JPH09137033A - Antistatic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic resin composition having persistent antistatic function and excellent thermal stability. SOLUTION: This antistatic resin composition comprises (A) 100 pts. by wt. of a rubber-reinforced thermoplastic resin composition containing a graft polymer where at least one of emulsifiers used in the emulsion graft polymerization is an emulsifier bearing, in its molecule, a radically polymerizable double bond, when a graft polymer is prepared by grafting at least one vinyl monomer copolymerizable with the rubber polymer onto the rubber polymer, (B) 0.5-30 pts. by wt. of at least one selected from polyether-amide, polyether-ester, polyether-ester-amide, polyamide-imide elastomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having a persistent antistatic ability and an antistatic property which is excellent in thermal stability.

[0002]

2. Description of the Related Art Conventionally, ABS resins and the like, which are representative of rubber-reinforced thermoplastic resins, have been represented by vinyl cyanide monomers represented by acrylonitrile and styrene by the presence of a conjugated diene rubber latex represented by polybutadiene. Emulsion graft polymerization of aromatic vinyl monomer by batch polymerization, semi-batch polymerization or continuous polymerization, and then coagulation,
It is often made through dehydration, drying and extrusion processes.

In this emulsion graft polymerization, in order to increase the stability of the latex and suppress the generation of coagulation products, an emulsifier consisting of a non-polymerizable carboxylic acid metal salt, metal sulfate salt or the like is generally used in the emulsion graft polymerization step. The method of addition is taken. However, the use of non-polymerizable emulsifiers causes foaming in the residual monomer recovery process, necessitating the use of antifoaming agents. It is not preferable because it causes mold contamination during processing.

Further, when processing a composition of a rubber-reinforced thermoplastic resin and an additive such as an antistatic agent, a residual emulsifier or a defoaming agent adversely affects the additive, resulting in a decrease in heat resistance of a molded product, It is not preferable because the phenomena of lower gloss and lower recyclability become remarkable. JP-A-3-2204 discloses the use of a specific emulsifier for preventing them, but the effect is not sufficient.

[0005] In addition, although various antioxidants are added at the time of extrusion or molding to suppress coloring and deterioration of impact resistance due to thermal deterioration, impact resistance and fluidity at high temperature are not always required. It is impossible to suppress the decrease in the impact strength and the impact strength during retention. As described above, it has been difficult to obtain a rubber-reinforced thermoplastic resin excellent in heat resistance, impact resistance, rigidity, and mold contamination resistance during molding by the conventional techniques.

[0006]

In contrast to the present situation, the present invention has very little free residual emulsifier and defoaming agent at the time of emulsion graft polymerization, is excellent in thermal stability, has impact resistance, rigidity and molding processing. It is intended to provide a resin composition having excellent anti-staining property of molds and recyclability, and having antistatic property in which antistatic performance is maintained for a long time.

[0007]

That is, the present invention provides:
(A) At least one emulsifier used for emulsion graft polymerization in the process of producing a graft polymer obtained by graft-polymerizing one or more vinyl compounds graft-copolymerizable with the rubber-like polymer on the rubber-like polymer. 100 parts by weight of a rubber-reinforced thermoplastic resin composition containing a graft polymer, which is an emulsifier having a double bond capable of radically polymerizing in the molecule, and (B) a polyetheramide, a polyetherester, a polyetheresteramide, One or more selected from polyamide-imide elastomer 0.5
To 30 parts by weight of the resin composition having an antistatic property.

The present invention will be described in detail below.
The composition and production method of the rubber-reinforced thermoplastic resin composition (A) of the present invention will be described. The rubber-reinforced thermoplastic resin can be obtained by graft-polymerizing a vinyl compound capable of being graft-polymerized with a rubber-like polymer, but a vinyl polymer which is simultaneously polymerized in this polymerization process may be contained. Further, the vinyl polymer may be simultaneously or separately polymerized and blended.

The rubber-like polymer used in the present invention includes:
Polybutadiene, polyisoprene, polychloroprene,
Conjugated diene rubbers such as butadiene-styrene copolymer and butadiene-acrylonitrile copolymer, ethylene-
Acrylic rubbers such as propylene rubber, ethyl acrylate, and butyl acrylate are preferable, and polybutadiene of a conjugated diene rubber, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer are preferable. These can be used in combination of two or more.

The content of the rubber-like polymer in the rubber-reinforced thermoplastic resin composition is 5 to 60% by weight, preferably 10 to 5%.
0% by weight. If it is less than 5% by weight, impact resistance cannot be obtained, and if it exceeds 60% by weight, the fluidity and gloss during molding are lowered, which is not preferable. The preferable particle size of the rubber-like polymer in the rubber-reinforced thermoplastic resin composition is not particularly limited because it varies depending on the type of the vinyl polymer used as the matrix. For example, in the case of ABS resin, the particle size is 1
50 to 600 nm, preferably 200 to 500 nm,
More preferably, it is 250 to 450 nm. If the particle size is smaller than 150 nm, impact resistance cannot be obtained, and 60
If it exceeds 0 nm, the gloss value decreases.

The vinyl compound which can be graft-polymerized to the rubber-like polymer particles used in the present invention includes aromatic vinyl compounds such as styrene, α-methylstyrene and paramethylstyrene, methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate. Alkyl (meth) acrylates such as, (meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, α, β-unsaturated carboxylic acids such as maleic anhydride, N Examples include maleimide-based monomers such as -phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide, and glycidyl group-containing compounds such as glycidyl methacrylate, but aromatic vinyl compounds and alkyl (meth) acrylates are preferable. ,cyan Vinyl compounds, a maleimide compound, more preferably, styrene, acrylonitrile, N- phenylmaleimide, butyl acrylate. These vinyl compounds may be used alone or in combination of two or more.

The vinyl polymer which can be contained in the rubber-reinforced thermoplastic resin composition (A) includes aromatic vinyl compounds such as styrene, α-methylstyrene and paramethylstyrene, methyl methacrylate, methyl acrylate, butyl acrylate, Alkyl (meth) acrylates such as ethyl acrylate, (meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, α, β-unsaturated carboxylic acids such as maleic anhydride, N Examples include maleimide compounds such as -phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, and glycidyl group-containing compounds such as glycidylmethacrylate, but preferably aromatic vinyl compounds, alkyl (meth) acrylates, and cyan. A Le compounds are maleimide compound, more preferably, styrene, acrylonitrile, N- phenylmaleimide, a polymer consisting of butyl acrylate. These vinyl compounds can be used singly, in combination of two or more, or copolymerized.

The method for producing the rubber-reinforced thermoplastic resin composition in the present invention is not particularly limited, but an emulsion graft polymerization method in which a vinyl compound is graft-polymerized to a rubber-like polymer latex produced by emulsion polymerization, and
An example is a two-stage polymerization method in which emulsion graft polymerization is combined with solution polymerization or suspension polymerization. These are continuous,
Both batch type and semi-batch type are possible. Further, a graft polymer having a high rubber content is prepared in advance by the above method, and a thermoplastic resin containing a vinyl compound as a main component, which is used at the time of graft polymerization produced by bulk polymerization, emulsion polymerization or suspension polymerization, is blended with the purpose. It is also possible to adopt a method of adjusting the rubber content of.

In the present invention, an emulsion grafting method is preferred in which a vinyl compound is continuously added to a rubbery polymer produced by emulsion polymerization together with an initiator, a molecular weight modifier and the like. The pH at the time of polymerization is not particularly limited, but is preferably around neutral (pH 7 to 9) from the viewpoint of the graft reaction.

The emulsifier having a double bond capable of radical polymerization in the molecule (hereinafter abbreviated as a polymerizable emulsifier) used in the present invention has a hydrophilic group and a hydrophobic group in the compound, and a gas-liquid, Of the compounds capable of lowering the liquid-liquid and solid-liquid interfacial tension, the compound has one or more double bonds, and in particular, a conjugated diene rubber, an aromatic vinyl compound, a vinyl cyanide compound and / or Alternatively, it means one capable of radical polymerization with a (meth) acrylic acid ester compound. The hydrophilic group of the polymerizable emulsifier may be anionic, nonionic or cationic, but preferably has anionic properties, more preferably has both nonionic and anionic properties.

A non-polymerizable emulsifier may be used together with the polymerizable emulsifier during the emulsion graft polymerization, but the total amount of the non-polymerizable emulsifiers derived from rubber is 4.0 parts by weight or less based on 100 parts by weight of the conjugated diene rubber. Should be. If it exceeds 4.0 parts by weight, the impact resistance of the rubber-reinforced thermoplastic resin composition is lowered, the rigidity is lowered, the gloss is lowered during high temperature molding, the mold is contaminated during molding, and the resin is colored, which is not preferable. . The non-polymerizable emulsifier referred to here may be an emulsifier generally used for emulsion polymerization, a rosin acid salt, a higher fatty acid salt,
Alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate,
Polyoxyethylene alkyl phenyl ether sulfate,
Examples thereof include anionic emulsifiers such as dialkylsulfosuccinates and nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers.

Examples of the polymerizable emulsifier used in the present invention include, but are not limited to, the followings. A polymerizable emulsifier represented by the following formula (1),

[0018]

Embedded image In the formula, R ₁ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aralkyl group, and R ₂ is hydrogen or 1 to 12 carbon atoms.
18 alkyl group, alkenyl group or aralkyl group, R ₃ is hydrogen or propenyl group, A is C 2-4
Alkylene group or substituted alkylene group, n is 1 to 20
Indicates an integer of 0. X represents a (meth) allyl group, a (meth) acryloyl group or a (1-propenyl) vinyl group.
Y is hydrogen, or -SO ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or carbon atoms 1
4 hydroxyalkylammonium) or a carboxylic acid represented by —CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms) A salt or a phosphoric acid monoester salt represented by the following formula (1 ′) is shown.

[0019]

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Specific examples of the polymerizable emulsifier represented by the formula (1) include the following formulas (5) to (8).

[0021]

Embedded image

[0022]

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A (meth) allyl glycidyl ether derivative and a (meth) acryl glycidyl ester derivative represented by the following formula (2):

[0024]

Embedded image In the formula, X represents a (meth) allyl group or a (meth) acryloyl group. Y is hydrogen, or -SO ₃ M (M is hydrogen,
Alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms) or a sulfate ester salt represented by -CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal) A carboxylic acid salt, a phosphoric acid monoester represented by the formula (1 ′), or a compound represented by the formula (1 ″) is shown.
Z is an alkyl group having 8 to 30 carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkylaryl group,
It represents a substituted alkylaryl group, an aralkylaryl group, a substituted aralkylaryl group, an acyl group or a substituted acyl group. A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, m is 0 to 100, and n is an integer of 0 to 50.

[0025]

[Chemical 6]

The following equations (9) to (15) are given as examples of equation (2).
An expression can be given.

[0027]

Embedded image (Y ₁ represents the following formula (11 ′).)

[0028]

Embedded image

A succinic acid derivative represented by the following formula (3),

[0030]

Embedded image In the formula, X represents a (meth) allyl group or a (meth) acryloyl group. B ₁ and B ₂ represent Y or Z shown below, and B ₁ and B ₂ are different from each other. Y is M or −
SO ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms) is shown. Z represents an alkyl group or an alkenyl group having 8 to 30 carbon atoms. A has 2 to 4 carbon atoms
An alkylene group, which is an alkylene group having a substituent,
m and n are integers of 0 to 50.

As a specific example of the expression (3), the following expression (1
6) to (19).

[0032]

Embedded image

A compound represented by the following formula (4),

[0034]

Embedded image In the formula, X represents a (meth) allyl group or a (meth) acryloyl group. Y is hydrogen, or -SO ₃ M (M is hydrogen,
Sulfuric acid ester salt represented by alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms, or -CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or carbon number) 1 to 4 hydroxyalkyl ammonium). R ₁ and R ₃ are hydrogen or an alkyl group having 1 to 25 carbon atoms and may be the same or different, and R ₂ and R ₄ are 1 to 2 carbon atoms.
5 represents an alkyl group, a benzyl group, or a styryl group, which may be the same or different, and p is 0 to
Indicates an integer of 2. A is an alkylene group having 2 to 4 carbon atoms and an alkylene group having a substituent, and m and n are integers of 0 to 50.

As a specific example of the equation (4), the following equation (2
0) and (21).

[0036]

Embedded image

A (meth) allyl ether derivative and a (meth) acrylic ester derivative represented by the following formula (22),

[0038]

Embedded image In the formula, X represents a (meth) allyl group or a (meth) acryloyl group. Y is hydrogen, a methyl group, or -SO
Sulfate ester salt represented by ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or -CH
₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or a phosphoric acid monoester salt represented by the formula (1 ′) Indicates. Z
Represents an alkyl group having 8 to 30 carbon atoms. A has 2 carbon atoms
~ 4 alkylene group or substituted alkylene group, m is 0
20 and n show the integer of 0-50.

As a specific example of the equation (22), the following equation (2)
3) and (24).

[0040]

Embedded image

A diol compound represented by the following formula (25),

[0042]

Embedded image In the formula, A is an alkylene group having 2 to 4 carbon atoms, R ₁ is a hydrocarbon group having 8 to 24 carbon atoms, R ₂ is hydrogen or a methyl group, and m and n have m + n of 0 to 100. And M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms.

As a concrete example of the equation (25), the following equation (2)
6) can be given.

[0044]

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A compound represented by the following formula (27),

[0046]

Embedded image In the formula, X represents a (meth) allyl group, a (meth) allyloxy group, a (meth) acryloyl group, a (meth) acryloyloxy group or the following formula (27 ′). Y is hydrogen, or (M hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkyl ammonium having from 1 to 4 carbon atoms) -SO ₃ M sulfuric acid ester salt represented by, or -CH ₂ COOM (M is A carboxylic acid salt represented by hydrogen, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms,
Alternatively, it represents a phosphoric acid monoester represented by the formula (1 ′) or a sulfosuccinic acid monoester salt represented by the formula (1 ″). Z may have a substituent having 6 to 30 carbon atoms. Represents an alkylene group, A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n and m represent an integer of 0 to 50.

[0047]

Embedded image

As a concrete example of the equation (27), the following equation (2)
8) to (30).

[0049]

Embedded image Of these polymerizable emulsifiers, the formula (1) is preferred,
It is a polymerizable emulsifier represented by formula (2), (3) or (4), and particularly preferably a polymerizable emulsifier represented by formula (1). Among the polymerizable emulsifiers represented by the formula (2), preferred structures are the polymerizable emulsifiers represented by the formulas (9) and (11), and a more preferable specific example of the formula (9) is (31) Formulas (34) and (11) are more preferably specific examples of Formulas (35) and (36).

[0050]

Embedded image

The polymerizable emulsifier represented by the formula (1) is
Particularly preferred, and specific examples thereof include the following (37) to (41)
Formulas are particularly preferred.

[0052]

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The polymer latex obtained by the present invention is usually coagulated with an inorganic salting-out agent and recovered by dehydration. The salting-out agent used is not limited, but specific examples include aluminum sulfate, magnesium sulfate, calcium chloride, sulfuric acid and the like. It is preferable that the amount of the component derived from the residual salting-out agent contained in the resin after the dehydration and recovery be smaller.

The (B) polyether amide, polyether ester, polyether ester amide, and polyamide imide elastomer of the present invention will be described.
Examples of the polyether amide, polyether ester, and polyether ester amide include a block or graft copolymer obtained by the reaction of a polyamide component with a polyester component and a compound having an alkylene oxide group.

Examples of the polyamide component include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. Or a lactam such as ε-caprolactam and enanthlactam, and a salt of diamine-dicarboxylic acid such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate. And mixtures thereof, preferably caprolactam, 12
-Aminododecanoic acid, hexamethylenediamine-adipate.

Examples of the polyester component include, as dicarboxylic acid, isophthalic acid, terephthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid and naphthalene-
Aromatic dicarboxylic acids such as 2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,
Alicyclic carboxylic acids such as 3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-dicarboxymethylcyclohexane,

Further, one or a mixture of two or more kinds of aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and decanedicarboxylic acid and an aliphatic diol such as ethylene glycol, 1,2-propylene glycol, One or a mixture of two or more of 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, neopentyl glycol, hexanediol and the like. The dicarboxylic acid is preferably
Terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sepacic acid, and ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3 as decanedicarboxylic acid diol.
4-butanediol.

Examples of the compound having an alkylene oxide group include poly (ethylene oxide) glycol,
Poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, block or random copolymer of ethylene oxide and tetramethylene oxide, and block of ethylene oxide and tetrahydrofuran Alternatively, a random copolymer and a diamine or dicarboxylic acid thereof may be used, and one kind or two or more kinds may be used. Among these, poly (ethylene oxide) glycol is preferable.

The reaction of the polyether amide, polyether ester, or polyether ester amide elastomer includes, for example, the reaction of a polyamide component or a polyester component with an alkylene oxide group-containing compound. Depending on the groups, ester or amide reactions are possible. Further, a third component such as dicarboxylic acid or diamine may be used depending on the reaction.

As the dicarboxylic acid component, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid,
Aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and decanedicarboxylic acid. Two or more types are used. Preferred are terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid and decanedicarboxylic acid.

As the polyamide-imide elastomer,
(A) caprolactam, (b) trivalent or tetravalent polycarboxylic acid, and (c) a mixture of polyoxyethylene glycol or polyoxyalkylene glycol mainly composed of polyoxyethylene glycol, and (a) Polyamideimide that serves as a hard segment is obtained from the component and the component (b), and these become a multi-block type copolymer in which the glycol of the component (c) that is the soft segment is linked by an ester bond.

As the component (b), a trivalent or tetravalent aromatic polycarboxylic acid capable of reacting with an amino group to form at least one imide ring, or an acid anhydride thereof is used. Specific examples of the trivalent tricarboxylic acid used as the component (b) include 1,2,4-trimetic acid, 1,2,5-naphthalene tricarboxylic acid, 2,
6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′,
4-tricarboxylic acid, diphenyl sulfone-3,3 ',
4-tricarboxylic acid, diphenyl ether-3,3 ',
4-tricarboxylic acid etc. are mentioned.

As the tetravalent tetracarboxylic acid,
Specifically, pyromellitic acid, diphenyl-2,2 ',
3,3′-tetracarboxylic acid, benzophenone-2,
2 ', 3,3'-tetracarboxylic acid, diphenyl sulfone-2,2', 3,3'-tetracarboxylic acid, diphenyl ether-2,2 ', 3,3'-tetracarboxylic acid and the like can be mentioned. These polycarboxylic acids are substantially equimolar to the glycol component (c), ie 0.9
It is used in the range of up to 1.1 times mol.

Polyamideimide which is a hard segment contributes to the heat resistance, strength and hardness of the elastomer and the compatibility with the thermoplastic resin for kneading the polyamideimide elastomer, and the content of polyamideimide in this elastomer is It is necessary to be 15 to 70% by weight. If this content is less than 15% by weight, the strength of the elastomer will be low, and when the polyamideimide elastomer is kneaded with the thermoplastic resin, the impact strength will be low, which is not preferable, and if it exceeds 70% by weight, the compatibility will be poor, It is not preferable because the antistatic effect may be lowered.

The number average molecular weight of polyamideimide is preferably 500 or more and 3000 or less,
It is more preferably 500 or more and 2000 or less. If the number average molecular weight of the polyamide-imide is less than 500, the melting point will be low and the heat resistance will be lowered, and if it exceeds 3000, the compatibility with the thermoplastic resin to be kneaded will be low, such being undesirable.

In order to improve the heat resistance, when (d) diamine is used together to introduce an imide ring into polyamideimide, the polycarboxylic acid is the total of glycol component (c) and diamine component (d). 0 to the number of moles.
It is used in 9 to 1.1 times the molar amount. Examples of the diamine of the component (d) include ethylene diamine, tetramethylene diamine, hexamethylene diamine, and phenylenediamine. This amount is 1 of glycol component (c)
It is preferable that the amount is not more than twice the molar amount, and if it is used in excess of this amount, it becomes difficult to obtain a homogeneous elastomer, and the compatibility with the thermoplastic resin to be kneaded decreases, which is not preferable.

(C) in the polyamide-imide elastomer
As the component, polyoxyethylene glycol or a mixture of polyoxyethylene glycol and polyoxyalkylene glycol other than polyoxyethylene glycol is used. The number average molecular weight of the polyoxyethylene glycol used is not particularly limited, but is 500 to 5
It is preferably in the range of 000. When it is less than 500, the melting point may be lowered and the heat resistance may be insufficient although it depends on the component of the elastomer, which is not preferable. On the other hand, when it exceeds 5,000, it becomes difficult to form a tough elastomer, and when kneaded with a thermoplastic resin, impact strength and rigidity may decrease, which is not preferable.

The polyoxyalkylene glycol which can be used in combination with the polyoxyethylene glycol is less than 50% by weight of the glycol component and has a number average molecular weight of 500 to 5000, such as polyoxytetramethylene glycol and modified polyoxytetramethylene glycol. Polyoxypropylene glycol or the like can be used.

Examples of the modified polyoxytetramethylene glycol include those obtained by substituting a part of — (CH ₂ ) ₄ —O— of ordinary polyoxytetramethylene glycol with —R—O—. Here, R is a C2-C10 alkylene group, for example, ethylene group, 1,2-propylene group, 1,3-propylene group, 2-methyl-1,3.
-Propylene group, 2,2-dimethyl-1,3-propylene group, pentamethylene group, hexamethylene group and the like. The amount of modification is not particularly limited, but usually 3 to
It is selected in the range of 50% by weight. Further, the amount of modification and the kind of the alkylene group are appropriately selected depending on the required properties of the one kneaded with the thermoplastic resin, such as low temperature impact resistance, antistatic property and heat resistance.

The modified polyoxytetramethylene glycol can be produced, for example, by copolymerization of tetrahydrofuran and diol with a heteropolyacid as a catalyst, copolymerization of cyclic ether which is a condensation product of diol or diol, and butanediol. You can

Regarding the method for producing the polyamide-imide elastomer, any method may be used as long as it can produce a homogeneous amide-imide elastomer, and for example, the following method is used. In a polymer produced by mixing the caprolactam component (a), the aromatic polycarboxylic acid component (b) and the glycol component (c) in a ratio such that the component (b) and the component (c) are substantially equimolar. While maintaining the water content of 0.1 to 1% by weight, the polymerization is carried out at 150 to 300 ° C, more preferably 180 to 280 ° C.
In the present method, the reaction temperature can be raised stepwise during the dehydration condensation.

At this time, some caprolactam remains unreacted, but this is distilled off under reduced pressure and removed from the reaction mixture.
The reaction mixture after removing the unreacted caprolactam can be further polymerized, if necessary, by post-polymerizing under reduced pressure at 200 to 300 ° C, more preferably at 230 to 280 ° C.

In this reaction method, coarse phase separation is prevented by simultaneously performing esterification and amidation in the course of dehydration condensation, whereby a homogeneous and transparent elastomer is produced. It is considered that this is one of the factors that exert excellent compatibility when the polyamide-imide elastomer is kneaded with the thermoplastic resin and bring about good antistatic properties, mechanical properties, surface gloss and the like.

In order to obtain an elastomer having transparency and homogeneity by simultaneously causing the esterification reaction and the polymerization of caprolactam and controlling the respective reaction rates, the produced water is removed from the system. Then, it is preferable to carry out the polymerization while maintaining the water content of the reaction system in the range of 0.1 to 1% by weight. If this water content exceeds 1% by weight, the polymerization of caprolactam takes precedence and coarse phase separation occurs,
On the other hand, if it is less than 0.1% by weight, the esterification has priority and the caprolactam does not react, and an elastomer having a desired composition cannot be obtained. The water content is appropriately selected within the above range according to the physical properties desired for the elastomer.

In this reaction, the water content in the reaction system may be gradually decreased as the reaction progresses, if desired. The water content can be controlled by, for example, controlling reaction conditions such as a reaction temperature, an inert gas introduction flow rate, and a degree of pressure reduction, or changing a reactor structure.

The degree of polymerization of the polyamide-imide elastomer can be arbitrarily changed as required, but the relative viscosity measured at 30 ° C. in metacresol at 0.5% (weight / volume) is 1.5 or more. Preferably.
If it is lower than 1.5, the mechanical properties cannot be sufficiently expressed, and the mechanical properties may be insufficient when kneaded with a thermoplastic resin. A preferable relative viscosity is 1.6 or more.

When the diamine (d) is used in combination, it can be carried out by either a one-step reaction method or a two-step reaction method. The former is a method in which caprolactam (a), polycarboxylic acid component (b), glycol component (c), and diamine component (d) are simultaneously charged and reacted. The latter is a method in which the polycarboxylic acid component (b) and the diamine component (d) are first reacted, and then the caprolactam (a) and the glycol component (c) are combined and reacted.

An esterification catalyst can be used as a polymerization accelerator when producing a polyamide-imide elastomer. Examples of this polymerization accelerator include phosphorus compounds such as phosphoric acid, polyphosphoric acid, and metaphosphoric acid; tetraalkyl orthotitanates such as tetrabutyl orthotitanate; tin-based catalysts such as dibutyltin laurate; manganese-based catalysts such as manganese acetate; Preferable are antimony-based catalysts such as antimony oxide; lead-based catalysts such as lead acetate. The catalyst may be added at the beginning of the polymerization or at the middle of the polymerization.

Further, in order to enhance the thermal stability of the obtained polyamide-imide elastomer, various stabilizers such as heat-resistant antioxidants and antioxidants can be used, and these stabilizers can be used in the initial, middle and final stages of the polymerization. It may be added at any stage. Examples of the heat resistance stabilizer include N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxycinnamic acid amide) and 4,4'-bis (2,6-di-amide).
t-butylphenol), 2,2′-methylenebis (4
-Ethyl-6-t-butylphenol) and various hindered phenols; N, N'-bis (β-naphthyl)
-P-phenylenediamine, N, N'-diphenyl-p
-Aromatic amines such as phenylenediamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline);
Copper salts such as copper chloride and copper iodide; sulfur compounds such as dilauryl thiodipropionate and phosphorus compounds.

In the present invention, by using (C) the organic electrolyte or the inorganic electrolyte in combination with the resin of the present invention, the antistatic performance is remarkably improved. Examples of the organic electrolyte include organic compounds having an acidic group and metal salts thereof, organic ammonium salts, organic phosphonium salts and the like. Examples of the organic compound having an acidic group and its metal salt include, for example,
Dodecylbenzene sulfonic acid, p-toluene sulfonic acid, dodecyl phenyl ether disulfonic acid, naphthalene sulfonic acid, condensate of naphthalene sulfonic acid and formalin, aromatic sulfonic acid such as polystyrene sulfonic acid,
Alkyl sulfonic acids such as lauryl sulfonic acid, organic carboxylic acids such as stearic acid, lauric acid and polyacrylic acid; organic phosphoric acids such as diphenyl phosphite and diphenyl phosphate; and alkali metal salts and alkaline earth metal salts thereof. Can be mentioned.

Although the free acid form exerts its effect, it is preferably used in the form of an alkali metal or alkaline earth metal salt, for example, sodium, lithium, potassium, magnesium, calcium salts and the like are preferable. Examples of the organic ammonium salt include quaternary ammonium salts such as trimethyloctylammonium bromide, trimethyloctylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and trioctylmethylammonium bromide, and examples of the organic phosphonium salt include , Quaternary phosphonium salts such as amyltriphenylphosphonium bromide and tetrabutylphosphonium bromide.

The inorganic electrolyte is, for example, Ag.
NO ₃ , BeSO ₄ , CaCl ₂ , Ca (NO ₃ ) ₂ ,
CdCl ₂ , Cd (NO ₃ ) ₂ , CoCl ₂ , CrCl
₂ , CsCl, CuCl ₂ , Cu (NO ₃ ) ₂ , CuS
O ₄ , FeCl ₂ , KBr, KH ₂ PO ₄ , KSCN,
KNO ₃ , LiCl, LiOH, LiNO ₃ , MgCl
₂ , Mg (NO ₃ ) ₂ , MgSO ₄ , MnCl ₂ , Mn
SO ₄ , NH ₄ Cl, NH ₄ NO ₃ , (NH ₄ ) ₂ SO
₄ , NaBr, Na ₂ CO ₃ , NaH ₂ PO ₄ , NaN
O ₃ , NiSO ₄ , Pb (NO ₃ ) ₂ , PrCl ₃ , R
Examples thereof include bCl, RbNO ₃ , Zn (NO ₃ ) ₂ and ZnSO ₄ .

The blending amount of (B) polyether amide, polyether ester, polyether ester amide, and polyamide imide elastomer is 0.5 to 30 parts by weight based on 100 parts by weight of (A) rubber-reinforced thermoplastic resin. And preferably 3 to 20 parts by weight. If it is less than 0.5 part by weight, the antistatic property is insufficient, and if it exceeds 30 parts by weight, the resin becomes soft and the mechanical properties are poor.

The compounding amount of (C) the organic electrolyte or the inorganic electrolyte is 0.01 to 10 parts by weight, and preferably 0.1 to 100 parts by weight of the rubber-reinforced thermoplastic resin (A).
5 parts by weight. If it is less than 0.01 part by weight, the antistatic effect is not sufficiently exhibited, and if it exceeds 10 parts by weight, mechanical properties are deteriorated, mold corrosion, and mold deposit occur.

Further, with respect to the resin composition of the present invention, known antioxidants, ultraviolet absorbers, lubricants, release agents, flame retardants, colorants or glass fibers, glass flakes, carbon fibers, talc, mica, etc. It is optional to add the inorganic filler. Furthermore, the molding method of a molded article made of these thermoplastic resin compositions includes extrusion molding, compression molding, injection molding, gas assist molding, and the like, and is not particularly limited. Examples of molded products include housings for personal computers,
A keyboard etc. are mentioned.

[0086]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail based on the following examples. The present invention is not limited by the embodiments. The parts used below are parts by weight.

(Manufacturing Method of Conjugated Diene Rubber): (Rubber Latex (S-1)) A substance (based on solid content) having the following composition was charged into a 50 liter autoclave whose inside was evacuated to a vacuum, and the temperature was raised to 65 ° C. Polymerization was carried out. 1,3-Butadiene 97.0 parts Acrylonitrile 3.0 parts t-dodecyl mercaptan 0.2 parts Potassium rosinate 0.7 parts Beef tallow saponified fossil Ken 0.3 parts Sodium persulfate 0.25 parts Sodium hydroxide 0.1 Part sodium hydrogen carbonate 0.35 part deionized water 60.0 part

During the 10th to 20th hours after the initiation of the polymerization, the polymerization was continued while continuously adding a solution having the following composition to the autoclave. Potassium rosinate 0.3 parts Beef tallow fossil soap 0.1 parts Sodium persulfate 0.1 parts Sodium hydroxide 0.05 parts Sodium hydrogen carbonate 0.15 parts Deionized water 50.0 parts

After the continuous addition was completed, the polymerization system was heated to 80 ° C. and cooled 26 hours after the initiation of the polymerization to complete the polymerization. After the polymerization, unreacted butadiene was removed. The weight average particle diameter of the latex determined by electron micrograph was 0.28 microns. The latex had a pH of 10.1. (S-2 to S-3) The operations were performed in the same manner as S-1, except for the facts shown in Table 1. The results are summarized in Table 1.

The rubber-reinforced resins R-1 to R-5 were obtained by the following method. (R-1) 40 parts of rubber latex S-1 (solid content), 100 parts of deionized water, and 10 parts of 0.3 part of potassium rosinate
After being placed in a liter reactor and replacing the gas phase with nitrogen, the initial solution was heated to 70 ° C. Next, an aqueous solution (C) having the composition shown below and a monomer mixed solution (E), and further the formula (3)
The aqueous solution (D) containing the polymerizable emulsifier represented by 7) was continuously added to the reactor over 5 hours. After the addition is complete
The temperature was kept for 1 hour to complete the reaction. The composition of the aqueous solution (C) is as follows. Ferrous sulfate 0.005 part Sodium formaldehyde sulfoxylate (SFS) 0.1 part Ethylenediaminetetraacetic acid disodium (EDTA) 0.04 part Ion-exchanged water 50 parts

The composition of the aqueous solution (D) is as follows. Polymerizable emulsifier Formula (37) 1.0 part Ion-exchanged water 20 parts The composition of the monomer mixture liquid (E) is as follows. Acrylonitrile 24 parts Styrene 36 parts t-Dodecyl mercaptan (t-DM) 0.6 parts Cumene hydroperoxide (CHP) 0.1 parts Next, after adding an antioxidant to the graft polymer latex prepared, sulfuric acid was added. Aluminum was added to coagulate, washed with water, dehydrated, and then dried by heating to obtain a graft copolymer powder.

(R-2) R-1 except that the polymerizable emulsifier contained in the aqueous solution (D) was changed to that shown in Table 2.
-1 was polymerized in the same manner.

(R-3) Polymerizable emulsifier (37) in rubber
40 parts (solid content) of rubber latex S-2 containing the formula and 100 parts of ion-exchanged water were put in a 10 liter reactor,
Carbon dioxide gas was bubbled in the reactor to adjust the pH to about 7. After further substituting the gas phase with nitrogen, the initial solution
The temperature was raised to 0 ° C. Next, an aqueous solution (C) having the composition shown below, a monomer mixed solution (E), and an aqueous solution (D) containing a polymerizable emulsifier represented by the formula (37) are continuously added to the reactor for 5 hours. Was added to. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction. The composition of the aqueous solution (C) is as follows. Ferrous sulfate 0.005 part Sodium formaldehyde sulfoxylate (SFS) 0.1 part Ethylenediaminetetraacetic acid disodium (EDTA) 0.04 part Ion-exchanged water 50 parts

The composition of the aqueous solution (D) is as follows. Polymerizable emulsifier Formula (37) 1.0 part Ion-exchanged water 20 parts The composition of the monomer mixture liquid (E) is as follows. Acrylonitrile 24 parts Styrene 36 parts t-Dodecyl mercaptan (t-DM) 1.0 part Cumene hydroperoxide (CHP) 0.1 part

(R-4) R- except that 40 parts (solid content) of the rubber latex S-3 in which the emulsifier in the rubber is a polymerizable emulsifier (37) was used and the other conditions were shown in Table 2. 1
The polymerization was carried out in the same manner as described above.

(R-5) 40 parts of rubber latex S-1 (solid content), 100 parts of ion-exchanged water, and 0.3 parts of potassium rosinate were placed in a 10-liter reactor, and the gas phase was replaced with nitrogen. The initial solution was heated to 70 ° C. Next, an aqueous solution (C) having the composition shown below, a monomer mixture solution (E), and an aqueous solution (D) were continuously added to the reactor over 5 hours. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction. The composition of the aqueous solution (C) is as follows. Ferrous sulfate 0.005 part Sodium formaldehyde sulfoxylate (SFS) 0.1 part Ethylenediaminetetraacetic acid disodium (EDTA) 0.04 part Ion-exchanged water 50 parts

The composition of the aqueous solution (D) is as follows. Potassium rosinate 2.0 parts Ion-exchanged water 20 parts The composition of the monomer mixture (E) is as follows. Acrylonitrile 24 parts Styrene 36 parts t-Dodecyl mercaptan (t-DM) 0.6 parts Cumene hydroperoxide (CHP) 0.1 parts

(Vinyl Polymer (T-1)) Copolymer T-
The composition in 1 was 40% by weight acrylonitrile, 60% by weight styrene from the IR spectrum, and the intrinsic viscosity measured in methyl ethyl ketone (copolymer T-1, 0.61).
30% in 7% by weight) was 0.41.

(Polyamideimide elastomer) Polyamideimide elastomer manufactured by Nissei Chemical Industry Co., Ltd. (sodium alkylbenzene sulfonate) Sodium dodecylbenzene sulfonate manufactured by Tokyo Chemical Industry Co., Ltd. (hard type) (Other additives) EBS is It is ethylenebisstearylamide.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

【Example】

Examples 1 to 4 and Comparative Example 1 The resins prepared as described above were blended with the compositions (units are parts by weight) listed in Table 3, and the twin-screw extruder (ZSK-25, which has a cylinder temperature set to 240 ° C., The product was kneaded and granulated by W & P) to obtain pellets, and the following evaluations were performed. The measuring method in the examples of the present invention is as follows.

(Physical Property Evaluation Method) (1) IZOD Impact Strength Pellets were molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C. to obtain test pieces. The test was performed on a test piece with a notch of ½ inch × 1/4 inch × 5/2 inch based on ASTM-D256. (Unit is Kg · cm / c
m) (2) Retention IZOD impact strength The pellets were retained in a molding machine at 260 ° C for 40 minutes, and then molded at a mold temperature of 65 ° C to obtain a test piece. The test is A
Based on STM-D256, a test piece having a notch of ½ inch × 1/4 inch × 5/2 inch was used.
(Unit is Kg · cm / cm)

(3) Residence Coloring Degree Pellets were molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C. to obtain reference test pieces. Subsequently, a test piece was obtained by allowing it to stay in the molding machine at 240 ° C. for 40 minutes and molding in the same manner. Test piece: length 216 mm x width 12.6 mm x thickness 3.2 m
m test was performed using Suga Test Instruments Co., Ltd. SM color computer, model SM-5, and the yellow index (YI of the sample before retention)-(YI of the sample after retention) of the test sample with respect to the reference test sample. (ΔYI) was measured. The sample was measured at the center. (4) Surface resistivity Using a flat plate with a thickness of 1/8 inch, room temperature 23 ° C, humidity 50%
It was measured in an RH atmosphere. For the measurement, a polar insulation meter SM-10E type manufactured by Toa Denpa Kogyo Co., Ltd. was used. (Unit: Ω / □) These results are summarized in Table 3.

[0105]

[Table 3]

The following is clear from the examples and comparative examples. The antistatic resin compositions (Examples 1 to 4) using the rubber-reinforced resin are all excellent in impact resistance (IZOD impact strength), and are suppressed from coloring during residence and impact strength, and decrease in molecular weight. , Excellent in mechanical strength and recyclability.

[0107]

INDUSTRIAL APPLICABILITY The present invention reduces the thermal decomposition of the rubber-reinforced thermoplastic resin, and as a result, suppresses the thermal deterioration of the resin during kneading and molding, and has excellent mechanical strength and recyclability. A resin composition having properties can be obtained.

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Claims (3)

[Claims] 1. In a process of producing a graft polymer obtained by graft-polymerizing (A) a rubber-like polymer with one or more vinyl compounds graft-copolymerizable with the rubber-like polymer, emulsion graft polymerization is performed. 100 parts by weight of a rubber-reinforced thermoplastic resin composition containing a graft polymer in which at least one kind of emulsifier used is an emulsifier having a radically polymerizable double bond in the molecule, and (B) a polyetheramide,
Polyetherester, polyetheresteramide,
A resin composition having antistatic properties, which comprises 0.5 to 30 parts by weight of one or more selected from polyamide-imide elastomers. 2. A rubber-reinforced thermoplastic resin composition (A) 10
0.01 to 1 of at least one kind of electrolyte selected from (C) organic electrolyte or inorganic electrolyte with respect to 0 part by weight.
The resin composition having an antistatic property according to claim 1, which contains 0 part by weight. 3. The resin composition having an antistatic property according to claim 1 or 2, wherein (B) is a polyamide-imide elastomer.