JP2906542B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition having permanent antistatic properties, excellent mechanical properties typified by impact resistance, and excellent surface gloss of molded articles. Things.

<Prior Art> Synthetic polymer materials are used in a wide range of fields due to their excellent properties. If these materials are given an antistatic property (antistatic property) in addition to the mechanical strength of the materials, their use is expanded especially to copiers and various dustproof parts for which it is desired to prevent troubles due to static electricity. be able to.

As a method for improving the antistatic property of a synthetic polymer material,
For example, as disclosed in JP-A-55-36237, a hydrophilic rubbery polymer obtained by copolymerizing a conjugated diene or / and an acrylate ester and a vinyl monomer having an alkylene oxide group is added to a vinyl-based polymer. There is a method in which a monomer or a vinylidene monomer is graft-polymerized, and a practicable antistatic property has been achieved. JP-A-60-23435 discloses a resin having a semi-permanent antistatic property by mixing 5 to 80 parts by weight of polyetheresteramide and 95 to 20 parts by weight of a modified vinyl polymer having a carboxyl group. Is disclosed.

<Problems to be Solved by the Invention> However, the antistatic resin obtained by graft-polymerizing a monomer to the hydrophilic rubbery polymer described in Japanese Patent Application Laid-Open No. 55-36237 is a special hydrophilic resin. The use of a conductive rubber-like polymer has the disadvantage that the production method is complicated and the mechanical properties of the obtained resin are inferior, which is not satisfactory.

Further, the antistatic resin disclosed in JP-A-60-23435 has a disadvantage that the surface gloss of a molded article is poor due to the use of a large amount of a modified vinyl polymer having a carboxyl group.

Accordingly, the present invention provides a thermoplastic resin composition having both excellent mechanical properties such as excellent impact resistance and permanent antistatic properties, and excellent surface gloss of a molded article, regardless of a complicated production method. Providing is an issue.

<Means for Solving the Problems> According to the study of the present inventors, it has been found that the above problems can be effectively achieved by blending a specific polyamide elastomer or polyester elastomer with a chlorinated polyethylene graft copolymer. The present invention has been reached.

That is, the present invention provides (A) a number average molecular weight of 200 to 10,000
At least one selected from the group consisting of polyether amides, polyether ester amides and polyether esters containing 10 to 90% by weight of a poly (alkylene oxide) glycol, and (B) a chlorine content of 10 to 60%. 90 to 10 parts by weight of an aromatic vinyl monomer, 0 to 80% by weight of a (meth) acrylate monomer, 1 to 60 parts by weight of a chlorinated ethylene (co) polymer Graft copolymerization obtained by copolymerizing 0 to 60% by weight of a vinylated monomer and 99 to 40 parts by weight of a monomer mixture comprising 0 to 60% by weight of another vinyl monomer copolymerizable therewith (C) a modified vinyl polymer containing at least one functional group selected from carboxyl groups, epoxy groups, amino groups, hydroxyl groups, polyalkylene oxide groups and derivatives thereof; 98 And (D) 90 to 10% by weight of an aromatic vinyl monomer, 0 to 80% by weight of a (meth) acrylate monomer, 0 to 60% by weight of a vinyl cyanide monomer and the like. 0 to 90% by weight of a copolymer comprising 0 to 60% by weight of another vinyl monomer copolymerizable with
Parts by weight of the thermoplastic resin composition, wherein the total amount of the components (A), (B), (C) and (D) is 100 parts by weight. It provides molded products.

 Hereinafter, the present invention will be described specifically.

Examples of (A) the polyetheramide, polyetheresteramide or polyetherester containing 10 to 90% by weight of a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 10,000 include (a) a polyamide-forming component or Examples include a polyester-forming component and (b) a block or graft copolymer obtained from a reaction with a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 10,000.

(A) -1 As the polyamide-forming component, specifically,
ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, aminocarboxylic acids such as 12-aminododecanoic acid or caprolactam, enantholactam, Lactams such as caprylactam and laurolactam and salts of diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate, especially caprolactam, 12-amino Dodecanoic acid and hexamethylenediamine-adipate are preferably used.

As the (a) -2 polyester-forming component, specifically, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 4'-diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid and 5-
Aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclohexane Alicyclic dicarboxylic acids such as pentanedicarboxylic acid, 1,3-dicarboxymethylcyclohexane, 1,4-dicarboxymethylcyclohexyl and dicyclohexyl-4,4'-dicarboxylic acid and succinic acid, oxalic acid, adipic acid, sebacic acid And aliphatic dicarboxylic acids such as dodecane diacid (decane dicarboxylic acid) and mixtures thereof and ethylene glycol as an aliphatic diol;
-Or 1,3-propylene glycol, 1,2-, 1,3-,
2,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and the like, and mixtures thereof, particularly terephthalic acid as a dicarboxylic acid,
Isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid and dodecanediic acid, ethylene glycol, 1,2- or 1,3-propylene glycol, and 1,4-butanediol as aliphatic diols are polymerizable, color and physical properties. It is preferably used from the viewpoint.

(B) The poly (alkylene oxide) glycol used in the present invention includes poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) Glycol, ethylene oxide and propylene oxide or a block or random copolymer of ethylene oxide and tetramethylene oxide and a block or random copolymer of ethylene oxide and tetrahydrofuran and their diamines or dicarboxylic acids, which may be one or two or more.
More than species are used.

Among them, poly (ethylene oxide) glycol is particularly preferably used because of its excellent antistatic property. The number average molecular weight of the poly (alkylene oxide) glycol is preferably in the range of 200 to 10,000, particularly 400 to 8,000.

Examples of the reaction of the elastomer of the component (A) used in the present invention include the reaction of (a) a polyamide-forming component or a polyester-forming component with (b) a poly (alkylene oxide) glycol. Depending on the terminal group of the (alkylene oxide) glycol, an ester reaction or an amide reaction can be considered.

Further, a third component such as a dicarboxylic acid or a diamine may be used depending on the reaction.

In this case, the dicarboxylic acid component has 4 carbon atoms.
~ 20 are preferably used.Specifically, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane Aromatic dicarboxylic acids such as dicarboxylic acid and 5-sodium sulfoisophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-
Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and 4,4'-dicyclohexanedicarboxylic acid and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanediacid (decanedicarboxylic acid) and the like; Mixtures are enumerated. In particular, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 5-sodiumsulfoisophthalic acid, sebacic acid, adipic acid and dodecanediacid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

Examples of the diamine component include aromatic, alicyclic, and aliphatic diamines. One or more of these may be used. Of these, hexamethylenediamine, an aliphatic diamine, is preferably used for economic reasons.

(B) The content of the poly (alkylene oxide) glycol is in the range of 10 to 90% by weight, preferably 30 to 80% by weight in the structural unit of polyetheramide, polyetheresteramide or polyetherester. If the amount is less than 90% by weight, the antistatic property of the resin composition is inferior, and if it exceeds 90% by weight, the affinity with the chlorinated polyethylene graft copolymer (B) is deteriorated, and laminar exfoliation (turning up by 1,000 sheets) is not preferred.

The relative viscosity of the polyether amide, polyether ester amide or polyether ester of the component (A) is not particularly limited, but is preferably 1.2 to 5.0 (0.5%
o-chlorophenol solution), particularly preferably 1.5 to 2.5.
It is. When the relative viscosity is 1.2 or more, the elastomer of the component (A) is easily dispersed uniformly in the resin composition, and the antistatic property is excellent. When the relative viscosity is 5.0 or less, the production time of the elastomer of the component (A) is short and economical.

The method for polymerizing the polyetheramide, polyetheresteramide, or polyetherester of the component (A) is not particularly limited. For example, (a) a mixture of polyethylene glycol diamine, dicarboxylic acid, and aliphatic diamine may be used in the presence of ε-caprolactam. below, under N ₂ atmosphere 22
A method of copolymerizing by heating to 0 to 270 ° C. or a method disclosed in (B) JP-A-52-27497 or JP-A-56-65026 can be used.

Examples of the chlorinated ethylene-based (co) polymer which is a component of the graft copolymer (B) used in the present invention include ethylene such as polyethylene, ethylene-propylene copolymer and ethylene-butene-1 copolymer. ) Chlorinated polymers and chlorosulfonated polyethylenes are preferred, with chlorinated polyethylene being particularly preferred. The chlorine content of the chlorinated ethylene (co) polymer is used in the range of 10 to 60% by weight, preferably 20 to 50% by weight.

If the chlorine content of the chlorinated ethylene (co) polymer is less than 10% by weight, the impact resistance of the resin composition is poor, and if it exceeds 60% by weight, the thermal stability of the resin composition becomes poor, which is not preferable. .

(B) Examples of the aromatic vinyl comonomer which is a component of the graft (co) polymer include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene and op.
-Dichlorostyrene and the like, with styrene being particularly preferred.

Although not an essential component, examples of the (meth) acrylate monomer include acrylic acid and methacrylic acid, such as methyl, ethyl, propyl, n-butyl, and n-hexyl, with methyl methacrylate being particularly preferred.

Although not an essential component, examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, and ethacrylonitrile, and acrylonitrile is particularly preferable.

Although not an essential component, other vinyl monomers include maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, and acrylamide monomers such as acrylamide and N-methylacrylamide. Monomer, maleic anhydride, unsaturated acid anhydrides such as itaconic anhydride, acrylic acid, unsaturated acids such as methacrylic acid, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate,
Examples thereof include 2-hydroxyethyl methacrylate and methoxypolyethylene glycol methacrylate, and the use of N-phenylmaleimide, acrylamide, glycidyl methacrylate, 2-hydroxyethyl methacrylate, and maleic anhydride is particularly preferable.

(B) The proportion of the aromatic vinyl monomer used in the graft copolymer is 90 to the total vinyl monomer used.
To 10% by weight, preferably 80 to 20% by weight. If the amount is less than 10% by weight, the impact resistance of the resin composition is inferior.
If the content is more than 10% by weight, the polymerizability deteriorates, which is not preferable.

On the other hand, if the proportion of the (meth) acrylic ester-based monomer exceeds 80% by weight based on the total amount of the vinyl-based monomer, the impact resistance of the resin composition deteriorates, which is not preferable.

Further, when the proportion of the vinyl cyanide monomer exceeds 60% by weight based on the total vinyl monomers, the graft copolymer is undesirably colored.

(B) The ratio of the chlorinated ethylene-based (co) polymer and the monomer mixture in the graft copolymer is such that the chlorinated ethylene-based (co) polymer is 1 to 6 in 100 parts by weight of the total graft copolymer.
0 parts by weight, preferably 5 to 50 parts by weight. This (B)
If the proportion of the chlorinated ethylene (co) polymer in the graft copolymer is less than 1 part by weight, the impact resistance of the resin composition is poor, and if it exceeds 60 parts by weight, the appearance of the molded article of the resin composition becomes poor. Not preferred. (B) The method for polymerizing the graft copolymer is not particularly limited.
The method disclosed in, for example, Japanese Patent No. 17057 can be used.

In the thermoplastic resin composition of the present invention, (C) a modified resin 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 and derivatives thereof. By using a vinyl polymer (hereinafter abbreviated as 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, and may be large as long as the performance as a resin is not impaired.

Usually, the effect of the present invention can be effectively exhibited if one molecule or more of the above-mentioned functional groups 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-
Polymerization initiator having a carboxyl group such as cyanoethyl) -p-benzoic acid and succinic peroxide and / or thioglycolic acid, α-mercaptopropionic acid, β
A method of (co) polymerizing a predetermined vinyl monomer using a polymerization degree regulator having a carboxyl group such as -mercaptopropionic acid, α-mercapto-isoacetic acid and 2,3 or 4-mercaptobenzoic acid; and A method of saponifying a (meth) acrylate-based (co) polymer such as methyl methacrylate or butyl acrylate with an alkali can be used.

There is no particular limitation on the method of introducing an epoxy group. (Wherein R ¹ is a hydrogen atom, a lower alkyl group or a lower alkyl group substituted with a glycidyl ester group). Specifically, glycidyl acrylate,
A method of copolymerizing 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, 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, a phenyl group or a cycloalkyl group having 6 to 12 carbon atoms, or derivatives thereof. ) At least one of an amino group or a substituted amino group represented by
A method of copolymerizing a vinyl monomer having a kind of functional group with a predetermined vinyl monomer, selected from the group consisting of amino groups, substituted amino groups and mineral salts thereof represented by the above (II) A method of (co) polymerizing a predetermined vinyl monomer by using the obtained chain transfer agent and / or initiator having at least one functional group can be used.

Here, specific examples of the vinyl monomer having at least one functional group of an amino group or a substituted amino group include aminoethyl acrylate, propylaminoethyl acrylate, methylaminoethyl methacrylate, ethylaminopropyl methacrylate, Alkyl or methacrylic acid alkyl ester derivatives such as phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methallylamine and N-methyl Allylamine derivatives such as allylamine, and (meth) acrylic acids such as acrylamide, methacrylamide, and N-methylacrylamide, butoxymethylacrylamide, and N-propylmethacrylamide. Ruamido based derivative and p- aminostyrene aminostyrene such as and the like.

Specific examples of the polymerization degree regulator having the above functional group include mercaptomethylamine, β-methylcaptoethylamine, γ-mercaptopropylamine, and N- (β
-Mercaptoethyl) -N-methylamine, N- (β-
Methylcaptoethyl) -N-phenylamine, N- (β
-Mercaptoethyl) -N-cyclohexylamine, bis- (4-aminophenyl) disulfide, bis-
(2-aminophenyl) disulfide, bis- (3-
Aminophenyl) disulfide, p-mercaptoaniline, 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.

There is no particular limitation on the method for introducing a hydroxyl group. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, or the like can be prepared by using a predetermined vinyl monomer. For example, a method of copolymerizing with a body can be used.

The method for introducing the polyalkylene oxide group or a derivative thereof is not particularly limited. For example, a vinyl-based monomer containing a polyalkylene oxide group represented by the following formulas (III) and (IV) is converted into a desired vinyl (Meth) acrylic ester such as poly (methyl methacrylate) or (meth) acrylic ester such as methyl methacrylate or butyl acrylate is copolymerized with a desired vinyl monomer. (Co) A method of subjecting a polymer to a polyalkylene oxide glycol of one end alkyl ether by an ester reaction and a method of copolymerizing acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and the like with a desired vinyl monomer. Of a carboxyl group-containing vinyl monomer and an alkyl ether at one end And a method for esterification of alkylene oxide glycol.

(Where R ⁴ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents an alkylene 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 of the compounds represented by the general formulas (III) and (IV) include polyethylene glycol acrylate, polyethylene glycol methacrylate, poly (propylene oxide) glycol acrylate, and 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 glycol) Sid) glycol acrylate, methoxy poly (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, methoxypolyethylene glycol acrylamide, methoxypolyethylene Glycol methacrylamide, methoxy poly (propylene oxide) glycol acrylamide, methoxy poly (propylene oxide) glycol methacrylamide, methoxy (tetramethylene oxide) glycol methacrylamide, etc., especially methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylamide And methoxypolyethylene glycol methacrylamide are preferred because of their excellent polymerizability and affinity with the polyetheresteramide (A).

Further, the ester reaction between a (meth) acrylic acid ester (co) polymer or a vinyl monomer having a carboxyl group or an anhydrous carboxyl group and a poly (alkylene oxide) glycol having an alkyl ether at one end is a high temperature. At normal pressure or under vacuum.

The poly (alkylene oxide) glycol having an alkyl ether at one end used herein includes, 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, block or random copolymer of methoxy (ethylene oxide) and propylene oxide, and block or random copolymer of methoxy (ethylene oxide) and tetrahydrofuran. Ether polyethylene glycol is preferred.

The poly (alkylene oxide) glycol having an alkyl ether at one end has a number average molecular weight 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. For example, aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene, acrylonitrile, methacrylonitrile Vinyl cyanide monomers such as, (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-mentioned 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.

The aromatic vinyl monomer which is a constituent component of the copolymer (D) used in the present invention includes styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, o-ethylstyrene and o-ethylstyrene. Examples thereof include -p-chlorostyrene, and styrene and α-methylstyrene are particularly preferable.

(Meth) acrylic ester monomers include acrylic acid and methacrylic acid methyl, ethyl, propyl,
Examples thereof include n-butyl and n-hexyl, and methyl methacrylate is particularly preferable.

Acrylonitrile as a vinyl cyanide monomer,
Examples thereof include methacrylonitrile and ethacrylonitrile, and acrylonitrile is particularly preferable.

Further, as other vinyl monomers copolymerizable therewith, maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, ethylene,
Olefinic monomers such as propylene and vinyl chloride, vinyl acetate and butadiene, and the like,
Particularly, use of N-phenylmaleimide is preferred.

(D) The proportion of the aromatic vinyl monomer as a component of the copolymer is 90 to 10% by weight, preferably 90% by weight, based on all monomers.
It is used in the range of 80 to 20% by weight, and if it exceeds 90% by weight, the polymerizability is lowered, and if it is less than 10% by weight, the impact resistance of the resin composition is inferior. On the other hand, if the proportion of the (meth) acrylic ester-based monomer exceeds 80% by weight based on all the monomers, the impact resistance of the resin composition deteriorates, which is not preferable. Further, when the proportion of the vinyl cyanide-based monomer exceeds 60% by weight based on all the monomers, the thermal stability of the copolymer deteriorates and the resin composition is undesirably colored.

(D) The method for producing the copolymer is also not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and bulk-suspension polymerization can be used.

(A) 1 to 40 parts by weight of at least one selected from polyetheresters, polyetheresteramides and polyetheresters,
Preferably 5 to 30% by weight, (B) graft copolymer 1 to 99
Parts by weight, preferably 5 to 90 parts by weight, not an essential component, but (C) 0 to 98 parts by weight, preferably 0 to 90 parts by weight of the modified vinyl polymer; 0 to 98 parts by weight, preferably 0 to 90 parts by weight, and the total amount of the components (A), (B), (C) and (D) is 10
By blending so as to be 0 parts by weight, the thermoplastic resin composition of the present invention can be obtained.

Here, the compounding amount of (A) polyether amide, polyether ester amide or polyether ester is 1
If the amount is less than 10 parts by weight, the antistatic properties of the resin composition will be insufficient, and if it exceeds 40 parts by weight, the resin composition will be soft and have poor mechanical properties.

When the amount of the graft copolymer (B) is less than 1 part by weight, the resin composition is brittle and cannot be used. When the amount exceeds 99 parts by weight, the antistatic properties of the resin composition are insufficient, which is not preferable.

Further, when the blending amount of the modified vinyl polymer (C) and the copolymer (D) exceeds the above range, the antistatic property of the resin composition is insufficient, which is not preferable.

Further, the amount of a vinyl monomer containing a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyalkylene oxide group or a derivative thereof, a polymerization initiator, a polymerization degree regulator and a poly (alkylene oxide) glycol adduct is The amount is preferably 30 parts by weight or less, more preferably 20% by weight or less based on 100 parts by weight of the resin composition.

If the content of the above functional group exceeds 30% by weight, the appearance, gloss and color tone of the molded article are undesirably deteriorated.

Furthermore, the ratio of the chlorinated ethylene (co) polymer in the resin composition is 1 to 40% by weight, preferably 5 to 30% by weight.
If the amount is less than 1% by weight, the impact resistance of the resin composition is poor, and if it exceeds 40% by weight, the resin composition becomes unpreferably soft.

The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include (A) polyetheramide, polyetheresteramide or polyetherester,
It is commercialized by melt-kneading a mixture of (B) the graft copolymer and (C) the modified vinyl polymer with a Banbury mixer, roll, extruder, kneader or the like. Further, by substituting a part of the graft copolymer (B) with the copolymer (D), the content of the chlorinated ethylene (co) polymer in the resin composition can be arbitrarily changed.

In the thermoplastic resin composition of the present invention, other compatible thermoplastic polymers can be further mixed. For example, (1) polyamide, polyethylene terephthalate,
Improve chemical resistance and impact resistance by mixing polybutylene terephthalate, etc. (2) Improve heat resistance without impairing impact resistance by mixing polycarbonate, polyphenylene ether and polyglutarimide It is possible to improve the flame retardancy by mixing (3) vinyl chloride resin.

Further, by adding an epoxy compound or an isocyanate compound containing at least two epoxy groups or isocyanate groups in the molecule, it is also possible to improve the laminar peel resistance of the resin composition.

Furthermore, it is also possible to further improve the antistatic property by adding an antistatic agent such as an inorganic alkali metal salt or an anionic, a cationic or a nonionic, and if necessary, a compatibilizer such as an oligomer, Various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants and plasticizers, glass fibers, metal fibers, and flame retardants can also be added.

<Examples> In order to more specifically explain the present invention, examples and comparative examples 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 Flexural modulus: ASTM D790 Surface resistivity: 2 mm t × 40 mmφ disk, room temperature 23
The measurement was performed in an atmosphere of 50 ° C and a humidity of 50% RH. A super insulation resistance meter SN-10E manufactured by Toa Denpa Kogyo KK was used for the measurement.

Surface gloss of molded product: Using a square plate of 80 mm × 120 mm × 2 mm t,
It was measured at a measurement angle of 60 °. For the measurement, a digital variable angle gloss meter UGV-5D manufactured by Suga Test Instruments Co., Ltd. was used.

Delamination prevention property: The molded article was bent and observed by observing the surface. ◎: extremely good, ：: good, ×: the molded article delaminated.

Further, the number of parts and% in the examples indicate parts by weight and% by weight, respectively.

Reference Examples (1) (A) Preparation of Elastomer A-1: 45 parts of caprolactam, 48.6 parts of polyethylene glycol having a number average molecular weight of 1,000 and 8.4 of terephthalic acid in 0.2 parts of "Irganox" 1098 (antioxidant) and antimony trioxide 0.1 part of the catalyst was charged into a reactor equipped with a helical ribbon stirring blade together with N ₂ , and the mixture was heated and stirred for 90 minutes while substituting N ₂ and flowing a small amount of N ₂ at 260 ° C. to form a transparent homogeneous solution, then 260 ° C., 0.5 mmHg Polymerization was performed for 3 hours under the following conditions to obtain a viscous and transparent polymer. The polymer was discharged in a gut shape on a cooling belt and pelletized to prepare pellet-like polyetheresteramide (A-1).

A-2: Acrylonitrile was reacted with polyethylene glycol having a number average molecular weight of 4,000, and hydrogenation was further performed to obtain polyethylene glycol diamine having amino groups at both ends. This was subjected to a salt reaction with terephthalic acid by a conventional method to obtain a 40% aqueous solution of polyethylene glycol diammonium terephthalate.

In a concentration can, 200 parts of the above 40% aqueous solution of polyethylene glycol diammonium terephthalate, caprolactam 102
After charging 16 parts of a 40% aqueous solution of hexamethylenediammonium adipate, the mixture was heated to 110 ° C and concentrated to a concentration of 80%. Subsequently, the above concentrated liquid was transferred to a polymerization vessel. After replacing with N ₂ , the temperature was raised to 120 ° C., and 10 parts of 1,3,5-trimethyl-2,4,6-tri (3,5-di-t-butyl-hydroxybenzyl) benzene was added. The mixture was stirred and heated to 245 ° C. Polymerization was performed at 245 ° C. for 10 hours to obtain a viscous and transparent polymer. As the polymer, pelletized polyetheramide (A-2) was prepared in the same manner as in A-1.

A-3: terephthalic acid 34.9 parts, 1,4-butadiol 32.7
Parts, polyethylene glycol with a number average molecular weight of 2,000 56.3
Parts, tetrabutyl titanate (0.05 parts) and "Irganox" 1010 (antioxidant) (0.2 parts) were charged into an esterification reactor and reacted at 220 ° C. for 2 hours in a N ₂ atmosphere. Then
After transferring the reaction solution to the polymerization vessel, tetrabutyl titanate
0.05 part was added, and polymerization was carried out at 250 ° C. under a condition of 0.5 mmHg or less for 3 hours. After completion of the polymerization, pellet-like polyetherester (A-3) was prepared in the same manner as in A-1.

(2) (B) Preparation of Graft Copolymer B-1: A suspension obtained by treating 20 parts of chlorinated polyethylene having a chlorine content of 41% and methyl methacrylate-acrylamide copolymer with sodium hydroxide in a 1:25 autoclave. And 150 parts of ion-exchanged water, and vigorously stirred at room temperature. 60 parts of styrene and 20 parts of acrylonitrile
Part, t-butyl peroxybenzoate 0.3 part, dicumyl peroxide 0.1 part and t-dodecyl mercaptan
After adding 0.3 part and replacing with N ₂ , the temperature was raised to 105 ° C. After polymerization at this temperature for 4 hours, polymerization was continued at 130 ° C. for 2 hours. After the completion of the polymerization, the resultant was cooled to room temperature. The obtained graft copolymer was filtered, washed, dehydrated and dried to prepare a powdery graft copolymer (B-1). The conversion of all monomers was 97%.

B-2: except that the chlorinated polyethylene used in B-1 was changed to 40 parts, styrene 45 parts, and acrylonitrile 15 parts.
Polymerization was performed under the same conditions as in Example 1 to prepare a powdery graft copolymer (B-2).

 The conversion of all monomers was 98%.

(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 had an intrinsic viscosity of 0.61 as measured at 30 ° C. in a 0.4% solution of methyl ethyl ketone.

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

C-3: a mixture 95 of 73% styrene and 27% acrylonitrile
Parts and 5 parts of acrylamide were subjected to emulsion polymerization. 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 intrinsic viscosity of the resulting modified vinyl polymer measured by the same method as in C-1 was 0.56.

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

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 subjected to suspension polymerization 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.

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

D-2: 72 parts of methyl methacrylate, 24 parts of styrene, and 4 parts of acrylonitrile were subjected to suspension polymerization to prepare a copolymer (D-2).

D-3: 50 parts of styrene, 30 parts of N-phenylmaleimide, and 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 12, Comparative Examples 1 to 9 (A) polyether amide, polyether ester amide or polyether ester, (B) graft copolymer, (C) modified vinyl polymer and (D) 0.5 part of dibutyltin maleate and 1.0 part of ethylenebisstearylamide were mixed with a mixture obtained by mixing the copolymer at the compounding ratio shown in Table 1, and the mixture was melt-kneaded at a resin temperature of 200 ° C. with a vented 40 mmφ twin-screw extruder. And extruded to obtain a pellet-shaped composition.

The pellet-shaped compositions obtained in Examples and Comparative Examples were subjected to a cylinder temperature of 220 ° C. and a mold temperature of 6 by an injection molding machine.
A test piece was molded at 0 ° C. and each physical property was measured. Table 2 shows the measurement results. Surface resistivity is 2mm thick by injection molding
Was measured 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. The humidity was measured for a period of time.

(2) After molding, leave it in 50% RH, 23 ° C for 200 days,
Wash with detergent "Mama Lemon" aqueous solution, then wash thoroughly with distilled water to remove surface moisture, then 50% RH, 23 ° C
For 24 hours. Table 2 shows the measurement results.

The following is clear from the results in Table 2.

The thermoplastic resin compositions of the present invention (Examples 1 to 12) are excellent in balance of mechanical properties represented by impact strength and flexural modulus and surface gloss of molded products, and furthermore, by surface cleaning and aging. The resistance value hardly changes, and it exhibits excellent permanent antistatic properties. Further, the molded article is extremely good without delamination.

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

On the other hand, when the blending amount of the elastomer (A) is less than 1% by weight (Comparative Example 1), the antistatic property (resistance value) is poor,
If it exceeds 40% by weight (Comparative Example 2), the flexural modulus is inferior.

When the blending amount of the (B) graft copolymer is less than 1% by weight (Comparative Examples 3, 5, and 6), the impact resistance is poor, and when it exceeds 99% by weight (Comparative Example 4), the antistatic property is low. Inferior.

<Effect of the Invention> The thermoplastic resin composition of the present invention has excellent mechanical properties typified by impact resistance and flexural modulus, and has a high degree of permanent antistatic properties. It is useful for applications.

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Claims (2)

(57) [Claims] (A) at least one selected from polyetheramides, polyetheresteramides and polyetheresters containing 10 to 90% by weight of a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 10,000.
1 to 40 parts by weight of seed, (B) 1 to 60 parts by weight of a chlorinated ethylene (co) polymer having a chlorine content of 10 to 60% by weight, 90 to 10 parts by weight of an aromatic vinyl monomer, A simple composition comprising 0 to 80% by weight of a (meth) acrylate monomer, 0 to 60% by weight of a vinyl cyanide monomer and 0 to 60% by weight of another vinyl monomer copolymerizable therewith. 5 to 90 parts by weight of a graft copolymer obtained by copolymerizing 99 to 40 parts by weight of a monomer mixture, (C) selected from carboxyl groups, epoxy groups, amino groups, hydroxyl groups, polyalkylene oxide groups and derivatives thereof. 2 to 98 parts by weight of a modified vinyl polymer containing at least one functional group, (D) 90 to 10% by weight of an aromatic vinyl monomer, and 0 to (meth) acrylate monomer. 80% by weight, 0 to 60% by weight of vinyl cyanide monomer and copolymerizable with them Copolymer 0-90 consisting of 0-60% by weight of other functional vinyl monomers
A thermoplastic resin composition characterized by being blended so that the total amount of the above components (A), (B), (C) and (D) is 100 parts by weight. 2. A molded article comprising the thermoplastic resin composition according to claim 1.