JPH11293098A - Polyester resin composition and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition significantly excellent in long-acting properties of antistatic effect by melt-kneading a thermoplastic polyester resin, an epoxy group-containing ethylene copolymer and an alkylene oxide adduct of a saponified product of an ethylene-saturated carboxylic acid vinyl ester copolymer. SOLUTION: (A) A thermoplastic polyester resin and (B) an epoxy group- containing ethylene copolymer are melt-kneaded, into which an alkylene oxide adduct of a saponified product of an ethylene-saturated carboxylic acid vinyl ester copolymer is then melt-kneaded. As for a blending ratio, by weight, A:C=80-97:3-20 and (A+C):B=100:3-20. As component A, polyethylene terephthalate and polybutylene terephthalate are preferred. Component B includes a copolymer comprising 20-99.9 wt.% of an ethylene unit, 0.1-30 wt.% of an epoxy group-containing monomer unit and 0-50 wt.% of an ethylene-based unsaturated ester compound unit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyester resin composition and a method for producing the same. More specifically, a polyester resin, an epoxy group-containing ethylene copolymer,
The present invention relates to a polyester resin composition having excellent antistatic properties, which is obtained by melt-kneading a saponified ethylene-saturated carboxylic acid vinyl ester copolymer and an alkylene oxide adduct.

[0002]

2. Description of the Related Art Polyester resins are widely used as engineering plastics because of their excellent weather resistance, chemical resistance, abrasion resistance and aging resistance. However, since the resin has an electrical insulation property, in a use related to an electronic component, there is a problem of an electrostatic failure caused by electrostatic charging, and improvement in antistatic property is desired. To improve the antistatic property, which is a disadvantage of such a polyester resin, for example, a polyester resin composition obtained by kneading an alkylene oxide adduct of a saponified ethylene-saturated carboxylic acid vinyl ester copolymer has been proposed. (Japanese Patent Laid-Open No. 6-80
No. 886). However, this composition has a drawback that the durability of the antistatic effect is not sufficient.

The present inventors have conducted intensive studies in order to find a polyester resin composition in which such difficulties have been improved, and as a result, have found that a polyester resin has only an alkylene oxide adduct of a saponified ethylene-saturated carboxylic acid vinyl ester copolymer. Instead, it has been found that by melt-kneading a specific compound called an ethylene copolymer containing an epoxy group, a polyester resin composition having a remarkably excellent antistatic effect can be obtained, thereby completing the present invention.

[0004]

That is, the present invention provides the following components (A), (B), and (C): (A): thermoplastic polyester resin (B): epoxy group-containing ethylene copolymer (C) A polyester resin composition having excellent antistatic properties, characterized by being melt-kneaded with an alkylene oxide adduct of a saponified ethylene-saturated carboxylic acid vinyl ester copolymer and a method for producing the same. Is what you do.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
As the thermoplastic polyester resin as the component (A) in the present invention, for example, those obtained from a diol and a dicarboxylic acid or a reactive derivative thereof are usually used. Examples of the diol include carbon numbers such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, and neopentyl glycol. About 2 to 20 linear or branched aliphatic diol, 1,4-cyclohexanediol, diol containing an alicyclic group such as 1,4-cyclohexanediethanol, polyethylene glycol having a molecular weight of about 400 to 6000, poly-1, Long-chain glycols such as 3-propylene glycol and polytetramethylene glycol are exemplified. The diol may be a mixture of two or more.

Examples of the dicarboxylic acids include aliphatic dicarboxylic acids having about 2 to 20 carbon atoms, such as azelaic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and bis (4-carboxylate). Phenyl) methane, 1,2-bis (4-carboxyphenyl) ethane, 4,4′-dicarboxybiphenyl ether, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, dicarboxylic acids containing alicyclic groups such as cyclohexanedicarboxylic acid, etc. Is mentioned. The dicarboxylic acid may be a mixture of two or more kinds, but preferably 40% by mole or more is terephthalic acid.

[0007] Representative examples of the thermoplastic polyester resin (A) include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexanediethylene terephthalate, polyneopentyl terephthalate. And mixtures of two or more of these. Among them, polyethylene terephthalate and polybutylene terephthalate are preferably used. Further, the thermoplastic polyester resin (A) is not particularly limited,
The intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is about 0.5 to 2.0 dl / g, and the concentration of terminal carboxyl groups is 1
What is about 5 to 200 meq / Kg is usually used.

The epoxy group-containing ethylene copolymer (B) comprises an ethylene unit and an epoxy group-containing monomer unit as essential components, and an ethylenically unsaturated ester compound unit as an optional component. Examples thereof include a copolymer comprising 20 to 99.9% by weight of an ethylene unit, 0.1 to 30% by weight of an epoxy group-containing monomer unit, and 0 to 50% by weight of an ethylenically unsaturated ester compound unit. As the epoxy group-containing monomer unit,
For example, unsaturated glycidyl ester units or unsaturated glycidyl ether units may be mentioned.

The unsaturated carboxylic acid glycidyl ester includes, for example, the following formula (1) (Wherein, R ₁ has 2 carbon atoms having an ethylenically unsaturated bond)
Represents up to 18 hydrocarbon groups. )). Typical examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, and the like.

As unsaturated glycidyl ethers,
For example, the following equation (2) (Wherein, R ₂ is a group having 2 carbon atoms having an ethylenically unsaturated bond)
And X represents a methyleneoxy group or a phenyleneoxy group. )). Representative examples include, for example, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-
p-glycidyl ether and the like.

Examples of the ethylenically unsaturated ester compounds other than the above-mentioned glycidyl esters include, for example, vinyl esters of saturated carboxylic acids such as vinyl acetate, vinyl propionate and vinyl butyrate, methyl acrylate, ethyl acrylate, butyl acrylate and methacrylic acid. And alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl methacrylate and butyl methacrylate. Among them, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate and the like are preferable. The ethylenically unsaturated ester compound unit in the epoxy group-containing ethylene copolymer (B) is usually from 0 to 50% by weight, but when the ester compound unit is present, it is about 3 to 50% by weight. Is preferred.

The epoxy group-containing ethylene copolymer (B) in the present invention may be any of a block copolymer, a graft copolymer, a random copolymer and an alternating copolymer. For example, Japanese Patent No. 6232980 Publication, a copolymer obtained by grafting an epoxy group-containing monomer to a propylene-ethylene block copolymer, and an ethylene-based unsaturated ester compound grafted to an ethylene-epoxy group-containing monomer copolymer described in Patent No. 2600248 May be used. Further, the epoxy group-containing ethylene copolymer (B) preferably has a melt index of about 0.5 to 100 g / 10 minutes as measured according to JIS K6760.
More preferably, it is about 50 g / 10 min. When the melt index is less than 0.5, the melt viscosity of the obtained polyester composition tends to be excessive, and the moldability tends to decrease. If it exceeds 100, the mechanical properties of the obtained polyester composition, for example, Izod impact strength tend to be insufficient. Further, those having a number average molecular weight of about 10,000 to 100,000 in terms of polystyrene measured by gel-permeation chromatography (GPC) are preferred. When it is less than 10,000, the mechanical properties of the obtained polyester composition, for example, Izod impact strength tend to be insufficient, and
When the ratio exceeds the above range, the melt viscosity of the obtained polyester composition tends to be excessive, and the moldability tends to decrease.

The epoxy group-containing ethylene copolymer of the present invention can be prepared by a known method, for example, by subjecting a monomer to be subjected to copolymerization to
In the presence of a radical generator, about 500-4000 atm, 100-
A method of copolymerizing at about 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent, mixing an epoxy group-containing monomer with polyethylene, an ethylenically unsaturated ester compound used as necessary, a radical generator, etc. And a method of melt graft copolymerization in an extruder.

The epoxy group-containing ethylene copolymer (B) can be used in the form of a mixture with a rubber component. Examples of such a rubber component include ethylene-propylene rubber, ethylene-butene rubber and ethylene-butadiene rubber. Rubber such as ethylene unit-alpha-olefin unit having 3 or more carbon atoms, ethylene-propylene-non-conjugated diene rubber and the like ethylene unit-ethylene having 3 or more carbon atoms-α-olefin unit-non-conjugated diene unit such as rubber -Based rubber, styrene-butadiene rubber, SBS rubber, styrene-based rubber such as hydrogenated SBS rubber, polyisobutylene bomb, butyl rubber, butadiene rubber, isoprene rubber, Alfie rubber, nitrile rubber, fluorine rubber, vinyl pyridine rubber, silicone rubber, butadiene- Methyl methacrylate rubber, acrylic rubber, Retangomu, epichlorohydrin rubber, chlorobutyl rubber, bromobutyl rubber,
Mixtures of two or more of these rubbers are included. Even if these rubber components are modified with a modifier such as maleic anhydride, halide, vinyl compound, acrylic compound, etc., they are used as long as they do not excessively react with the epoxy group-containing ethylene copolymer and adversely affect them. obtain.

The mixture of the epoxy group-containing ethylene copolymer and the rubber component is, for example, dry-blended with each other,
It can be manufactured by melt-kneading with a single-screw or twin-screw extruder, Banbury mixer, roll, various kneaders, and the like. The ratio of the epoxy group-containing ethylene copolymer to the rubber component is usually about 20 to 70:80 to 30 on a weight basis,
It is preferably about 30 to 60: 70 to 40.

The alkylene oxide adduct of a saponified ethylene-saturated vinyl carboxylate copolymer as the component (C) in the present invention is produced, for example, by copolymerizing ethylene with a saturated vinyl carboxylate to produce a copolymer. Then, the copolymer can be completely or partially saponified to produce a saponified product, followed by adding an alkylene oxide to the saponified product (JP-A-3-227307).

Here, the method for producing the ethylene-saturated carboxylic acid vinyl ester copolymer is not particularly limited, and can be produced by a known method, for example, a high-pressure radical polymerization method. The vinyl ester of a saturated carboxylic acid as a raw material for copolymerization is not particularly limited, but has 2 to 4 carbon atoms.
Vinyl esters of aliphatic carboxylic acids are preferred,
For example, vinyl acetate, vinyl propionate, vinyl butyrate and the like can be mentioned, and these can be used by being appropriately mixed. Of these, vinyl acetate is most preferred.
As the raw material for copolymerization, in addition to ethylene and saturated vinyl carboxylate, a small amount of an alkyl ester of unsaturated carboxylic acid, for example, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid Butyl acid, a mixture of two or more of these, and the like can also be used.

The ethylene unit content in the ethylene-saturated carboxylic acid vinyl ester copolymer is usually about 1 to 90% by weight, preferably about 40 to 80% by weight. The number average molecular weight is usually about 1000 to 20000, preferably 1000
It is about 10,000.

The saponification reaction of the ethylene-saturated carboxylic acid vinyl ester copolymer is not particularly limited, and may be, for example, a general method of saponification using an alkali in the presence of an alcohol. Heterogeneous liquid phase system with alcohol, alcohol solution system, depending on the molecular weight of the carboxylic acid vinyl ester copolymer, the properties caused by the content of the saturated carboxylic acid vinyl ester, etc.
A saponification method such as a pellet dispersion system in alcohol can be appropriately employed. The saponification ratio varies depending on the content of the saturated carboxylic acid vinyl ester of the ethylene-saturated carboxylic acid vinyl ester copolymer, and is not particularly limited.
%, Preferably about 50 to 100%.

The method for adding the alkylene oxide to the saponified ethylene-saturated carboxylic acid vinyl ester copolymer is not particularly limited, but it is general to react the saponified product with the alkylene oxide in a gaseous state.
The alkylene oxide is not particularly limited, but usually preferably has about 2 to 4 carbon atoms, and examples thereof include ethylene oxide, propylene oxide, and butylene oxide. Among them, ethylene oxide is preferably used. Two or more alkylene oxides can be used. In this case, the alkylene oxides may be added in blocks or randomly. The amount of the alkylene oxide added is not particularly limited, but is usually about 20 to 1,000 parts by weight, preferably about 50 to 500 parts by weight, per 100 parts by weight of the saponified compound.

The polyester composition of the present invention is characterized in that the above components (A), (B) and (C) are melt-kneaded. The melt-kneading method is not particularly limited, and is carried out using, for example, a commonly used mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a roll, and various kneaders.
The order of kneading each component in the present invention is not particularly limited, but it is preferable to melt-knead the component (A) and the component (B) and then melt-knead the component (C). Physical properties such as Izod impact strength are significantly improved. The method of melt-kneading the component (C) is not particularly limited. For example, in the case of kneading using an extruder, the first-stage kneading is first performed with the components (A) and (B). A two-stage kneading method in which the kneading in the second stage is carried out with the kneaded product obtained in the first stage and the component (C), or
A one-stage kneading method in which the component (C) is charged and kneaded in the middle of an extruder for kneading the components (A) and (B) is exemplified.

The weight ratio of component (A) to component (C) is preferably from 80 to 97: 3 to 20, and (B)
The weight ratio of the components is preferably 3 to 20 with respect to the total weight of the components (A) and (C) being 100. Here, when the weight ratio of the component (C) in the above is less than 3, the antistatic performance of the obtained polyester composition tends to be insufficient, and when it exceeds 20, the mechanical properties of the obtained polyester composition become poor. Physical properties tend to decrease. When the weight ratio of the component (B) is less than 3, the resulting polyester composition tends to have insufficient antistatic effect, and when it exceeds 20, the melt viscosity of the obtained polyester composition is low. Since it tends to be excessive, the moldability tends to decrease.

The kneading temperature is not particularly limited, but is usually in the range of about 200 to 320 ° C. In the polyester composition of the present invention, if necessary, other compounding agents used for the thermoplastic resin, for example, a heat stabilizer, an antioxidant, a weathering agent, a light stabilizer, a nucleating agent, a lubricant, a release agent , Pigments,
Flame retardants, fillers and reinforcing agents such as glass fibers can be included. For the purpose of further improving the antistatic effect, an antistatic agent can be used in addition to the component (C).

[0024]

According to the present invention, a polyester composition having an excellent antistatic effect can be provided. In addition, the polyester composition of the present invention can be used in fields such as electronic component-related applications by utilizing its excellent properties.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

The evaluation was performed by the following method. (1) MFR (melt flow rate): ASTM D12
38 (250 ° C., 2160 g). Unit: g / 10 minutes (2) Izod impact strength: ASTM D256 (specimen thickness
1/8 inch, notched, measurement temperature 23 ° C). Unit J / m (3) Antistatic property: The surface resistivity of a 1 / 8-inch thick flat plate whose condition has been adjusted for 24 hours or more under the conditions of 23 ° C. and 50% RH is manufactured by Toa Denpa Kogyo KK The measurement was performed in an atmosphere of 23 ° C. and 50% RH using a super-insulation meter DSM-electrode for plate SME-8331. The durability of the antistatic effect was measured by ultrasonic cleaning the flat plate in water for 10 minutes in water, conditioning the plate at 23 ° C. and 50% RH for 24 hours or more, and then measuring the surface resistivity by the above apparatus. . In the tables describing the examples and comparative examples, the former surface specific resistivity value is described as “initial”, and the latter surface specific resistivity value is described as “after cleaning”. Unit Ω
/ □

<Each component> The following polybutylene terephthalate (hereinafter abbreviated as PBT) was used as the component (A). A-1: "Toughpet PBT" manufactured by Mitsubishi Rayon Co., Ltd.
N1000 ", intrinsic viscosity = 1.0 dl / g, terminal carboxyl group = 63 meq / Kg (B) An ethylene copolymer containing the following epoxy group-containing monomer as a component was used. The melt index (MI) value was 190 ° C. in accordance with JIS K6760.
It is a value measured under a weight of 2160 g.

B-1: "Bond First 2C" manufactured by Sumitomo Chemical Co., Ltd., MI = 3 g / 10 min, glycidyl methacrylate = 6% by weight B-2: "Bond First" manufactured by Sumitomo Chemical Co., Ltd.
E ", MI = 3 g / 10 min, glycidyl methacrylate = 1
2% by weight B-3: "Bond First 2" manufactured by Sumitomo Chemical Co., Ltd.
A ", MI = 3 g / 10 min, glycidyl methacrylate = 3
% By weight, vinyl acetate = 8% by weight B-4: "Bond First 2" manufactured by Sumitomo Chemical Co., Ltd.
B ", MI = 3 g / 10 min, glycidyl methacrylate = 1
2% by weight, vinyl acetate = 5% by weight B-5: "Bond First 7" manufactured by Sumitomo Chemical Co., Ltd.
L ", MI = 9 g / 10 min, glycidyl methacrylate = 3
% By weight, methyl acrylate = 30% by weight B-6: "Bond First 7" manufactured by Sumitomo Chemical Co., Ltd.
M ", MI = 9 g / 10 min, glycidyl methacrylate = 6
% By weight, methyl acrylate = 30% by weight B-7: "Bond First 2" manufactured by Sumitomo Chemical Co., Ltd.
0M ", MI = 20 g / 10 min, glycidyl methacrylate = 6% by weight, methyl acrylate = 30% by weight The adduct obtained in Reference Example 1 below was used as the component (C).

Reference Example 1 (Production Example of Ethylene-Vinyl Acetate Copolymer) Tertiary butyl peroxy-2-ethylhexanoate using ethylene and vinyl acetate as polymerization initiators in a high-pressure reactor, controlling the molecular weight 1400Kg pressure in the presence of propane
The copolymer was copolymerized at a temperature of 190 ° C./cm ² to obtain an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) having a vinyl acetate content of 31% by weight, a number average molecular weight of 1800 and a softening point of 30 ° C.

(Production of ethylene oxide adduct of saponified ethylene-vinyl acetate copolymer) In a 700-liter stainless steel autoclave equipped with a stirrer, an outlet line, and a feed line, 160 kg of the EVA obtained above, 320 kg of methanol, And 0.96 kg of sodium hydroxide, and the mixture was heated and stirred at 65 ° C. for 2 hours while opening the outflow line. After that, the temperature in the system was 142 ° C over 1 hour.
To remove all volatiles out of the system. The obtained saponified substance was a wax-like substance having a melting point of 83 ° C., and the saponification rate was 90%. Next, 0.27 kg of potassium hydroxide was added, the temperature in the system was raised to 180 ° C., and ethylene oxide was added to a pressure of ² kg / cm ² . After confirming the pressure drop due to the ethylene oxide addition reaction, ethylene oxide was continuously supplied intermittently so as to keep the pressure at ² kg / cm ² , and a total of 272 kg of ethylene oxide was charged over 1 hour. When the pressure drops to 0.4 kg / cm ² , the temperature is raised to 100 kg / cm ^2.
The temperature was lowered to ° C. and the product was discharged. 408 kg of ethylene
An ethylene oxide adduct of a saponified vinyl acetate copolymer was obtained. Its melting point is 51 ° C and its hydroxyl value is 110K
OH / g. The adduct obtained above is converted to C-
Used as 1.

Examples 1 to 3 and Comparative Examples 1 and 2 (A), (B) and (C) at the weight ratios shown in Table 1.
After dry blending each component, the mixture was supplied to a 30 mmφ twin screw extruder (L / D = 42) and melt-mixed at a temperature of 230 ° C. and a screw rotation speed of 200 rpm. The obtained polyester composition was supplied to a 5.5 oz injection molding machine and molded into various test pieces at a cylinder temperature of 270 ° C and a mold temperature of 70 ° C. Table 1 also shows the measurement results of the mechanical properties and antistatic performance of each polyester composition.

[0032]

TABLE 1 implementation example comparisons Example 1 2 3 1 2 A-1 92 92 92 100 98 C-1 8 8 8 - 2 B-1 10 - - - - B-4 - 10 - - - B-5 − − 10 − − MFR 62 38 45 27 45 Impact strength 34 32 28 48 49 Initial 3.0 × 10 ¹² 1.6 × 10 ¹² 1.4 × 10 ¹² 7.0 × 10 ¹⁶ 7.4 × 10 ¹² After washing 2.2 × 10 ¹² 2.9 × 10 ¹² 2.5 × 10 ¹² 2.0 × 10 ¹⁶ 4.6 × 10 ¹⁵

Examples 4 to 22 After dry blending the components (A) and (B) at the weight ratios shown in Tables 2 to 4, a 30 mmφ twin screw extruder (L / D
= 42) and melt-mixed at 230 ° C at a screw rotation speed of 200 rpm. Next, this and the component (C) were dry-blended at the weight ratios shown in Tables 2 to 4, and then supplied to a 30 mmφ twin-screw extruder (L / D = 42) at 230 ° C.
Under the temperature conditions described above, and melted and mixed at a screw rotation speed of 200 rpm. The obtained polyester composition was supplied to a 5.5 oz injection molding machine and molded into various test pieces at a cylinder temperature of 270 ° C and a mold temperature of 70 ° C. The measurement results of the mechanical properties and the antistatic performance of each polyester composition were measured in the second to fourth.
It is also shown in the table.

[0034]

TABLE 2 implementation Example 4 5 6 7 8 9 A- 1 92 92 92 92 92 92 C-1 8 8 8 8 8 8 B-1 5 10 - - - - B-2 - - 5 10 - - B -3----510 MFR 44 26 35 19 4 328 Impact strength 65 76 63 85 61 61 89 Initial 2.0 × 10 ¹² 3.0 × 10 ¹² 7.0 × 10 ¹² 2.0 × 10 ¹² 1.0 × 10 ¹² 1.0 × 10 ¹² Cleaning After 5.2 × 10 ¹³ 1.0 × 10 ¹⁴ 3.0 × 10 ¹⁴ 5.0 × 10 ¹³ 4.0 × 10 ¹² 3.0 × 10 ¹²

[0035]

Table 3 Example 10 11 12 13 13 14 15 A-1 292 292 292 292 292 C- 188 88 88 88 B-4 510---- B-5--510--B −6 − − − − − 5 10 MFR 35 15 36 21 39 23 23 Impact strength 66 93 96 370 82 140 Initial 2.0 × 10 ¹² 2.0 × 10 ¹⁴ 6.0 × 10 ¹² 2.0 × 10 ¹² 3.0 × 10 ¹² 8.0 × 10 ¹¹ Cleaning After 4.0 × 10 ¹² 2.0 × 10 ¹³ 5.0 × 10 ¹² 4.0 × 10 ¹² 8.0 × 10 ¹³ 2.0 × 10 ¹³

[0036]

[Table 4] After washing 2.0 × 10 ¹³ 3.0 × 10 ¹²

Claims (22)

[Claims] 1. The following components (A), (B) and (C): (A) component: thermoplastic polyester resin (B) component: epoxy group-containing ethylene copolymer (C) component: ethylene-saturated carboxylic acid A polyester resin composition obtained by melt-kneading an alkylene oxide adduct of a saponified acid vinyl ester copolymer. 2. The composition according to claim 1, wherein the melt kneading is a method in which the component (A) and the component (B) are melt kneaded, and then the component (C) is melt kneaded. 3. The composition according to claim 1, wherein the component (A) is polyethylene terephthalate and / or polybutylene terephthalate. 4. The copolymer (B) is a copolymer comprising 20 to 99.9% by weight of an ethylene unit, 0.1 to 30% by weight of an epoxy group-containing monomer unit, and 0 to 50% by weight of an ethylenically unsaturated ester compound unit. The composition according to claim 1. 5. The composition according to claim 4, wherein the epoxy group-containing monomer is an unsaturated glycidyl carboxylate and / or an unsaturated glycidyl ether. 6. The component (B) has a number average molecular weight of 10,000 to 100.
6. The composition according to claim 1, wherein the melt index is 0.5 to 100 g / 10 min. 7. The composition according to claim 1, wherein the component (C) is obtained by adding 20 to 1,000 parts by weight of an alkylene oxide to 100 parts by weight of a saponified ethylene-saturated carboxylic acid vinyl ester copolymer. Composition. 8. The method according to claim 1, wherein the alkylene oxide is ethylene oxide and / or propylene oxide.
8. The composition according to 7. 9. The composition according to claim 1, wherein the saponified ethylene-saturated carboxylic acid vinyl ester copolymer is obtained by saponifying an ethylene-saturated carboxylic acid vinyl ester copolymer by 30 to 100%. . 10. The composition according to claim 9, wherein the ethylene-saturated carboxylic acid vinyl ester copolymer has a number average molecular weight of 1,000 to 20,000. 11. The composition according to claim 9, wherein the ethylene-saturated carboxylic acid vinyl ester copolymer has an ethylene content of 1 to 90% by weight. 12. The following components (A), (B) and (C): (A): thermoplastic polyester resin (B): epoxy group-containing ethylene copolymer (C): ethylene-saturated carboxylic acid A method for producing a polyester resin composition, comprising melt-kneading a saponified acid vinyl ester copolymer with an alkylene oxide adduct. 13. The production method according to claim 12, wherein the melt kneading is carried out with the components (A) and (B), and then the component (C) is added thereto. 14. The method according to claim 12, wherein the component (A) is polyethylene terephthalate and / or polybutylene terephthalate. 15. A copolymer in which the component (B) comprises 20 to 99.9% by weight of ethylene units, 0.1 to 30% by weight of epoxy group-containing monomer units, and 0 to 50% by weight of ethylenically unsaturated ester compound units. The production method according to claim 12. 16. The method according to claim 15, wherein the epoxy group-containing monomer is an unsaturated carboxylic acid glycidyl ester and / or an unsaturated glycidyl ether. 17. The component (B) has a number average molecular weight of 10,000 to 1
17. The method according to claim 12, wherein the melt index is 0.5 to 100 g / 10 min. 18. Component (C) is based on 100 parts by weight of a saponified ethylene-saturated carboxylic acid vinyl ester copolymer.
The method according to any one of claims 12 to 17, wherein the alkylene oxide is added with 20 to 1000 parts by weight. 19. The method according to claim 1, wherein the alkylene oxide is ethylene oxide and / or propylene oxide.
20. The production method according to any one of 2 to 18. 20. The process according to claim 12, wherein the saponified ethylene-saturated carboxylic acid vinyl ester copolymer is obtained by saponifying an ethylene-saturated carboxylic acid vinyl ester copolymer by 30 to 100%. . 21. The method according to claim 20, wherein the ethylene-saturated carboxylic acid vinyl ester copolymer has a number average molecular weight of 1,000 to 20,000. 22. The process according to claim 20, wherein the ethylene-saturated vinyl carboxylate copolymer has an ethylene content of 1 to 90% by weight.