JPH09176414A - Antistatic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic resin compsn. excellent in permanent antistatic properties by compounding an arom. vinyl compd.-vinyl cyanide compd. copolymer, a graft copolymer formed by grafting an arom. vinyl compd. and a vinyl cyanide compd. onto a rubber, a functional-group-modified vinyl copolymer, a polyamide elastomer, etc. SOLUTION: This resin compsn. is prepd. by compounding 10-40 pts.wt. graft copolymer formed by grafting an arom. vinyl compd. and a vinyl cyanide compd. onto a rubbery polymer, 13-81.8 pts.wt. arom. vinyl compd./vinyl cyanide compd. copoylmer, 8-30 pts.wt. polyamide elastomer, 0.1-15 pts.wt. vinyl copolymer modified by functional groups such as carboxyl, epoxy, or amino groups, and 0.1-2 pts.wt. acrylamide copolymer. The graft copolymer may be the one obtd. by grafting, onto the rubbery polymer, an α,β-unsatd. carboxylic ester in place of the arom. vinyl compd. or in additio to the arom. vinyl compd. and the vinyl cyanide compd. A pref. rubbery polymer is polybutadiene or SBR. A pref. arom. vinyl compd. is a styrene compd. Thus prepd. resin compsn. is permanently antistatic, is excellent in moldability, mechanical strengths, etc., and does not cause layered separation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic resin composition excellent in permanent antistatic property. More specifically, the present invention relates to an antistatic resin composition containing an acrylamide copolymer and a modified vinyl copolymer and having excellent permanent antistatic properties.

[0002]

2. Description of the Related Art Acrylonitrile is added to a diene rubber component.
So-called ABS resin containing a graft copolymer obtained by copolymerizing a vinyl cyanide compound such as methacrylonitrile, styrene, and an aromatic vinyl compound component such as α-methylstyrene has excellent impact resistance, mechanical properties and OA as a semi-engineering plastic with intermediate properties between general-purpose resin and engineering resin because of its excellent moldability
With the expansion of applications for appliances and home appliances, with the aim of preventing failure due to the generation of static electricity and dust adhesion due to electrification,
The development of materials having antistatic performance has been actively pursued.

As a method for semi-permanently imparting antistatic performance to an ABS resin, there is known a method of blending with a polyamide elastomer such as polyether ester amide (for example, JP-A-60-23435). 61-73765, 61-246244, etc.). However, when a polyamide elastomer is used as a permanent antistatic agent, the addition amount is large and the antistatic performance itself is absolutely insufficient. Therefore, it has been attempted to use two or more types of permanent antistatic agents together. (JP-A-5-93118 and JP-A-5-93118)
-39388 gazette etc.). According to this method, although it is excellent in permanent antistatic property, it cannot be said to be sufficiently satisfactory from the viewpoint of mechanical strength such as impact resistance and delamination prevention property.

As a technique for improving the mechanical strength such as impact resistance and the layered delamination preventing property of the permanent antistatic ABS resin which is a mixture of ABS resin and polyether ester amide,
Techniques for blending carboxyl group-modified vinyl copolymers (see, for example, JP-A-62-241945 and 61-
246244), and a technique of blending an acrylamide-modified rubbery polymer (JP-A-62-250049). According to this method, a good permanent antistatic performance is maintained, and a resin composition having excellent delamination resistance and impact resistance can be obtained.However, since the amount of polyether ester amide is large, the rigidity is lowered. Remarkable.

On the other hand, a permanent antistatic ABS resin using an alkylene oxide and an ammonium salt has also been proposed, and the layered antipeeling property is imparted by a blend of an epoxy group- or carboxyl group-modified vinyl copolymer. (Japanese Patent Laid-Open No. 5-1201 and the like). Further, in recent years, there has been proposed a method of imparting a permanent antistatic property to an ABS resin by using a quaternary ammonium salt group-containing acrylamide copolymer having a small surface specific resistance value (for example,
JP-A-5-295229 and JP-A-5-320526). However, although these technologies are sufficiently satisfactory in permanent antistatic performance, they have problems such as impairing the mechanical strength, particularly the balance between impact resistance and rigidity, and insufficient compatibility with matrix resin components.

[0006]

DISCLOSURE OF THE INVENTION The object of the present invention is to eliminate the above-mentioned drawbacks of the prior art, to have excellent antistatic property, mechanical strength and delamination preventive property, and to have good molding processability. The purpose of the present invention is to provide a resin composition.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
"10 to 40 parts by weight of a graft copolymer (A) obtained by grafting 5 to 80 parts by weight of a rubbery polymer (A-1) with an aromatic vinyl (a) and a vinyl cyanide (b), 13 to 81.8 parts by weight of a copolymer (B) composed of aromatic vinyl (a) and vinyl cyanide (b), 8 to 30 parts by weight of a polyamide elastomer (C), a carboxyl group,
Achieved by an antistatic resin composition comprising 0.1 to 15 parts by weight of a modified vinyl copolymer (D) having at least one functional group selected from the group consisting of epoxy group, amino group and amide group ". To be done.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The rubbery polymer (A
Examples of -1) include polybutadiene and styrene-
Butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, butyl acrylate-butadiene copolymer, polyisoprene rubber, etc., among which polybutadiene, styrene-butadiene copolymer rubber, etc. are resistant. It is preferable in terms of impact.

As the aromatic vinyl (a) used in the graft component of the graft copolymer (A) or the copolymer (B) in the present invention, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, Examples thereof include t-butyl styrene, o-ethyl styrene, o-chloro styrene and o, p-dichloro styrene, and styrene and α-methyl styrene are particularly preferable in terms of moldability and color tone. One or more of these can be used.

Examples of vinyl cyanide (II) include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferable from the viewpoint of chemical resistance.

When an α, β-unsaturated carboxylic acid ester (C) is further used as a monomer forming the graft copolymer (A) or the copolymer (B), the bathochromic property at the time of coloring is improved. It is preferable in that Examples of such α, β-unsaturated carboxylic acid ester (C) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, T-Butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth)
Chloromethyl acrylate and (meth) acrylic acid 2-
Chloroethyl and the like can be mentioned. Among them, methyl methacrylate is preferable from the viewpoint of moldability.

Further, as a vinyl monomer (d) copolymerizable with the above compound, N-methylmaleimide,
Use of a maleimide compound such as N-cyclohexylmaleimide or N-phenylmaleimide, an unsaturated dicarboxylic acid such as maleic acid, an unsaturated dicarboxylic acid anhydride such as maleic anhydride, or an unsaturated amide such as acrylamide depending on its purpose. You can In addition, these can use 1 type (s) or 2 or more types.

Aromatic vinyl (a), vinyl cyanide (b), α, β-unsaturated carboxylic acid ester (c) and other substances used in the graft copolymer (A) or copolymer (B). The composition ratio of the copolymerizable vinyl-based monomer (d) is such that the aromatic vinyl (a) and the α, β-unsaturated carboxylic acid ester (c) are 45 to 85% by weight in terms of impact resistance. Is preferable in terms of moldability and moldability, and 5
0 to 80% by weight is more preferable. Further, vinyl cyanide (II) is preferably 15 to 55% by weight, from the viewpoint of chemical resistance and molding processability, and more preferably 20 to 50% by weight. It is preferable from the viewpoint of heat resistance that the other copolymerizable vinyl monomer (d) is 0 to 40% by weight.

The content of the rubbery polymer (A-1) in the graft copolymer (A) is 5 to 80 parts by weight, preferably 10 to 80 parts by weight, from the viewpoint of mechanical strength and moldability.
60 parts by weight. When the content of the rubbery polymer (A-1) in the graft copolymer (A) is less than 5 parts by weight, the resulting antistatic resin composition has insufficient impact resistance and also 80 parts by weight. Even if it exceeds, the impact resistance will decrease.

The weight average particle diameter of the rubber of the rubbery polymer (A-1) in the graft copolymer (A) is preferably 0.1 to 2.0 μm from the viewpoint of impact resistance and moldability. More preferably, it is 0.2 to 1.0 μm. If the weight average particle diameter of the rubber is less than 0.1 μm, the resulting antistatic resin composition may have insufficient impact resistance, and if it exceeds 2.0 μm, the molding processability may deteriorate. .

The graft ratio of the graft copolymer (A) is from 15 to 150 from the viewpoint of impact resistance and molding processability.
% Is preferable, and more preferably 20 to 70%. If the graft ratio is less than 15%, the resulting antistatic resin composition may have insufficient impact resistance, and if the graft ratio exceeds 150%, moldability and heat resistance may decrease.

The content of the graft copolymer (A) in the total antistatic resin composition is 10 to 40 parts by weight. The content is preferably 15 to 35 parts by weight from the viewpoint of the balance between impact resistance and rigidity. The content of the graft copolymer (A) is 1
If it is less than 0 parts by weight, the impact resistance of the obtained antistatic resin composition is insufficient, and if it exceeds 40 parts by weight, moldability, heat resistance and rigidity are lowered.

The reduced viscosity of the copolymer (B) is 0.2 to 1.5 dl / in view of impact resistance and moldability.
g is preferable, and 0.4 to 1.0 dl / g is more preferable. When the reduced viscosity of the copolymer (B) is less than 0.2 dl / g, the resulting antistatic resin composition may not have sufficient impact resistance, resulting in 1.5d ■
If it exceeds / g, molding processability and antistatic property may decrease.

The content of the copolymer (B) is 13 to 81.
8 parts by weight. The content is preferably 25 to 75 parts by weight from the viewpoint of the balance between impact resistance, rigidity and molding processability. The method for producing the graft copolymer (A) and the copolymer (B) may be any polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization and solution polymerization, and is not particularly limited. There is also no particular limitation on the type of monomer, initiator and chain transfer agent or charging method, and initial charging at once, or part or all of the charging monomer in order to suppress the formation of the composition distribution of the copolymer. May be polymerized continuously or in a divided manner.

Examples of the polyamide elastomer (C) in the present invention include a polyamide-forming component (a) having 6 or more carbon atoms, and a graft or block copolymer (b) obtained by a reaction with a poly (alkylene oxide) glycol. To be Here, as the amide-forming component (a) having 6 or more carbon atoms, specifically, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid , 1
Aminocarboxylic acids such as 1-aminoundecanoic acid and 12-aminododecanoic acid, or lactams such as caprolactam, enantholactam, caprylactam, laurolactam, hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylene Nylon salts such as diamine-isophthalate are exemplified. Examples of the poly (alkylene oxide) glycol (b) include polyethylene oxide glycol, poly (1,2-
(Propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, a block of ethylene oxide and tetrahydrofuran, or A random copolymer or the like is used. The number average molecular weight of the poly (alkylene oxide) glycol is preferably 200 to 6000 from the viewpoint of polymerizability and rigidity, and more preferably 300 to 4000. If necessary, both terminals of the component (b) may be aminated or carboxylated.

The bond between the polyamide-forming component (a) having 6 or more carbon atoms and the poly (alkylene oxide) glycol component (b) of the present invention is usually an ester bond or an amide bond, but is not particularly limited thereto. It is also possible to use a third component such as dicarboxylic acid or diamine as a reaction component of both components. In this case, as the dicarboxylic acid component (c), terephthalic acid having 4 to 20 carbon atoms, isophthalic acid, or phthalic acid Acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, Alicyclic dicarboxylic acids such as 2,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanediacid; In particular, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid and dodecanediacid are polymerizable, color , From the viewpoint of physical properties. On the other hand, as the diamine component (d), aromatic, alicyclic and aliphatic diamines are used, and among them, hexamethylene diamine of an aliphatic diamine is preferable from the viewpoint of polymerizability, color tone and physical properties.

The content of the polyamide elastomer (C) in the total antistatic resin composition is 8 to 30 parts by weight. The content is preferably 10 to 25 parts by weight from the viewpoint of the balance among antistatic property, rigidity and moldability. When the content is less than 8 parts by weight, the antistatic property of the obtained antistatic resin composition is lowered, while when it exceeds 30 parts by weight, rigidity and impact resistance are lowered.

The method for polymerizing the polyamide elastomer (C) is not particularly limited. For example, a polyamide having carboxylic acid groups at both ends is prepared by reacting an aminocarboxylic acid or lactam (a) with a dicarboxylic acid (c) in an equimolar ratio. A method of preparing a prepolymer and reacting it with a poly (alkylene oxide) glycol (b) under vacuum, or charging each of the compounds (a), (b) and (c) into a reaction tank,
A method in which a carboxylic acid-terminated polyamide prepolymer is produced by performing a pressure reaction at a high temperature in the presence or absence of water, and then the polymerization is allowed to proceed under normal pressure or reduced pressure. Known methods such as a method in which the compounds (b) and (c) are simultaneously charged into a reaction vessel and melt-polymerized, and then the polymerization is performed at once in a high vacuum can be employed.

The antistatic resin composition of the present invention contains a modified vinyl polymer (D) having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group and an amide group. By doing so, the compatibility between the polyamide elastomer (C) and the copolymer (B) is improved, the mechanical strength such as impact resistance is improved, and the delamination prevention property is also improved.

The modified vinyl copolymer (D) in the present invention has a structure obtained by copolymerizing two or more vinyl monomers, and has a carboxyl group, an epoxy group, an amino group in the molecular chain. And at least one functional group of an amide group. As the content of these functional groups,
It may be contained in a very small amount, or may be contained in a large amount as long as the performance such as appearance and molding processability is not impaired. Usually, one or more functional groups are present on average in one molecular chain. Is enough. The method for introducing at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, and an amide group into the modified vinyl copolymer (D) is not particularly limited, but is usually the same as described above. Examples thereof include a method of copolymerizing a vinyl monomer having a functional group, and a method of copolymerizing a predetermined vinyl monomer using a polymerization initiator or a chain transfer agent having the above functional group.

Specific examples of the vinyl-based monomer having the above functional group, the polymerization initiator and the chain transfer agent are as follows.

Examples of vinyl monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or itaconic acid, glycidyl acrylate, glycidyl methacrylate or glycidyl itaconate. A monomer having an epoxy group, aminoalkyl ester derivatives of (meth) acrylic acid such as aminoethyl acrylate, ethylaminopropyl methacrylate and phenylaminoethyl methacrylate, vinylamine derivatives such as N-acetylvinylamine, Examples thereof include allylamine derivatives such as methallylamine, monomers having an amino group such as aminostyrene, and monomers having an amide group such as acrylamide and N-methylmethacrylamide.

Examples of the polymerization initiator include an initiator having a carboxyl group such as γ, γ'-azobis (γ-cyanovaleic acid) or peroxysuccinic acid, and α, α'-azobis (γ-amino-α). , γ-divaleronitrile) or an initiator having an amino group such as p-aminobenzoyl peroxide.

Examples of the chain transfer agent include a chain transfer agent having a carboxyl group such as mercaptopropion, 4-mercaptobenzoic acid or thioglycolic acid, mercaptomethylamine and N- (β-mercaptoethyl) -N-methylamine. , Bis- (4-aminophenyl) disulfide, mercaptoaniline and other amino group-containing chain transfer agents.

The modified vinyl copolymer (D) is a copolymer composed of 50 to 79.9% by weight of an aromatic vinyl compound, 20 to 40% by weight of a vinyl cyanide compound and 0.1 to 10% by weight of methacrylic acid. Is preferable because the layered peeling prevention property is particularly improved.

The reduced viscosity of the modified vinyl copolymer (D) in the antistatic resin composition of the present invention is 0.2 dl / g to 1.5 dl / g from the viewpoint of layered delamination prevention property and impact resistance. Is preferred. More preferably 0.4 dl / g to 1.0 dl /
g. The reduced viscosity of the modified vinyl copolymer (D) is 0.
When it is less than 2 dl / g, the antistatic resin composition obtained may not have sufficient layered peeling resistance and impact resistance, and when it exceeds 1.5 dl / g, the layered peeling prevention property and molding processability may be poor. It may decrease.

The content of the modified vinyl copolymer (D) in the antistatic resin composition of the present invention is 0.1 to 15 parts by weight. The content is preferably 3 to 10 parts by weight from the viewpoint of delamination prevention and balance between mechanical strength and moldability. When the content of the modified vinyl copolymer (D) is less than 0.1 part by weight, the antistatic layer composition of the obtained antistatic resin composition has insufficient layered peeling prevention property, and when it exceeds 15 parts by weight, impact resistance is high. And the surface gloss of the molded product is reduced.

The polymerization method for copolymerizing the modified vinyl copolymer (D) is not particularly limited, but suspension polymerization, bulk polymerization, emulsion polymerization, solution polymerization and the like are preferable.

The acrylamide copolymer (E) in the present invention comprises ethylene (a) and methyl acrylate, ethyl acrylate, n-propyl acrylate, i-acrylic acid.
Acrylic acid ester (b) such as propyl, n-butyl acrylate, i-butyl acrylate, and acrylic acid (c) are copolymerized by a thermal degradation method to obtain N, N-dimethylaminoethylamine, N, N- After amidation with an N, N-dialkylaminoalkylamine (d) such as dimethylaminopropylamine, N, N-dimethylaminoneopentylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, etc. It is obtained by cation modification with a known quaternizing agent (e) such as methyl chloride, benzyl chloride, alkylbenzyl chloride, diethylsulfate and the like.

From the viewpoint of compatibility with the copolymer (B), the acrylamide copolymer (E) has 65 to 99 mol% of ethylene structural units in the molecule and 15 acrylate structural units.
It is preferable that the amount of the acrylamide structural unit is 1 to 35 mol% or less.

The content of the acrylamide copolymer (E) in the antistatic resin composition of the present invention is 0.1 to 2 parts by weight. The content is preferably 0.5 to 1.5 parts by weight from the viewpoint of antistatic property and balance between mechanical strength and molding processability. The content of the acrylamide copolymer (E) is 0.
If it is less than 1 part by weight, the antistatic property of the obtained antistatic resin composition is insufficient, and if it exceeds 2 parts by weight, impact resistance and heat resistance are deteriorated.

Regarding the method for producing the antistatic resin composition of the present invention, various methods such as melt kneading with a Banbury mixer, rolls, and a single-screw or multi-screw extruder can be adopted.

The antistatic resin composition of the present invention contains, within the range not impairing the object of the present invention, polyolefins such as vinyl chloride, polyethylene and polypropylene, polyamides such as nylon 6 and nylon 66, polyethylene terephthalate,
The mechanical properties of the molding resin can be improved by adding polyesters such as polybutylene terephthalate and polycyclohexane dimethyl terephthalate, polycarbonates and various elastomers.

If necessary, antioxidants such as hindered phenols, sulfur-containing organic compounds and phosphorus-containing organic compounds, heat stabilizers such as phenols and acrylates,
UV absorbers such as benzotriazole, benzophenone and salicylate, various stabilizers such as light stabilizers such as organic nickel and hindered amine, metal salts of higher fatty acids, lubricants such as higher fatty acid amides, phthalates , Halogen-containing compounds such as plasticizers such as phosphoric acid esters, polybromodiphenyl ether, tetrabromobisphenol-A, brominated epoxy oligomers, brominated polycarbonate oligomers, phosphorus compounds, flame retardants such as antimony trioxide, etc. Auxiliary agents, carbon black, titanium oxide, pigments and dyes can also be added.

Further, reinforcing agents and fillers such as glass fibers, glass flakes, glass beads, carbon fibers and metal fibers can be added. When adding such a reinforcing material or the like, various methods such as melt kneading with a Banbury mixer, a roll, and a single-screw or multi-screw extruder can be adopted.

The antistatic resin composition obtained as above is molded by a known method such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, gas assist molding and the like which is currently used for molding thermoplastic resins. It is possible and is not particularly limited.

[0042]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below, but these examples do not limit the present invention. In addition, "%" represents% by weight unless otherwise specified. With respect to general properties such as mechanical strength and heat resistance of the antistatic resin composition, a test piece was molded by injection molding and measured according to the following test method.

(1) Graft ratio Acetone was added to a predetermined amount (m) of the graft copolymer, and the mixture was refluxed for 3 hours. p. m. (1000
After centrifugation at 0 G) for 40 minutes, the insoluble matter was filtered, and the insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, and the weight (n) was measured. The graft ratio was calculated from the formula (I). Where L
Is the rubber content of the graft copolymer. Graft ratio (%) = {(n−m × L) / (m × L)} × 100 (I)

(2) Reduced viscosity η _{sp / c To} 1 g of the sample, 200 ml of acetone was added, and the mixture was refluxed for 3 hours. p. m. (10000G)
After centrifuging at 40 minutes, the insoluble matter is filtered. The filtrate was concentrated with a rotary evaporator, and the precipitate (acetone-soluble matter) was dried under reduced pressure at 60 ° C. for 5 hours, and then a methyl ethyl ketone solution (0.4 g / d) was measured using an Ubbelohde viscometer.
l), η _{sp / c} was measured at 30 ° C.

(3) Tensile Yield Strength Measured according to ASTM D638 (23 ° C.).

(4) Flexural Modulus Measured according to ASTM D790 (23 ° C.).

(5) Deflection temperature under load Measured according to ASTM D648 (6.4 mm, load stress 1.82 MPa).

(6) IZOD Impact Strength It was measured according to ASTM D256 (23 ° C., 12.7 mm, notched).

(7) MFR (Melt Flow Rate) It was measured according to ISO 1133 (220 ° C., 98N load).

(8) Surface resistivity Measured according to ASTM D257 (23 ° C., 50% RH).

(9) Delamination Prevention Property In the delamination prevention evaluation, the tensile test piece was bent and broken, and the state of the fracture surface was visually observed. The evaluation criteria were ◎: extremely good, ：: good, Δ: slightly poor, and X: extremely poor.

Reference Example (A) Graft Copolymer A ₁ : 120 parts of pure water, 0.5 part of glucose, 0.5 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and a table in a reactor substituted with nitrogen. The predetermined amount of polybutadiene latex shown in 1 was charged, and the temperature in the reactor was raised to 65 ° C. while stirring. The polymerization was initiated when the internal temperature reached 65 ° C., and a predetermined amount of the monomer and t-dodecyl mercaptan mixture shown in Table 1 was continuously added over 5 hours.
At the same time, an aqueous solution comprising cumene hydroperoxide and potassium oleate shown in Table 1 was continuously added over 7 hours to complete the reaction.

To the obtained latex, 1 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) was added to 100 parts by weight of the latex solid content.
Subsequently, this latex was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered, and dried to obtain a powdery graft copolymer A ₁ . The graft ratio of this graft copolymer was 45%.

Graft copolymers A _{2 to} A ₆ were obtained in the same composition ratio as shown in Table 1 by the same method as A _{2 to} A ₆ : ₁ .

(B) Copolymer B ₁ : A monomer mixture comprising 73 parts of styrene and 27 parts of acrylonitrile was suspension polymerized to obtain a bead-shaped copolymer B ₁ . The reduced viscosity of the copolymer was 0.65 dl / g.

B ₂ : A monomer mixture consisting of 73 parts of styrene and 27 parts of acrylonitrile was suspension polymerized to obtain a bead-like copolymer B ₂ . The reduced viscosity of the copolymer is 1.60 d.
1 / g.

B ₃ : A monomer mixture consisting of 76 parts of styrene and 24 parts of acrylonitrile was suspension polymerized to obtain a bead-like copolymer B ₃ . The reduced viscosity of the copolymer is 0.15d.
1 / g.

B ₄ : A monomer mixture of 40 parts of styrene, 30 parts of acrylonitrile and 30 parts of α-methylstyrene was emulsion polymerized to obtain a bead-like copolymer B ₄ . The reduced viscosity of the copolymer was 0.60 dl / g.

B ₅ : Copolymer B ₅ was obtained by emulsion polymerization of a monomer mixture consisting of 40 parts of styrene, 30 parts of acrylonitrile and 30 parts of N-phenylmaleimide. The reduced viscosity of the copolymer was 0.65 dl / g.

(C) Polyamide Elastomer C ₁ : Polyethylene glycol having a number average molecular weight of 4000 was reacted with acrylonitrile, and hydrogenation reaction was further carried out to obtain polyethylene glycol diamine having amino groups at both ends. This was reacted with terephthalic acid in a conventional manner to give a 40% solution of polyethylene glycol diammonium terephthalate. 4 in the can
120 parts of a 0% polyethylene glycol diammonium terephthalate aqueous solution and 16 parts of a 40% hexamethylene diammonium adipate aqueous solution were charged, and the internal temperature was 1 at normal pressure.
Heated to 10 ° C. for about 2 hours and concentrated to 80% concentration. Subsequently, the concentrated solution was transferred to a polymerization vessel, and heating was started while flowing nitrogen into the polymerization vessel. When the internal temperature reaches 120 ° C., a predetermined amount of sodium dodecylbenzenesulfonate and 1,3,5-trimethyl-2,4,6-tri (3,5-di-t-butylhydroxybenzyl) benzene are added. 10 parts were added, stirring was started, the temperature was raised until the internal temperature reached 245 ° C., and the mixture was heated for 18 hours to complete the polymerization. The resulting polymer was discharged in a strand form, pellet-like polyether cut - give the Teruamido C _1.

C ₂ : 40.0 parts of caprolactam, 53.1 parts of polyethylene glycol having a number average molecular weight of 1000 and 9.2 parts of terephthalic acid were added to "Irganox" 109.
8 (antioxidant) 0.2 part and antimony trioxide catalyst 0.1 part were charged into a reaction vessel equipped with a helical ribbon stirring blade, and the atmosphere was replaced with nitrogen and heated and stirred at 260 ° C. for 1 hour to obtain a transparent homogeneous solution. After that, polymerization was carried out at 260 ° C. under the condition of 0.5 mmHg or less for 4 hours to obtain a viscous and transparent polymer. The resulting polymer was discharged in a strand form, pellet-like polyether cut - to give the ether ester amide C _2.

(D) Modified vinyl copolymer D ₁ : 72 parts of styrene, 25 parts of acrylonitrile, and 3 parts of methacrylic acid were subjected to suspension polymerization to obtain a bead-shaped modified vinyl copolymer D ₁ . The reduced viscosity of the modified vinyl copolymer was 0.55 dl / g.

D ₂ : 77 parts of styrene, 21 parts of acrylonitrile, and 2 parts of methacrylic acid were suspension-polymerized to obtain a modified vinyl copolymer D ₂ in the form of beads. The reduced viscosity of the modified vinyl copolymer was 0.15 dl / g.

D ₃ : 70 parts of styrene, 27 parts of acrylonitrile, and 3 parts of methacrylic acid were suspension-polymerized to obtain a modified vinyl copolymer D ₃ in the form of beads. The reduced viscosity of the modified vinyl copolymer was 1.60 dl / g.

(E) Acrylamide-based copolymer E ₁ : 4 liters of xylene, 1.5 kg of ethylene / ethyl acrylate / acrylic acid copolymer (93/3/4)
And 10 g of paratoluenesulfonic acid was charged into the reactor, 210 g of N, N-dimethylaminopropylamine was added, and the mixture was reacted at 140 ° C. for 17 hours. The reactor is then cooled to 80 ° C. and 310 g of diethyl sulphate are added,
The reaction is carried out for 4 hours, and acrylamide copolymer E ₁
I got

Examples 1 to 13 and Comparative Examples 1 to 10 (A) Graft copolymer, (B) copolymer, (C) polyamide elastomer, (D) modified vinyl copolymer and ( E) After blending the acrylamide copolymer at a ratio shown in Table 2, a 40 mmφ single-screw extruder (cylinder temperatures are Examples 1 to 4, 7 to 13 and Comparative Examples 1 to 1).
0 was 230 ° C. and the others were set to 260 ° C.) to obtain a resin pellet.

The pellets thus obtained were injected into an IS-50A injection molding machine manufactured by Toshiba Machine Co., Ltd.
~ 4, 7-13 and Comparative Examples 1-10 are 230 ° C, the others are set to 260 ° C, the mold temperature is set to 60 ° C), the test pieces are molded, various characteristics are evaluated, and the results are shown in Tables 3 to 6. Listed in.

From Examples 1 to 13, it can be seen that the thermoplastic resin compositions having the compounding ratios set forth in the claims of the present invention are excellent in permanent antistatic property, layer delamination preventive property and mechanical property.

However, in Comparative Examples 1 to 10, (A) graft copolymer, (B) copolymer, (C) polyamide elastomer, (D) modified vinyl copolymer and (E) acrylamide copolymer Since the blending ratio of the coalescence is outside the range specified in the present invention, Comparative Examples 1-2, 4-5 and 7-1
No. 0 had low delamination resistance, and Comparative Examples 2 to 3 and 6 had low permanent antistatic properties. Furthermore, Comparative Examples 2, 4, 7-8
Has low impact resistance and heat resistance, Comparative Example 9 has low rigidity and heat resistance, Comparative Example 10 has low impact resistance, and Comparative Example 4
And 8 also had low rigidity.

[0070]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[0071]

EFFECT OF THE INVENTION The antistatic resin composition of the present invention provides excellent permanent antistatic property without impairing the balance between moldability and mechanical strength, and is also excellent in layered peeling prevention property. It is suitable as a molding material for electric appliances for home appliances and other applications.

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Claims (14)

[Claims] 1. A graft copolymer (A) in which 5 to 80 parts by weight of a rubbery polymer (A-1) is grafted with at least an aromatic vinyl (a) and a vinyl cyanide (b).
10 to 40 parts by weight, at least aromatic vinyl (a) and vinyl cyanide (b)
13 to 81.8 parts by weight of copolymer (B), 8 to 30 parts by weight of polyamide elastomer (C), at least one selected from the group consisting of carboxyl group, epoxy group, amino group and amide group. An antistatic resin composition comprising 0.1 to 15 parts by weight of a modified vinyl copolymer (D) having a functional group and 0.1 to 2 parts by weight of an acrylamide copolymer (E). 2. The graft component of the graft copolymer (A), in place of the aromatic vinyl (a), or further has an α, β-unsaturated carboxylic acid ester (c). Antistatic resin composition. 3. The graft copolymer (A) comprises at least aromatic vinyl (a), vinyl cyanide (b), α,
The antistatic resin composition according to claim 1, which is a copolymer in which the β-unsaturated carboxylic acid ester (C) and a vinyl-based monomer (D) copolymerizable therewith are grafted. 4. The antistatic resin composition according to claim 1, wherein the copolymer (B) further contains an α, β-unsaturated carboxylic acid ester (C) as a copolymerization component. . 5. The copolymer (B) is an aromatic vinyl compound (a), vinyl cyanide (b), an α, β-unsaturated carboxylic acid ester (c), and a vinyl-based monomer copolymerizable therewith. The antistatic resin composition according to claim 4, which is a copolymer composed of a monomer (d). 6. The weight average particle diameter of the rubber in the rubbery polymer (A-1) is 0.1 to 2.0 μm.
The antistatic resin composition according to any one of 5 above. 7. The antistatic resin composition according to claim 1, wherein a graft ratio of the graft copolymer (A) is 15 to 150%. 8. The reduced viscosity of the copolymer (B) is 0.2.
The antistatic resin composition according to any one of claims 1 to 7, wherein the antistatic resin composition has a viscosity of 1.5 dl / g. 9. The antistatic resin composition according to claim 1, wherein the polyamide elastomer (C) is a polyetheresteramide. 10. The antistatic resin composition according to claim 1, wherein the modified vinyl copolymer (D) is a copolymer containing at least aromatic vinyl, vinyl cyanide and methacrylic acid. Stuff. 11. The modified vinyl copolymer (D) comprises 50 to 79.9% by weight of an aromatic vinyl compound, 20 to 40% by weight of a vinyl cyanide compound, and 0.1 to methacrylic acid.
The antistatic resin composition according to claim 10, which is a copolymer composed of 10% by weight. 12. The reduced viscosity of the modified vinyl copolymer (D) is 0.2 to 1.5 d / g.
The antistatic resin composition according to any one of 1. 13. The acrylamide-based copolymer (E)
The antistatic resin composition according to claim 1, wherein is an acrylamide-based copolymer having an ethylene structural unit, an acrylate structural unit, and an acrylamide structural unit. 14. The acrylamide-based copolymer (E)
Is 65 to 99 mol% of ethylene structural units, 15 mol% or less of acrylate structural units, and 1 of acrylamide structural units.
The antistatic resin composition according to claim 1, wherein the antistatic resin composition is a copolymer having a content of ˜35 mol%.