KR20160062459A - Eco-friendly thermoplastic polyester resin composition having good reheating rroperty - Google Patents

Abstract

Disclosed is a polyester resin composition having transparency while having an excellent reheating property, which is not harmful to a human body but eco-friendly by using an eco-friendly catalyst rather than antimony and by not using a cobalt compound harmful to a human body as a colorant, and capable of fully resolving problems, such as a reaction speed in a solid state polymerization, occurrence of aldehyde, an intrinsic viscosity suitable for container molding, a yellowing phenomenon. The composition comprises: 12 to 50 ppm (based on an atomic weight of P) of a phosphorous compound; 0.2 to 20 ppm of a non-cobalt based color improver; 20 to 40 ppm of black ferric oxide and 20 to 40 ppm of black manganese as a reheating property improving additive; and (10 to 25)/(10 to 30) ppm (based on an atomic weight of Ti/Ge) of a Ti-Ge complex catalyst compound, wherein the compound has an intrinsic viscosity of 0.7 to 1.0 dl/g, an L-value of color coordinates of 70.0 or more, and a b-value of the color coordinate of 0.0 or less.

Description

(ECO-FRIENDLY THERMOPLASTIC POLYESTER RESIN COMPOSITION HAVING GOOD REHEATING RROPERTY)

The present invention relates to a polyester resin composition, and more particularly, to a polyester resin composition having excellent transparency and color and suitable for manufacturing a beverage container by a reheating process.

(Sb ₂ O ₃ ), a phosphorus compound, a cobalt compound, an inorganic particle and the like as a polyester resin used for producing a beverage container by a conventional reheating process as a composition containing a dicarboxylic acid compound and a diol compound A method has been proposed in which a large amount is added to improve the reheating performance of the preform.

Antimony catalysts are excellent in color and high in activity due to esterification (ES) and polycondensation (PC) reactions. However, antimony is regulated as harmful to human body due to its toxicity, The development of a new catalyst that is safe and environmentally friendly to the human body is required. In Japan, a germanium catalyst has been used as an alternative to such a problem to produce polyester resin. However, since the price of germanium catalyst is several tens times higher than that of antimony catalyst, there is a concern about a new catalyst which is low in catalyst price, harmless to human body, 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 yellowish phenomenon, and a solid state polymerization reaction Crystallization rate and reaction rate are slowed to deteriorate the productivity. In addition, acetaldehyde is generated due to rapid pyrolysis rate in the process of forming a container such as a container, a sheet, a film or a fiber and the inherent viscosity (IV) There is a problem that it is limited to use as

As a method for solving the problem with such a titanium catalyst, U.S. Patent No. 6,143,837 discloses a method of producing a polyester by using a titanium compound catalyst, wherein titanium alkoxide, acetylacetonate, dioxides, titanates, and phosphites (IV), but the information on the branching agent is limited, and polyethylene terephthalate (hereinafter referred to as PET) using a titanium catalyst compound is used. ), There is a problem that there is no solution for color improvement which is the biggest problem in manufacturing.

In addition, U.S. Patent No. 5,744,571 proposes many color improving agents for color improvement by using alkyl titanate as a titanium catalyst compound, but there is a problem that an organic coloring agent is used to lower the b value of the color value, Speed and thermal stability.

In addition, U.S. Patent No. 7,199,210 discloses a method of adding a blue agent and a red agent to color agents for improving the color value in the production of PET by using a titanium catalyst compound, A method of using pyromellitic dianhydride (PMDA) has been disclosed as a means for achieving the above object, but this method has limitations as a fundamental color improving agent by using an organic color toner, As a method, PMDA is used only as a multifunctional additive, which is insufficient in terms of diversity.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polyester resin composition having excellent reheat performance and transparency, which is harmless to the human body because it does not use a cobalt compound harmful to the human body as an environment- The present invention provides a polyester resin composition that is environmentally friendly and capable of solving all of problems such as reaction rate, acetaldehyde generation, intrinsic viscosity suitable for container molding, and yellowing during solid phase polymerization.

In order to solve the above problems, the present invention provides a composition wherein the molar ratio of the diol compound to the dicarboxylic acid compound is 1.05 to 1.4, and the composition contains 12 to 50 ppm of the phosphorus compound (based on the amount of the P element) A cobalt-based color improving agent of 0.2 to 20 ppm, and a reheat performance improving additive comprising 20 to 40 ppm of black iron oxide, 20 to 40 ppm of black manganese and 10 to 25/10 to 30 ppm of titanium-germanium composite catalyst compound (based on the amount of Ti / Ge element) Wherein the composition has an intrinsic viscosity of 0.7 to 1.0 dl / g, a color coordinate L value of 70.0 or more, and a color coordinate b value of 0.0 or less.

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, 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 triethylphosphonoacetate.

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

In addition, the titanium-germanium complex catalyst compound provides a polyester resin composition characterized in that a mixture of a titanium precursor and a germanium precursor is dissolved in ethylene glycol.

Wherein the titanium precursor is titanium dioxide (TiO ₂ ) and silicon dioxide (SiO ₂ ) composite oxide, and the germanium precursor is germanium dioxide (GeO ₂ ).

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.

Further, in applying an environmentally friendly catalyst, it is economical to apply a titanium-germanium complex catalyst compound having an optimum composition and maintain a further improved color coordinate value as compared with the case of using an existing titanium catalyst compound, thereby providing a polyester resin having 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 12 to 50 ppm of phosphorus compound (based on the amount of P element) Discloses a polyester resin composition comprising 20 to 40 ppm of black iron oxide, 20 to 40 ppm of black manganese and 10 to 25/10 to 30 ppm of titanium / germanium complex catalyst compound (based on the amount of Ti / Ge element) as a reheat performance improving additive . Such a polyester resin composition has an intrinsic viscosity of 0.7 to 1.0 dl / g, a color coordinate L value of 70.0 or more, and a color coordinate b value of 0.0 or less.

The present invention relates to a process for producing a polyester resin, which comprises the steps of: yellowing of the resin color caused by using a titanium catalyst compound in the production of a polyester resin; defects of chromatic coordinates due to pyrolysis during production of a molded article; concurrent occurrence of acetaldehyde generation and transparency; By suggesting the harmful problem to the optimum amount of the components such as the specific phosphorus compound, the color improving agent, the reheating performance improving additive and the titanium-germanium complex catalyst compound. 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. The phosphorus compound is contained in an amount of 12 to 50 ppm (based on the amount of the P element) based on the total weight of the polyester resin composition. Preferably 15 to 35 ppm. If the content of the phosphorus compound is less than 12 ppm, the thermal stability may be deteriorated and yellowing may occur. If the content of the phosphorus compound exceeds 50 ppm, the production cost may be deteriorated. 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. Conventionally, cobalt compounds used as colorants have been limited in their use due to human toxicity such as pulmonary vascularization and classification of human carcinogenic substances. In the present invention, it has been confirmed that when a blue dye or a red dye is used in an optimal amount as the non-cobalt-based color improving agent, there is no deterioration of the reheating performance while the cobalt compound is substituted, .

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 5 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, black iron oxide and black manganese are included as reheating performance improving additive components that do not affect color improvement while improving reheat performance during molding of a container using a polyester resin composition.

The black iron oxide and the black manganese are contained in an amount of 20 to 40 ppm based on the total weight of the polyester resin composition to be finally produced, preferably 30 to 40 ppm of black iron oxide and 22 to 32 ppm of black manganese.

The catalyst used in the preparation of the polyester resin composition according to the present invention uses a titanium-germanium complex catalyst compound, unlike the conventional titanium catalyst compound alone.

On the other hand, in the present invention, a titanium-germanium complex catalyst compound is used in the polyester resin composition in order to further improve the yellowing phenomenon of the polymer and the lowering of the productivity due to the increase in the viscosity of the solid phase polymerization when the existing titanium catalyst compound is used alone.

The titanium-germanium complex catalyst compound is preferably used as a solution formed by dissolving a titanium precursor and a germanium precursor mixture in ethylene glycol. At this time, the mixing ratio of the titanium precursor and the germanium precursor is 10-25 / 10-30 ppm (based on the amount of Ti / Ge element) based on the total weight of the final polyester resin composition. As the titanium precursor, a titanium dioxide (TiO ₂ ) / silicon dioxide (SiO ₂ ) composite oxide may be used, and as the germanium precursor, germanium dioxide (GeO ₂ ) is preferably used.

In the present invention, the titanium-germanium complex catalyst compound is contained in an amount of 10-25 / 10-30 ppm (based on the amount of Ti / Ge element) based on the total weight of the polyester resin composition to be finally produced. And preferably 11 to 15/14 to 20 ppm. The content of the titanium-germanium complex catalyst compound is particularly excellent in the degree of improvement in hue and intrinsic viscosity of the polyester resin composition according to the present invention, and the range capable of maximizing the reheat performance of the preform during the manufacture of the container using the titanium- Results. Specifically, when the titanium content is less than 10 ppm and the germanium content is less than 10 ppm, the reaction may not be performed or may be slowed. When the titanium content exceeds 25 ppm and the germanium content exceeds 30 ppm, a high content of titanium and germanium catalyst The color of the polymer may not be good due to the activity, and the reheating performance of the preform may be deteriorated during the manufacture of the container.

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 preparation of the polyester resin composition according to the present invention comprises the steps of (A) mixing a dicarboxylic acid compound and a diol compound quantified by the above-mentioned contents to prepare a slurry, (B) adding a titanium- (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 produce a molten chip, and (F) crystallizing the molten chip to perform solid phase polymerization.

Here, the titanium-germanium complex catalyst compound and the reheat performance enhancing additive may be added between step (A) or between steps (B) and (C). The phosphorus compound and the color improving agent may be added in the step (A).

The titanium-germanium complex catalyst compound and the reheat performance enhancing additive are stirred in a prepared stirrer using a dicarboxylic acid and a diol as main components and a slurry And the mixture is transferred to an esterification reactor. After the esterification reaction proceeds to at least 80%, preferably 90% or more, the other additives such as a heat stabilizer 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 can be carried out under stirring at a temperature of 220 to 290 ° C, preferably 245 to 265 ° C and a pressure of 0.1 to 5 kg / cm 2, preferably 0.5 to 3 kg / cm 2, for about 1 to 10 hours have. At this time, the water generated during the esterification reaction is desirably removed immediately.

The polycondensation reaction can be carried out under stirring at a temperature of 250 to 300 ° C, preferably 270 to 290 ° C, and a pressure of 0.1 to 5 torr, preferably 0.1 to 2 torr, for about 1 to 20 hours. At this time, it is preferable that ethylene glycol and byproducts generated by the condensation polymerization reaction can be removed immediately.

Like the above-mentioned method, the catalyst compound, the phosphorus compound and the color improving agent 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.

Manufacturing example

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 condensation polymerization reaction was carried out for 2 to 3 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, 16 ppm of a compound (phosphoric acid), 32 ppm of black iron oxide, 27 ppm of black iron oxide, 2.5 ppm of a blue dye (Global PRT, Color Matrix) and 6.0 ppm of a red dye (Global PRT, Color Matrix) And 10 / 14ppm of the titanium-germanium complex catalyst compound (prepared by dissolving titanium dioxide / silicon dioxide complex oxide (C-94, Zertleven, Germany) and germanium dioxide in ethylene glycol) To prepare a slurry. Thus, a polyester resin was prepared.

Example  2

A polyester resin was prepared in the same manner as in Example 1 except that 15/20 ppm of the titanium-germanium complex catalyst compound was added in Example 1.

Example  3

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

Example  4

A polyester resin was prepared in the same manner as in Example 3, except that 10/10 ppm of the titanium-germanium complex catalyst compound and 20 ppm of triethylphosphonoacetate (TEPA) were added as the phosphorus compound in Example 3.

Example  5

A polyester resin was prepared in the same manner as in Example 1, except that 35 ppm of triethylphosphonoacetate (TEPA) was added as the phosphorus compound in Example 1.

Example  6

A polyester resin was prepared in the same manner as in Example 3, except that 2.5 ppm of a blue dye and 2.5 ppm of a red dye were added.

Example  7

A polyester resin was prepared in the same manner as in Example 3, except that 5 ppm of a blue dye and 10 ppm of a red dye were added in Example 3.

Example  8

A polyester resin was prepared in the same manner as in Example 3, except that 30 ppm of black iron oxide and 22 ppm of black manganese were added in Example 3.

Example  9

A polyester resin was prepared in the same manner as in Example 3, except that 40 ppm of black iron oxide and 32 ppm of black manganese were added in Example 3.

Comparative Example  One

A polyester resin was prepared in the same manner as in Example 1, except that 28 ppm of triethyl phosphate (TEP) as the phosphorus compound and 270 ppm of the antimony catalyst compound were used instead of the titanium-germanium complex catalyst compound.

Comparative Example  2

A polyester resin was prepared in the same manner as in Example 1, except that 3/1 ppm of the titanium-germanium complex catalyst compound was added.

Comparative Example  3

A polyester resin was prepared in the same manner as in Example 1 except that 5/10 ppm of the titanium-germanium complex catalyst compound was added.

Comparative Example  4

A polyester resin was prepared in the same manner as in Example 1 except that 30/35 ppm of the titanium-germanium complex catalyst compound was used in Example 1.

Comparative Example  5

A polyester resin was prepared in the same manner as in Example 1, except that 10 ppm of triethylphosphonoacetate (TEPA) was added as the phosphorus compound in Example 1.

Comparative Example  6

A polyester resin was prepared in the same manner as in Example 3, except that 3 ppm of triethylphosphonoacetate (TEPA) was added.

Comparative Example  7

A polyester resin was prepared in the same manner as in Example 3, except that 55 ppm of triethylphosphonoacetate (TEPA) was added.

Comparative Example  8

A polyester resin was prepared in the same manner as in Example 3, except that 0.05 ppm of a blue dye and 0.05 ppm of a red dye were added.

Comparative Example  9

A polyester resin was prepared in the same manner as in Example 3, except that 10 ppm of a blue dye and 20 ppm of a red dye were added in Example 3.

Comparative Example  10

A polyester resin was prepared in the same manner as in Example 3, except that 10 ppm of black iron oxide and 10 ppm of black manganese were added in Example 3.

Comparative Example  11

A polyester resin was prepared in the same manner as in Example 3, except that 50 ppm of black iron oxide and 50 ppm of black manganese 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 the use of antimony catalysts and cobalt compounds in polyester resin compositions prepared with optimum amounts of specific catalytic compounds, color improvers, phosphorus compounds and reheat performance enhancing additives according to the present invention, But also exhibits excellent intrinsic viscosity, hue and reheat characteristics.

In contrast, when the content of the titanium-germanium complex catalyst is too low (Comparative Examples 2 and 3), the polymerization reactivity is lowered and the polymerization reaction product may not be formed. When the content is too high (Comparative Example 4) .

When the content of the phosphorus compound is too low (Comparative Examples 5 and 6), thermal stability of the polymer is degraded and pyrolysis may occur, resulting in no polymerisation. When the content of the phosphorus compound is too high (Comparative Example 7) May not be created.

When the color improver content is too low (Comparative Example 8), the color of the polymer can be lowered. When the color improver content is too high (Comparative Example 9), the color of the polymer is darkened.

When the reheat performance improving additive amount is too low (Comparative Example 10), reheating performance of the preform may be lowered. When the reheat performance improving additive is too high (Comparative Example 11), reheating performance of the preform is improved, .

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 from 12 to 50 ppm (based on the P element) of the phosphorus compound, from 0.2 to 20 ppm of the non-cobalt color improver, Wherein the polyester resin composition comprises 20 to 40 ppm of black iron oxide, 20 to 40 ppm of black manganese, and 10 to 25/10 to 30 ppm of titanium / germanium complex catalyst compound (based on the amount of Ti / Ge element)
Wherein the composition has an intrinsic viscosity of 0.7 to 1.0 dl / g, an L value of a color coordinate of 70.0 or more, and a color coordinate b value of 0.0 or less. 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. The method according to claim 1,
Wherein the color improving agent is a blue dye or a red dye. The method according to claim 1,
Wherein the titanium-germanium complex catalyst compound is formed by dissolving a titanium precursor and a germanium precursor mixture in ethylene glycol. 8. The method of claim 7,
Wherein the titanium precursor is a titanium dioxide (TiO ₂ ) and a silicon dioxide (SiO ₂ ) composite oxide, and the germanium precursor is germanium dioxide (GeO ₂ ).