KR20110065827A - Polyester resin with enhanced crystallization rate - Google Patents

Abstract

PURPOSE: A method for preparing a polyester resin is provided to improve a crystallization rate and productivity by controlling crystallization features of the polyester resin using an antimony-free catalyst. CONSTITUTION: A method for preparing a polyester resin comprises the steps of: (i) performing esterification of slurry including a dicarboxylic acid compound, diol compound, and catalyst compound; (ii) polycondensing the resultant obtained by esterification; (iii) manufacturing pellets by extruding the polycondensed reactant; and (iv) performing solid phase polymerization by crystallizing the pellets. The catalyst compound has an antimony content of 50 ppm or less.

Description

Polyester resin with enhanced crystallization rate

The present invention provides a crystallization rate that is suitable for applications requiring a crystallization process while having a total content of antimony in the PET resin of 50 ppm or less in a polyethylene terephthalate (PET) resin manufacturing process used as a material for bottles, sheets, and films. Relates to improved PET resins and their preparation.

PET is polymerized from a diacid component represented by terephthalic acid and a diol component represented by ethylene glycol, and is used as a material for packaging materials such as bottles, sheets, as well as fibers and films. As a well-known fact, PET production process is carried out by esterifying terephthalic acid and ethylene glycol at around 250 ° C. to produce bis (hydroxyl ethyl terephthalate), and then converting bis (hydroxyl ethyl terephthalate) to 0.1 to 10 torr. The polycondensation reaction is carried out at a vacuum degree of about 280 ° C. and a PET polymer is obtained. The first reaction, the esterification reaction, is an auto-catalytic reaction of terephthalic acid. The reaction proceeds without a separate catalyst, but the second reaction, the polycondensation reaction, requires a separate polycondensation catalyst. Most of PET produced in the world is based on antimony catalysts such as antimony oxide (Sb ₂ O ₃ ) and antimony acetate (Sb (CH ₃ COO) ₃ ). It is manufactured using. However, since antimony is a heavy metal, there is a movement to regulate the amount of antimony catalyst or the amount of antimony leaching from PET containers, considering the use of PET as a material for food and beverage containers. In countries such as Europe, EU directives and Japan, the migration amount of heavy metals such as antimony from PET containers is limited to a certain level. Despite the unremitting controversy regarding safety, antimony-based catalysts are still widely used as PET polycondensation catalysts to date, but a technique for producing PET using polyester polycondensation catalysts other than antimony-based catalysts has recently been attempted. One example is the production of PET using a poly- or germanium-based catalyst as a polycondensation catalyst of PET. These non-antimony catalysts have a number of characteristics when compared to the widely used antimony catalysts. For example, germanium dioxide catalysts are more active than antimony oxide catalysts, allowing the polycondensation reaction to proceed with a small amount of 50 to 200 ppm, but the catalyst is very expensive and the polycondensation reaction is carried out. The catalyst component flows out together with the ethylene glycol component flowing out, and the catalyst content in the system is changed during the reaction, making it difficult to control the process, and the material cost is higher than that of the PET polymerized with a general antimony catalyst. (US Patent 4133800, US Patent Publication 2008/0051530 A1)

Titanium based catalysts, which are often used as non-antimony based catalysts, are the best in terms of reaction activity compared to antimony and germanium based catalysts, and can be reacted with small catalysts of 5 to 20 ppm. There is a yellowing problem. In order to control the activity of side reactions that cause such discoloration, techniques for using appropriate stabilizers and limiting the catalyst input to a certain level have been disclosed. (Japanese Patent Laid-Open No. 2001-200044, Japanese Patent Laid-Open No. 2000-143789)

When polymerizing polyesters using the above-mentioned non-antimony-based catalysts, i.e., germanium-based or titanium-based catalysts, the PET resin produced is different in several respects (compared to PET resins using conventional antimony-based catalysts). One of the notable changes in physical properties is the slow crystallization rate of the resin. As a related patent, in US Pat. No. 7129317, a temperature rising crystallization temperature (T _ch ) when measured at a scan rate of 10 ° C./min using DSC (Differential Scanning Calorimeter), which is widely used as a thermal analyzer of representative polymer materials, is used. The PET resin is described above is 140 ℃ or more and the antimony content is 25 ppm or less. In other words, when using a non-antimony-based titanium or germanium-based catalyst, compared to the PET resin using an antimony-based catalyst that has been used in the past, when producing a PET having a certain level or less of antimony contained in the PET resin, The crystallization rate is remarkably slowed to obtain PET, US Patent No. 729317, mentioned above, focuses on this point to limit the crystallization temperature on DSC, which is an indicator of the rate of crystallization, to 140 ° C. or more and to include it in the scope of the claims. .

The crystallization characteristics of the PET resin have a great influence on the processing of the PET resin and the physical properties of the PET molded article. For example, in order to obtain a transparent PET molded article, the case where the PET crystallization rate is slow is more advantageous than the case where the crystallization of the resin during the molding process impairs the transparency of the molded article. However, in some cases, PET molded articles are molded by utilizing these crystallization characteristics. For example, when manufacturing a 'hot-fillable PET bottle' capable of high temperature filling, in order to improve the heat resistance of the PET bottle, the bottleneck part is crystallized during the bottle making process, and the temperature of the bottle mold is 130 ~ The so-called 'heat-set technology' is applied to improve the heat resistance of the bottle by increasing the crystallization degree of the bottle body to 30% or more by proceeding the bottle making process at a temperature up to 170 ° C. Most of the current hot-fill bottle manufacturing processes are manufactured and installed in accordance with the crystallization characteristics of antimony PET resins, which have been used in the past, so that non-antimony catalysts which are considered to be more friendly to the environment and human body are used. When processing using PET resin, the process conditions such as temperature and residence time of the crystallization process may be adjusted due to the difference in the crystallization rate of the resin being lowered, or the productivity of the crystallization process is decreased, or in some cases, the crystallization process It may cause a problem to change or replace a part of the molding machine.

The present inventors quickly adjust the slow crystallization rate (which is an intrinsic property of PET resins prepared with non-antimony-based catalysts) than the crystallization rate of PET resins produced with antimony-based catalysts, so that the antimony content is low or no antimony component is present. Even when using a PET resin manufactured using a more environmentally friendly catalyst, the crystallization can be performed even at a low temperature or a short residence time even in the existing crystallization process equipment, using DSC (Differential Scanning Calorimeter). When measured at a scan rate of ℃ / min, the PET resin with an elevated crystallization temperature (Tch) of less than 145 ℃ (below) and an antimony content of 50 ppm or less has been developed.

Accordingly, an object of the present invention is that the antimony (antimony) metal content in the PET resin is 50 ppm or less, most preferably the antimony content is zero, and the crystallization rate is faster than the conventional PET resin for excellent productivity and process characteristics in the crystallization process To provide a PET resin and a method for producing the same.

Method for producing a polyester resin according to the present invention for achieving the above object,

(A) esterifying a slurry containing a dicarboxylic acid compound, a diol compound, and a catalyst compound, (B) condensation-polymerizing the resultant obtained by the esterification reaction, (C) extruding the condensation-polymerization reactant to pellet Preparing a; And (D) crystallizing the pellets to perform solid phase polymerization, wherein the catalytic compound has an antimony content of 50 ppm or less, and a crystallization rate adjusting agent is added to step (A) or (B). do.

Polyester resin according to the present invention of another aspect for achieving the above object is produced by the above production method, the antimony content contained in the resin is 50 ppm or less, using a DSC to increase the temperature at a scan rate of 10 ℃ / min When measured, the crystallization peak temperature (Tch) is characterized in that it appears at 145 ℃ or less.

According to the present invention, by adjusting the crystallization characteristics of PET produced using an antimony-free catalyst such as titanium-based or germanium-based to speed up the crystallization rate, PET molded articles requiring heat resistance such as heat-setting bottle and heat-setting film are manufactured. In this case, a non-antimony-based PET resin (antimony-free PET) can be obtained in which the crystallization process proceeds more effectively in various crystallization processes performed to increase heat resistance.

As another technical significance of the present invention, most of the current crystallization process equipments, such as most heat-fixing mills and heat-fixing film processing equipments, manufactured according to the crystallization rate properties of current antimony-based PET, are environmentally friendly non-antimony-based. Even when using a PET resin, there is an advantage that it can be used without a separate facility modification or a sudden change in the crystallization process conditions.

Hereinafter, the technical spirit of the present invention will be described in more detail.

The present invention relates to a polyester resin using a non-antimony-based catalyst having a controlled crystallization rate. The polyester resin according to the present invention is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polyester (Glycol modified polyester (PETG), polyethylene naphthalate (PEN), polypropylene terephthalate (PPT) , Polytrimethylene terephthalate (PTT) resin, and the like, and preferably polyethylene terephthalate resin.

PET resins are typically polymerized from dicarboxylic acids and diols, as known in the art. Dicarboxylic acids and derivatives thereof used in the polymerization of the PET resin are mainly terephthalic acid (TPA), isophthalic acid (IPA), naphthalene 2,6-dicarboxylic acid (2,6-naphthalenedicarboxylic acid; 2, 6-NDA), dimethyl terephthalic acid (DMT), dimethylisophthalate (DMI), dimethyl naphthalene 2,6-dicarboxylic acid (dimethyl 2,6-naphthalenedicarboxylate; 2,6-NDC), but are not limited thereto. It doesn't become

The term "diol component" as used herein refers mainly to ethylene glycol, but other diols such as monoethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propane diol, 1, One or more selected from the group consisting of 4-cyclohexane-dimethanol and neopentyl glycol can be used, preferably ethylene glycol or cyclohexane dimethanol is used.

In the production method according to the present invention, as a raw material of the dicarboxylic acid, one of terephthalic acid (TPA) and dimethyl terephthalic acid (DMT) is used in an amount of 90 mol% or more relative to the total number of moles of acid, and the whole ethylene glycol is used as the diol compound. It is preferably carried out using 90 mol% or more relative to the number of moles of diol. If the mole% of the main component is not sufficient, there is a problem that the physical properties of the polyester is changed very differently from PET, so that it is difficult to apply to a purpose developed for crystalline PET resin.

According to one embodiment of the present invention, a method for preparing a polyester resin includes (A) mixing a dicarboxylic acid compound, a diol compound, a phosphorus stabilizer compound, and a crystallization rate adjusting agent followed by an esterification reaction, and (B) the esterification reaction. Adding a catalyst compound to the resultant, followed by a condensation polymerization reaction, (C) extruding the condensation polymerization reactant to prepare pellets; And (D) crystallizing the pellets to perform solid phase polymerization.

In another embodiment of the present invention, the method for producing a polyester resin of the present invention comprises the steps of (A) a dicarboxylic acid compound, a diol compound, and a phosphorus stabilizer compound followed by esterification reaction, (B) the esterification reaction Adding a catalyst compound and a crystallization rate regulator to the resultant, followed by a condensation polymerization reaction, (C) extruding the condensation polymerization reactant to prepare pellets; And (D) crystallizing the pellets to perform solid phase polymerization.

As described above, in the present invention, the conventional antimony component is preferably 50 ppm or less, more preferably 30 ppm or less, and most preferably does not contain the conventional antimony component as a catalyst. Instead of the catalyst of the antimony component, a titanium compound or a germanium compound is used. Is used as a catalyst, and the titanium compound is, for example, titanium oxide, titanium chelate compound, tetra-n-propyl titanate, tetra-isofurophyll titanate, tetra-n-butyl titanate, tetra-isobutyl titanate At least one selected from butyl-isopropyl titanate and the like may be used, and the amount of the titanium element is preferably 1 to 50 ppm based on the weight of the polymer in order to control side reactions causing discoloration.

In addition, germanium dioxide is preferably used as the germanium compound, and the amount of the germanium compound is preferably 10 to 200 ppm based on the polymer weight in view of economical efficiency and process control.

In addition, compounds such as tri-ethyl phosphate, tri-methyl phosphate, tri-phenyl phosphate, phosphoric acid, and phosphorous acid may be used as the phosphorus stabilizer. The selected phosphorus stabilizer is added to 3 to 50 ppm based on the phosphorus atom content relative to the weight of the polymer, and preferably at the beginning of the esterification reaction, more preferably before the esterification reaction, as the preferred loading point and position. It is preferable to add to a slurry of. When the content of phosphorus stabilizer is lower than 3 ppm on the basis of phosphorus atom, the color of the polymer becomes poor and the concentration of by-products due to pyrolysis reaction, such as acetaldehyde, is increased. When the content of phosphorus stabilizer is higher than 50 ppm on the basis of phosphorus atom, There is a disadvantage in that the reaction rate in melt polymerization and solid phase polymerization is lowered.

In the present invention, the crystallization rate control agent is added during the esterification reaction, and the preferred crystallization rate control agent is low density polyethylene, high density polyethylene, polypropylene, carbon black. , Clay, silicon dioxide, talc, mica, stearic acid, linear fatty acids with 10 or more carbon atoms and molecular weight of 10,000 or less, linear polymers with molecular weight of 10,000 or less It may be selected from one or more materials selected.

If the amount of the crystallization rate adjusting agent used in the present invention is too small, there is no effect. When used in excess of an appropriate amount, the crystallization may be faster, but there is a disadvantage that the color tone and transparency of the polymer are lowered. Therefore, the crystallization rate regulator preferably contains 0.5 to 500ppm based on the weight of the polymer.

Preferably, the present invention is prepared by preparing a slurry by stirring a catalyst and a crystallization rate regulator in a prepared tank using dicarboxylic acid (terephthalic acid and optionally further isophthalic acid) and diol (ethylene glycol or cyclohexane dimethanol) as main components. It is transferred to an esterification reactor, the esterification reaction proceeds to at least 90% or more, and then to the condensation polymerization reactor to carry out condensation polymerization (or also called polycondensation). Thereafter, the reaction is carried out up to 100 degrees or more in the condensation polymerization, and then cut in water to make pellets having an intrinsic viscosity (I.V) of 0.5-0.7 (dl / g).

The cut pellets are transferred to a solid state polymerization (SSP) machine to prepare a polyester resin for container molding having an inherent viscosity of 0.7-0.9 (dl / g).

In addition, the esterification reaction in the present invention can be carried out at the temperature, time and pressure conditions known in the art, preferably for 4 to 10 hours at a temperature of 230-270 ℃, pressure 0.5-3.0kg / ㎠ Can be carried out.

In addition, the system is configured such that water during the esterification reaction can be removed immediately.

The polycondensation reaction may be performed for 100 to 300 minutes under conditions of a temperature of 270-290 ° C. and a pressure of 0.1-2.0 torr. Ethylene glycol and by-products resulting from the polycondensation reaction are configured to be readily removable.

The solid phase polymerization reaction is at a temperature of 190 to 230 ° C., and the pressure can be carried out at a vacuum degree of 0.2 to 2.0 torr or under a nitrogen atmosphere.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples.

Example  One

151 Kg of terephthalic acid, 3.5 Kg of isophthalic acid and 62 Kg of ethylene glycol as raw materials, 9 g of triethylphosphate as stabilizer and 3.6 g of high density polyethylene component as crystallization rate regulators, namely 250 ° C., After the esterification reaction at 1.5 atmosphere for 6 hours, 19 g of germanium oxide (GeO2) was added thereto, followed by a polyester polycondensation reaction at 275 ° C. and a vacuum degree of 0.5 to 2 torr for 200 minutes. Was obtained by melt polymerization, pelletized and then subjected to solid phase polymerization in a nitrogen atmosphere at 210 ° C. for 12 hours to obtain PET having an intrinsic viscosity of 0.76 dl / g in solid phase polymerization.

Example  2

151 Kg of terephthalic acid, 3.5 Kg of isophthalic acid and 62 Kg of ethylene glycol as raw materials, 9 g of triethylphosphate as stabilizer and 3.6 g of low density polyethylene component as crystallization rate regulators, namely 250 ° C. After the esterification reaction was carried out at 1.5 atm for 6 hours, 14.3 g of germanium oxide (GeO ₂ ) and 9 g of antimony oxide (Sb ₂ O ₃ ) were added thereto, followed by vacuum at 275 ° C. and a vacuum of 0.5 to 2 torr. PET polymer was obtained from melt polymerization by polyester polycondensation for 200 minutes, and then pelletized, followed by solid phase polymerization in a nitrogen atmosphere at 210 ° C. for 12 hours to obtain PET having an intrinsic viscosity of 0.74 dl / g in solid phase polymerization.

Example  3

Titanium oxide-based catalyst (Sachtleben Co. Under the conditions other than using 12 g of Hombifast PC) as a catalyst, melt polymerization and solid phase polymerization were carried out in the same manner as in Example 1, whereby a PET resin having an inherent viscosity of 0.70 dl / g was obtained.

Example  4

Using 151 Kg of terephthalic acid, 3.5 Kg of isophthalic acid and 62 Kg of ethylene glycol as a raw material, 9 g of triethylphosphate as a stabilizer, and 180 g of Adeka's nucleating agent (trade name T-1465N) as a crystallization rate regulator, titanium The inherent viscosity was 0.72 as a result of performing melt polymerization and solid phase polymerization in the same manner as in Example 1 except that 9 g of an oxide-based catalyst (trade name Hombifast PC Co., Ltd.) and 9 g of antimony oxide (Sb ₂ O ₃ ) were used as catalysts. A dl / g PET resin was obtained.

Example  5

All experimental conditions were conducted in the same manner as in Example 1 except that 154.5 Kg of terephthalic acid and 62 Kg of ethylene glycol were used as the main materials, and the intrinsic viscosity of the PET resin obtained after the solid phase polymerization was 0.73 dl / g.

Example  6

All experimental conditions were conducted in the same manner as in Example 3 except that 154.5 Kg of terephthalic acid and 62 Kg of ethylene glycol were used as the main materials, and the intrinsic viscosity of the PET resin obtained after the solid phase polymerization was 0.73 dl / g.

Example  7

All experimental conditions were used except that 154.5 Kg of terephthalic acid, 60 Kg of ethylene glycol and 3.1 Kg of cyclohexane dimethanol were used as main materials, and 360 g of stearic acid was used as a crystallization rate regulator. Proceeding as described above, the intrinsic viscosity of the PET resin obtained after the solid state polymerization was 0.76 dl / g.

Example  8

Solid phase polymerization was carried out in the same manner as in Example 3 except that 154.5 Kg of terephthalic acid, 60 Kg of ethylene glycol and 3.1 Kg of cyclohexane dimethanol were used as the main materials, and 360 g of stearic acid was used as a crystallization rate regulator. The intrinsic viscosity of the obtained PET resin was 0.74 dl / g.

Comparative example  One

After esterification at 151 Kg of terephthalic acid, 3.5 Kg of isophthalic acid and 62 Kg of ethylene glycol as a raw material, and 9 g of triethylphosphate as a stabilizer, a known method, that is, 250 ° C and 1.5 atm, 19 g of germanium oxide was added as a catalyst, followed by a polyester polycondensation reaction at 275 ° C. and a vacuum degree of 0.5 to 2 torr to obtain a PET polymer by melt polymerization, and then pelletizing it for 16 hours in a 210 ° C. nitrogen atmosphere. During the solid phase polymerization, PET having an intrinsic viscosity of 0.77 dl / g was obtained in the solid phase polymerization.

Comparative example  2

After using 151 Kg of terephthalic acid, 3.5 Kg of isophthalic acid and 62 Kg of ethylene glycol as a main material and 9 g of triethylphosphate as a stabilizer, the esterification reaction was carried out at a known method, that is, 250 ° C and 1.5 atm. 12 g of titanium oxide catalyst (Sachtleben Corporation Hombifast PC) was charged as a catalyst, followed by a polyester polycondensation reaction at 275 ° C. and a vacuum degree of 0.5 to 2 torr to obtain a PET polymer by melt polymerization, and then pelletizing it. After the solid phase polymerization was carried out for 16 hours at 210 ℃ nitrogen atmosphere to obtain a PET of intrinsic viscosity 0.73 dl / g in the solid phase polymerization.

Comparative example  3

154.5 Kg of terephthalic acid and 62 Kg of ethylene glycol as the main material, 9 g of triethylphosphate as a stabilizer, and 19 g of germanium oxide as the main catalyst were subjected to melt polymerization and solid phase in the same manner as in Comparative Example 1. The polymerization was carried out to obtain a PET resin having an inherent viscosity of 0.72 dl / g.

Comparative example  4

Melt polymerization and solid state polymerization were carried out in the same manner as in Comparative Example 1 except that 154.5 Kg of terephthalic acid and 62 Kg of ethylene glycol were used as the main materials and 12 g of a titanium oxide catalyst (Hachbifast PC, manufactured by Sachtleben) was used as a catalyst. To give a PET resin having an intrinsic viscosity of 0.68 dl / g.

Comparative example  5

Comparative Examples of 154.5 Kg of terephthalic acid and 62 Kg of ethylene glycol as main materials, except that 9 g of titanium oxide catalyst (Hmbifast PC manufactured by Sachtleben) and 9 g of antimony oxide (Sb ₂ O ₃ ) were used as catalysts Melt polymerization and solid phase polymerization were carried out as in step 1 to obtain a PET resin having an inherent viscosity of 0.70 dl / g.

Comparative example  6

Melt polymerization and solid phase polymerization were carried out in the same manner as in Comparative Example 1 except that 154.5 Kg of terephthalic acid and 62 Kg of ethylene glycol were used as the main materials and 36 g of antimony oxide (Sb ₂ O ₃ ) was used as a catalyst. 0.75 dl / g of PET resin was obtained.

Comparative Example 7

154.5 Kg of terephthalic acid and 62 Kg of ethylene glycol were used as the main material, 0.36 g of carbon black was used as a crystallization nucleating agent, and 36 g of antimony oxide (Sb ₂ O ₃ ) was used as catalyst. Melt polymerization and solid state polymerization were performed to obtain a PET resin having an intrinsic viscosity of 0.74 dl / g.

Experimental Example  One Preform  Molding, physical property analysis, bottle heat resistance evaluation test

Nissei ASB 150 preform injection machine after drying the PET resin obtained in Examples 1, 2, 3, 4, 5, 6 and Comparative Examples 1, 2, 3 and 4 for 10 hours in a vacuum oven at 150 ° C. and 1 torr or less, respectively. 50 g of a transparent preform was injected at a temperature of 290 ° C., a mold cooling time of 6 seconds, and a total cycle time of 20 seconds. The preform obtained here was measured at a scan rate of 10 ° C./min using a DSC (Differential Scanning Calorimeter) to measure the elevated temperature crystallization temperature (Tch), and in the PET preform using an ICP (Inductively coupled Plasma) metal content analyzer. The antimony content contained was analyzed and the results are summarized in Table 1.

Preforms made as described above, using the LB01E bottle molding machine manufactured by Krupp, were designed to provide a primary pressure of 7 Kg / cm ² , a secondary pressure of 25 Kg / cm ² , an infrared lamp heater heating time of 26.5 seconds, and thermal equilibrium time of preform heating. Secondly, after heating the infrared lamp heater, the bottle was molded under the same bottle conditions such as preform temperature 112-120 ° C. and bottle mold temperature 150 ° C. immediately before blowing to form a 'hot-fillable bottle'. The volume of the bottle was measured by putting water in the molded hot-fill bottle. After emptying the water again, store it in an oven at 80 ℃ for 1 hour, and then measure the internal volume of the hot-fill bottle in the same way. The degree was measured. In this manner, the bottle heat resistance molded from the resins obtained in the Examples and Comparative Examples was measured for volume shrinkage and bottle volume shrinkage due to volume retention at 80 ° C. in an oven. In addition, the density of the flank of the bottle was measured using a density gradient tube and the crystallinity according to the density was calculated by the following equation.

X = (d-da) / (dc-da) × 100 <Equation 1>

Where X is the degree of crystallinity

d is the density of the sample

da is the density of 100% amorphous PET, 1.333 g / cc

dc is 1.455 g / cc as the density of 100% crystalline PET

Experimental Example  2 Hot - fillable prform  Bottleneck Crystallization Test

The bottleneck of the PET preform molded in Example 7 was crystallized using the same infrared heater energy for 180 seconds using the Frontier bottleneck crystallization molding machine, and then the crystallinity of the bottleneck was measured by measuring the density of the bottleneck. Table 1 shows the results of comparing the degree of crystallinity of the bottle necks molded with the resins obtained in the respective examples and the comparative examples in this manner.

As can be seen from the results of the above examples and comparative examples, it can be seen that the production of PET hot-fill bottles with excellent dimensional stability against heat is possible by using an antimony-free PET resin with improved crystallization rate. have. In addition, the results of applying the effect of the present technology is not limited to only Examples and Comparative Examples, and various PET molding processes and applications involving crystallization, such as heat-set film, C-PET (crystallized PET), PET foam, etc. It can be applied to the use and molding method.

Raw material catalyst Resin
inherence
Viscosity
(dl / g) Used nuclear agent Preform 內
antimony
content
(ppm) Preform
Crystallization temperature,
Tch (℃) Oven
After stay
Bottle volume
Change (cc) bottle
Shrinkage
(%) bottle
side
Crystallinity
(%) bottleneck
Crystallinity
(%) Example 1 TPA, IPA, EG Ge 0.76 HDPE ND * 137 30 2 43 35 Example 2 TPA, IPA, EG Ge, Sb 0.74 LDPE 48 135 21 1.4 42 36 Example 3 TPA, IPA, EG Ti 0.70 HDPE ND 138 42 2.8 41 33 Example 4 TPA, IPA, EG Ti, Sb 0.72 T1465N 45 134 24 1.6 44 36 Example 5 TPA, EG Ge 0.73 HDPE ND 132 35 2.3 43 36 Example 6 TPA, EG Ti 0.73 HDPE ND 133 41 2.7 45 35 Example 7 TPA, EG, CHDM Ge 0.76 stearic acid ND 142 46 3.1 43 34 Example 8 TPA, EG, CHDM Ti 0.74 stearic acid ND 141 47 3.1. 41 33 Comparative Example 1 TPA, IPA, EG Ge 0.77 - ND 153 71 4.7 36 29 Comparative Example 2 TPA, IPA, EG Ti 0.73 - ND 154 80 5.3 36 28 Comparative Example 3 TPA, EG Ge 0.72 - ND 150 65 4.3 37 30 Comparative Example 4 TPA, EG Ti 0.68 - ND 149 63 4.2 37 29 Comparative Example 5 TPA, EG Ti 0.70 - ND 151 68 4.5 36 30 Comparative Example 6 TPA, EG Sb 0.75 - 180 146 50 3.3 40 31 Comparative Example 7 TPA, EG Sb 0.74 carbon
black 182 130 39 2.6 43 35

* ND; Not detected

Claims (7)

(A) esterifying a slurry containing a dicarboxylic acid compound, a diol compound, and a catalyst compound, (B) condensation-polymerizing the resultant obtained by the esterification reaction, (C) extruding the condensation-polymerization reactant to pellet Preparing a; And (D) crystallizing the pellets to perform solid phase polymerization, wherein the catalyst compound has an antimony content of 50 ppm or less, and a crystallization rate adjusting agent for speeding up the crystallization rate is the step (A) or (B). Method for producing a polyester resin, characterized in that added to. The method of claim 1, wherein the catalytic compound is a titanium or germanium compound. The method of claim 2, wherein the titanium compound is a titanium oxide or a titanium chelate compound, and the amount of the titanium compound is 1 to 50 ppm based on the weight of the polymer. The method of claim 2, wherein the germanium compound is germanium dioxide, and the amount of the germanium compound is 10 to 200 ppm based on the weight of the polymer. The method of claim 1, wherein the crystallization rate regulator is low density polyethylene, high density polyethylene, polypropylene, carbon black, clay, silicon dioxide, talc, mica, stearic acid, linear fatty acids having 10 or more carbon atoms, molecular weight of 10,000 or less, molecular weight of 10,000 or less Method for producing a polyester resin, characterized in that at least one selected from linear polymers. The method of claim 1, wherein one of terephthalic acid (TPA) and dimethyl terephthalic acid (DMT) is used as a raw material of the dicarboxylic acid 90 mol% or more relative to the total number of moles of acid, ethylene glycol as the diol compound compared to the total number of moles of diol A method for producing a polyester resin, characterized in that used for 90 mol% or more. Prepared according to any one of claims 1 to 6, the antimony content contained in the resin is 50 ppm or less, when measured at a scan rate of 10 ℃ / min using DSC (Differential Scanning Calorimeter), Crystallization peak temperature (Tch) appears at 145 degrees C or less, The polyester resin characterized by the above-mentioned.