JPH036253A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prevent the delamination and improve the permanent antistatic properties and mechanical properties by compounding an epihalohydrin copolymer and a specific graft (co)polymer as essential components. CONSTITUTION:20-99 pts.wt. monomer component comprising a mixture of 100-40wt.% (meth)acrylic acid ester monomer, 0-60wt.% arom. vinyl monomer and 0-60wt.% vinyl monomer copolymerizable with said two monomers is (co) polymerized in the presence of 1-80 pts.wt. rubbery polymer to give a graft (co)polymer (A). Separately, said monomer component is copolymerized in the absence of said rubbery polymer to give a copolymer (B). 1-50 pts.wt. epihalohydrin copolymer, 1-99 pts.wt. said graft copolymer A, 0-98 pts.wt. modified vinyl polymer having at least one group selected from the group consisting of carboxyl, epoxy, amino, hydroxyl, and polyoxyalkylene group, and 0-98 pts.wt. said copolymer B are compounded.

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 layer peeling (thousand peeling). 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 applications of these materials can be further expanded if antistatic properties are added to the mechanical strength of the materials. In other words, it is possible to expand the application to copying machines and various dustproof parts where it is desired to prevent failures due to static electricity.

As a method of adding an antistatic agent to synthetic polymer materials,
(1) A method of kneading a water-absorbing compound such as polyalkylene oxide or an antistatic agent into the resin, and (2)
A commonly used method is to apply a surfactant or the like to the surface of a molded product. However, sufficient antistatic performance has not been achieved by any of these methods, and when the surface of the molded product is washed or wiped with water, the antistatic property disappears, and the kneaded ingredients bleed out to the surface, impairing the quality of the material. There are problems such as deterioration of antistatic properties and deterioration of antistatic properties over time.

On the other hand, a method for imparting permanent antistatic properties to a resin is to add vinyl to a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or/and acrylic ester with a vinyl monomer having an alkylene oxide group. Practical antistatic properties have been achieved by methods such as graft polymerization of monomers or vinylidene monomers (Japanese Unexamined Patent Publication No. 55-36237).

Further, JP-A-61-1748 discloses that by mixing a styrene polymer, an evihalohydrin copolymer, and an acrylate polymer, a resin having semi-permanently antistatic properties can be obtained.

[Problems to be Solved by the Invention] However, the antistatic resin obtained by graft polymerizing a monomer to a hydrophilic rubber-like polymer described in JP-A-55-36237 has a special hydrophilic property. Since a rubbery polymer is used, the production method is complicated and the resulting resin has poor mechanical properties, so it is not fully satisfactory. Furthermore, Japanese Patent Application Laid-Open No. 1748/1983 does not provide satisfactory layer peeling.

Therefore, the present invention provides an antistatic resin composition that has excellent mechanical properties such as permanent antistatic properties and impact resistance, and has significantly improved delamination without using complicated manufacturing methods. The challenge is to provide.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, we found that in order to solve the above problems, a shrimp halohydrin copolymer, a rubber graft (co)polymer, and a material containing a specific functional group were used. We have discovered that it is important to blend a modified vinyl polymer, and have arrived at the present invention.

That is, the present invention comprises (A) 1 to 507H 1% of a shrimp halohydrin copolymer (B) 1 to 80 parts of a rubbery polymer, 100 to 40% by weight of a (meth)acrylic acid ester monomer, and an aromatic vinyl-based monomer. By (co)polymerizing 99 to 20 weight percent of a polymer or single temperature polymer consisting of 0 to 60 weight percent of a polymer and 0 to 60 weight percent of other vinyl monomers copolymerizable with these. (C) Contains at least one functional group selected from a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyalkylene oxide group, or a derivative thereof. Modified vinyl polymer 0 to 98% by weight, and (D) (meth)acrylic acid ester monopolymer 100 to 4
0% by weight, 0% to 60% by weight of an aromatic vinyl polymer, and 0% to 98% by weight of a (co)polymer consisting of 0% to 60% by weight of other vinyl spinning wheels that can be copolymerized with these. The present invention provides a blended thermoplastic resin composition.

The present invention will be specifically explained below.

The shrimp halohydrin copolymer (A) used in the present invention is composed of (a) shrimp halohydrin monomer, (b) alkylene oxide, and (C) a monomer copolymerizable with these.

(A) Constituent component of shrimp halohydrin copolymer (a
) Shrimp halohydrin monomer is shrimp chlorohydrin,
Shrimp bromohydrin and shrimp iodohydrin are mentioned, with shrimp chlorohydrin being particularly preferred.

(A) Constituent component of shrimp halohydrin copolymer (b
) Alkylene oxides include ethylene oxide, 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-
Examples include epoxyhebutane, but ethylene oxide is particularly preferred because of its excellent antistatic properties.

(A) Monomers that can be copolymerized with the above components (a) and (b), which are constituent components of the shrimp halohydrin copolymer, are not particularly limited, and examples include styrene oxide, 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, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate Examples include.

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

If the proportion of the (a) epihalohydrin monomer in this (A) epihalohydrin copolymer is less than 2% by weight, the mechanical properties of the epihalohydrin copolymer will be poor, and 90% by weight
If it exceeds this value, the antistatic properties of the resin composition will be poor, which is not preferable.

Furthermore, if the proportion of ('O)alkylene oxide is less than 10% by weight, the antistatic properties of the resin composition will be poor, and if it exceeds 90% by weight, the resin composition will become flexible and have poor mechanical properties, which is not preferable.

(A) The method for producing the epihalohydrin copolymer is not particularly limited; for example, U.S. Patent No. 3,642.667
It can be manufactured using

The rubbery polymer that is a component of the graft (co)polymer product (B) used in the present invention is preferably one having a glass transition temperature of 0°C or lower, and specifically, polybutadiene, polystyrene-butadiene, etc. , diene rubbers such as polyacrylonitrile-butadiene, acrylic rubbers such as polyisoprene, polychloroprene, and butyl polyacrylate, and rubbery polymers such as ethylene-propylene-diene monomer terpolymers.

Particularly preferred are polybutadiene or butadiene copolymers.

(B) is a constituent of the graft (co)polymer product (
As the meth)acrylic acid ester monomer, methyl, ethyl, propyl, n of acrylic acid and methacrylic acid
-butyl, n-hexyl, etc., but methyl methacrylate is particularly preferred.

In addition, aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, 〇-ethylstyrene,
Examples include 0-p-dichlorostyrene, and styrene is particularly preferred.

Other vinyl spinning wheel groups include vinyl cyanide monomers such as acrylonitrile, methacrylaterile, ethacrylonitrile, maleimide, N-methylmaleimide, N-
- Maleimide monomers such as cyclohexylmaleimide and N-phenylmaleimide, acrylamide monomers such as acrylamide and N-methylacrylamide, unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, acrylic acid, Unsaturated acids such as methacrylic acid, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
Examples include methoxypolyethylene glycol methacrylate, vinyl acetate, and especially acrylonitrile, N
-Phenylmaleimide, acrylamide, glycidyl methacrylate, 2-hydroxyethyl methacrylate, and maleic anhydride are preferred.

(B) The proportion of the (meth)acrylic acid ester monomer used in the graft (co)polymer product is 100 to 40% by weight, preferably 100 to 50% by weight based on the total vinyl monomers used. It is.

If the proportion of the (meth)acrylic acid ester monomer is less than 40% by weight, the compatibility with the epihalohydrin copolymer will be poor and the molded product will cause delamination, which is not preferable.

In the present invention, the desired physical properties can be obtained by using a (meth)acrylic acid ester polymer, but in addition, aromatic vinyl When a type polymer is used, impact resistance can be improved, and when a maleimide type monomer is used, heat resistance can be improved. Furthermore, when acrylamide, glycidyl methacrylate, 2-hydroxyethyl methacrylate, maleic anhydride, methacrylic acid, methoxypolyethylene glycol methacrylate, etc. are used, the compatibility with the epihalohydrin copolymer can be further improved.

(B) The proportion of rubbery polymer and polymer or monomer mixture in the graft (co)polymer product is determined by the total graft (co)polymer product.
Co) In 100 parts by weight of the polymer product, rubbery polymers 1 to 8
0 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
It is a heavy part.

If the proportion of the rubbery polymer in the (B) graft (co)polymer product is less than 1 part by weight, the resulting resin composition will have poor impact resistance, and if it exceeds 80 parts by weight, the rubbery polymer will be This is not preferable because it causes poor dispersion and impairs the appearance of the molded product.

(B) The method for producing the graft (co)polymer is a known polymerization method,
For example, a method can be used in which a monomer or a monomer mixture, a polymerization initiator, and an emulsifier are continuously supplied in the presence of a rubbery polymer latex to carry out emulsion polymerization.

The present invention provides (C) a modified vinyl polymer (hereinafter referred to as By using a modified vinyl polymer (abbreviated as a modified vinyl polymer), the compatibility of the components (A) and (B) can be further improved.

The modified vinyl polymer (C) used in the present invention is:
It has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers, and contains carboxyl groups, epoxy groups, amino groups, hydroxyl groups, polyalkylene oxide groups, or derivatives thereof in the molecule. It is a polymer having at least one kind of functional group selected from the group consisting of: The content of these functional groups may be very small;
Further, it can be contained in a large amount as long as the performance as a resin is not impaired. Usually, the effects of the present invention can be effectively exhibited if the modified vinyl polymer contains substantially one or more of the above functional groups on average in one molecule.

(C) There are no particular restrictions on the method of introducing a carboxyl group into the modified vinyl polymer, but there are two methods: A method of copolymerizing a vinyl monomer having a predetermined vinyl monomer with a predetermined vinyl monomer, ■ γ, γ′-azobis (γ-cyatubaleic acid), α, α′-azobis (α-cyanoethyl)-p
- polymerization initiators with carboxyl groups such as benzoic acid and succinic acid peroxide and/or thioglycolic acid, α-mercaptopropionic acid, β-mercaptoprobionic acid, α-mercapto-isobutyric acid and 2,3 or 4- Using a polymerization degree regulator having a carboxyl group such as mercaptobenzoic acid, a predetermined vinyl monomer is (co)polymerized.
Polymerization method, and (co-)methacrylic acid esters such as methyl methacrylate and butyl acrylate.
A method such as saponifying a polymer with an alkali can be used.

There are no particular restrictions on the method of introducing the epoxy group, but for example, it can be represented by the following formula (% formula %) (wherein R1 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, etc. with a predetermined vinyl monomer can be used.

There are no particular restrictions on the method of introducing an amino group or a substituted amino group, but for example, the zero-order formula (wherein R2 represents hydrogen, a methyl group, or an ethyl group, and R3 represents hydrogen or a carbon atom number of 1 ~12 alkyl groups, 2 carbon atoms~
12 alkanoyl group, phenyl group or cycloalkyl group having 6 to 12 carbon atoms, or derivatives thereof. ) A method of copolymerizing a vinyl polymer having at least one functional group of an amino group or a substituted amino group represented by (II) with a predetermined vinyl spinning wheel; and a method of (co)polymerizing a predetermined vinyl monomer using a chain transfer agent and/or initiator having at least one functional group selected from the group consisting of mineral salts thereof. be able to.

Here, specific examples of vinyl monomers having at least one functional group such as an amino group or a substituted amino group include aminoethyl acrylate, propylaminoethyl acrylate, methylaminoethyl methacrylate, and ethylaminoethyl methacrylate. Propyl, alkyl ester derivatives of acrylic acid or methacrylic acid such as phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methalylamine and allylamine derivatives such as N-methylallylamine, acrylamide, methacrylamide and (meth)acrylamide derivatives such as N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, and p-
Examples include aminostyrenes such as aminostyrene.

Further, 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 of polymerization initiators include 0-mercaptoaniline, m-mercaptoaniline, and their hydrochlorides, and specific examples of polymerization initiators 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-
Examples include aminobenzoyl peroxide.

There are no particular restrictions on the method for introducing hydroxyl groups, but for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. are introduced into a predetermined vinyl polymer. For example, a method of copolymerizing with

Furthermore, there is no particular restriction on the method of introducing the polyalkylene oxide group or its derivative, but for example, (1)
A method of copolymerizing a vinyl polymer containing a polyalkylene oxide group represented by the following formula (I[[), (IV)] with a desired vinyl monomer, (2) Polymethyl methacrylate or methyl methacrylate and butyl acrylate (
A method of ester-reacting a (meth)acrylic ester-based (co)polymer obtained by copolymerizing a meth)acrylic ester with a desired vinyl monomer and a polyalkylene oxide glycol having an alkyl ether at one end, (3) Acrylic acid ,
A vinyl polymer containing a carboxyl group obtained by copolymerizing methacrylic acid, maleic acid, maleic anhydride, phthalic acid, etc. with a desired vinyl monomer, and a polyalkylene oxide glycol with an alkyl ether at one end. Examples include a method of causing an ester reaction.

40 1 CH2=C-C-0(R50) R6(III) 40 1 CH2=C-C-NH(R5O) nR6(TV) (wherein, R4 is hydrogen or an alkyl group having 1 to 4 carbon atoms , R5 represents an alkylene group having 2 to 6 carbon atoms, R6 represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and n represents 2 to 500.) Specific examples include polyethylene glycol acrylate, polyethylene glycol methacrylate, Poly(
propylene oxide) glycol acrylate, poly(
propylene oxide) methacrylate, poly(tetramethylene oxide) glycol acrylate, 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, methoxypoly(tetramethylene oxide)
Glycol methacrylate, ethoxypolyethylene glycol acrylate, ethoxypolyethylene glycol methacrylate, ethoxypoly (propylene oxide) glycol acrylate, polyethylene glycol acrylamide, polyethylene glycol methacrylamide, poly (propylene oxide) glycol acrylamide, poly (propylene oxide) glycol methacrylamide, poly (tetra) methylene oxide) glycol acrylamide, poly(tetramethylene oxide) glycol methacrylamide, methoxypolyethylene glycol acrylamide, methoxypolyethylene glycol methacrylamide, methoxypoly(propylene oxide) glycol acrylamide, methoxy poly(propylene oxide) glycol methacrylamide, methoxy(tetramethylene oxide) Examples include glycol methacrylamide, and methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylamide, and methoxypolyethylene glycol methacrylamide are particularly preferred because of their excellent polymerizability and affinity with (A) polyether ester amide.

In addition, a (co)polymer of (meth)acrylic acid ester or a vinyl polymer containing a carboxyl group or anhydrous carboxyl group and a poly(
The ester reaction with glycol (alkylene oxide) is
It can be carried out at high temperature under normal pressure or vacuum.

The poly(alkylene oxide) glycol having an alkyl ether at one end used here includes, for example, methoxypolyethylene glycol, methoxypoly(1,2-propylene oxide) glycol, methoxypoly(1,3-propylene oxide) glycol, methoxypoly(tetramethylene oxide) glycol, and methoxypoly(1,3-propylene oxide) glycol. ) glycol, methoxypoly(hexamethylene oxide) glycol, methoxy (block or random copolymer of ethylene oxide and propylene oxide), and methoxy (block or random copolymer of ethylene oxide and tetrahydrofuran), but especially those with alkyl at one end Ether polyethylene glycols are preferred.

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

(C) There are no particular restrictions on the vinyl spinning wheel combination used in the polymerization of the modified vinyl polymer (for example, styrene,
Aromatic vinyl monomers such as α-methylstyrene and vinyltoluene; vinyl cyanide monomers such as acrylonitrile and methacrylate; ) Acrylic acid ester monomers, maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, olefin monomers such as ethylene and propylene, vinyl chloride, acetic acid One or more vinyl monomers such as vinyl and butadiene can be selected and used depending on the purpose. In particular, aromatic vinyl monomers such as styrene, (meth)acrylic acid ester 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 in the body are excellent.

In addition, 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 added to the above. It can also be used in combination with vinyl monomers.

Further, as the method for introducing the functional group, any of the various methods described above can be used in combination.

(C) There are no particular restrictions on the method for producing the modified vinyl polymer, including bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization,
Conventional methods such as bulk-suspension polymerization methods can be used.

Examples of the (meth)acrylic acid ester monomer that is a component of the (D) (co)polymer used in the present invention include methyl, ethyl, propyl, n-butyl, and n-hexyl of acrylic acid and methacrylic acid. Among them, methyl methacrylate is particularly preferred.

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, pt-butylstyrene,
Examples include 0-ethylstyrene and 0-p-dichlorostyrene, with styrene being particularly preferred.

Other vinyl monomers that can be copolymerized with these include cyanide vinyl spinning wheel combinations such as acrylonitrile, methacrylonitrile, and ethacrylonitrile, maleimide, N-methylmaleimide, N-ethylmaleimide, and N-ethylmaleimide.
Maleimide monomers such as cyclohexylmaleimide and N-phenylmaleimide, olefin monomers such as ethylene and propylene, vinyl chloride, vinyl acetate,
Examples include butadiene, but styrene and N-phenylmaleimide are particularly preferred.

(D) The ratio of (meth)acrylic acid ester monomers as constituent components of the (co)polymer is 100 to 40% of the total monomers.
% by weight, preferably 100-50% by weight. If the proportion of the (meth)acrylic acid ester monomer is less than 40% by weight, the resin composition will have poor impact resistance, which is not preferable.

In the present invention, satisfactory physical properties can be obtained by using the above-mentioned (co)polymer, but in addition, aromatic vinyl monomers and maleimide monomers are preferably added in an amount of 60% by weight or less based on the total monomers. By using 50% by weight or less, impact resistance and heat resistance can be further improved.

If the proportion of the aromatic vinyl monomer exceeds 60% by weight, the compatibility with the shrimp halohydrin copolymer will be poor and the molded product will cause delamination, which is not preferable.

(D) There is no particular restriction on the method for producing the (co)polymer, and known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and bulk-suspension polymerization can be used. can.

The thus obtained polymer contains (A) epihalohydrin copolymer 1 to 50% by weight, preferably 5 to 30% by weight, (
B) Graft (co)polymer product 1-99% by weight, preferably 5-90% by weight, (C) Modified vinyl polymer 0-99% by weight
98% by weight, preferably 1 to 90% by weight, (D) (co)
The polymer content is 0 to 97% by weight, preferably 0 to 89% by weight, and more preferably 10 to 80% by weight.

(A) If the shrimp halohydrin copolymer is less than 1% by weight,
If the antistatic property of the resin composition is insufficient, and the amount exceeds 50% by weight, the resin composition becomes flexible and has poor mechanical properties, which is not preferable.

If the amount of the (B) graft (co)polymer product is less than 1% by weight, the resin composition will be too brittle to be used, and if it exceeds 99% by weight, the antistatic properties of the resin composition will be insufficient, which is not preferred.

(C) When the modified vinyl polymer exceeds 98% by weight,
The antistatic property of the resin composition is insufficient, which is not preferable.

(D) If the (co)polymer content exceeds 97% by weight, the antistatic properties of the resin composition will be insufficient, which is not preferable.

The resin composition of the present invention comprises (A) component and (B) component, or (A) component, (B) component and (C) component, and (
A transparent resin composition can also be obtained by controlling the difference in refractive index of component A), component (B), component (C), and component (D) to 0.02 or less.

The resin composition of the present invention can be produced by mixing other thermoplastic polymers that are compatible with the resin composition of the present invention, such as (1) polyesters such as polyamide and polybutylene ethylene phthalate, to provide chemical resistance and impact resistance. (2) By mixing polycarbonate, polyphenylene ether, and polyglutarimide, heat resistance is improved without impairing impact resistance. (3)
) The flame retardance can be improved by mixing vinyl chloride resin.

In addition, metal salts of sulfonic acid, anionic type, cationic type,
It is also possible to further improve antistatic properties by adding antistatic agents such as nonionic surfactants and inorganic alkali metal salts, and if necessary, compatibilizers such as oligomers, antioxidants, and ultraviolet rays can be added. Various stabilizers such as absorbents, pigments, dyes, lubricants, plasticizers, glass fibers, metal fibers, flame retardants, etc. can also be added.

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

Izotsu impact strength: A S TM D25B-5
6A tensile strength: ASTM D638 Flexural modulus: ASTM D790 Specific volume resistivity: 2mm+tX40mmφ disk,
Measurement was carried out at a room temperature of 23° C. and an atmosphere of 50% RH.

For measurement, use a super insulation resistance meter 5M-10E manufactured by Toa Denpa Kogyo Co., Ltd.
A mold was used.

Tensile test specimens specified in ASTM D638 are prepared from the compositions obtained in each of the Examples and Comparative Examples. In addition, a 10% solution of this test piece and the same composition was prepared in methyl ethyl ketone.

Using this solution as an adhesive, adhere two test pieces at right angles to each other (the bonded surface is 3.1mm x 12°7mm).
After release at 23° C. for 24 hours, tensile stress was measured at a strain rate of 5 mm/m1n.

Appearance: Visually judge the test piece. The criteria for judgment are as follows.

◎: Appearance is very good O: Good ×: The surface of the molded product is damaged and is defective. In addition, the number of parts and % in the examples indicate coulometric parts and weight %, respectively.

Reference example <1) (A) Preparation of shrimp halohydrin copolymer A-1=
Zekron 2000H (Mooney viscosity (ML 100)
℃) 110 and Nippon Zeon ■) 1+4 were used.

A-2: Zekron 3100 (, Mooney viscosity (ML)
(100°C) 70, Nippon Zeon Kan) 1+4 was used.

(2) (B) Preparation of graft (co)polymer B-1 = Polybutadiene latex (rubber particle size 0.25μ, gel content 76%) in the presence of 60 parts (solid content equivalent), methacrylic acid 40 parts of a polymer mixture consisting of 75% metal and 25% styrene was subjected to emulsion polymerization. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (B-1).

B-2: In the presence of 40 parts (solid content equivalent) of the polybutadiene latex used in B-1, 68% methyl methacrylate, 24% styrene, 4% acrylonitrile, 2-
After emulsion polymerizing 60 parts of a monomer mixture consisting of 4 parts of hydroxyethyl methacrylate, a powdery graft polymer (B-2) was prepared in the same manner as B-1.

(3) (C) Preparation of modified vinyl polymer C-1 = Suspension polymerization of a monomer mixture of 70% methyl methacrylate, 25% styrene, and 5% methacrylic acid to form beads of modified vinyl polymer. Combined (C-1) was prepared. The obtained modified vinyl polymer had an intrinsic viscosity [η] of 0.51 when measured in a 0.4% chloroform solution at 30°C.

C-2: Methyl methacrylate 75%, styrene 24.5
%, glycidyl methacrylate 0.5% monomer mixture was subjected to suspension polymerization to prepare a bead-shaped modified vinyl polymer (C-2). The obtained modified vinyl polymer had a [η] of 0.48 when measured in the same manner as C-1.

C-3: 67% methyl methacrylate, 24% styrene,
A modified vinyl polymer (C-3) was prepared by suspension polymerization of a monomer mixture of 4% acrylonitrile and 5% 2-hydroxyethyl methacrylate. The obtained modified vinyl polymer had a [η] of 0.5 as measured by the same method as C-1.
It was 5.

C-4 = methyl methacrylate 65%, styrene 22%,
A bead-shaped modified vinyl polymer was prepared by suspension polymerization of a 13% monomer mixture of methoxypolyethylene glycol methacrylate (average number of ethylene oxide groups: 9). The obtained modified vinyl polymer had a [η] of 0.53 when measured in the same manner as C-1.

C-5: 70% methyl methacrylate, 25% styrene,
A monomer mixture containing 5% acrylamide was emulsion polymerized. The obtained modified vinyl polymer latex was coagulated with magnesium sulfate, washed, filtered, and dried to prepare a powdery modified vinyl polymer (C-5). The obtained modified vinyl polymer had [η] of 0 when measured in the same manner as C-1.
．． It was 53.

<4) Preparation of (D) (co)polymer [)-1: Methyl methacrylate 75%, styrene 25%
A bead-shaped copolymer (
D-1) was prepared.

D-2 = methyl methacrylate 72%, styrene 24%,
Suspension polymerization of a monomer mixture of 4% acrylonitrile,
A bead-shaped copolymer (D-2) was prepared.

Examples 1 to 5 Epihalohydrin copolymer (A) prepared in Reference Example, (
B) Graft (co)polymer, (C) modified vinyl polymer, and (D) copolymer were mixed at the blending ratio shown in Table 1, and Bussco Kneader (manufactured by Buss Japan ■) was prepared. 200
Pellets were produced by melt-kneading and extrusion at °C.

Next, an injection molding machine was used to reduce the cylinder temperature to 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 an injection molded disk with a thickness of 2 mm under the following conditions.

(1) Immediately after molding, wash with an aqueous solution of the detergent "Mama Lemon" (manufactured by Lion Oil), then thoroughly wash with distilled water to remove surface moisture, and then store at 50% RH and 23°C for 2 hours.
The humidity was adjusted for 4 hours and then measured.

(2) After molding, it was left for 200 days at 50% RH, 123°C, and then washed with a detergent "Mama Lemon" aqueous solution, and then thoroughly washed with distilled water to remove surface moisture. % after 24 hours of humidity control. The measurement results are shown in Table-2.

Comparative Examples 1 to 6 Table 1 shows the (A,) shrimp halohydrin copolymer, (B) graft (co)polymer, (C) modified vinyl polymer, and (D) copolymer prepared in Reference Examples. They were mixed at the indicated blending ratio, and each physical property was measured in the same manner as in Example 1.

The measurement results are shown in Table-2.

Margin below From the results in Table 2, the following is clear.

The resin compositions of the present invention (Examples 1 to 15) have excellent mechanical properties represented by impact strength and flexural modulus, and low specific volume resistivity. Furthermore, the resistance value hardly changes even when the surface of the molded product is washed or changes over time.
Demonstrates excellent permanent antistatic properties. Furthermore, the molded product has no delamination and has an extremely good appearance.

That is, the resin composition of the present invention is an extremely good composition that has both excellent mechanical properties and permanent antistatic properties.

On the other hand, when the amount of (A) epihalohydrin copolymer is less than 1% by weight (Ratio/Example 1), the antistatic property (resistivity) is poor, and when it exceeds 50% by weight (Comparative Example 2), the flexural elasticity is poor. rate is inferior.

When the amount of the graft (co)polymer (B) 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.

When the blending ratio of (C) modified vinyl polymer or (D) (co)polymer exceeds 98% by weight (Comparative Example 5.6), the antistatic properties are poor, which is not preferable.

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

Claims (1)

Scope of Claims: (A) 1 to 50 parts by weight of epihalohydrin copolymer (B) 1 to 80 parts by weight of rubbery polymer, 100 to 40 parts by weight of (meth)acrylic acid ester monomer, aromatic vinyl By (co)polymerizing 99 to 20 parts by weight of a monomer or a monomer mixture consisting of 0 to 60% by weight of the vinyl monomer and 0 to 60% by weight of another vinyl monomer copolymerizable with these. 1 to 99% by weight of a graft (co)polymer product (C) Modified product containing at least one functional group selected from carboxyl groups, epoxy groups, amino groups, hydroxyl groups, polyalkylene oxide groups, or derivatives thereof 0 to 98% by weight of vinyl polymer and 100 to 4% of (D) (meth)acrylic acid ester monomer
0% by weight, 0% to 60% by weight of an aromatic vinyl polymer, and 0% to 98% by weight of a (co)polymer consisting of 0% to 60% by weight of other vinyl monomers copolymerizable with these. A thermoplastic resin composition blended with.