TW201525017A - Preparation method of polycyclohexylenedimethylene terephthalate resin - Google Patents

Abstract

The preparation method of the polycyclohexylenedimethylene terephthalate resin according to one embodiment of the present invention provides a resin having high crystallization temperature. The resin can crystallize at a high temperature and shows improved crystallization rate, and thus it can provide a resin product of high crystallinity. Therefore, the preparation method is expected to provide an article of high quality effectively.

Description

Method for preparing poly(ethylene terephthalate) resin

The present invention relates to a process for preparing a polycyclohexylene dimethylene terephthalate resin having an increased crystallization temperature.

Polyalkylene terephthalate has properties such as abrasion resistance, durability, heat resistance, and the like, and has been used as a material for articles such as fibers, films, articles, and the like. Like polyalkylene terephthalate, poly(ethylene terephthalate, hereinafter referred to as "PET"), polybutylene terephthalate (poly(butylene terephthalate), hereinafter referred to as "PBT"), poly(cyclohexylene dimethylene terephthalate) (hereinafter referred to as "PCT") and other materials have been commercialized. Among them, the most widely used commercially is PET for making fibers or bottles.

Despite the good properties of PET, due to its relatively low crystallization rate, the use of nucleating agents and crystallization catalysts is still needed in engineering plastic applications where high crystallinity (or crystallinity) is required. Furthermore, since the production speed in the process of injection molding is lowered, there is inconvenience in controlling the mold temperature.

At the same time, PBT has been widely used in engineering plastics applications because of its higher crystallization rate than PET. However, although PBT has better formability than PET, it is because of PBT. The heat deflection temperature is lower than that of PET, so PBT still has limitations in applications requiring high heat resistance.

For the above reasons, in order to compensate for the poor moldability and low heat distortion temperature of PET and PBT, a method of adding various nucleating agents to a PCT resin having a high heat distortion temperature has been proposed in the industry to improve moldability. In particular, Patent Document 1 discloses a method of using an aliphatic polyester as a nucleating agent to improve the crystallization rate of a PCT resin, wherein the aliphatic polyester has an average molecular weight of 8,000 or more, and a patent document 2 discloses a polyalkylene terephthalate composition comprising an aromatic polyester as a nucleating agent. Further, Patent Document 3 discloses a polyalkylene terephthalate composition comprising a low polymer polyester having an average molecular weight of 4,000 or less.

However, Patent Documents 1 to 3 are all related to preparing a composition by adding various nucleating agents to a PCT resin in a synthetic process to increase the crystallization rate of the PCT resin, but these patent documents do not mention how to improve the PCT resin itself. Crystallization rate. Therefore, it is extremely urgent to find a fundamental solution to improve the crystallization rate of the PCT resin itself.

Traditional technical documents:

Patent Document 1: US Patent 5,242,967

Patent Document 2: US Patent 4,223,125

Patent Document 3: US Patent 4,223,113

It is an object of the present invention to provide a process for preparing a polyethylene terephthalate resin which has an increased crystallization temperature.

The method of the present invention to achieve the above object is described below. According to an embodiment of the present invention, there is provided a process for producing a poly(ethylene terephthalate) resin comprising the steps of: reacting a reaction of a dicarboxylic acid or a derivative thereof with a diol compound; a poly-terephthalate resin having more than 70% trans-form added to the mixture; and the poly-ethylene terephthalate having more than 70% trans-form The resin has a melting point at which the reactant mixture is subjected to a polycondensation reaction.

In the above preparation method, the dicarboxylic acid may be one or more dicarboxylic acids selected from the group consisting of phthalic acid, isophthalic acid, 2,6-nadicarboxylic acid; the derivative of the dicarboxylic acid may be One or more dicarboxylic acid derivatives selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, and dimethyl 2,6-nadicarboxylate; and the diol compound may It is one or more glycol compounds selected from the group consisting of cyclohexanedimethanol, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, and neopentyl glycol.

Meanwhile, the reactant mixture in the above preparation reaction can be obtained by reacting a dicarboxylic acid or a derivative thereof with a glycol compound in the presence of a titanium compound.

The ratio of the polybutylene terephthalate resin to the dicarboxylic acid or its derivative having more than 70% of trans is added to the reactant mixture may be from 0.2 to 20 weight percent to 100 weight percent. Within the above content range, the polymerization process of the polyethylene terephthalate resin is not disturbed, and a resin having an increased crystallization temperature can be provided.

Furthermore, the polycondensation reaction of the reactant mixture is carried out at a temperature of at least 2 ° C and lower than the melting point of the trans-polyethylene terephthalate resin having more than 70%, possibly providing an increased crystal Temperature of resin.

The efficacy of the present invention is illustrated as follows: An embodiment of a method of preparing a poly(ethylene terephthalate) resin according to the present invention, which provides a resin having a high crystallization temperature. The resin can be crystallized at a high temperature and exhibits an improved crystallization rate, and it can provide a resin product having high crystallinity. Therefore, it can be expected that the preparation method can effectively provide articles having high quality.

The drawings are not provided in this specification.

Table 1 lists the viscosity, melting point and crystallization temperature of the PCT resins of the examples and comparative examples.

A specific embodiment of the method of the present invention for preparing a polyethylene terephthalate resin will be explained hereinafter.

According to an embodiment of the present invention, a method for preparing a poly(ethylene terephthalate) resin comprises the steps of: adding a reaction mixture obtained by reacting a dicarboxylic acid or a derivative thereof with a diol compound 70% trans-form poly(ethylene terephthalate) resin; and at a temperature below the melting point of the polyethyl terephthalate resin having more than 70% trans, the reaction is allowed to proceed The mixture of materials undergoes a polycondensation reaction.

In the above production method, the reactant mixture can be obtained by subjecting a dicarboxylic acid to a glycol compound to carry out an esterification reaction or a transesterification reaction of a derivative of a dicarboxylic acid with a glycol compound.

The dicarboxylic acid or a derivative thereof and the diol compound are not particularly limited in the invention as long as it can be used for the preparation of a PCT resin.

In a non-limiting example, the dicarboxylic acid can be one or more dicarboxylic acids selected from the group consisting of phthalic acid, isophthalic acid, 2,6-nadicarboxylic acid. In this case, the amount of the phthalic acid may be 80 mol% or more, 90 mol% or more, or 95 mol% or more, depending on the monocarboxylic acid. If the content of the phthalic acid is less than the above range, the prepared polyester resin may not exhibit sufficient crystallinity and moldability, and thus the resin may be difficult to apply to the intended use.

The derivative of the dicarboxylic acid may be an ester compound of a dicarboxylic acid. In a non-limiting example, the derivative of the dicarboxylic acid may be one or more dicarboxylic acid derivatives selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, and 2,6. - dimethyl dicarboxylate. In this case, the dimethyl terephthalate used may be 80 mol% or more, 90 mol% or more, or 95 mol% or more, depending on the monocarboxylic acid derivative. If the content of dimethyl terephthalate is less than the above range, the prepared polyester resin may not exhibit sufficient crystallinity and moldability, and thus the resin may be difficult to apply to the intended use.

Furthermore, in a non-limiting example, the diol compound may be one or more diol compounds selected from the group consisting of cyclohexanedimethanol, ethylene glycol, diethylene glycol, and 1,4-butylene. Glycol, 1,3-propanediol, and neopentyl glycol. In this case, the amount of cyclohexanedimethanol used may be 80 mol% or more, 90 mol% or more, or 95 mol% or more, depending on the entire diol compound. If the content of cyclohexanedimethanol is less than the above range, the prepared polyester resin may not exhibit sufficient crystallinity and moldability, and thus the resin may be difficult to apply to the intended use.

The mixing ratio of the dicarboxylic acid or a derivative thereof and the diol is not particularly limited, and the reaction can be provided by using 0.8 to 2 moles of a diol compound per 1 mole of the dicarboxylic acid or a derivative thereof. Mixture of substances.

The reaction of the dicarboxylic acid or its derivative with the diol compound can be carried out in the presence of a catalyst which is often used in the field to which the present invention pertains. For example, the catalyst may be a titanium compound, a ruthenium compound or a mixture of the above. The content of the titanium compound to be used can be controlled so that the content of the titanium component finally remaining in the PCT resin is 20 ppm or less, depending on the total weight of the PCT resin, and the content of the ruthenium compound used can be controlled so that it remains in the PCT resin. The niobium content is below 1,000 ppm, depending on the total weight of the PCT resin.

Further, in the initial stage of the reaction of the dicarboxylic acid or the derivative with the diol compound, a phosphorus-based stabilizer can be added, thereby inhibiting the possibility of high-temperature esterification or transesterification. A side reaction occurred. In this case, a phosphoric acid compound (for example, phosphoric acid, phosphorous acid, and the like) and a phosphate compound (for example, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl acetate, and the like) It can be used as a phosphorus-based stabilizer in the above reaction.

The esterification reaction or transesterification reaction can be carried out according to methods known in the art to which the present invention pertains. For example, a precursor mixture containing the dicarboxylic acid or a derivative thereof and the diol compound can be reacted at a temperature of about 230 to 290 ° C and a pressure of about 0 to 3 atm. The above temperature and pressure can be controlled by considering the boiling point of the monomer used. The reaction time is not particularly limited in the present invention, however, for example, the reaction time may be from 1 to 5 hours.

A PCT resin having a high crystallization temperature can be prepared by adding a specific resin to a reactant mixture obtained by an esterification reaction or a transesterification reaction, and then performing the reaction at a temperature lower than the melting point of the specific resin. A polycondensation reaction of a mixture of substances. In particular, the PCT resin used in the present preparation method has a trans form of more than 70% as the above specific resin.

The cyclohexanedimethanol used in the polymerization of PCT resin has a trans isomer and a cis isomer. In general, cyclohexanedimethanol includes about 70 mol% of the trans isomer and about 30 mol% of the cis isomer. When a PCT resin is polymerized using cyclohexanedimethanol consisting of a mixture of a trans isomer and a cis isomer, a PCT resin including both trans and cis is obtained, wherein the trans PCT resin is obtained. From the trans isomer of cyclohexanedimethanol, the cis PCT resin is derived from the cis isomer of cyclohexanedimethanol. For example, if the cyclohexanedimethanol used in the polymerization of the PCT resin is a mixture comprising about 70 mol% of the trans isomer and about 30 mol% of the cis isomer, then it will be obtained to include about 70% trans and about 30% cis. The PCT resin of the formula depends on the total amount of trans and cis in the resin. Thus, the ratio of trans to cis in the PCT resin prepared can be determined by the ratio of the trans isomer to the cis isomer in the cyclohexanedimethanol used.

The polymerization of the resin can be carried out using cyclohexanedimethanol containing more than 70 mol% of the trans isomer to give a PCT resin having more than 70% trans. Since the cyclohexanedimethanol generally used contains about 70 mol% of the trans isomer, the isomerization reaction of cyclohexanedimethanol containing about 70 mol% of the trans isomer can be carried out in the presence of a catalyst. To obtain cyclohexanedimethanol containing more than 70 mol% of the trans isomer.

In particular, an ester compound of cyclohexanedimethanol having a trans isomer content of more than 70 mol% and phthalic acid or phthalic acid can be polymerized to obtain a PCT resin having more than 70% of trans. The above polymerization can be carried out using methods known in the art to which the present invention pertains.

According to the present invention, a PCT resin having an improved crystallization temperature can be prepared by placing a PCT resin having more than 70% of trans in a preparation process of a PCT resin. The above results were obtained, which was presumed to be because the added PCT resin having more than 70% trans would act as a nucleating agent in the prepared PCT resin. Therefore, the above PCT resin having more than 70% trans is referred to in this specification. The designation "Nucleating Agent A" is distinguished from the PCT resin prepared by the present invention from a PCT resin having more than 70% trans, that is, a process manufacturer added to a PCT resin.

Nucleating agent A can be added to the reactant mixture (obtained after esterification or transesterification of the monomer mixture) to introduce nucleating agent A to the polymerized PCT resin to minimize polymerization of the PCT resin. effect.

The nucleating agent A content added to the reactant mixture may range from 0.2 to 20 parts by weight relative to the 100 weight percent of the dicarboxylic acid or derivative thereof added to prepare the PCT resin. If the nucleating agent A content is lower than the above range, the effect of increasing the crystallization temperature of the prepared PCT resin may be inconspicuous. Further, if the content of the nucleating agent A is higher than the above range, the nucleating agent A may crystallize in the reactor during the polycondensation reaction, and may affect the polymerization reaction of the PCT resin. Further, if the nucleating agent A content accounts for 25 parts by weight or more, the polymerization reaction of the PCT resin may not occur.

After the addition of nucleating agent A to the reactant mixture, the polycondensation reaction of the reactant mixture can be carried out at a temperature below the melting point of nucleating agent A. If the polycondensation reaction of the reactant mixture is carried out at the same temperature as the melting point of the nucleating agent A, or at a higher temperature, the nucleating agent A will melt in the polycondensation reaction, and the PCT contains Nucleating agent A does not exhibit crystallinity and therefore cannot be used as a nucleating agent, even if nucleating agent A is added to the final PCT resin. Thus, the polycondensation reaction of the reactant mixture can be carried out at a temperature below the melting point of the nucleating agent A. In particular, the polycondensation reaction of the reactant mixture can be carried out at a temperature of at least 2 ° C, or can be carried out at a temperature of about 5 to 15 ° C, which is lower than the melting point of the nucleating agent A. More specifically, since the melting point of the PCT resin (nucleating agent A) having more than 70% trans is about 295 to 305 ° C, the polycondensation reaction of the reactant mixture may be from about 280 to 300 ° C or about 285 to It is carried out at a temperature of 295 °C.

In addition to the reaction temperature, the polycondensation reaction of the reactant mixture can be carried out under conditions known in the art to which the present invention pertains. For example, the polycondensation reaction can be carried out at about 0.1 to 2.0 torr and can be carried out for about 100 to 300 minutes.

Further, in addition to the foregoing processes, the preparation method of the present invention may further comprise other processes which are often used in the related art. For example, the preparation method may further comprise the steps of: forming a polycondensation reaction product into a pellet; and/or crystallizing the polycondensation reaction product and, if necessary, solid-state polymerization. When the above process comprises a solid state polymerization process, the solid state polymerization can be carried out at a temperature of from about 230 to 270 ° C and a nitrogen pressure of from 0.2 to 2.0 torr.

As described above, the PCT resin having a high crystallization temperature can be provided by adding the nucleating agent A to the polymerization reaction of the PCT resin and controlling the temperature of the polymerization of the PCT resin to be lower than the melting point of the nucleating agent A.

In the following, preferred examples of the invention will be explained in detail. However, the examples are only intended to illustrate the invention and are not intended to limit the scope of the invention.

Example 1: Preparation of nucleating agent A-1 and PCT resin

(1) Preparation of nucleating agent A-1

55 kg of 1,4-cyclohexanedimethanol (CHDM) containing 75 mol% of the trans isomer, 48 kg of phthalic acid (TPA), 7 g of triethyl phosphate, 10 g of titanium oxide catalyst (Sachtleben The company's trade name: Hombifast PC ^® , effective Ti ratio in the catalyst: 15%) is added to the reactor. Next, the temperature of the reaction is raised to about 280 ° C, and an esterification reaction is carried out at a temperature of about 280 ° C under normal pressure for about 3 hours.

Then, the temperature of the reactor was raised to 300 ° C, and the esterification reaction was obtained. The product was subjected to a polycondensation reaction at a pressure of 0.5 to 1 torr for about 150 minutes to obtain a PCT resin. Next, a nucleating agent A-1 was obtained by using a pulverizer to pulverize the PCT resin.

(2) Preparation of PCT resin

55 kg of 1,4-cyclohexanedimethanol (CHDM) containing 68 mol% of the trans isomer, 48 kg of phthalic acid (TPA), 7 g of triethyl phosphate, 10 g of titanium oxide catalyst ( Sachtleben's trade name: Hombifast PC ^® , effective Ti ratio in the catalyst: 15%) is added to the reactor. Next, the temperature of the reactor was raised to about 280 ° C, and then an esterification reaction was carried out at a temperature of about 280 ° C under normal pressure for about 3 hours.

Then, 2.4 kg of the nucleating agent A-1 prepared as described above was added to the reactor. Next, the reactant mixture obtained by the esterification reaction was subjected to a polycondensation reaction with the nucleating agent A-1 at a temperature of about 290 ° C under a pressure of 0.5 to 1 torr for about 150 minutes to obtain a PCT resin.

Example 2: Preparation of nucleating agent A-2 and PCT resin

(1) Preparation of nucleating agent A-2

55 kg of 1,4-cyclohexanedimethanol (CHDM) containing 80 mol% of the trans isomer, 48 kg of phthalic acid (TPA), 7 g of triethyl phosphate, 10 g of titanium oxide catalyst ( Sachtleben's trade name: Hombifast PC ^® , effective Ti ratio in the catalyst: 15%) is added to the reactor. Next, the temperature of the reactor was raised to about 280 ° C, and then an esterification reaction was carried out at a temperature of about 280 ° C under normal pressure for about 3 hours.

Then, the temperature of the reactor was raised to 300 ° C, and the resulting product of the esterification reaction was subjected to a polycondensation reaction for 150 minutes under a pressure of 0.5 to 1 torr to obtain a PCT resin. Subsequently, a nucleating agent A-2 was obtained by using a pulverizer to pulverize the PCT resin.

(2) Preparation of PCT resin

A PCT resin was obtained in the same manner as described in Example 1 except that the nucleating agent A-1 of Example 1 was replaced with the nucleating agent A-2.

Example 3: Preparation of nucleating agent A-3 and PCT resin

(1) Preparation of nucleating agent A-3

55 kg of 1,4-cyclohexanedimethanol (CHDM) containing 85 mol% of the trans isomer, 48 kg of phthalic acid (TPA), 7 g of triethyl phosphate, 10 g of titanium oxide catalyst (Sachtleben The company's trade name: Hombifast PC ^® , effective Ti ratio in the catalyst: 15%) is added to the reactor. Next, the temperature of the reactor was raised to about 280 ° C, and then an esterification reaction was carried out at a temperature of about 280 ° C under normal pressure for about 3 hours.

Then, the PCT resin was obtained by subjecting the temperature of the reactor to 300 ° C and subjecting the resulting product of the esterification reaction to a polycondensation reaction for 150 minutes at a pressure of 0.5 to 1 torr. Next, a nucleating agent A-3 was obtained by using a pulverizer to pulverize the PCT resin.

(2) Preparation of PCT resin

A PCT resin was obtained in the same manner as described in Example 1 except that the nucleating agent A-1 of Example 1 was replaced with the nucleating agent A-3.

Example 4: Preparation of PCT resin

A PCT resin was obtained in the same manner as described in Example 2 except that 96 g of the nucleating agent A-2 was used.

Example 5: Preparation of PCT resin

Using the same as described in Example 2 except that 4.8 kg of nucleating agent A-2 was used Method PCT resin was prepared.

Example 6: Preparation of PCT resin

A PCT resin was obtained in the same manner as described in Example 2 except that 9.6 kg of the nucleating agent A-2 was used.

Comparative Example 1: Preparation of PCT resin

A PCT resin was obtained by the same method as described in Example 1, except that the temperature of the polycondensation reaction was adjusted to 300 °C.

Comparative Example 2: Preparation of PCT resin

A PCT resin was obtained by the same method as described in Example 2 except that the temperature of the polycondensation reaction was adjusted to 305 °C.

Comparative Example 3: Preparation of PCT resin

A PCT resin was obtained by the same method as described in Example 3 except that the temperature of the polycondensation reaction was adjusted to 310 °C.

Experimental example: Evaluation of the properties of PCT resins

The viscosity, melting point and crystallization temperature of the PCT resin obtained from Examples 1 to 6 and Comparative Examples 1 to 3 were measured by the methods disclosed below, and the results are shown in Table 1.

(1) The intrinsic viscosity of the PCT resin obtained in Examples 1 to 6 and Comparative Examples 1 to 3 was obtained by dissolving the resin in 2-concentration at a concentration of 1.2 g/dL. Ubbelohde viscosity measurement was used. The temperature of the viscometer was maintained at 35 ° C and the flow time (t) of the solvent flowing through the interior ab of the viscometer and the time (t ₀ ) of the solution flowing through the inner ab were measured. Then, the specific viscosity is calculated by substituting the substitution t value and the t ₀ value in Formula 1, and the intrinsic viscosity is calculated by substituting the specific viscosity in Formula 2.

In Formula 2, A represents a Huggins constant having a value of 0.247, and c represents a concentration of 1.2 g/dL.

(2) The melting points and crystallization temperatures of the PCT resins prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were measured by the following methods.

The PCT resin was heated from room temperature to 320 ° C using a differential scanning calorimeter (DSC) at a scan rate of 20 ° C/min to exclude the thermal history of the PCT resin. Next, the PCT resin was cooled, and then its melting point was measured at a scanning rate of 10 ° C/min while heating it from room temperature to 320 ° C. Subsequently, the crystallization temperature of the PCT resin was measured at a scanning rate of 20 ° C/min while cooling the PCT resin from 320 ° C to room temperature.

The high crystallization temperature of the resin means that the resin is more likely to have a better crystalline resin in a mold of the same temperature.

(1) Trans content: content of the trans isomer added in order to prepare the nucleating agent A in 1,4-cyclohexanedimethanol (CHDM).

(2) Nucleating agent A content (unit: weight basis): the weight ratio of the nucleating agent A added for the preparation of the PCT resin, which is 100 parts by weight of the dicarboxylic acid added for the preparation of the PCT resin. Benchmark.

Please refer to Table 1. It can be understood from Table 1 that PCT resin with high crystallization temperature can be Prepared by adding a nucleating agent A prepared from CHDM to a reactant mixture obtained by esterification of a dicarboxylic acid with a diol compound, wherein the trans isomer content of CHDM is higher than 70 mol. %, then the polycondensation reaction of the reactant mixture containing nucleating agent A below the melting point of nucleating agent A is carried out. Further, the foregoing results are inferred from the fact that the nucleating agents A-1 to A-3 having a melting point of 295 to 305 ° C are not melted at a reaction temperature of 290 ° C of the polycondensation reaction, and are added to the PCT. The crystal phase is maintained in the resin and acts as a nucleating agent for the PCT resin.

In particular, it can be seen from Examples 1 to 3 that the PCT resin obtained by polycondensation in the presence of the nucleating agent A when the content of the trans isomer in the CHDM for preparing the nucleating agent A is increased The crystallization temperature will increase.

Further, it can be seen from Examples 4 to 6 that when the nucleating agent A used is increased within a specific content range, the PCT resin obtained by the polycondensation reaction in the presence of the nucleating agent A has a good crystal. Quality / crystallinity.

On the contrary, as can be seen from Comparative Examples 1 to 3, when the polycondensation reaction of the reactant mixture with the nucleating agent A is carried out at a temperature higher than the melting point of the nucleating agent A, the PCT resin has a low crystallization temperature, which is about 231 ° C to 232 ° C, even in the same polycondensation reaction, the nucleating agent A prepared from CHDM having a trans isomer content of more than 70 mol% is added to the esterification of the dicarboxylic acid with the diol compound. The reaction mixture obtained by the reaction. It is inferred that the above results are because the crystals of the nucleating agents A-1 to A-3 (melting point: 295 to 305 ° C) are melted at a reaction temperature of 300 to 310 ° C in the polycondensation reaction, and are melted in the PCT resin. The nucleating agents A-1 to A-3 cannot be used as nucleating agents for PCT resins.

The present invention has been described in detail with reference to the preferred embodiments of the present invention. therefore, The essential scope of the invention can be determined by combining the claims and their equivalents.

The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should be within the scope of the present invention.

Claims (7)

A method for preparing a polycyclohexylene dimethylene terephthalate resin, comprising the steps of: reacting a dicarboxylic acid or a derivative thereof with a diol compound to obtain a reactant mixture, in the reactant mixture Adding a poly(ethylene terephthalate) resin having more than 70% of trans; and the poly(ethylene terephthalate) resin having more than 70% of trans has a melting point below which The polycondensation reaction of the reactant mixture is carried out at a temperature. The method for producing a poly(ethylene terephthalate) resin according to claim 1, wherein the dicarboxylic acid is one or more dicarboxylic acids selected from the group consisting of phthalic acid, isophthalic acid, and 2, 6-naphthalene dicarboxylic acid. The method for producing a poly(ethylene terephthalate) resin according to claim 1, wherein the derivative of the dicarboxylic acid is one or more dicarboxylic acid derivatives selected from the group consisting of: dimethyl terephthalate Ester, dimethyl isophthalate and dimethyl 2,6-nadicarboxylate. The method for producing a poly(ethylene terephthalate) resin according to claim 1, wherein the diol compound is one or more diol compounds selected from the group consisting of cyclohexanedimethanol and ethylene glycol. , diethylene glycol, 1,4-butanediol, 1,3-propanediol, and neopentyl glycol. The method for producing a poly(ethylene terephthalate) resin according to claim 1, wherein the reactant mixture is obtained by reacting a dicarboxylic acid or a derivative thereof with a glycol compound in the presence of a titanium compound. The method for producing a poly(ethylene terephthalate) resin according to claim 1, wherein the total amount of the poly(ethylene terephthalate) resin having more than 70% of trans added to the reactant mixture is 0.2 to 20 parts by weight per 100 parts by weight of the dicarboxylic acid or a derivative thereof. The method for producing a poly(ethylene terephthalate) resin according to claim 1, wherein the polycondensation reaction of the reactant mixture is at least 2 ° C and lower than the polyparaphenylene having more than 70% trans The temperature of the melting point of the formic acid ring ethyl ester resin is carried out.