KR101721770B1 - Eco-friendly thermoplastic polyester resin composition having good color and reheating rroperty - Google Patents

Abstract

The present invention provides an eco-friendly polyester resin composition which is excellent in reheat performance and excellent in transparency and color. It is an object of the present invention to provide an eco-friendly polyester resin composition which is excellent in transparency and color and which uses an environmentally friendly catalyst that is not an antimony metal and does not use conventional black iron oxide and black manganese as reheating additives, Which is harmless to the human body and is environmentally friendly, can solve all the problems such as the reaction rate in solid phase polymerization, the generation of acetaldehyde, the intrinsic viscosity suitable for container molding, and the yellowing phenomenon. The present invention relates to a composition wherein the molar ratio of the diol compound to the dicarboxylic acid compound is 1.05 to 1.4, and the composition comprises 5 to 50 ppm of phosphorus compound (based on the amount of P element) Based composite oxide catalyst containing titanium (Ti), aluminum (Al) and magnesium (Mg) in an amount of 5 to 30 ppm (based on the amount of Ti element) of 1 to 10 ppm of carbon black and 20 to 20 ppm of reheat performance improving additive Wherein the polyester resin produced by using the composition has a color coordinate L value of not less than 70.0 and a color coordinate b value of not more than 0.0.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an eco-friendly thermoplastic polyester resin composition,

The present invention relates to a polyester resin composition having excellent transparency and color and excellent reheat performance, and more particularly, to a polyester resin composition suitable for manufacturing a beverage container by a reheating step, To a polyester resin excellent in the color of the container through the process.

(Sb ₂ O ₃ ) and 5.0 to 50 ppm of phosphorus compound (based on the amount of P element) as a composition having a molar ratio of the diol compound to the dicarboxylic acid compound as a raw material of the polyester resin in the past is 1.05 to 1.4, , 10 to 40 ppm of cobalt compound (based on the amount of Co element), and inorganic particles (20 to 100 ppm of black iron oxide) are added to improve the reheat performance of the preform.

Antimony catalysts are excellent in color and high in productivity due to their high activity during esterification and polycondensation reactions. However, antimony is regulated as harmful to human body due to its toxicity, Development of a new environmentally friendly catalyst is required.

In Japan, germanium catalysts have been used to produce polyester resins as an alternative to this problem. However, since the price of germanium catalysts is more than several times higher than that of antimony catalysts, they are interested in new catalysts that are cheap and harmless to the human body and environmentally friendly. Has been amplified.

As an alternative to the antimony catalyst, a catalyst of a titanium compound has been developed. However, the polyester resin produced by the titanium catalyst disclosed is unsuitable for forming a container due to the yellowish phenomenon. In the solid state polymerization reaction, Crystallization rate and reaction rate are slowed to lower the productivity. In addition, acetaldehyde is generated due to a rapid pyrolysis rate in the process of forming a container such as a container, a sheet, a film or a fiber and a low intrinsic viscosity (IV) There is a problem that it is limited to use as

As a method for solving the problem of the titanium catalyst, U.S. Patent No. 6,143,837 discloses a method of producing a polyester by using a titanium compound catalyst using titanium alkoxide, acetylacetonate, a dioxide, a titanate and a phosphite , The use of pyromellitic dianhydride has been proposed to improve the intrinsic viscosity (IV) in the solid state polymerization. However, the information on the branching agent is limited, and the largest amount of polyethylene terephthalate (PET) There is a problem that there is no solution for color improvement.

In addition, in US 5,744,571, alkyl titanate is used as a titanium catalyst compound, and many color improving agents are proposed for color improvement. However, there is a problem that an organic coloring agent is used to lower the b value of the color value, The improvement of the polymerization rate and the thermal stability has not been proposed yet.

In addition, US Patent No. 7,199,210 discloses the use of a titanium catalyst compound to add a blue agent and a red agent as color agents for improving the color value in the production of PET, A method of using pyromellitic dianhydride (PMDA) has been disclosed as an improvement method, but this method has limitations as an essential color improving agent by using an organic color toner, The use of PMDA as a multifunctional additive is insufficient in terms of diversity.

An object of the present invention is to provide an environmentally friendly polyester resin composition which is excellent in reheating performance and excellent in transparency and color. It is an object of the present invention to provide an eco- It does not use iron oxide and black manganese. It does not use cobalt compound as a coloring agent. It is harmless to the human body and environmentally friendly. It solves all problems such as reaction rate, solidification temperature, acetaldehyde generation, To provide a polyester resin composition.

In order to solve the above problems, the present invention provides a composition in which the molar ratio of the diol compound to the dicarboxylic acid compound is 1.05 to 1.4, and the composition contains 5 to 50 ppm of phosphorus compound (based on the amount of P element) Titanium composite metal oxide catalyst containing 1 to 10 ppm of carbon black and titanium (Ti), aluminum (Al) and magnesium (Mg) as additives for enhancing reheating performance of from 0.2 to 20 ppm as a cobalt-based color improving agent ), Wherein the polyester resin prepared using the composition has a color coordinate L value of not less than 70.0 and a color coordinate b value of not more than 0.0 in the polyester resin composition.

The dicarboxylic acid compound may be at least one selected from the group consisting of phthalic acid, terephthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylenedioxydicarboxylic acid, 4,4'-diphenyldicarboxylic acid, '-Diphenyltetradicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid And 2,6-naphthalene dicarboxylic acid. The present invention also provides a polyester resin composition comprising the polyester resin composition.

And the dicarboxylic acid compound comprises 90 to 100 mol% of the terephthalic acid and 0 to 10 mol% of the isophthalic acid.

The diol compound is at least one selected from the group consisting of monoethylene glycol, diethylene glycol, 1,3-propylene diol, 1,4-butylene diol, 1,4-cyclohexanedimethanol and neopentyl glycol By weight of a polyester resin composition.

The phosphorus compound may also be phosphoric acid, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, methyl acid phosphate, ethyl acid phosphate, isopropyl phosphate, Wherein the polyester resin composition is at least one selected from the group consisting of diethyl phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate, triethylene glycol acid phosphate and triethyl phosphonoacetate.

Also, the color improving agent is a blue dye or a red dye.

Also, the present invention provides a catalyst composition for polyester polymerization, wherein the titanium-based composite metal oxide catalyst is represented by the following general formula (1) or (2).

[Chemical Formula 1]

(2)

(In the formula (2), n is an integer of 2 to 20)

The titanium-based composite metal oxide catalyst is formed by dissolving in ethylene glycol.

The polyester resin composition according to the present invention is excellent in the reheating performance of the preform, is harmless to the human body, and is environmentally friendly. In addition, the polyester resin composition according to the present invention reduces the generation of acetaldehyde due to pyrolysis There is provided an effect of providing a polyester resin composition which is excellent in heat resistance.

In the application of environmentally friendly catalysts, titanium dioxide / silicon dioxide composite oxides, which are conventional commercial catalysts, do not increase the viscosity in solid phase polymerization and degrade the color when used excessively. However, titanium complex metal oxide catalysts of specific composition The present invention provides a polyester resin composition which is capable of improving the viscosity and color of the resin and which is economical and maintains a further improved color coordinate value and has a high viscosity and improved yellowing.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. It is to be understood that various equivalents and modifications may be substituted for those at the time of the present application.

The present invention relates to a composition wherein the molar ratio of the diol compound to the dicarboxylic acid compound is 1.05 to 1.4, and the composition comprises 5 to 50 ppm of phosphorus compound (based on the amount of P element) Based composite oxide catalyst containing titanium (Ti), aluminum (Al) and magnesium (Mg) in an amount of 5 to 30 ppm (based on the amount of Ti element) of 1 to 10 ppm of carbon black and 20 to 20 ppm of reheat performance improving additive A resin composition is disclosed. Such a polyester resin composition has physical properties such that the color coordinate L value is 70.0 or more and the color coordinate b value is 0.0 or less.

The present invention relates to a process for producing a polyester resin composition, which comprises the steps of: preparing a polyester resin composition containing a phosphorus compound, a color improving agent, a reheat performance improving additive, and titanium And a composite metal oxide catalyst, which is a component of the composite metal oxide. Hereinafter, the respective components of the present invention will be described in detail.

The polyester resin composition according to the present invention is composed of a dicarboxylic acid compound and a diol compound as main raw materials.

The dicarboxylic acid compound includes aromatic molecules as a main component of the diacid compound. In the present invention, the dicarboxylic acid compound is not limited to phthalic acid, terephthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenyl Diphenyl dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, -Diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like, preferably terephthalic acid and / or other dicarboxylic acid Mixtures of compounds may be used. When the mixture is used, the terephthalic acid content is preferably at least 90 mol%, more preferably at least 95 mol%, and most preferably at least 99 mol% of the total dicarboxylic acid compound. The most preferred composition of the mixture is a mixture of terephthalic acid and isophthalic acid.

The diol compound may be, but is not limited to, monoethylene glycol, diethylene glycol, 1,3-propylene diol, 1,4-butylene diol, 1,4-cyclohexanedimethanol, neopentyl glycol, May be monoethylene glycol alone, monoethylene glycol or a mixture of diethylene glycol and / or other diol compounds. When the mixture is used, the content of the monoethylene glycol or diethylene glycol is preferably at least 95 mol%, more preferably at least 98 mol%, of the total diol compound. The most preferred composition of the mixture is a mixture of monoethylene glycols or diethylene glycol and neopentyl glycol.

In the present invention, the content ratio of the diol compound to the dicarboxylic acid compound is 1.05 to 1.4 on a molar basis. At this time, in order to improve the hue and intrinsic viscosity of the polyester resin composition according to the present invention and to prevent deterioration of properties of the prepolymerized polymer, the content ratio is preferably 1.1 to 1.3.

In the present invention, the phosphorus compound is used as a heat stabilizer to prevent changes in the physical and chemical properties of the resin due to heat, and is contained in an amount of 5 to 50 ppm (based on the amount of the P element) based on the total weight of the polyester resin composition to be finally produced. Preferably 10 to 35 ppm. If the content of the phosphorus compound is less than 5 ppm, the thermal stability may be deteriorated and yellowing may occur. If it exceeds 50 ppm, the production cost may be disadvantageous, Can act disadvantageously.

Such phosphorus compounds include, but are not limited to, phosphoric acid, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, methyl acid phosphate, ethyl acid phosphate, isopropyl phosphate, Diethyl phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate, triethylene glycol acid phosphate, triethyl phosphonoacetate and the like can be used, and preferably phosphoric acid, triethyl phosphate, ethyl acid phosphate or Triethylphosphonoacetate can be used, more preferably phosphoric acid or triethylphosphonoacetate can be used.

In the present invention, a non-cobalt-based color improving agent is used as a coloring agent. The color improving agent is used for color improvement of a container or the like molded using a polyester resin. The cobalt compound used as a conventional coloring agent is limited in its use due to human toxicity such as pulmonary vascularization and classification of human carcinogenic substances . Therefore, in the present invention, when a blue dye or a red dye is used in an optimal amount as the non-cobalt color improver, the cobalt compound is replaced, but the reheat performance and color are not deteriorated, Respectively.

The color improving agent is contained in an amount of 0.2 to 20 ppm based on the total weight of the polyester resin composition to be finally produced. Preferably 3 to 15 ppm. When the color improving agent content is less than 0.2 ppm, the color improving effect may be insufficient. When the color improving agent content is more than 20 ppm, the color may be somewhat darkened.

In the present invention, as a reheating performance improving additive component that does not affect color degradation while improving reheat performance during molding of a container using a polyester resin composition, it is possible to use an existing reheat additive such as black iron oxide and black manganese, Carbon black as a phosphorus raw material in an amount of 1 to 10 ppm, preferably 3 to 10 ppm, more preferably 3 to 8 ppm. When the carbon black content is less than 3 ppm, the reheating property is low. When the carbon black content is more than 10 ppm, the reheating property is excellent, but the resin color becomes very dark.

As the catalyst used in the production of the polyester resin composition according to the present invention, a titanium-based composite metal oxide catalyst containing a specific metal component is used instead of a conventional titanium catalyst compound.

In order to solve the yellowing phenomenon of the polymer and the deterioration of the productivity due to the rise of the solid state viscosity, the phosphorus (P) compound, which is a heat stabilizer, is added in the composition for preparing a polyester resin when the existing titanium catalyst compound is used. There is a limit in the use of an excessive amount of the phosphorus (P) compound. However, since the titanium-based composite metal oxide catalyst used in the present invention is less degraded in catalytic activity due to phosphorus (P) and can be used in excess of phosphorus (P), pyrolysis is less and yellowing phenomenon is improved and high viscosity can be maintained .

In the present invention, the titanium-based composite metal oxide catalyst is a titanium-based composite metal oxide catalyst containing aluminum (Al) and magnesium (Mg), and titanium, aluminum and magnesium are reacted with oxygen And may be a compound having a structure represented by the following general formula (1) or (2). Reference is made to Patent No. 1386223 owned by the present applicant for a specific production process of these compounds.

[Chemical Formula 1]

(2)

In the general formula (2), n is an integer of 2 to 20.

These titanium-based composite metal oxide catalysts are stable to moisture and easy to store, and unlike antimony catalysts, the metal itself has a relatively low toxicity so that it is unlikely to cause human and environmental problems.

The titanium-based composite metal oxide catalyst is preferably a solution formed by dissolving in ethylene glycol.

In the present invention, the titanium based composite metal oxide catalyst is contained in an amount of 5 to 30 ppm (based on the amount of Ti element) based on the total weight of the polyester resin composition to be finally produced. Preferably 8 to 15 ppm. The content of the titanium-based composite metal oxide catalyst is a result obtained by grasping the best range of improvement in hue and intrinsic viscosity of the polyester resin composition according to the present invention. Specifically, when the titanium content is less than 5 ppm, the reaction may not be performed or may be slowed. If the titanium content exceeds 30 ppm, the color of the polymer may not be good due to high activity of the titanium catalyst.

If necessary, the polyester resin composition according to the present invention may further contain an antioxidant, an ultraviolet screening agent, an antistatic agent, a flame retardant, a surfactant, etc. in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin composition.

The production of the polyester resin composition according to the present invention may be based on a method commonly used in the art to which the present invention belongs, and the method thereof is not particularly limited. For example, it can be produced by the following method using a batch type reactor. Of course, it may be carried out continuously and is not particularly limited.

That is, the production of the polyester resin composition according to the present invention comprises the steps of (A) mixing a dicarboxylic acid compound and a diol compound determined by the above-mentioned contents to prepare a slurry, (B) (C) adding a phosphorus compound and a color improving agent after the esterification reaction to prepare a polymerized product, (D) condensing the polymerized product, and (E) discharging a reactant formed by the condensation polymerization reaction to prepare a molten chip, and (F) crystallizing the molten chip to perform solid phase polymerization.

Here, the titanium-based composite metal oxide and the reheat performance improving additive may be added between the step (A) and the step (B) and the step (C). The phosphorus compound and the color improving agent may be added in the step (A).

The titanium composite metal oxide catalyst and the reheat performance improving additive are stirred in a prepared stirrer using a dicarboxylic acid and a diol as main components and the slurry And then transferred to an esterification reactor. After the esterification reaction proceeds to at least 80% or more, preferably 90% or more, a thermal stabilizer and a color improving agent are added and transferred to a condensation polymerization reactor to perform condensation polymerization. Thereafter, the reaction is carried out at a polymerization degree of 100 or more in the condensation polymerization reaction, followed by cutting in water to prepare a molten chip having an intrinsic viscosity of 0.5 to 0.7 dl / g. The cut molten chips are transferred to a solid phase polymerization machine to produce a polyester resin for forming a container having an intrinsic viscosity of 0.7 to 1.0 dl / g.

The esterification reaction may be carried out at a temperature of 245 to 265 DEG C and a pressure of 0.5 to 3 kg / cm < 2 >. At this time, the water generated during the esterification reaction is desirably removed immediately.

The polycondensation reaction can be carried out at a temperature of 270 to 290 DEG C and a pressure of 0.1 to 2 torr. At this time, it is preferable that ethylene glycol and byproducts generated by the condensation polymerization reaction can be removed immediately.

Like the above-described method, the catalyst, the phosphorus compound, the color improver and the reheat performance improving additive may be added at any stage of the slurry preparation step, the esterification step, or the polycondensation step.

The solid phase polymerization may be carried out at a temperature of 195 to 230 ° C and a pressure of 0.2 to 2 torr or under a nitrogen atmosphere.

The polyester resin prepared according to the above method exhibits physical properties with a color coordinate L value of 70.0 or more, a color coordinate b value of 0.0 or less and an intrinsic viscosity (IV) of 0.7 to 1.0 dl / g, Suitable. Here, the L value of the chromaticity coordinates is indicative of the brightness of the resin and indicates how bright the sample is, and the chromaticity coordinate b indicates the degree of yellowishness of the resin. If the L value is high, it is bright. If the b value is high, it is yellowish. If the L value is low (especially, if it is a negative value), it is blue.

Hereinafter, the present invention will be described in more detail with reference to specific production examples, examples and comparative examples.

Production Example 1: Preparation of titanium-based composite metal oxide catalyst

30.38 mmol of titanium isopropoxide and 4.89 mmol of aluminum isopropoxide were dissolved in 100 ml of ethanol by heating. Magnesium methoxide (6-7 wt% in methanol, 5.0 mL) was slowly added thereto using a syringe. After mixing the distilled water and ethanol, the diluted solution was slowly added dropwise at room temperature (23 ° C). After the mixture was stirred for 1 hour, the resulting white precipitate was filtered using a glass filter, and the collected solid was extracted in air and the residue was washed with distilled water and again washed with ethanol. Thereafter, the product was dried at 70 to 80 DEG C for 8 hours in a vacuum to obtain a metal oxide catalyst having the above-described structure of Formula 1 including three metals of Ti, Al and Mg.

Production Example 2: Production of polyester resin

A batch type polymerization reactor was used as a melt polymerization reactor used in the production of polyester resin. The reactor contained one esterification reactor, one condensation polymerization reactor and a reactor equipped with a cutting system. The esterification reaction was carried out for 3 to 4 hours, The polycondensation reaction was carried out for 2 to 4 hours, and the temperature was raised to 285 DEG C while the pressure was reduced so that the final degree of vacuum was 1.0 torr or less to prepare a polyester resin. In addition, a batch-type reactor in which a solid-state polymerization was carried out at a reaction temperature of 225 ° C and a pressure of 0.4 torr or lower for 6 to 8 hours was used.

Example  One

A diol compound consisting of 100 mol% of monoethylene glycol was added to the dicarboxylic acid compound consisting of 97 mol% of terephthalic acid and 3 mol% of isophthalic acid as a main raw material in a molar ratio of 1.2, , 25 ppm of a compound (triethylphosphonoacetate; TEPA), 5 ppm of carbon black (Joule RBK, Color Matrix) as a reheat performance improving additive, 1 ppm of a blue dye (Solvaperm Blue 2B, Clariant) Matrix) was added to the esterification step and the polycondensation step, and 12 ppm of the titanium composite metal oxide catalyst prepared above was quantitatively added to the slurry preparation step to prepare a polyester resin.

Example  2

A polyester resin was prepared in the same manner as in Example 1, except that 30 ppm of triethylphosphonoacetate (TEPA) was added in Example 1.

Example  3

A polyester resin was prepared in the same manner as in Example 1 except that 7 ppm of carbon black was added in Example 1.

Example  4

A polyester resin was prepared in the same manner as in Example 1, except that 10 ppm of the titanium-based composite metal oxide catalyst was added in Example 1.

Example  5

A polyester resin was prepared in the same manner as in Example 1 except that 20 ppm of triethylphosphonoacetate (TEPA) was added in Example 1.

Comparative Example  One

Except that 270 ppm of an antimony catalyst compound (antimony acetate) was used instead of the titanium-based composite metal oxide catalyst in Example 1, and 32 ppm of black iron oxide and 27 ppm of black manganese were used instead of carbon black as a reheating additive. To prepare an ester resin.

Comparative Example  2

The procedure of Example 1 was repeated except that 12 ppm of titanium dioxide / silicon dioxide composite oxide (C-94, Jatelven, Germany) was used instead of the titanium-based composite metal oxide catalyst in Example 1, .

Comparative Example  3

In the same manner as in Example 1, except that 14 ppm of a titanium dioxide / silicon dioxide composite oxide (C-94, Jatelven Co., Germany) was used instead of the titanium-based composite metal oxide catalyst in Example 1, .

Comparative Example  4

A polyester resin was prepared in the same manner as in Example 1, except that 270 ppm of the antimony catalyst compound and 30 ppm of triethylphosphonoacetate (TEPA) were used instead of the titanium-based composite metal oxide catalyst in Example 1.

Comparative Example 5

A polyester resin was prepared in the same manner as in Example 1, except that 6 ppm of the titanium-based composite metal oxide catalyst and 130 ppm of the antimony catalyst compound were added.

The content (unit: ppm) of the additives excluding the dicarboxylic acid compound and the diol compound in the polyester resin prepared according to the above Examples and Comparative Examples is summarized in Table 1 below.

Experimental Example

The intrinsic viscosity, color L, a and b, and reheating characteristics of the melt chips and solid chips prepared according to the above Examples and Comparative Examples were measured by the following methods, Respectively. The evaluation of process properties was based on the combination of physical properties such as intrinsic viscosity, color and reheat characteristics. The evaluation of the process properties was expressed by very good (?), Good (?), Normal (?) And poor (X).

[How to measure]

(1) intrinsic viscosity

ASTM evaluation method D4603.

(2) Color tone L, a, b

And measured according to JIS evaluation method Z8730.

(3) Reheat characteristics

A preform was prepared by using the resin composition prepared according to Examples and Comparative Examples, and the preform was placed in a preform holder, and light was emitted at a temperature of 2,000 DEG C (maximum, 1100 nm wavelength) using a halogen lamp heater, And the temperature of the preform was measured to record the endothermic performance.

Table 2 shows that, in the case of a resin composition containing a titanium-based composite metal oxide catalyst, a color improver, a phosphorus compound, and carbon black as a reheating additive, the use of an antimony catalyst and a cobalt compound can be excluded in accordance with the present invention to produce an environment- It can be confirmed that it exhibits excellent intrinsic viscosity, color and reheating characteristics.

On the other hand, although the conventional antimony catalyst is used as the catalyst or the conventional black iron oxide and black manganese are used as the reheating additive (Comparative Examples 1, 4 and 5), they are not preferable from the viewpoint of environmental friendliness .

In addition, when titanium dioxide / silicon dioxide composite oxides, which are conventional commercial catalysts, are used as titanium catalysts (Comparative Examples 2 and 3), there is a problem in that the viscosity is not increased in solid phase polymerization and the color is lowered when used excessively.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (8)

Wherein the composition comprises 10 to 35 ppm of a phosphorus compound (based on the amount of the P element) based on the weight of the phosphorus compound, a blue dye or a non-cobalt-based color improver, 3 to 15 ppm of a red dye and 3 to 8 ppm of carbon black as a reheat performance improving additive and a titanium based composite metal oxide catalyst containing titanium (Ti), aluminum (Al) and magnesium (Mg) Wherein the polyester resin has a chromaticity coordinate L value of 70.0 or more and a chromaticity coordinate b value of 0.0 or less of polyester resin prepared by using the composition, Ester resin composition.
[Chemical Formula 1]

(2)

(In the formula (2), n is an integer of 2 to 20) The method according to claim 1,
The dicarboxylic acid compound may be at least one selected from the group consisting of phthalic acid, terephthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalic acid, phenylenedioxy dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, and 4,4'-diphenyl sulfone dicarboxylic acid. 2,6-naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid. 3. The method of claim 2,
Wherein the dicarboxylic acid compound comprises 90 to 100 mol% of the terephthalic acid and 0 to 10 mol% of the isophthalic acid. The method according to claim 1,
The diol compound is at least one selected from the group consisting of monoethylene glycol, diethylene glycol, 1,3-propylene diol, 1,4-butylene diol, 1,4-cyclohexane dimethanol and neopentyl glycol By weight. The method according to claim 1,
The phosphorus compound may be phosphoric acid, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, methyl acid phosphate, ethyl acid phosphate, isopropyl phosphate, Wherein the polyester resin composition is at least one selected from the group consisting of ethyl phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate, triethylene glycol acid phosphate and triethylphosphonoacetate. delete delete The method according to claim 1,
Wherein the titanium-based composite metal oxide catalyst is formed by dissolving in ethylene glycol.