JPH07242803A - Thermoplastic polyester resin composition - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a thermoplastic polyester resin composition having excellent impact resistance and weather resistance. [Structure] 99 to 50% by weight of a thermoplastic polyester resin (A), and 0.01 to 3.0% by weight of an unsaturated carboxylic acid based on an ethylene copolymer composed of ethylene and an α-olefin having 3 or more carbon atoms. Antioxidant (C) 0.01 to 1.0 to 100 parts by weight of a polyester mixed resin consisting of 1 to 50% by weight of a modified ethylene copolymer (B) obtained by graft reaction of an acid or a derivative thereof. A thermoplastic polyester resin composition characterized by being mixed with 0.01 to 3.0 parts by weight of a weather resistance agent (D).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyester resin composition having excellent impact resistance and weather resistance, which is used for automobile parts, electric parts, machine parts, industrial parts,
It can be used for a wide range of purposes such as miscellaneous goods.

[0002]

2. Description of the Related Art Thermoplastic polyester resins represented by polyethylene terephthalate and polybutylene terephthalate are excellent in heat resistance, chemical resistance and mechanical properties and are used in many industrial products. However, its use is limited because of its poor impact resistance and weather resistance. Various methods for improving the impact resistance have been proposed. Japanese Patent Publication 45-262
No. 25 publication, a method of blending an ionomer, Japanese Patent Publication No. 58-47419 publication, a method of blending an α-olefin-glycidyl methacrylate copolymer, and JP-A No. 63-312313 discloses an olefin unit and an epoxy group-containing unsaturated. A method of blending a graft copolymer in which a (meth) acrylic acid alkyl ester is grafted on a copolymer mainly composed of compound units is disclosed. However, satisfactory impact resistance cannot be obtained by these methods. Also, in Japanese Patent Publication No. 57-54058, a copolymer obtained by grafting an α, β-unsaturated dicarboxylic acid or its acid derivative onto a copolymer of ethylene and an α-olefin having 3 or more carbon atoms is blended. A method of doing so is disclosed. Although impact resistance is improved by this method, weather resistance is insufficient.

Painting is also used as a method for improving the weather resistance of polyester, but this method is costly and not an advantageous method. Further, a method of adding an ultraviolet absorber has been tried, but satisfactory results have not been obtained.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems of the prior art and to provide a thermoplastic polyester resin composition excellent in impact resistance and weather resistance.

[0005]

SUMMARY OF THE INVENTION The above-mentioned object is obtained by using a thermoplastic polyester resin (A) of 99 to 50% by weight, and an ethylene-based copolymer comprising ethylene and an α-olefin having 3 or more carbon atoms. Antioxidation to 100 parts by weight of a polyester mixed resin consisting of 1 to 50% by weight of a modified ethylene copolymer (B) obtained by grafting an unsaturated carboxylic acid or a derivative thereof in an amount of 01 to 3.0% by weight 0.01 to 1.0 parts by weight of the agent (C) and 0.01 of the weatherproofing agent (D)
It is achieved by a thermoplastic polyester resin composition characterized by being mixed with ˜3.0 parts by weight.

The present invention will be described in detail below. The thermoplastic polyester resin (A) used in the present invention is a polymer or copolymer obtained by a condensation reaction containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as main components.

Terephthalic acid as the dicarboxylic acid component,
Isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4, 4'-diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4
-Cyclohexanedicarboxylic acid, or ester-forming derivatives thereof, and the like, which may be used alone or in a mixture.

On the other hand, as the diol component, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexane. Diol, long-chain glycol having a molecular weight of 400 to 6,000,
Alternatively, examples thereof include ester-forming derivatives,
These may be used alone or in a mixture.

Specific examples of the thermoplastic polyester resin include polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate,
There are poly (ethylene terephthalate / ethylene isophthalate) copolymers, poly (butylene terephthalate / butylene dodecadioate) copolymers, and the like. Particularly, when polyethylene terephthalate or polybutylene terephthalate is used, an excellent effect can be obtained, which is preferable.

The intrinsic viscosity of the thermoplastic polyester resin (value measured in a solution of tetrachloroethane / phenol = 2/3 at 20 ° C.) is 0.5 or more, preferably 0.6 or more. If it is less than 0.5, the impact resistance is extremely low, which is not preferable.

The modified ethylene-based copolymer (B) used in the present invention is 0.01 to 3.0% by weight of an unsaturated carboxylic acid based on the ethylene-based copolymer composed of ethylene and an α-olefin having 3 or more carbon atoms. It is obtained by a graft reaction of an acid or its derivative.

Examples of the α-olefin include propylene, butene-1, hexene-1, decene-1,4-methylbutene-1,4-methylpentene-1 and the like. Of these, propylene and butene-1 are particularly preferable.

The unmodified ethylene-based copolymer comprising ethylene and an α-olefin having 3 or more carbon atoms has a molar ratio of ethylene / α-olefin having 3 or more carbon atoms of 40 /.
60-99 / 1, preferably 70 / 30-95 /
It is 5. Less than 40 mol% or 99 mol% ethylene
If it exceeds, the effect of improving impact resistance is small.

As the unsaturated carboxylic acid or its derivative, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butenedicarboxylic acid or alkyl ester, glycidyl ester of these acids, Examples thereof include acid anhydrides and imides. Among these, glycidyl methacrylate,
Maleic anhydride and maleic imide are particularly preferable.

The amount of the α, β-unsaturated carboxylic acid or its derivative to be graft-reacted with respect to the ethylene copolymer consisting of ethylene and an α-olefin having 3 or more carbon atoms,
It is 0.01 to 3.0% by weight. Preferably 0.1-
It is 2.5% by weight. If the amount is too small, the compatibility with the polyester becomes poor and the impact resistance is insufficiently improved. If the amount is too large, the degree of crosslinking of the graft-modified product increases and the dispersibility in the polyester decreases, resulting in poor impact resistance. Improvement is insufficient.

The crystallinity of the modified ethylene copolymer is 40.
% Or less, preferably 30% or less, more preferably 10%
It is the following. If the crystallinity exceeds 40%, the impact resistance of the polyester is insufficiently improved. The crystallinity is
Journal of Polymer Science Volume 18 (19
55) The values measured by the X-ray method according to the description on pages 17 to 26.

Melt Flow Rate of Modified Ethylene Copolymer (MFR: ASTM D1238 Measurement Temperature 190
C.) is preferably 0.01 to 50 g / 10 min. When the amount is out of this range, the effect of improving the impact resistance of polyester is small.

The amount of the modified ethylene copolymer added is 1 to 5
It is 0% by weight, preferably 10 to 50% by weight. If it is too small, the effect of improving impact resistance and weather resistance is small, and if it is too large, the physical properties and fluidity are deteriorated, which is not preferable.

The modified ethylene copolymer can be prepared by the usual method,
For example, it can be easily produced by adding α, β-unsaturated carboxylic acid to an unmodified ethylene polymer and usually melt-kneading at 150 to 300 ° C. A screw extruder, a Banbury mixer, etc. can be used for melt-kneading. Further, when the organic peroxide is used in an amount of 0.001 to 0.1% by weight based on the unmodified ethylene copolymer during the melt-kneading, the graft reaction can be caused more efficiently. Specific examples of the organic peroxide include tert-butyl cumyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, and 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane,
Examples include α, α′-di (tert-butylperoxy) diisopropylbenzene.

The antioxidant (C) used in the present invention may be a hindered phenol type compound or a phosphite type compound, and may be used either alone or in combination. Addition of an antioxidant not only prevents thermal deterioration during processing but also improves weather resistance. The antioxidant is added in an amount of 100 parts by weight of a polyester resin composed of a thermoplastic polyester resin and a modified ethylene copolymer.
It is 0.01 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight. If it is too small, the effect will be small, and if it is too large, the impact resistance will decrease, which is not preferable.

As the hindered phenol compound, pentaerythrityl-tetrakis [3- (3,5-di-t] is used.
-Butyl-4-hydroxyphenylpropionate]
(Irganox 1010 manufactured by Ciba Geigy), triethylene glycol-bis [3- (3-t-butyl-5)
-Methyl-4-hydroxyphenyl) propionate (Irganox 245 manufactured by Ciba Geigy), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by Ciba Geigy), 3, 9-bis [2- {3- (3-
t-butyl-4-hydroxy-5-methylphenyl)-
Propionyloxy} -1,1-dimethylethyl] -2,
4,8,10-Tetraoxaspiro [5.5] undecane (Sumilyzer GA-80 manufactured by Sumitomo Chemical Co., Ltd.), tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (Ciba Geigy) Manufactured by Irganox 3114) and the like.

Examples of the phosphite compound include tris (2,4-di-t-butylphenyl) phosphite (Irgafos 168 manufactured by Ciba-Geigy) and tetrakis (2,4-di-t-butylphenyl) 4,4'-. Biphenylene Diphosphonate (Sandstab P made by Sand Co.)
-EPQ), bis (2,4-di-t-butylphenyl)
Pentaerythritol-di-phosphite (manufactured by GE)
Ultra Knox 626, MARK made by Asahi Denka Co., Ltd.
PEP-24), bis (2,6-di-t-butyl-4-
Methylphenyl) pentaerythritol-di-phosphite (Adeka Stab PEP-36 manufactured by Asahi Denka Co., Ltd.) and the like can be mentioned.

The weather resistance agent (D) used in the present invention contains an ultraviolet absorber as an essential component, and it may be used alone or in combination with an ultraviolet stabilizer. The amount of the weatherproofing agent added is 0.01 to 100 parts by weight of the polyester resin composed of the thermoplastic polyester resin and the modified ethylene copolymer.
3.0 parts by weight. It is preferably 0.1 to 2.0 parts by weight. More preferably, it is 0.1 to 1.0 part by weight.
If the amount is too small, the effect of improving the weather resistance is small, and if the amount is too large, the impact resistance is lowered, which is not preferable. As the ultraviolet absorber, any of benzotriazole type, benzophenone type, and salicylate type may be used, but initial coloring is small,
Benzotriazoles, which have good coloring stability, are preferred. As the UV absorber, 2- [2'-hydroxy-3 ',
5'-bis (α, α-dimethylbenzyl) phenyl]-
Benzotriazole (Tinubin 23 manufactured by Ciba Geigy)
4), 2- [2-hydroxy-3- (3,4,5,6-
Tetra-hydrophthalimido-methyl) -5-methylphenyl] benzotriazole (Sumisorb 250 manufactured by Sumitomo Chemical Co., Ltd.), 2,2-methylenebis [4- (1,
1,3,3-Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] (Adeka Stab LA-31 manufactured by Asahi Denka Co., Ltd.), 2- (5-methyl-2-hydroxyphenyl) benzo Examples thereof include triazole (Tinuvin P manufactured by Ciba-Geigy).

The ultraviolet stabilizer may be a hindered amine compound. A hindered amine compound having a group represented by the following chemical formulas 1 and 2 is particularly preferable.

[Chemical 1]

[Chemical 2] The hindered amine compound having a molecular weight of 1,000 or more is preferable because it has low volatility and good retention. As the hindered amine compound, for example, tinuvin 622LD
(Ciba Geigy), ADEKA STAB LA-63 (Asahi Denka Kogyo) and the like.

In the present invention, known pigments, dyes, plasticizers, lubricants, release agents, antistatic agents, nucleating agents, glass fibers, carbon fibers, glass flakes, calcium carbonate, calcium sulfate, talc, silica, mica, w Known modifiers such as inorganic or organic reinforcing materials such as rustite and potassium titanate fibers, and fillers may be added within a range that does not impair the object of the present invention.

For the production of the thermoplastic polyester resin composition of the present invention, an ordinary kneading machine and kneading method can be used.

The thermoplastic polyester resin composition of the present invention can be easily molded by a usual method such as injection molding, extrusion molding, compression molding, foam molding, blow molding, and the obtained molded product is an automobile. It can be used for a wide range of purposes such as parts, electrical parts, mechanical parts, industrial parts, and miscellaneous goods.

The contents of the present invention will be specifically described below with reference to examples. The evaluation items shown in the examples were performed according to the method shown in Table 1.

[0029]

[Table 1]

Production of Modified Ethylene Copolymer Ethylene / propylene copolymer {ethylene / propylene = 75/25 (molar ratio), crystallinity 5%, MFR 0.5
g / 10 minutes} 100 parts by weight, 0.025 parts by weight of α, α'-bis-t-butylperoxy-diisopropylbenzene and 1.5 parts by weight of maleic anhydride dissolved in acetone, respectively. 0 parts by weight and 7.6 parts by weight were blended with a Henschel mixer and extruded at a cylinder temperature of 240 ° C. using a 40φ extruder to obtain modified ethylene copolymers [A], [B] and [C]. When the amount of grafted maleic anhydride was quantified by infrared absorption spectrum, it was 1.0% by weight based on the ethylene / propylene copolymer, respectively.
It was 0% by weight and 5.0% by weight.

Examples 1 to 9, Comparative Examples 1 to 10 Polyethylene terephthalate having an intrinsic viscosity of 0.74 [EFG-7 manufactured by Kanebo Co., Ltd.], an elastomer, an antioxidant,
The weatherproofing agents were blended in the compositions shown in Tables 2 and 3 and kneaded with a twin-screw kneader [TEX-30 manufactured by Japan Steel Works] to form pellets. Then, the composition was vacuum dried at 130 ° C. for 5 hours, and then a test piece was injection-molded to evaluate initial physical properties and weather resistance. The evaluation results are shown in Table 4.

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

The compositions of the examples have initial physical properties (especially tensile elongation,
Good impact strength) and weather resistance. On the other hand, the compositions of Comparative Examples have poor initial physical properties or weather resistance.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 17, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

[0034]

[Table 4]

Claims (1)

[Claims] 1. A thermoplastic polyester resin (A) 99-
50% by weight, and 0.01 to 3 with respect to an ethylene-based copolymer composed of ethylene and an α-olefin having 3 or more carbon atoms.
Modified ethylene copolymers (B) 1 to 5 obtained by grafting 0% by weight of unsaturated carboxylic acid or its derivative
0.01 to 1.0 parts by weight of an antioxidant (C) and 0.01 to 3.0 parts by weight of a weathering agent (D) are mixed with 100 parts by weight of a polyester mixed resin consisting of 0% by weight. A thermoplastic polyester resin composition characterized by the above.