 mm) —4 ί >-505668

A

7 B Μ 明 一 说明 ， WQ printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ i Stop waste η OO tH cs y—i cn 鲥 缌 ir t > JQ O) cs o cn cn < η < CN ^ I inch IT) rH CO H wn t—im H VO un rH te (Μ ^ t; wn ON m 赃 panning aa τ—H 〇cn cn C5 VO cn CO 〇cn o Μ m 9ππ i ^ | < N y— < swallow H cn rH swallow t—H wo H swallow t—H CN g CO r—H swallow τ—HS f: cn cn g cn inch cn σ \ cn cn >% mmg oo o art ! > cn o Csl o ON o; _ (tl town ow rH r ^ HW Csl t—H cn rH w 'vq ϋ crown «镒 ^: · × Η · ο 匡 fcMdpq This paper size applies Chinese National Standard (CNS ) A4 size (210X 297mm) _ 41 _ π Ii! (Please read the precautions on the back before filling this page)

1T 505668 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention Gentle) Table 1 0 Number of broken yarns IV The number of broken yarns The maximum speed of broken yarn winding dl / g times / polymer 106 m / min The height of foreign matter on the surface of the spinning plate caused by bending g (//) Ex. 14 0.949 0.5 7600 10 Ex. 15 0.954 0.6 7400 13 C.Ex. 7 0.955 2.3 6550 18 not seen

Ex .: Examples; C.Ex .: Comparative Examples The paper size applies to the Chinese National Standard (CNS) A4 gauge (210X297 mm) _ 42-(Please read the precautions on the back before filling this page)

505668 Printed by A7 B7, Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the Invention 舛) Example 1 6 Makes 0.01 mol trioxide chain and 0.01 mol zinc acetate dihydrate present in 3 2 9 g In the diol, heat and mix at 80 ° C for 2 hours to prepare a transparent catalyst solution. After that, a slurry of 3,600 parts of terephthalic acid and 2,100 parts of ethylene glycol was prepared at room temperature and poured into an autoclave equipped with a stirrer at a temperature of 2700 ° C. The reaction was carried out under an increased pressure of 3 kg / cm2. When the amount of distilled water becomes 600 parts, the pressure decreases, and the reaction is further carried out at 27 ° C and normal pressure. Further, when the amount of distilled water exceeds 740 parts, add 0.21 parts of orthophosphoric acid and add a transparent catalyst solution prepared in advance after 10 minutes to ensure that the amounts of antimony and zinc are not as shown in Table 11. . Subsequently, polyester compounding was performed at a temperature of 2 8 ° C under a reduced pressure of 0.1 mm Hg for 2.5 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of 0.64 1 . The quality of this polymer is shown in Table 11, its thermal characteristics (measured by DSC) and its color are shown in Table 12, and the physical properties of the film made by him are shown in Table 13. Example 17 A transparent catalyst solution was prepared in the same manner as in Example 16. After that, a slurry of 3,600 parts of terephthalic acid and 2,100 parts of ethylene glycol was prepared at room temperature and poured into an autoclave equipped with a stirrer at a temperature of 2700 ° C. The reaction was carried out under an increased pressure of 3 kg / cm2. When the amount of distilled water becomes 600 parts, the pressure is reduced. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 43 _ (Please read the precautions on the back before filling this page)

505668 A7 B7 V. Description of the invention M) is low 'and the reaction is further carried out at 27 ° C under normal pressure. Furthermore, when the amount of distilled water exceeds 740 parts, 0.21 parts of orthophosphoric acid and DEG (the amounts are shown in Table 1) are added, and a transparent catalyst solution prepared in advance is added after 10 minutes. Subsequently, a polycondensation reaction was performed at a temperature of 2 5 ° C under a reduced pressure of 0.1 mm Hg for about 1.8 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of about 0.56. ester. The polymer was further solid-state polymerized at 210 ° C in an N2 atmosphere having a pressure of 0.5 mmHg to increase the intrinsic viscosity of the polymer to about 0.86. The properties of the polymer after this solid state polymerization are shown in Table 1, and its thermal characteristics (measured by DSC) and color are shown in Table 2. The properties of the bottles molded from this polymer are shown in Table 4. Example 1 8 0. 01 mol of antimony trioxide and 0. 005 mol of zinc acetate dihydrate were present in 275 g of ethylene glycol, heated at 8 and mixed for 2 hours to prepare a transparent catalyst solution . Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). In the same manner as in Example 17, a polyethylene terephthalate with an intrinsic viscosity of about 0.86 In addition to using this catalyst solution to replace the catalyst solution of a mixture of antimony trioxide and zinc acetate dihydrate. The properties of this polymer after this solid state polymerization are shown in Table 11 and its thermal characteristics (measured by DSC) and color are shown in Table 12. The properties of the bottles molded from this polymer are shown in Table 14. After that, 3,600 parts of terephthalic acid and this paper are prepared at room temperature. The Chinese National Standard (CNS) A4 specification (210X297 mm) -44-505668 A7 B7 is used. 5. Description of the invention 峠) 2,1 0,0 parts of ethylene glycol slurry was poured into an autoclave equipped with a stirrer to carry out the reaction at a temperature of 270 ° C under an increased pressure of 3 kg / cm2. When the amount of distilled water becomes 600 parts, the pressure decreases, and the reaction proceeds further at 270 ° C and under normal pressure. Furthermore, when the amount of distilled water exceeds 740 parts, 0.21 parts of orthophosphoric acid and DEG (the amounts of which are shown in Table 11) are added and after 10 minutes, a previously prepared dissolved in ethylene glycol is added. Antimony trioxide catalyst solution and zinc acetate dihydrate catalyst solution in ethylene glycol. This addition was performed to ensure that the amounts of zinc and antimony added were as shown in Table 11. Subsequently, a polycondensation reaction was performed at a temperature of 2 8 5 ° C under a reduced pressure of 0.1 mm η g for about 1.8 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of about 0.56. ester. The polymer was further solid-state polymerized at 2 10 ° C in an N2 atmosphere having 0.5 mmHg t to increase the intrinsic viscosity of the polymer to about 0.86. The properties of the polymer after this solid state polymerization are not shown in Table 11, and its thermal characteristics (measured by DSC) and color are shown in Table 12. The properties of the bottles molded from this polymer are shown in Table 14. (Please read the notes on the back before filling this page)

、 1T Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) _ 45-505668 IV Metal content in the polymer Zn / Sb DEG dl / g Sb Μη Molar ratio wt% Εχ.16 0.645 275 81 0.554 1.10 Εχ.17 0.863 138 39 0.532 1.83 Ex. 18 0 861 144 21 0.274 1.80 Ex. 19 0.994 185 51 0.519 1.21 A7 B7 V. Description of the invention 峠) Table 11 Polymer properties

Ex .: Example ---: -I:-Install one 丨 (Please read the precautions on the back before filling this page)

、 1T 4 Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper is printed in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 mm) _ 46-505668 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Β7 V. Invention Note M) Table 1 2 Thermal properties and colors of polymers Tci Tm Ted Col ° C ° C ° CL b Ex. 16 155 254 176 76 1.6 Ex. 17 164 250 167 81 -0.4 Ex. 18 162 251 166 81 -0.2 Ex.19 166 253 164 79 0.8 ---; —.--- install— (Please read the precautions on the back before filling this page)

、 1T Φ This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) -47-505668 A7 B7 V. Description of the invention Table 13 Evaluation results of film Film IV Turbidity dl / g% Ex. 1 6 0.581 0.5

Ex .: Example (Please read the notes on the back before filling this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -48-505668 A7 7 Β V. Description of the invention 鲊) Μ #! Continued printing by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Width of heating time (transparent bottle) 〇〇Η ο Bending strength 47.6 47.6 Compressive strength kg / cm2 CO in τ-Η 15.4 Turbidity inch · Side wall ν 'stripe thickness mm 0.338 0.340 Volume 1480.8 1481.0 Axial tensile ratio 3.04 3.04 Pre-plastic IV ^ 3 0.797 0.796 Ex. 17 Ex. 18 ^ fcJH (Please read the precautions on the back before filling out this page) • 1 Pack · Binding-This paper size applies Chinese National Standard (CNS) Α4 size (210X297) (Centimeter) _ 49 _ 505668 IV Number of broken yarns Maximum broken yarn take-up speed dl / g times / polymer 106 m / min Extent of foreign matter on g of the spinning plate (g) Ex (#) Ex. 16 0.954 0.8 7100 12 A7 B7 not seen V. Description of the invention β) Table 15 Physical properties of yarn

Ex .: Example (please read the precautions on the back before filling this page) Order the paper printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) _ 5〇_ 505668 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention Secondary) Example 19 A transparent catalyst solution was prepared in the same manner as in Example 16. After that, a slurry of 3,600 parts of terephthalic acid and 2,100 parts of ethylene glycol was prepared at room temperature and poured into an autoclave equipped with a stirrer at a temperature of 2700 ° C. The reaction was carried out under an increased pressure of 3 kg / cm2. When the amount of distilled water becomes 600 parts, the pressure is reduced 'and the reaction is further carried out at 27 ° C under normal pressure. Furthermore, when the amount of distilled water exceeds 740 parts, 0.21 parts of orthophosphoric acid and DEG (the amounts of which are shown in Table 11) are added and a transparent catalyst solution prepared in advance is added after 10 minutes. Subsequently, a polycondensation reaction was performed at a temperature of 2 5 ° C under a reduced pressure of 0.1 mm Hg for about 2.5 hours to obtain poly (ethylene terephthalate) having an intrinsic viscosity of about 0.64 ester. The polymer was further solid-state polymerized at 210 ° C in an N2 atmosphere with 0.5 mmHg t to increase the intrinsic viscosity of the polymer to about 0.99. The properties of the polymer after this solid state polymerization are shown in Table 11, and its thermal characteristics (measured by DSC) and color are shown in Table 12. The properties and drawability of the fibers spun from this polymer are shown in Tables 15. According to the present invention, although an inexpensive Sb-based catalyst is used, PET whose crystallinity is suppressed can be obtained, and a copolymer component which is substantially free from turbidity and whitening and whose crystallinity is substantially free of copolymer components can be obtained. Inhibited PET. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) _ 51-i ^ i ^ — ^^ 1 11_1 nm «Βϋιϋ ϋϋ m ··· ϋϋ · 1 11 —-ml in ^ i — · * —Flu— · 11_1 —flu (Please read the notes on the back before filling this page}

Claims (1)

1505668 8 8 8 8 ABCD No. 8 710705 Patent Application No. 8 Chinese Version Amendment of Patent Range ---- 90, ii · «, Annex of Patent Application Range (A): Amendment in January 1st of 1990 of the Republic of China 1. An aromatic polyester, which includes the amount Terephthalic acid that accounts for at least 95 mol% of all acid components and ethylene glycol that accounts for at least 95 mol% of all diol components, which contains antimony and optional Mg, Ca, Sr, Ba, Ra , Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn are at least one divalent metal element in a group, and the amount of these two substances satisfies the following formulae (1) and (2) ): 90 ^ Μχ ^ 300 (1) where M1 is the amount of element S b (p pm) contained in the aromatic polyester (please read the precautions on the back before filling this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed 〇 Its% and S and its phenol and temperature measured at 4 ° C. 0 Μ b is its key. 〔[Chloroethyl content of 4 5SM2 / SbS5.0 (2) 2 is an aromatic polymer The atomic mole% of the element antimony contained in the divalent metal element atomic molar aromatic polyester contained in the ester has an intrinsic viscosity and a crystalline system satisfying the following formulae (3) to (5): 65 S [//] S0.90 (3) 7?] Is the intrinsic viscosity (dg) of the aromatic polyester, which is in a mixture solvent of alkane (3/2 weight ratio) at 3 5 STcd — 24 · 6 / 〔Τ?〕 ^ 142 〇 This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) 505668 A8 B8 C8 D8 VI. Patent application scope [7?] As defined above, T cd is measured by DSC When the temperature decreases, the peak temperature of the crystalline exothermic peak of the aromatic polyester (it), (Please read the precautions on the back before filling this page) 130 · 〇STc i- 34 · 5χ 〔77〕 g 1 3 8. 〇 (5) where [β] is as defined above, and T ci is measured by DS c. As the temperature rises, the peak temperature of the crystalline exothermic peak of the aromatic polyester (C). 2. The aromatic polyester according to item 1 of the patent application, wherein the content of terephthalic acid accounts for at least 97 mole% of all the acid components. 3. If the aromatic polyester of item 1 of the patent application scope, the total diol content is at least 95 mol% of ethylene glycol and 5 mol% or less of other diols (including diethylene glycol) composition. 4. The aromatic polyester according to item 3 of the patent application, wherein the total amount of ethylene glycol and diethylene glycol accounts for at least 99_5 mole% of all glycol components. 5. As the aromatic polyester in item 1 of the patent application scope, which contains antimony and divalent metal elements, the amount of both meets the following formula (2) -1: 0.05SM2 / Sb $ 5.〇 (2)-1 Ministry of Economic Affairs Printed by the Intellectual Property Bureau employee consumer cooperative where M 2 and S b are as defined in equation (2) above. 6 · A transparent bottle made of an aromatic polyester such as in the scope of patent application. Item 1. 7. The transparent bottle according to item 6 of the patent application, wherein the aromatic polyester has an intrinsic viscosity of 0.65 to 0.90. 8 · If the aromatic polyester in item 1 of the scope of patent application is used, it is used as the raw material for the production of paper. The Chinese national standard (CNS) A4 specification (210X297 mm) is applicable. 505668 A8 B8 C8 D8 (Please read the notes on the back before filling out this page) II The paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 3-