JP2778098B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention has permanent antistatic properties, excellent mechanical properties such as impact resistance, and no delamination (thousand-turned-up). The present invention relates to an antistatic resin composition.

[Prior Art] Synthetic polymer materials are used in a wide range of fields due to their excellent properties. The use of these materials can be further expanded if antistatic properties are imparted in addition to the mechanical strength of the materials. That is, it can be applied to copying machines, various dustproof parts, etc., which are desired to prevent troubles due to static electricity.

Examples of the method of imparting an antistatic agent to a synthetic polymer material include (1) a method of kneading a resin having a water-absorbing compound such as a polyalkylene oxide or an antistatic agent, and (2) molding a surfactant or the like. A method of coating the product surface is generally used. However, sufficient antistatic performance has not been realized by any of the methods, and the antistatic property disappears when the surface of the molded product is washed or wiped off, and the kneaded components bleed out to the surface to improve the quality as a material. There are problems such as lowering the antistatic property and deterioration of the antistatic property with time.

On the other hand, as a method for imparting permanent antistatic property to a resin, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or / and an acrylic acid ester and a vinyl monomer having an alkylene oxide group may be used. There is a method of graft polymerization of a vinyl monomer or a vinylidene monomer (Japanese Patent Application Laid-Open No. 55-36237) to achieve practical antistatic properties.

JP-A 64-1748 discloses that a resin having semi-permanent antistatic properties can be obtained by mixing a styrenic polymer, an epihalohydrin copolymer and an acrylate polymer.

[Problems to be Solved by the Invention] However, the antistatic resin obtained by graft polymerizing a monomer to a hydrophilic rubbery polymer described in JP-A-55-36237 has a special hydrophilic property. Since a rubber-like polymer is used, the production method is complicated and the mechanical properties of the obtained resin are inferior. Further, Japanese Patent Application Laid-Open No. 64-1748 is not satisfactory in delamination.

Thus, the present invention provides an antistatic resin composition having excellent permanent antistatic properties and mechanical properties typified by impact resistance, and significantly improved delamination, regardless of a complicated production method. The task is to provide.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, in order to solve the above problems, an epihalohydrin copolymer, a rubber graft (co) polymer and a specific functional group are contained. The present inventors have found that it is important to incorporate a modified vinyl polymer, and have reached the present invention.

That is, the present invention provides (A) 1 to 50% by weight of an epihalohydrin copolymer, (B) 1 to 80% by weight of a rubbery polymer, 100 to 40% by weight of an aromatic vinyl monomer, and a vinyl cyanide monomer. 0 to 60% by weight and other vinyl monomers copolymerizable therewith
(C) 1 to 98% by weight of a graft (co) polymer product obtained by (co) polymerizing 99 to 20 parts by weight of a monomer or a monomer mixture consisting of 1 to 98% by weight of a modified vinyl polymer containing at least one functional group selected from a group, a hydroxyl group, a polyalkylene oxide group or a derivative thereof; and (D) 100 to 40 aromatic vinyl monomers. 0 to 60% by weight of a vinyl cyanide monomer, and 0 to 97% by weight of a (co) polymer comprising 0 to 40% by weight of another vinyl monomer copolymerizable therewith. The present invention provides a thermoplastic resin composition blended with the above.

 Hereinafter, the present invention will be described specifically.

The (A) epihalohydrin copolymer used in the present invention comprises (a) an epihalohydrin monomer, (b) an alkylene oxide, and (c) a monomer copolymerizable therewith.

The (A) epihalohydrin monomer which is a component of the (A) epihalohydrin copolymer includes epichlorohydrin, epibromohydrin, and epiiodohydrin, and epichlorohydrin is particularly preferred.

(A) Alkylene oxide, which is a component of the epihalohydrin copolymer, is ethylene oxide, 1,2-
Examples thereof include epoxypropane, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, and 1,2-epoxyheptane. Ethylene oxide is particularly preferred because of its excellent antistatic properties.

The monomer copolymerizable with the component (a) and the component (b), which is a component of the epihalohydrin copolymer (A), is not particularly limited. Examples thereof include styrene oxide and 3-chloro-1,2-epoxy. Butane, 3,3-dichloro-1,2-epoxypropane, 2-bromo-1,2-epoxybutane,
3-fluoro-1,2-epoxybutane, 3-iodo-1,2
-Epoxybutane, ethyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, n-hexyl glycidyl ether, 2-ethyl glycidyl ether, heptafluoroisopropyl glycidyl ether, phenyl glycidyl ether, 4-methylphenyl Glycidyl ether, benzyl glycidyl ether, 2-phenylethyl glycidyl ether, alliglycidyl ether,
Glycidyl acrylate, glycidyl methacrylate and the like can be mentioned.

(A) The composition ratio of the epihalohydrin copolymer is (a)
2-90% by weight of epihalohydrin monomer, preferably 5-
70% by weight, (b) 98 to 10% by weight, preferably 95 to 30% by weight of alkylene oxide, and (c) 0 to 88% by weight, preferably 0 to 65% by weight of a monomer copolymerizable therewith. .

In this (A) epihalohydrin copolymer, (a)
When the proportion of the epihalohydrin monomer is less than 2% by weight, the mechanical properties of the epihalohydrin copolymer are inferior and 90% by weight.
When the ratio is more than 1, the antistatic property of the resin composition is poor, which is not preferable.

When the proportion of (b) alkylene oxide is less than 10% by weight, the antistatic property of the resin composition is poor, and when it exceeds 90% by weight, the resin composition becomes soft and has poor mechanical properties, which is not preferable.

(A) The method for producing the epihalohydrin copolymer is not particularly limited, and it can be produced using, for example, US Patent No. 3,642,667.

As the rubbery polymer which is a component of the graft (co) polymer product (B) used in the present invention, those having a glass transition temperature of 0 ° C. or lower are suitable, and specifically, polybutadiene and polystyrene-butadiene And diene rubbers such as polyacrylonitrile-butadiene, acrylic rubbers such as polyisoprene, polychloroprene and polybutyl acrylate, and rubbery polymers such as ethylene-propylene-diene monomer terpolymer. Particularly, polybutadiene or butadiene copolymer is preferable.

(B) The aromatic vinyl monomer which is a component of the graft (co) polymer product includes styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, and o-ethylstyrene.
Examples thereof include p-dichlorostyrene, and styrene is particularly preferable.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferable.

Other vinyl monomers include maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, acrylamide monomers such as acrylamide and N-methylacrylamide, and maleic anhydride. Acids, unsaturated acid anhydrides such as itaconic anhydride, unsaturated acids such as acrylic acid and methacrylic acid, glycidyl acrylate, glycidyl methacrylate,
Examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and methoxypolyethylene glycol methacrylate. Of these, N-phenylmaleimide, acrylamide, glycidyl methacrylate, 2-hydroxyethyl methacrylate, and maleic anhydride are particularly preferable.

The proportion of the aromatic vinyl monomer used in the graft (co) polymer product (B) is 100 to 40% by weight, preferably 100 to 50% by weight, based on all vinyl monomers used. If the proportion of the aromatic vinyl monomer is less than 40% by weight,
It is not preferable because the impact resistance of the resin composition is poor.

In the present invention, the desired physical properties can be obtained by using an aromatic vinyl monomer.
When the vinyl cyanide monomer is used in an amount of 50% by weight or less, impact resistance can be improved, and when a maleimide monomer is used, heat resistance can be improved. When acrylamide, glycidyl methacrylate, 2-hydroxyethyl methacrylate, maleic anhydride, methacrylic acid, methoxypolyethylene glycol methacrylate, or the like is used, the compatibility with the polyamide elastomer can be further improved.

By using a vinyl cyanide-based monomer or a maleimide-based monomer at 60% by weight or less, preferably 50% by weight or less based on all monomers, impact resistance and heat resistance can be further improved.

(B) The ratio of the rubbery polymer to the monomer or monomer mixture in the graft (co) polymer product is such that the rubbery polymer is 1 to 80 parts by weight in 100 parts by weight of the total graft (co) polymer product.
Parts by weight, preferably 5 to 70 parts by weight, 99 to 20 parts by weight of monomer or monomer mixture, preferably 95 to 30 parts by weight.

When the proportion of the rubbery polymer in the graft (co) polymer product (B) is less than 1 part by weight, the resulting resin composition has poor impact resistance. Dispersion is poor and the appearance of the molded article is impaired, which is not preferable.

(B) A method for producing a graft (co) polymer is a known polymerization method, for example, emulsification by continuously supplying a monomer or a monomer mixture, a polymerization initiator and an emulsifier in the presence of a rubbery polymer latex. A polymerization method or the like can be used.

The present invention relates to (C) a modified vinyl polymer containing at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyalkylene oxide group or a derivative thereof (hereinafter, referred to as a “modified vinyl polymer”). By using a modified vinyl polymer), the compatibility between the component (A) and the component (B) can be further improved.

The modified vinyl polymer (C) used in the present invention has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers, and has a carboxyl group or an epoxy group in the molecule. And a polymer having at least one functional group selected from the group consisting of amino groups, hydroxyl groups, polyalkylene oxide groups and derivatives thereof. The content of these functional groups may be very small or may be large as long as the performance as a resin is not impaired. In general, the effect of the present invention can be effectively exhibited if one molecule or more of the above-mentioned functional group is contained on average in one molecule of the modified vinyl polymer.

(C) The method for introducing a carboxyl group into the modified vinyl polymer is not particularly limited, but a carboxyl group or a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid can be used. Γ, γ′-azobis (γ-cyanovaleic acid), α, α′-azobis (α-cyanoethyl)-
a polymerization initiator having a carboxyl group such as p-benzoic acid and succinic peroxide and / or thioglycolic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, α-mercapto-isobutyric acid, and 2,3 or 4 A method of (co) polymerizing a predetermined vinyl monomer using a polymerization degree regulator having a carboxyl group such as mercaptobenzoic acid, and a (meth) acrylate ester such as methyl methacrylate or butyl acrylate For example, a method of saponifying the (co) polymer with an alkali can be used.

Although there is no particular limitation on the method of introducing an epoxy group, for example, (In the formula, R ¹ is a hydrogen atom, a lower alkyl group or a lower alkyl group substituted with a glycidyl ester group.)
Specifically, a method of copolymerizing glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and the like with a predetermined vinyl monomer can be used.

The method for introducing an amino group or a substituted amino group is not particularly limited. (Wherein, R ² represents hydrogen, a methyl group, or an ethyl group; R ³ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, and 6 to 12 carbon atoms) Is a phenyl group or a cycloalkyl group or a derivative thereof.) A vinyl monomer having at least one functional group of an amino group or a substituted amino group represented by Using a chain transfer agent and / or an initiator having at least one functional group selected from the group consisting of the amino group, substituted amino group and mineral salts thereof represented by (II) above. (Co) polymerization of a vinyl monomer of the above.

Here, at least one of an amino group or a substituted amino group
Specific examples of vinyl monomers having various functional groups include:
Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate; Vinylamine derivatives such as vinyl diethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methallylamine and N-methylallylamine, acrylamide, methacrylamide and N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide (Meth) acrylamide derivatives and aminostyrenes such as p-aminostyrene.

Specific examples of the polymerization degree regulator having the above functional group include mercaptomethylamine, β-mercaptoethylamine, γ-mercaptopropylamine, N- (β-
Mercaptoethyl) -N-methylamine, N- (β-mercaptoethyl) -N-phenylamine, N- (β-mercaptoethyl) -N-cyclohexylamine, bis-
(4-aminophenyl) disulfide, bis- (2-
Aminophenyl) disulfide, bis- (3-aminophenyl) disulfide, p-mercaptoaniline,
Examples thereof include o-mercaptoaniline, m-mercaptoaniline, and hydrochlorides thereof. Specific examples of the polymerization initiator include α, α′-azobis (γ-amino-α, γ-
Dimethylvaleronitrile), α, α'-azobis (γ-
Methylamino-α, γ-dimethylvaleronitrile),
α, α′-azobis (γ-ethylamino-α, γ-dimethylvaleronitrile), α, α′-azobis (γ-dimethylamino-α, γ-dimethylvaleronitrile) and p-aminobenzoyl peroxide No.

There is no particular limitation on the method for introducing a hydroxyl group, but, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, or the like may be used to obtain a predetermined vinyl polymer A method of copolymerizing with the coalescence can be used.

The method of introducing the polyalkylene oxide group or a derivative thereof is not particularly limited. For example, (1) a vinyl polymer containing a polyalkylene oxide group represented by the following formulas (III) and (IV) is desired. (2) Poly (methyl methacrylate) or (meth) acrylic acid ester such as methyl methacrylate or butyl acrylate is copolymerized with a desired vinyl monomer. A method of subjecting an acrylic ester (co) polymer and a polyalkylene oxide glycol of an alkyl ether at one end to an ester reaction, (3) converting acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, etc. to a desired vinyl monomer Carboxyl group-containing vinyl polymer obtained by copolymerization with And a method for esterification of polyalkylene oxide glycol in Le and the like.

(Wherein, R ⁴ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents an alkynylene group having 2 to 6 carbon atoms, R ⁶ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and n represents 2 Specific examples include polyethylene glycol acrylate, polyethylene glycol methacrylate, poly (propylene oxide) glycol acrylate, poly (propylene oxide) methacrylate, poly (tetramethylene oxide) glycol acrylate, and poly (tetramethylene oxide). ) Glycol methacrylate, poly (hexamethylene oxide) glycol methacrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypoly (propylene oxide) glycol acrylate, methoxypoly (Propylene oxide) glycol methacrylate, methoxy poly (tetramethylene oxide) glycol methacrylate, ethoxy polyethylene glycol acrylate, ethoxy polyethylene glycol methacrylate, ethoxy poly (propylene oxide) glycol acrylate, polyethylene glycol acrylamide, polyethylene glycol methacrylamide, poly (propylene oxide) glycol acrylamide , Poly (propylene oxide) glycol methacrylamide, poly (tetramethylene oxide) glycol acrylamide, poly (tetramethylene oxide) glycol methacrylamide, methoxy polyethylene glycol acrylamide, methoxy polyethylene glycol methacrylamide, methoxy poly ( (Propylene oxide) glycol acrylamide, methoxy poly (propylene oxide) glycol methacrylamide, methoxy (tetramethylene oxide) glycol methacrylamide, and the like. Particularly, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylamide, methoxy polyethylene glycol methacrylamide Is preferred because of its excellent polymerizability and affinity with the polyetheresteramide (A).

In addition, the ester reaction of a (meth) acrylic ester (co) polymer or a vinyl polymer having a carboxyl group or a carboxyl anhydride group with a poly (alkylene oxide) glycol having an alkyl ether at one end is carried out at a high temperature. It can be performed under normal pressure or under vacuum.

The poly (alkylene oxide) glycol having an alkyl ether at one end used herein is, for example, methoxypolyethylene glycol, methoxypoly (1,2-propylene oxide) glycol, methoxypoly (1,3-propylene oxide) glycol, methoxypoly (tetramethylene oxide) ) Glycol, methoxy poly (hexamethylene oxide) glycol, methoxy (a block or random copolymer of ethylene oxide and propylene oxide) and methoxy (a block or random copolymer of ethylene oxide and tetrahydrofuran). Ether polyethylene glycol is preferred.

The number average molecular weight of the poly (alkylene oxide) glycol having an alkyl ether at one end is in the range of 75 to 20,000.

(C) The vinyl monomer used for the polymerization of the modified vinyl polymer is not particularly limited, and examples thereof include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyl toluene, acrylonitrile, and methacryloyl. Vinyl cyanide monomers such as nitrile, (meth) acrylate monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, butyl acrylate,
From maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, olefin monomers such as ethylene and propylene, and vinyl monomers such as vinyl chloride, vinyl acetate and butadiene. One or more kinds can be selected and used according to the purpose. In particular, aromatic vinyl monomers such as styrene, (meth) acrylate monomers such as methyl methacrylate, vinyl cyanide monomers such as acrylonitrile, and maleimide monomers such as N-phenylmaleimide It is preferably used because the mechanical properties of the resin composition that can be used as a body are excellent.

If necessary, rubber-like polymers such as polybutadiene, acrylonitrile / butadiene copolymer (NBR), styrene / butadiene copolymer (SBR), polybutyl acrylate, and ethylene / propylene / diene rubber (EPDM) may be used. Can be used in combination with the vinyl monomer.

Further, as the method for introducing a functional group, any of the above-described various methods can be arbitrarily used.

(C) The method for producing the modified vinyl polymer is not particularly limited, and ordinary methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and bulk-suspension polymerization can be used. it can.

As the aromatic vinyl monomer which is a component of the (D) (co) polymer used in the present invention, styrene, α-
Methyl styrene, p-methyl styrene, pt-butyl styrene, o-ethyl styrene, op-chloro styrene and the like are exemplified, and styrene and α-methyl styrene are particularly preferred.

Examples of the (meth) acrylate-based monomer include methyl, ethyl, propyl, n-butyl, and n-hexyl of acrylic acid and methacrylic acid, with methyl methacrylate being particularly preferred.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferable.

Other vinyl monomers copolymerizable therewith include maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide, ethylene and propylene. Olefin monomers, and vinyl chloride,
Examples include vinyl acetate and butadiene, and particularly, N-
Phenylmaleimide is preferred.

(D) The proportion of the aromatic vinyl monomer and / or the (meth) acrylate monomer as a component of the (co) polymer is 100 to 40% by weight, preferably 100% by weight, based on all monomers. 1
00 to 50% by weight. If the proportion of the aromatic vinyl monomer and / or the (meth) acrylate monomer is less than 40% by weight, the impact resistance of the resin composition is poor, which is not preferable.

In the present invention, satisfactory physical properties can be obtained by using the (co) polymer, but furthermore, a vinyl cyanide-based monomer or a maleimide-based monomer is not more than 60% by weight based on all monomers,
When the content is preferably 50% by weight or less, impact resistance and heat resistance can be further improved.

If the proportion of the vinyl cyanide-based monomer exceeds 60% by weight, the thermal stability of the copolymer deteriorates and the resin composition is significantly colored, which is not preferable.

(D) The method for producing the (co) polymer is not particularly limited, either.
Known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and bulk-suspension polymerization can be used.

The polymer thus obtained comprises (A) 1 to 50% by weight, preferably 5 to 30% by weight of an epihalohydrin copolymer,
(B) 1 to 98% by weight, preferably 5 to 90% by weight, of the graft (co) polymer product; (C) 0.1 to 98% by weight of the modified vinyl polymer
% By weight, preferably 1 to 90% by weight, and 0 to 97% by weight of the (D) (co) polymer, preferably 0 to 89% by weight, and more preferably 5 to 80% by weight.

If the (A) epihalohydrin copolymer is less than 1% by weight, the antistatic properties of the resin composition will be insufficient, and if it exceeds 50% by weight, the resin composition will be soft and have poor mechanical properties, which is not preferable.

If the (B) graft (co) polymer product is less than 1% by weight, the resin composition is brittle and cannot be used. If it exceeds 98% by weight, the antistatic properties of the resin composition are insufficient, which is not preferable.

When the content of the modified vinyl polymer (C) is less than 0.1% by weight, the resin composition cannot be used due to delamination, and cannot be used.
When the ratio is more than 3, the antistatic property of the resin composition is insufficient, which is not preferable.

When (D) the (co) polymer exceeds 97% by weight, the antistatic property of the resin composition is insufficient, which is not preferable.

The resin composition of the present invention contains other thermoplastic polymers compatible with the resin composition of the present invention, for example, (1) polyamide,
Polyester such as polybutylene terephthalate is mixed to improve chemical resistance, impact resistance and heat resistance. (2) Polycarbonate, polyphenylene ether and polyglutarimide are mixed to improve heat resistance without impairing impact resistance.
(3) The flame retardancy can be respectively improved by mixing a vinyl chloride resin.

It is also possible to further improve the antistatic property by adding an antistatic agent such as a metal salt of sulfonic acid or an anionic, cationic or nonionic surfactant, and further, if necessary, an oligomer or the like. Various stabilizers such as compatibilizers, antioxidants, and ultraviolet absorbers, pigments, dyes, lubricants and plasticizers, glass fibers, metal fibers, and flame retardants can also be added.

[Example] In order to more specifically explain the present invention, an example and a comparative example will be described below. In addition, after the resin composition finally obtained was molded by an injection molding method, various physical properties were measured by the following test methods.

Izod impact strength: ASTM D256-56A Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Volume resistivity: 2 mm t × mmφ disk, room temperature 23 ° C,
The measurement was performed in a 50% RH atmosphere. A super insulation resistance meter SM-10E manufactured by Toa Denpa Kogyo KK was used for the measurement.

Adhesive rupture stress: A tensile test specimen specified in ASTM D638 is prepared from the compositions obtained in each of Examples and Comparative Examples.
The same composition as the test piece was treated with methyl ethyl ketone for 10 minutes.
Adjust the% solution. Using this solution as an adhesive, test piece 2
Adhere the sheets at right angles to each other (adhesion surface is 3.1 mm x 1
2.7mm), left at 23 ° C for 24 hours, then pulled at a strain rate of 5mm / min, and measured the breaking stress.

Appearance: The specimen is visually determined. The criteria are as follows.

：: Extremely good appearance 良好: Good ×: The surface of the molded product was damaged and defective Further, the number of parts and% in the examples indicate parts by weight and% by weight, respectively.

Reference Examples (1) (A) Preparation of epihalohydrin copolymer A-1: Zeklon 2000H (Mooney viscosity (ML _{1 + 4} 100 ° C) 1
00 (manufactured by Zeon Corporation) (ethylene oxide / epichlorohydrin = about 35/65% by weight).

A-2: Zeklon 3100 (Mooney viscosity (ML _{1 + 4} 100 ° C) 7
0, manufactured by Zeon Corporation) Ethylene oxide / epichlorohydrin = about 25/65% by weight.

(2) (B) Preparation of graft (co) polymer B-1: polybutadiene latex (rubber particle diameter 0.25
In the presence of 60 parts (in terms of solid content) of 60 parts (μ, gel content 80%), 40 parts of a monomer mixture composed of 70% styrene and 30% acrylonitrile were emulsion-polymerized. The obtained graft copolymer is
The mixture was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, dried, and dried to prepare a powdery graft copolymer (B-1).

B-2: 10 parts of diene NF35A (manufactured by Asahi Kasei Corporation) are dissolved in 90 parts of styrene, and then the resulting mixture is subjected to bulk polymerization to obtain a graft polymer (B).
-2) was prepared.

B-3: Polybutadiene latex 15 used in B-1
Of a monomer mixture consisting of 75% of styrene and 25% of acrylonitrile was emulsion-polymerized in the presence of parts (in terms of solid content), and then a powdery graft polymer (B-3) was prepared in the same manner as in B-1. Was prepared.

B-4: AES resin (Uniplite UB-300, manufactured by Sumitomo Nogatack Co., Ltd.) was used.

B-5: AAS resin (Vitax 6100, Hitachi Chemical Co., Ltd.)
Was used.

B-6: Polybutadiene latex 45 used in B-1
In the presence of parts (solid content), a weight mixture of 21.6 parts of styrene and 8.4 parts of acrylonitrile was emulsion-polymerized, and a monomer mixture of 17.5 parts of styrene, 7 parts of acrylonitrile, and 0.5 part of glycidyl methacrylate was emulsion-polymerized. After that, a powdery graft copolymer (B-6) was prepared in the same manner as in B-1.

B-7: Polybutadiene latex 45 used in B-1
35 parts of styrene, 15 parts of acrylonitrile, and 5 parts of 2-hydroxyethyl methacrylate in the presence of
A part of the monomer mixture was emulsion-polymerized, and then a powdery graft copolymer (B-7) was prepared in the same manner as in B-1.

(3) (C) Preparation of modified vinyl polymer C-1: A monomer mixture of 70% styrene, 25% acrylonitrile, and 5% methacrylic acid is subjected to suspension polymerization to bead-shaped modified vinyl polymer (C -1) was prepared. The resulting modified vinyl polymer was prepared by adding a 0.4% solution of methyl ethyl ketone to 30
The intrinsic viscosity measured at 0 ° C was 0.61.

C-2 A weight mixture of 71.5% of styrene, 28% of acrylonitrile, and 0.5% of glycidyl methacrylate was subjected to suspension polymerization to form a bead-shaped modified vinyl polymer (C-
2) was prepared. The resulting modified vinyl polymer was C-
The intrinsic viscosity measured by the same method as in Example 1 was 0.57.

C-3: a mixture of 73% styrene and 27% acrylonitrile
95 parts and 5 parts of acrylamide were emulsion-polymerized. The resulting modified vinyl polymer latex was coagulated with magnesium sulfate, washed, dried and dried to prepare a powdery modified vinyl polymer (C-3). The resulting modified vinyl polymer had an intrinsic viscosity of 0.56 as measured by the same method as in C-1.

C-4 67% styrene, 28% acrylonitrile, 2-
A monomer mixture of 5 parts of hydroxyethyl methacrylate is subjected to suspension polymerization to form a bead-shaped modified vinyl polymer (C-
4) was prepared. The resulting modified vinyl polymer was C-
The intrinsic viscosity measured by the same method as in Example 1 was 0.60.

C-5: A monomer mixture of 63% styrene, 24% acrylonitrile, and 13% methoxypolyethylene glycol methacrylate (the average number of ethylene oxide groups is 9) is suspension-polymerized to form a bead-shaped modified vinyl polymer (C -5) was prepared. The resulting modified vinyl polymer had an intrinsic viscosity of 0.52 as measured by the same method as in C-1.

C-6: A monomer mixture of 95% styrene and 5% methacrylic acid is subjected to suspension polymerization to form a bead-shaped modified vinyl polymer (C
-6) was prepared. The resulting modified vinyl polymer had an intrinsic viscosity of 0.40 as measured at 30 ° C. in a 0.4% solution of toluene.

(4) Preparation of (D) (co) polymer D-1: 72 parts of styrene and 28 parts of acrylonitrile were subjected to suspension polymerization to prepare a copolymer (D-1).

D-2: 50 parts of styrene, 30 parts of N-phenylmaleimide,
20 parts of acrylonitrile were emulsion-polymerized. The obtained copolymer latex was coagulated with magnesium sulfate, then secondary aggregated at a high temperature, washed, dried and dried to prepare a powdery copolymer (D-3).

Examples 1 to 17 (A) Epihalohydrin copolymers prepared in Reference Examples,
The (B) graft (co) polymer, (C) modified vinyl polymer, and (D) copolymer were mixed at the compounding ratio shown in Table 1, and the mixture was mixed with a bus-co-kneader (Bus Japan Co., Ltd.) Made)
At 200 ° C., and extruded to produce pellets.

Next, with an injection molding machine, the cylinder temperature was 230 ° C,
A test piece was molded at a mold temperature of 60 ° C., and each physical property was measured.

The specific volume resistivity was measured using a 2 mm-thick injection molded disk under the following conditions.

(1) Immediately after molding, wash with an aqueous solution of detergent "Mama Lemon" (manufactured by Lion Oil & Fats Co., Ltd.), and then sufficiently wash with distilled water to remove water on the surface, then at 50% RH at 23 ° C for 24 hours. The humidity was adjusted and measured.

(2) After molding, leave it at 50% RH at 23 ° C for 200 days, wash it with detergent “Mama Lemon” aqueous solution, then wash it thoroughly with distilled water, remove the surface moisture, then make 50% R
H, measured at 23 ° C. for 24 hours. Table 2 shows the measurement results.
It was shown to.

Comparative Examples 1 to 6 (A) Epihalohydrin copolymer prepared in Reference Example,
(B) A graft (co) polymer, (C) a modified vinyl polymer, and (D) a copolymer were mixed at the compounding ratio shown in Table 1, and the physical properties were measured in the same manner as in Example 1. It was measured. Table 2 shows the measurement results.

From the results in Table 2, the following is clear. The resin compositions of the present invention (Examples 1 to 17) have excellent mechanical properties typified by impact strength and flexural modulus, and have low volume resistivity. In addition, the resistance value hardly changes even when the surface of the molded article is washed or changes with time, so that excellent permanent antistatic properties are exhibited. Further, the molded article has no delamination and has an extremely good appearance.

That is, the resin composition of the present invention is a very good composition having both excellent mechanical properties and permanent antistatic properties.

On the other hand, when the blending amount of the (A) epihalohydrin copolymer is 1
When the amount is less than% by weight (Comparative Example 1), antistatic property (resistivity)
When it exceeds 50% by weight (Comparative Example 2), the flexural modulus is inferior.

When the blending amount of the (B) graft (co) polymer is less than 1% by weight (Comparative Example 3), the impact resistance is poor, and when it exceeds 98% by weight (Comparative Example 4), the antistatic property is poor.

(C) When the blending amount of the modified vinyl polymer is less than 1% by weight (Comparative Example 5), the molded article undergoes delamination, and when it exceeds 98% by weight (Comparative Example 6), the molded article has poor antistatic properties and is used. Can not.

[Effects of the Invention] The thermoplastic resin composition of the present invention is excellent in mechanical properties such as permanent antistatic properties and impact resistance, and has remarkably improved delamination.

Claims (2)

(57) [Claims] (1) 1 to 50% by weight of an epihalohydrin copolymer (B) 1 to 80% by weight of a rubbery polymer, 100 to 40% by weight of an aromatic vinyl monomer, and a vinyl cyanide monomer 0 to 60% by weight and other vinyl monomers copolymerizable therewith
(C) 1 to 98% by weight of a graft (co) polymer product obtained by (co) polymerizing 99 to 20 parts by weight of a monomer or a monomer mixture consisting of 1 to 98% by weight of a modified vinyl polymer containing at least one functional group selected from a group, a hydroxyl group, a polyalkylene oxide group or a derivative thereof, and (D) an aromatic vinyl monomer 100 to 40 0 to 60% by weight of a vinyl cyanide monomer, and 0 to 97% by weight of a (co) polymer comprising 0 to 40% by weight of another vinyl monomer copolymerizable therewith. The thermoplastic resin composition blended in the above. 2. The method of claim 1, wherein (A) the epihalohydrin copolymer is (a)
2. The thermoplastic according to claim 1, which is derived from 2 to 90% by weight of an epihalohydrin monomer, 98 to 10% by weight of (b) an alkylene oxide, and 0 to 88% by weight of a monomer copolymerizable therewith. Resin composition.