JPH10139974A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic resin composition which can give a molding having permanent antistatic properties, well-balanced and excellent mechanical properties typified by impact resistance and surface gloss, and does not undergo delamitation by blending specified three components. SOLUTION: This composition is prepared by blending 1-40 pts.wt. polyamide elastomer containing polyether ester units or polyether units and being a block or graft copolymer obtained by the reaction of a polyamide-forming component such as caprolactam or 12-aminododecananoic acid with a poly(alkylene oxide) glycol, 50-98 pts.wt. acrylic resin comprising a (meth)acrylic ester and is being e.g. a polymethyl acrylate being a (co)polymer of an alkyl (meth)acrylate compound and obtained by e.g. suspension polymerization or emulsion polymerization, and 0.1-10 pts.wt. carboxylic modified vinyl polymer and modified vinyl polymer containing at least one type of functional group selected among epoxy groups, amino groups, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has permanent antistatic properties, excellent balance of mechanical properties represented by impact resistance and gloss of molded articles, and has no delamination (thousands of pages turned). The present invention relates to an antistatic resin composition.

[0002]

2. Description of the Related Art Synthetic polymer materials are used in a wide range of fields due to their excellent properties. The use of these materials can be further expanded if antistatic properties are imparted in addition to the mechanical strength of the materials. That is,
It can be used for copiers and various dust-proof parts that require protection from static electricity.

As a method for improving the antistatic property of a synthetic polymer material, a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and / or an acrylate ester and a vinyl monomer having an alkylene oxide group is known. Obtained by graft-polymerizing a vinyl monomer onto the polymer (JP-A-55-3623)
No. 7 publication), etc., and achieves a practical antistatic effect.

Japanese Patent Application Laid-Open No. Sho 60-23435 discloses that
It discloses that a resin having semi-permanent antistatic properties can be obtained by mixing 5 to 80 parts by weight of a polyamide elastomer and 95 to 20 parts by weight of a modified vinyl polymer having a carboxyl group.

[0005]

However, the antistatic resin obtained by graft-polymerizing a monomer to a hydrophilic rubbery polymer described in JP-A-55-36237 is a special hydrophilic rubbery polymer. Since the polymer is used, the production method is complicated, and the mechanical properties of the obtained resin are inferior.

The antistatic resin disclosed in Japanese Patent Application Laid-Open No. 60-23435 has a large amount of a modified vinyl polymer containing a carboxyl group. The surface gloss is remarkably deteriorated, which is still unsatisfactory.

An object of the present invention is to have permanent antistatic properties,
Another object of the present invention is to provide an antistatic resin composition which is excellent in mechanical properties typified by impact resistance and excellent in surface gloss of a molded product, and has no delamination.

[0008]

As a result of intensive studies to solve the above-mentioned problems, in order to solve the above-mentioned problems, a polyamide elastomer, an acrylic resin, and a modified vinyl polymer having a specific functional group have a specific ratio. It has been found that it is important to mix them with the present invention, and arrived at the present invention.

That is, the present invention relates to (A) 1 to 40 parts by weight of a polyamide elastomer containing a polyether ester unit or a polyether unit, (B) 50 to 98 parts by weight of an acrylic resin comprising a (meth) acrylate ester, (C) 0.1 to 10 parts by weight of a modified vinyl polymer containing a carboxyl group is added to (A), (B) and (C).
Wherein the total amount of the thermoplastic resin composition is 100 parts by weight. And (A) 1 to 40 parts by weight of a polyamide elastomer containing a polyether ester unit or a polyether unit, and (B) an acrylic resin composed of a (meth) acrylate ester 20 to
98 parts by weight, (C) a modified vinyl polymer containing at least one functional group selected from the group consisting of epoxy groups, amino groups and substituted amino groups, hydroxyl groups and polyalkylene oxide groups and derivatives thereof. 1
A thermoplastic resin composition characterized in that 〜40 parts by weight are blended so that the total amount of (A), (B) and (C) is 100 parts by weight. ".

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below.

The (A) polyamide elastomer in the present invention is, for example, a block or graft copolymer obtained from the reaction of (a) a polyamide-forming component with (b) poly (alkylene oxide) glycol.

(A) 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, 12
Aminocarboxylic acids such as aminododecanoic acid or lactams such as caprolactam, enantholactam, caprylactam and laurolactam and hexamethylenediamine-adipate, hexamethylenediamine
Salts of diamine-dicarboxylic acids such as sebacate and hexamethylenediamine-isophthalate;
Particularly, caprolactam, 12-aminododecanoic acid and hexamethylenediamine-adipate are preferably used.

Examples of (b) poly (alkylene oxide) glycol preferably used in the present invention include poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol and poly (1,3-propylene oxide) glycol. And poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. 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 from 200 to 6000, especially from 400 to
A range of 4000 is preferred.

Further, in combination with (b) poly (alkylene oxide) glycol, the following formulas (I) to (II)
The diol compound represented by I) can be used.

[0015]

Embedded image (Wherein, R ¹ and R ² represent an ethylene oxide group and / or
Or a propylene oxide group, and Y represents a covalent bond, an alkylene group having 1 to 6 carbon atoms, an alkylidene group, a cycloalkylidene group, an arylalkylidene group, O, SO, S
O ₂ , CO, S, CF ₂ , C (CF ₃ ) ₂ or NH is shown. )

Specific examples include bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, brominated bisphenol A ethylene oxide adduct, bromine Ethylene oxide of bisphenols such as propylene oxide adduct of hydrogenated bisphenol A and / or
Or propylene oxide adduct, ethylene oxide and / or propylene oxide adduct of hydroquinone, ethylene oxide and / or propylene oxide adduct of dihydroxynaphthalene and their block (co) polymers, ethylene oxide addition of 4,4 '-(hydroxy) biphenyl Propylene oxide adduct of 4,4'-bis (hydroxy) biphenyl, ethylene oxide adduct of bis (4-hydroxyphenyl) sulfide, propylene oxide adduct of bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy Phenyl) sulfoxide ethylene oxide adduct, bis (4-hydroxyphenyl) sulfoxide propylene oxide adduct, bis (4-hydroxyphenyl) methane ethyleneoxy Adduct, propylene oxide adduct of bis (4-hydroxyphenyl) methane, ethylene oxide adduct of bis (4-hydroxyphenyl) ether, propylene oxide adduct of bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) A) ethylene oxide adduct of amine, propylene oxide adduct of bis (4-hydroxyphenyl) amine, ethylene oxide adduct of 2,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) ethane Propylene oxide adduct of 4,
Bisphenols such as ethylene oxide adduct of 4′-dihydroxybenzophenone, ethylene oxide adduct of 1,1-bis (4-hydroxyphenyl) cyclohexane, and propylene oxide adduct of 1,1-bis (4-hydroxyphenyl) cyclohexane are exemplified. be able to.

Preferred diol compounds include ethylene oxide adduct of hydroquinone, ethylene oxide adduct of bisphenol A, ethylene oxide adduct of brominated bisphenol A, ethylene oxide adduct of bisphenol S, ethylene oxide adduct of dihydroxynaphthalene and block copolymers thereof. In particular, an ethylene oxide adduct of bisphenol A and a block polymer thereof are preferable. Also, brominated bisphenol A
By using an ethylene oxide adduct of brominated bisphenol S or an ethylene oxide adduct of brominated bisphenol S, the flame retardancy of the resin composition can be improved.

These poly (alkylene oxide) glycols and the diol compounds represented by formulas (I) to (III) can be used alone or in combination of two or more as required. The amount of the diol compound represented by any one of the general formulas (I) to (III) is not particularly limited.
Preferably, it is in the range of ６０60% by weight, especially 1-50% by weight.

Further, other diol compounds can be copolymerized as long as the effects of the present invention are not impaired.
Specifically, ethylene glycol, 1,4-butanediol, aliphatic diols such as hexanediol, p-xylylene glycol, aromatic diols such as m-xylylene glycol, 1,2-cyclohexanediol,
1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,
An alicyclic diol compound such as 1,3-cyclohexanedimethanol can be copolymerized.

Examples of the reaction of the polyamide elastomer of the present invention include an ester reaction or an amide reaction depending on the terminal groups of (a) a polyamide-forming component and (b) poly (alkylene oxide) glycol. Further, depending on the reaction, a third component (c) such as a dicarboxylic acid or a diamine can be used.

In this case, as the dicarboxylic acid component, those having 4 to 20 carbon atoms are preferably used. Specifically, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-
Aromatic dicarboxylic acids such as 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid and fats such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanediacid (decanedicarboxylic acid) Group carboxylic acids, especially terephthalic acid, isophthalic acid, 1,4-
Cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanediacid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

The diamine component includes, for example, aromatic, alicyclic and aliphatic diamines. Of these, hexamethylenediamine, an aliphatic diamine, is preferably used for economic reasons.

The polyetherester or polyether component is a constituent unit of a polyamide elastomer and has a content of 90 to 10%.
% By weight, and if it exceeds 90% by weight,
Polyamide has poor mechanical properties, and if it is less than 10% by weight, the resin has poor antistatic properties, which is not preferable.

(A) The method for producing the polyamide elastomer is not particularly limited, and for example, the methods disclosed in JP-A-56-65026 and JP-A-60-177022 can be used.

The acrylic resin (B) comprising a (meth) acrylic acid ester used in the present invention is a (co) polymer of an alkyl ester compound of (meth) acrylic acid such as methyl, ethyl, propyl and butyl. Specifically, polymethyl methacrylate, polyethyl methacrylate,
Polypropyl methacrylate, polymethyl acrylate, polyethyl acrylate, methyl methacrylate-ethyl methacrylate copolymer, methyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-methyl acrylate copolymer, methacrylic acid Examples thereof include a methyl-ethyl acrylate copolymer and a methyl methacrylate-butyl acrylate copolymer, and polymethyl methacrylate is particularly preferably used. These acrylic resins are one or two
More than one species can be used.

(B) The method for producing the acrylic resin comprising the (meth) acrylic acid ester is not particularly limited.
A known method such as emulsion polymerization can be used.

The carboxyl-containing modified vinyl polymer (C) used in the present invention and at least one selected from the group consisting of epoxy groups, amino groups and substituted amino groups, hydroxyl groups, and polyalkylene oxide groups and derivatives thereof. A modified vinyl polymer containing various kinds of functional groups (hereinafter collectively referred to as a modified vinyl polymer) is obtained by polymerizing or copolymerizing one or more vinyl monomers. At least one selected from the group consisting of a carboxyl group, an epoxy group, an amino group and a substituted amino group, a hydroxyl group and a polyalkylene oxide group and a derivative thereof in a molecule;
It is a modified vinyl polymer containing various functional groups. The content of these functional groups may be very small or may be large as long as the performance as a resin is not impaired.

In general, the effects of the present invention can be effectively exhibited if one molecule of the modified vinyl polymer substantially contains one or more of the above functional groups on average.

(C) The method for introducing a carboxyl group into the modified vinyl polymer is not particularly limited. (1) Carboxyl groups such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid (2) γ, γ′-azobis (γ-cyanovaleic acid), α, α′-azobis (α)
-Cyanoethyl-p-benzoic acid) and a polymerization initiator having a carboxyl group such as succinic peroxide and / or thioglycolic acid, α-mercaptopropionic acid,
A predetermined vinyl monomer is (co) polymerized using a polymerization degree regulator having a carboxyl group such as β-mercaptopropionic acid, α-mercaptoisobutyric acid and 2,3 or 2,4-mercaptobenzoic acid. And (3) a method of saponifying a (meth) acrylate-based (co) polymer such as methyl methacrylate or butyl acrylate with an alkali.

The method for introducing an epoxy group is not particularly limited. For example, it is represented by the formula (IV). Specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, etc. A method of copolymerizing with a system polymer can be used.

[0031]

Embedded image (In the formula, R ³ is a hydrogen atom, a lower alkyl group or a lower alkyl group substituted with a glycidyl ester group.)

The method of introducing an amino group or a substituted amino group is not particularly limited, either. For example, (1)
A method of copolymerizing a vinyl monomer having at least one functional group of an amino group or a substituted amino group represented by the formula (V) with a predetermined vinyl monomer, (2) represented by the formula (V) Using a chain transfer agent and / or an initiator having at least one functional group selected from the group consisting of an amino group, a substituted amino group and a mineral salt thereof, a predetermined vinyl monomer is (co) A polymerization method or the like can be used.

[0033]

Embedded image (Wherein, R ⁴ represents hydrogen, a methyl group, or an ethyl group; R ⁵ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms,
2 phenyl group or cycloalkyl group or derivatives thereof. )

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, dimethylaminoethyl methacrylate, and methacrylic acid. Alkyl or methacrylic acid alkyl ester derivatives such as ethylaminopropyl, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methallylamine And allylamine derivatives such as N-methylallylamine, (meth) acrylamide derivatives such as acrylamide, methacrylamide and N-methylacrylamide, and p
And aminostyrenes such as aminostyrene.

Specific examples of the above chain transfer agent having a functional group include mercaptomethylamine, β-mercaptoethylamine, γ-mercaptopropylamine,
-(Β-mercaptoethyl) -N-methylamine, N-
(Β-mercaptoethyl) -N-phenylamine, N-
(Β-mercaptoethyl) -N-cyclohexylamine, bis- (4-aminophenyl) disulfide, bis- (2-aminophenyl) disulfide, bis-
Examples thereof include (3-aminophenyl) disulfide, p-mercaptoaniline, o-mercaptoaniline, m-mercaptoaniline, and hydrochlorides thereof. Specific examples of the 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), p-aminobenzoyl peroxide and the like.

The method for introducing a hydroxyl group is not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate and the like can be used in a predetermined vinyl monomer. For example, a method of copolymerizing with a body can be used.

The method for introducing the polyalkylene oxide group and its derivative is not particularly limited, either.
For example, (1) a method of copolymerizing a vinyl polymer having a polyalkylene oxide group represented by formulas (VI) and (VII) with a desired vinyl monomer, (2) polymethyl methacrylate or methacrylic (Meth) acrylate-based (co) polymers obtained by copolymerizing (meth) acrylate monomers such as methyl acrylate and butyl acrylate with desired vinyl monomers and poly (ether) having one end alkyl ether
Examples thereof include a method of subjecting an alkylene oxide glycol to an ester reaction, and (3) a method of subjecting the above-mentioned vinyl (co) polymer having a carboxyl group in the molecule to an ester reaction of a polyalkylene oxide glycol having an alkyl ether at one end.

[0038]

Embedded image (Wherein, R ⁶ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁷ is an alkyl group having 2 to 6 carbon atoms, R ⁸ is hydrogen or an alkyl group having 1 to 6 carbon atoms, and n is 2-500
Is shown. )

As specific examples, polyethylene glycol acrylate, polyethylene glycol methacrylate, poly (propylene oxide) glycol acrylate, poly (propylene oxide) glycol methacrylate, poly (tetramethylene oxide) glycol acrylate, poly (tetramethylene oxide) glycol Methacrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypoly (propylene oxide) glycol acrylate, methoxypoly (propylene oxide)
Glycol methacrylate, methoxy poly (tetramethylene oxide) glycol acrylate, methoxy poly (tetramethylene oxide) glycol methacrylate, ethoxy polyethylene glycol acrylate, ethoxy polyethylene glycol methacrylate, ethoxy poly (propylene oxide) glycol acrylate, ethoxy poly (propylene oxide) glycol methacrylate, polyethylene glycol acrylamide , Polyethylene glycol methacrylamide, poly (propylene oxide) glycol acrylamide, poly (propylene oxide) glycol methacrylamide, poly (tetramethylene oxide) glycol acrylamide, poly (tetramethylene oxide) glycol methacrylamide, methoxy Triethylene glycol acrylamide, methoxy polyethylene glycol methacrylamide, methoxy poly (propylene oxide) glycol acrylamide, methoxy poly (propylene oxide) glycol methacrylamide, etc. methoxypoly (tetramethylene oxide) glycol methacrylamide.

In addition, one end of which is a polyether having an alkyl ether
Examples of the alkylene oxide glycol include methoxy polyethylene glycol, methoxy poly (propylene oxide) glycol, methoxy poly (tetramethylene oxide) glycol, methoxy poly (hexamethylene oxide) glycol, ethoxy polyethylene glycol, ethoxy poly (propylene oxide) glycol, and ethoxy poly (hexamethylene oxide). ) Glycol, methoxy (a block or random copolymer of ethylene oxide and propylene oxide), and methoxy (a block or random copolymer of ethylene oxide and tetrahydrofuran).

The polyalkylene oxide glycol having an alkyl ether at one end has a number average molecular weight of 75 to 20.
000 range.

The vinyl monomer used for the polymerization of the modified vinyl polymer (C) is not particularly limited. For example, aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene, acrylonitrile, Vinyl cyanide monomers such as methacrylonitrile, (meth) acrylate monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, butyl acrylate, maleimide, N-methylmaleimide, N- It is possible to use one or more of maleimide monomers such as phenylmaleimide, olefin monomers such as ethylene and propylene, and vinyl monomers such as vinyl chloride and vinyl acetate. it can. In particular, the mechanical properties of resin compositions that can be obtained by using aromatic vinyl monomers such as styrene, (meth) acrylate monomers such as methyl methacrylate, and vinyl cyanide monomers such as acrylonitrile. It is preferably used because of its excellent properties.

If necessary, polybutadiene, acrylonitrile / butadiene copolymer (NBR), styrene / butadiene copolymer (SBR), polybutyl acrylate and ethylene / propylene / diene rubber (E
Rubber-like polymers such as PDM) can also be used in combination with the above-mentioned vinyl monomers.

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

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, and condensation reaction Can be used.

The polymer thus obtained comprises (A) 1 to 40 parts by weight of a polyamide elastomer, preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight, and (B) (meth)
In the range of 50 to 98 parts by weight, preferably 50 to 90 parts by weight of an acrylic resin composed of an acrylate ester, and (C) 0.1 to 10 parts by weight of a modified vinyl polymer having a carboxyl group, (A), ( The total amount of B) and (C) is 10
Acrylic resin consisting of (A) 1 to 40 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight of (A) polyamide elastomer, or (B) (meth) acrylate 20 to 98 parts by weight, preferably 50 to 90 parts by weight, (C) at least one functional group selected from the group consisting of epoxy groups, amino groups and substituted amino groups, hydroxyl groups and polyalkylene oxide groups and derivatives thereof In the range of 0.1 to 40 parts by weight, preferably 0.1 to 10 parts by weight of the modified vinyl polymer containing (A), the total amount of (A), (B) and (C) becomes 100 parts by weight. Mix as follows.

When the amount of the polyamide elastomer (A) is less than 1 part by weight, the antistatic property of the resin composition is insufficient, and when it exceeds 40 parts by weight, the resin composition becomes soft and the mechanical properties are inferior.

(B) If the amount of the acrylic resin comprising the (meth) acrylic acid ester is less than 20 parts by weight, the surface gloss of the molded article of the resin composition becomes poor, and if it exceeds 98 parts by weight, the antistatic property of the resin composition becomes poor. Shortage and not preferred.

(C) If the amount of the modified vinyl polymer containing a carboxyl group is less than 0.1 parts by weight, the resin composition cannot be used because of delamination, and if it exceeds 10 parts by weight,
The surface gloss of the molded article is significantly deteriorated, which is not preferable. The modified vinyl polymer containing at least one functional group selected from the group consisting of an epoxy group, an amino group and a substituted amino group, a hydroxyl group and a polyalkylene oxide group and a derivative thereof is less than 0.1 part by weight. When the resin composition is used in excess of 40 parts by weight, the surface gloss of the molded article is significantly deteriorated, which is not preferable.

The method for producing the resin composition of the present invention is not particularly limited. For example, (A) a polyamide elastomer and (B) an acrylic resin and (C) a modified vinyl polymer containing a carboxyl group, or an epoxy group, A resin mixture of a modified vinyl polymer containing at least one functional group selected from the group consisting of an amino group and a substituted amino group, a hydroxyl group, and a polyalkylene oxide group and a derivative thereof is prepared by mixing a Banbury mixer, a roll, an extruder, or the like. It is commercialized by melt-kneading in.

The resin composition of the present invention may be made of another thermoplastic polymer compatible with the resin of the present invention, for example, polyamide, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyphenylene ether, vinyl chloride resin, polyglutarimide, etc. Can be mixed to improve the performance as a molding resin. Further, from the viewpoint of the surface gloss of the molded article, it does not contain a rubber graft copolymer.

Further, a sulfonic acid metal salt or an anionic compound may be used.
It is also possible to further improve the antistatic properties by adding an antistatic agent such as a cationic or nonionic surfactant, and further, if necessary, a compatibilizer such as an oligomer, an antioxidant, and an ultraviolet absorber. And various stabilizers such as pigments, dyes, lubricants, plasticizers, glass fibers, and flame retardants. When a modified vinyl polymer containing an epoxy group is used, the compatibility between the components (A) and (B) is further improved by adding a sulfonic acid salt, a tertiary amine and a phosphorus compound. Can also.

[0053]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. 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.

(1) Izod impact strength: ASTM D
256-56A

(2) Flexural modulus: ASTM D790

(3) Surface gloss of molded article: 80 mm × 12
The measurement was performed at a measurement angle of 60 ° using a square plate of 0 mm × 2 mmt. For the measurement, a digital variable gloss meter UGV-5D manufactured by Suga Test Instruments Co., Ltd. was used.

(4) Volume specific resistance: 2 mmt × 40 m
The measurement was performed at room temperature 23 ° C. and humidity 50% RH using a mφ disk. For the measurement, a super insulation resistance meter SM-10 manufactured by Toa Denpa Kogyo KK was used.

The delamination of the molded article was performed by observing the surface where the molded article was bent and broken, and the evaluation criteria were: ○: extremely good, Δ: good, ×: the molded article caused delamination.

In the examples, parts and% indicate parts by weight and% by weight, respectively.

(Reference Example) [(A) Preparation of polyamide elastomer] 50 parts of caprolactam, 44.2 parts of polyethylene glycol having a number average molecular weight of 1000 and 7.8 parts of terephthalic acid were mixed with "Irganox" 1098 (an antioxidant). 0.3 parts and 0.1 part of antimony trioxide catalyst were charged into a reactor equipped with a helical ribbon stirring blade, and purged with nitrogen at 260 ° C. for 6 hours.
After heating and stirring for 0 minutes to obtain a transparent homogeneous solution,
C., polymerization for 3 hours 30 minutes under the condition of 0.5 mmHg or less,
A viscous, clear polymer was obtained. The polyamide elastomer (A) in the form of pellets was prepared by discharging the polymer onto a cooling belt on a gut and pelletizing.

[(B) Preparation of acrylic resin comprising (meth) acrylate] B-1: Parapet G (manufactured by Kyowa Gas Chemical Industry Co., Ltd.) was used. MFI value (ASTM D1238, 230
C, 3.8 kg, I condition) is 8.5 g / 10 min.

B-2: Parapet GF (manufactured by Kyowa Gas Chemical Industry Co., Ltd.) was used. MFI value (ASTM D123
8, 230 ° C, 3.8 kg) is 15 g / 10 min.

B-3: 95 parts of methyl methacrylate and 5 parts of methyl acrylate were subjected to suspension polymerization to prepare a copolymer (B-3). The MFI value measured by the same method as B-1 was 1
It was 2 g / 10 minutes.

[(C) Preparation of modified vinyl polymer] C-1: 70 parts of styrene, 25 parts of acrylonitrile and 5 parts of methacrylic acid were subjected to suspension polymerization to obtain a modified vinyl polymer having a carboxyl group by (C) -1) was prepared. The resulting modified vinyl polymer (C-1) had an intrinsic viscosity ([η]) of 0.55 as measured in methyl ethyl ketone (MEK) at 30 ° C. at a concentration of 0.4%.

C-2: 99 parts of methyl methacrylate and 1 part of glycidyl methacrylate were subjected to suspension polymerization to prepare a modified vinyl polymer having an epoxy group (C-2). [Η] of the obtained modified vinyl polymer (C-2) measured at 30 ° C. and 0.4 concentration in chloroform was 0.46.

C-3: 73 parts of methyl methacrylate, 25 parts of styrene, and 2 parts of acrylamide were emulsion-polymerized to prepare a modified vinyl polymer (C-3) containing an amide group. The resulting modified vinyl polymer (C-3) is C-2
[Η] measured by the same method as in Example 1 was 0.51.

C-4: 90 parts of methyl methacrylate and 10 parts of methoxypolyethylene glycol methacrylate (an average of 9 ethylene oxide groups) are subjected to suspension polymerization to obtain a modified vinyl polymer containing polyalkylene oxide groups (C -4) was prepared. The obtained modified vinyl polymer (C-4) had a [η] of 0.57 as measured by the same method as that of C-2.

C-5: 94 parts of methyl methacrylate, 2-
6 parts of hydroxyethyl methacrylate are subjected to suspension polymerization,
Modified vinyl polymer containing hydroxyl group (C-
5) was prepared. The resulting modified vinyl polymer (C-
5) was measured by the same method as C-2, and [η] was 0.4.
Nine.

C-6: 95 parts of methyl methacrylate and 5 parts of methacrylic acid were subjected to suspension polymerization to prepare a modified vinyl polymer having a carboxyl group (C-6). The obtained modified vinyl polymer (C-6) had a [η] of 0.46 as measured by the same method as that of C-2.

[(D) Preparation of Rubber Graft Copolymer] In the presence of 60 parts (in terms of solid content) of polybutadiene latex (rubber particle diameter 0.25 μm, gelation ratio 80%), styrene 72% and acrylonitrile 28% Was subjected to emulsion polymerization. The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered and dried to prepare a powdery graft copolymer (D).

Examples 1 to 7 (A) Polyamide elastomer prepared in Reference Example, (B)
An acrylic resin composed of a (meth) acrylic acid ester and a modified vinyl polymer (C) are mixed at the compounding ratio shown in Table 1 and melt-kneaded and extruded at a resin temperature of 210 ° C. by a 40 mmφ extruder with a pent. Pellets were produced.

Next, test pieces were molded at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C. using an injection molding machine, and each physical property was measured.

The volume specific resistance value is 2 m in the injection molded thickness.
The measurement was carried out under the following conditions using a m.

(1) Immediately after molding, the surface was washed with an aqueous solution of a detergent "Mama Lemon" (manufactured by Lion Oil & Fat Co., Ltd.), and then sufficiently washed with distilled water to remove water on the surface.
H, measured at 23 ° C. for 24 hours.

(2) After molding, 20% in 50% RH and 23 ° C.
After leaving for 0 days, wash with detergent "Mama Lemon" aqueous solution,
Subsequently, after sufficient washing with distilled water to remove water on the surface, humidity was measured at 50% RH and 23 ° C. for 24 hours, and the measurement was performed.

Table 3 shows the measurement results.

Comparative Examples 1 to 7 (A) Polyamide elastomer prepared in Reference Example, (B)
Acrylic resin consisting of (meth) acrylic acid ester,
(C) The modified vinyl polymer and (D) the rubber graft polymer were mixed at the compounding ratio shown in Table 2, and their physical properties were measured in the same manner as in the examples. The results are shown in Table 3.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

The following is clear from the examples and comparative examples.

The resin compositions of the present invention (Examples 1 to 7)
In all cases, the mechanical properties typified by impact strength and flexural modulus and the surface gloss of the molded product are balanced and excellent, and have low volume resistivity. In addition, the resistance value hardly changes even when the surface is washed or changes with time, and it exhibits excellent permanent antistatic properties.

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

On the other hand, when the compounding amount of the polyamide elastomer (A) is less than 1 part by weight (Comparative Examples 1, 3, and 6), the antistatic property (resistance value) is inferior, and the compounding amount of the polyamide elastomer (A) is 40 parts by weight. (Comparative Example 2), the flexural modulus is inferior. When the amount of the acrylic resin (B) (meth) acrylate exceeds 98 parts by weight (Comparative Example 3), the antistatic property is poor. When the compounding amount of (C) the modified vinyl polymer containing a carboxyl group is less than 0.1 part by weight (Comparative Example 4), the molded article undergoes laminar exfoliation, and (C) the modified vinyl polymer containing a carboxyl group. When the amount of the polymer exceeds 10 parts by weight (Comparative Examples 2 and 5)
Is not preferable because the surface gloss of the molded product is deteriorated. In addition, the molded article in which the rubber graft copolymer was mixed (Comparative Example 7) was inferior in surface gloss to the molded article in which the rubber graft copolymer was not mixed.

[0085]

The thermoplastic resin composition of the present invention contains a specific amount of (A) a polyamide elastomer, (B) an acrylic resin and (C) a modified vinyl polymer in a specific amount. It is excellent in both mechanical properties such as impact resistance and the surface gloss of a molded product, and is free from delamination.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuhisa Yano 9-9 Oe-cho, Minato-ku, Nagoya-shi, Aichi

Claims (2)

[Claims] 1. A polyamide elastomer (A) containing a polyetherester unit or a polyether unit.
40 parts by weight (B) Acrylic resin composed of (meth) acrylic ester 50 to 98 parts by weight (C) Modified vinyl polymer containing carboxyl group
A thermoplastic resin composition, wherein 0.1 to 10 parts by weight is blended so that the total amount of (A), (B) and (C) becomes 100 parts by weight. 2. A polyamide elastomer (A) containing a polyether ester unit or a polyether unit (A).
40 parts by weight (B) Acrylic resin composed of (meth) acrylate 20 to 98 parts by weight (C) selected from the group consisting of epoxy groups, amino groups and substituted amino groups, hydroxyl groups, and polyalkylene oxide groups and derivatives thereof And 0.1 to 40 parts by weight of a modified vinyl polymer containing at least one functional group, so that the total amount of (A), (B) and (C) is 100 parts by weight. Thermoplastic resin composition.