JPH05320497A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Structure] (A) 1 to 40 parts by weight of a polyamide elastomer whose soft component is polyalkylene glycol containing polyethylene glycol as a main component, (B) 95 to 1 parts by weight of polyphenylene ether, and (C) a polyamide. Resin 1-6
0.1 parts by weight of a modified vinyl polymer containing 0 part by weight, (D) at least one functional group selected from a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyalkylene oxide group and an oxazoline group. Parts and (E) styrene resin 0 to 95 parts by weight ((A) + (B)
+ (C) + (D) + (E) in 100 parts by weight). [Effect] The thermoplastic resin composition of the present invention has excellent balance of permanent antistatic property, mechanical property, and heat resistance, and excellent delamination preventive property of molded products, and it can be used for OA equipment, home appliances, automobile interior parts, etc. It is useful for housings and parts requiring heat resistance thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a permanent antistatic property and is excellent in mechanical properties represented by impact resistance, heat resistance, rigidity, chemical resistance, workability, and delamination (thousands of peeled sheets). ) -Free thermoplastic resin composition.

[0002]

2. Description of the Related Art Synthetic polymer materials are electrical insulators although they are used in a wide range of fields due to their excellent mechanical properties and processability. If the antistatic property is added to the mechanical strength of these materials, their applications can be further expanded. That is, copy machines, facsimiles, word processors,
Applications such as personal computers, electronic devices such as televisions, electromechanical parts, and various dustproof parts can be developed.

A hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and / or an acrylic ester with a vinyl monomer having an alkylene oxide group is known as a method for improving the electrostatic property of a synthetic polymer material. A method in which a vinyl-based monomer or a vinylidene monomer is graft-polymerized with (JP-A-55-36237), and a composition comprising a polyphenylene ether-based resin and a polyamide elastomer (JP-A-60-186560). JP-A 2-1), a composition comprising a polyether ester amide, a polyphenylene ether resin, and a polyamide resin.
No. 67363).

[0004]

However, since the hydrophilic rubber-like polymer described in JP-A-55-36237 is used, the manufacturing method thereof is complicated, and the resulting resin machine is mechanical. There is a drawback that the target property is inferior. Further, the composition described in JP-A-60-186560 has improved abrasion resistance, but is inferior in antistatic property and delamination preventive property. Furthermore, although the composition described in JP-A-2-167363 has excellent impact resistance and antistatic property, it is flexible and
In addition, since a large amount of expensive polyether ester amide is used, the rigidity and the delamination prevention property are poor, and the cost is high, which is economically disadvantageous.

The present invention has a permanent antistatic property, is excellent in mechanical properties represented by impact resistance, heat resistance, chemical resistance, molding processability and delamination prevention property, and is economically advantageous. An object is to provide an antistatic resin.

[0006]

Means for Solving the Problems The present invention has been made as a result of extensive studies to solve the above problems. As a result, by blending a specific polyamide elastomer with a specific polyphenylene ether-based resin and a polyamide resin, the above-mentioned object can be efficiently achieved. The inventors have reached the present invention by finding out what is achieved.

That is, in the present invention, (A) 1 to 40 parts by weight of a polyamide elastomer whose soft component is polyalkylene glycol containing polyethylene glycol as a main component, (B) 95 to 1 parts by weight of polyphenylene ether,
(C) 1 to 60 parts by weight of polyamide resin, (D) modified vinyl-based polymer containing at least one functional group selected from a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyalkylene oxide group and an oxazoline group. Combined amount of 0.1 to 50 parts by weight and (E) styrene resin 0 to 95 parts by weight ((A) + (B) + (C) + (D) +
(E) = 100 parts by weight), (F) alkali metal,
A thermoplastic resin composition comprising 0 to 10 parts by weight of an inorganic metal salt selected from alkaline earth metals, transition metals, and aluminum metals.

The present invention will be specifically described below.

The (A) polyamide elastomer in the present invention is a polyether ester amide obtained by the reaction of (a) a polyamide forming component and (b) a polyethylene glycol soft component and a polyether ester forming component consisting of a dicarboxylic acid. And (a) a polyamide-forming component, and (b) a polyethylene amide obtained by reacting a polyether-forming component composed of a dicarboxylic acid or a diamine with a product obtained by aminating or carboxylating both ends of polyethylene glycol.

Specific examples of the (a) polyamide-forming component include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid and ω.
-Aminocapric acid, and aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid or lactams such as caprolactam, enantolactam, capryllactam and laurolactam, and hexamethylenediamine-adipate, hexamethylenediamine-sebacine Acid salt and hexamethylenediamine
Examples thereof include salts of diamine-dicarboxylic acid such as isophthalic acid salt, particularly preferably caprolactam, 12-aminododecanoic acid, and hexamethylenediamine-adipate.

The polyethylene glycol (b) used in the present invention preferably has a number average molecular weight of 200 to 10,000, particularly 400 to 6,000, in terms of excellent polymerizability.

In the present invention, it is important to select polyethylene glycol as the soft component of the (A) polyamide elastomer.

When another component such as polytetramethylene glycol is used as the soft component, the antistatic property and mechanical properties, which are the objects of the present invention, are not improved in balance and the object of the present invention is achieved. I can't.

The polyethylene glycol (b) used in the present invention may be aminated or carboxylated at both ends.

The dicarboxylic acid component used in the present invention preferably has 4 to 20 carbon atoms. Specifically, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and 3-sulfo. Aromatic dicarboxylic acids such as sodium isophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and alicyclic dicarboxylic acids such as dicyclohexyl-4,4'-dicarboxylic acid and succinic acid, oxalic acid, adipine Acids, aliphatic dicarboxylic acids such as sebacic acid and dodecanedicarboxylic acid (decanedicarboxylic acid), and the like, particularly terephthalic acid, isophthalic acid, 1,
4-Cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedioic acid are preferably used in terms of polymerizability, color tone and physical properties.

Examples of the diamine component include aromatic, alicyclic and aliphatic diamines. Among them, the aliphatic diamine hexamethylenediamine is preferably used for economical reasons.

The ratio of (a) polyamide-forming component / (b) polyether ester-forming component or polyether-forming component of (A) polyamide elastomer used in the present invention is from 10/90 to 90/10% by weight, particularly 20/80
The range of 70/30% by weight is preferable because the resin composition is excellent in impact resistance and antistatic property.

The method for producing the (A) polyamide elastomer is not particularly limited, and is, for example, JP-A-56-65026.
The methods disclosed in Japanese Patent Laid-Open Publication No. 55-133424 and Japanese Laid-Open Patent Publication No. 55-133424 can be used.

The polyphenylene ether (B) used in the present invention is preferably a homopolymer or copolymer having a unit of the following formula (I).

[0020]

[Chemical 1] (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of hydrogen, halogen, hydrocarbon, halohydrocarbon, hydrocarbonoxy and halohydrocarbonoxy, and n is a monomer. It represents an integer of a unit and is an integer of 20 or more.)

The polyphenylene ether (B) also includes a graft polymer obtained by graft-polymerizing an aromatic vinyl monomer to the polyphenylene ether.

The method for producing the polyphenylene ether is not particularly limited, but for example, US Pat. No. 3,306,874 is used.
No. 3,306,875 and U.S. Pat. No. 3,257,357 and 3,2.
It can be prepared by the reaction of phenols according to the procedure as described in 57,358. These phenols include 2,6-dimethylphenol,
2,6-diethylphenol, 2,6-dibutylphenol, 2,6-dilaurylphenol, 2,6-dipropylphenol, 2,6-diphenylphenol, 2-
Methyl-6-ethylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl-6-tolylphenol, 2-methyl-6-butylphenol, 2,6-dimethoxyphenol, 2,3,6-trimethylphenol, 2 , 3,5,6-tetramethylphenol, and 2,6-diethoxyphenol are included, but are not limited thereto.

Each of these may be reacted alone to give the corresponding homopolymer or may be reacted with another phenol to give the corresponding copolymer having different units included in the above formula. Specifically, 2,6-dimethylphenol and its corresponding polymers, namely poly (2,6-dimethyl-1,4-phenol) ether,
And a combination of 2,6-dimethylphenol with other phenols such as 2,3,6-trimethylphenol, 2-methyl-6-butylphenol and the like and corresponding copolymers such as poly (2,6-dimethyl-phenol). Co-2-methyl-6-butyl-1,4-phenylene)
Examples include ether.

The polyphenylene ether (B) used in the present invention contains a modified polyphenylene ether resin obtained by reacting a polyphenylene ether with an unsaturated dicarboxylic acid or an unsaturated carboxylic acid in an amount of 50% by weight or less based on the total polyphenylene ether. By this, the compatibility of the polyamide elastomer (A), polyphenylene ether (B) and polyamide resin (C) can be further improved.

Examples of the unsaturated dicarboxylic acid or unsaturated carboxylic acid in the (B) modified polyphenylene ether resin used in the present invention include maleic acid, chloromaleic acid, citraconic acid, phthalic acid and itaconic acid. Unsaturated carboxylic acids such as saturated dicarboxylic acid, acrylic acid, branic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid and angelic acid are mentioned, and maleic acid, maleic anhydride, acrylic acid and methacrylic acid are particularly polyamide elastomers. It is preferable because it has excellent compatibility with the polyamide resin.

The (B) modified polyphenylene ether resin used in the present invention can also be prepared by reacting a polyphenylene ether with an unsaturated dicarboxylic acid or an unsaturated carboxylic acid in the presence of a radical initiator.

The radical initiator is not particularly limited, but for example, in a benzene solvent, a half-life temperature of 6 hours is 6 hours.
Examples thereof include organic peroxides or azo compounds having a temperature of 0 ° C. or higher. Specifically, benzoyl peroxide, 1,1-
Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, methyl ethyl ketone Peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,
Organic peroxides such as 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, cumene hydroperoxide, t-butyl hydroperoxide, azobisisobutyronitrile, azobiscyclohexylnitrile, etc. The azo compound of is mentioned.

There are no particular restrictions on the preparation of the (B) modified polyphenylene ether used in the present invention. For example, (1) polyphenylene ether and an unsaturated dicarboxylic acid or unsaturated carboxylic acid, and optionally a radical initiator may be used. 200 ~ 3 using roll, Banbury mixer, extruder
A method of melt-kneading and reacting in a temperature range of 50 ° C.,
(2) Using a method in which a polyphenylene ether is reacted with an unsaturated dicarboxylic acid or unsaturated carboxylic acid in a solvent such as benzene, toluene, xylene, decalin, or tetralin, and optionally a radical initiator under heating. You can

Examples of the polyamide resin (C) in the present invention include lactams such as caprolactam, enantolactam, dodecanolactam and undecanolactam, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergon. Acids, aminocarboxylic acids such as ω-aminocapric acid and 11-aminoundecanoic acid, 12-aminododecanoic acid, nylon-6,6,-
6 · 9, −6 · 10, −6 · 12, −11 · 6, −12
There are polymers of salts of diamine-dicarboxylic acid which is a precursor of 6, such as caprolactam, 11-aminoundecanoic acid, 12-aminododecanoic acid, nylon-6.
Polymers of 6-salt, -6.10-salt, -6.12-salt and -11.6-salt are preferred.

The degree of polymerization of the (C) polyamide resin is not particularly limited, but the relative viscosity measured in sulfuric acid at 25 ° C. and a 1.0% concentration is 1.1 to 5.0, particularly 1.5 to 4.0. Is preferred. The method for producing the (C) polyamide resin is not particularly limited, and a usual polymerization method can be used.

The modified vinyl polymer (D) containing at least one functional group selected from the group consisting of (D) carboxyl group, epoxy group, amino group, hydroxyl group, polyalkylene oxide group and oxazoline group in the present invention (hereinafter referred to as modified vinyl). Abbreviated as a polymer) has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers, and has a carboxyl group, an epoxy group, an amino group, a hydroxyl group in the molecule. , A polymer containing at least one functional group selected from a polyalkylene oxide group and an oxazoline group. Although the content of the compound having these functional groups is not limited, it is particularly preferably in the range of 0.1 to 20% by weight based on 100 parts by weight of the modified vinyl polymer.

Generally, the effect of the present invention is effectively exhibited when one molecule of the modified vinyl polymer substantially contains an average of one or more of the above functional groups.

The method of introducing the carboxyl group into the modified vinyl polymer (D) is not particularly limited, but the carboxyl group or the anhydride such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid is used. A method of copolymerizing a vinyl monomer having a carboxyl group with a predetermined vinyl monomer, γ, γ′-azobis (γ
-Cyanovaleic acid), α, α′-azobis (α-cyanoethyl) -p-benzoic acid and a polymerization initiator having a carboxyl group such as persuccinic acid and / or thioglycolic acid, α-mercaptopropionic acid, β- Method for (co) polymerizing a predetermined vinyl polymer using a polymerization degree modifier having a carboxyl group such as mercaptopropionic acid, α-mercapto-isobutyric acid and 2,3 or 4-mercaptobenzoic acid, and methacrylic acid A method of saponifying a copolymer of a (meth) acrylic acid ester monomer such as methyl or methyl acrylate and an aromatic vinyl monomer, and optionally a vinyl cyanide monomer with an alkali. Can be used.

The method for introducing the epoxy group is not particularly limited, but for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, glycidyl itaconic acid, allyl glycidyl ether, styrene-p.
-A method of copolymerizing glycidyl ether, p-glycidyl styrene or the like with a predetermined vinyl-based monomer can be used.

The method of introducing an amino group is not particularly limited, but for example, the following formula (II)

[Chemical 2] (However, in the formula, R ⁵ represents hydrogen, a methyl group, or an ethyl group, R ⁶ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, or ^{6 to} 1 carbon atoms.
2 represents a phenyl group or a cycloalkyl group or derivatives thereof. ), A method of copolymerizing a vinyl-based monomer having at least one functional group of an amino group or a substituted amino group with a predetermined vinyl-based monomer, and the like.

Specific examples of vinyl monomers having at least one functional group of amino group or substituted amino group include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylamino methacrylate. Alkyl ester derivatives of acrylic acid or methacrylic acid such as propyl, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methallylamine and N -Allylamine derivatives such as methylallylamine, acrylamide, methacrylamide and N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide. Such as (meth) aminostyrene such as acrylamide derivatives and p- amino styrene.

The method for introducing the hydroxyl group is not particularly limited, but examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and acrylic acid 2. 3,4,5,6-pentahydroxyhexyl, methacrylic acid 2,3,4,5,6-pentahydroxyhexyl, acrylic acid 2,3,4,5-
Tetrahydroxypentyl, methacrylic acid 2,3,4
5-tetrahydroxypentyl, 3-hydroxy-1-
Propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2
-Butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-
5-hydroxy-2-pentene, 4-dihydroxy-2
-A method of copolymerizing butene or the like with a predetermined vinyl monomer can be used.

The method of introducing the polyalkylene oxide group is not particularly limited, but for example, (1) the following formulas (III) and (IV)

[Chemical 3] (In the formula, R ⁷ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁸ is an alkyl group having 2 to 6 carbon atoms, R ^8
9 represents hydrogen or an alkyl group having 1 to 6 carbon atoms,
n shows 2-500. The method of copolymerizing a vinyl-based monomer having a polyalkylene oxide group represented by (4) with a predetermined vinyl-based monomer can be used.

Specific examples include polyethylene glycol acrylate, polyethylene glycol methacrylate, poly (propylene oxide) glycol acrylate, poly (propylene oxide) methacrylate, poly (tetramethylene oxide) glycol acrylate, poly (tetramethylene oxide) glycol methacrylate. , Poly (hexamethylene oxide) glycol methacrylate, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy poly (propylene oxide) glycol acrylate, methoxy poly (propylene oxide) glycol methacrylate, methoxy poly (tetramethylene oxide) glycol methacrylate, ethoxy polyethylene glycol Acrylate, ethoxy polyethylene glycol methacrylate, Etokishipori (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, methoxy polyethylene glycol acrylamide, methoxy polyethylene glycol methacrylamide, methoxy poly (propylene oxide) glycol acrylamide, methoxy poly (propylene oxide) glycol methacrylamide,
Methoxy (tetramethylene oxide) glycol methacrylamide and the like can be mentioned.

Further, (2) acrylic acid, methacrylic acid,
A maleic acid, maleic anhydride, phthalic acid and the like are obtained by a method of copolymerizing with a desired vinyl monomer, etc. A method of carrying out the ester reaction at high temperature under normal pressure or reduced pressure can also be used.

The poly (alkylene oxide) glycol having an alkyl ether at one end as used herein is, for example, methoxypolyethylene glycol or methoxypoly (1,2).
-Propylene oxide) glycol, methoxy poly (1,3-propylene oxide) glycol, methoxy poly (tetramethylene oxide) glycol, methoxy poly (hexamethylene oxide) glycol, methoxy (block or random copolymer of ethylene oxide and propylene oxide) and methoxy ( And a block or random copolymer of ethylene oxide and propylene oxide). The number average molecular weight of poly (alkylene oxide) glycol having an alkylene ether at one end is in the range of 75 to 20,000.

The method of introducing the oxazoline group is not particularly limited, but examples thereof include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 2-
Isopropenyl-2-oxazoline, 2-acroyl-
2-oxazoline, 2-styryl-2-oxazoline,
4,4-dimethyl-2-vinyl-2-oxazoline,
A method of copolymerizing 4,4-dimethyl-2-isopropenyl-2-oxazoline or the like with a predetermined vinyl monomer can be used.

There is no particular limitation on the vinyl polymer used in the polymerization of the (D) modified vinyl polymer, and examples thereof include aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene, acrylonitrile, Vinyl cyanide monomers such as methacrylonitrile, methyl methacrylate, ethyl methacrylate, methyl acrylate,
(Meth) acrylic acid ester-based monomers such as butyl acrylate, maleimide-based monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, olein-based monomers such as ethylene and propylene One or more of vinyl monomers such as vinyl chloride, vinyl acetate and butadiene can be selected and used according to the purpose. In particular, aromatic vinyl monomers such as styrene, (meth) acrylic acid ester monomers such as methyl methacrylate, vinyl cyanide monomers such as acrylonitrile, and maleimide monomers such as N-phenylmaleimide. The body is preferred.

If necessary, polybutadiene, acrylonitrile / butadiene copolymer (NBR), styrene / butadiene copolymer (SBR), polybutyl acrylate and ethylene / propylene / diene rubber (E
A rubber-like polymer such as PDM) may be used in combination with the above vinyl-based monomer.

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

The method for producing the (D) modified vinyl polymer is not particularly limited, and may be a bulk polymerization method, a solution polymerization method, a suspension polymerization method,
Conventional methods such as emulsion polymerization method and bulk-suspension polymerization method can be used.

The (E) styrenic resin in the present invention means a (co) polymer containing 10% by weight or more of styrene units, or a monomer or a single amount of 1 to 80 parts by weight of a rubbery polymer containing 10% by weight or more of styrene. A graft (co) polymer obtained by graft-polymerizing 99 to 20 parts by weight of a body mixture and a mixture thereof.

As the rubbery polymer, those having a glass transition temperature of 0 ° C. or lower are preferable, and specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and styrene-butadiene block are preferred. Diene rubbers such as copolymers, butyl acrylate-butadiene copolymers and hydrogenated products thereof, acrylic rubbers such as polybutyl acrylate, polyisoprene,
Examples thereof include polychloroprene, ethylene-propylene-diene-based monomer terpolymer, and chlorinated polyethylene.

Specific examples of the styrene resin (E) in the present invention include polystyrene, rubber-modified polystyrene (HI-PS resin), styrene-acrylonitrile copolymer, styrene-rubber polymer-acrylonitrile copolymer ( ABS resin, AES resin, AAS resin, ACS resin) and the like. Two or more of these may be used. Further, a part of these styrenes and / or a part or all of acrylonitrile may be used as α-methylstyrene, p-methylstyrene, pt-butylstyrene,
(Meth) acrylic acid methyl, ethyl, propyl, n-
Also included are those substituted with styrene-copolymerizable vinyl-based monomers such as ester compounds such as butyl, maleimides, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and other maleimide-based monomers. Be done.

Here, as the styrene resin, particularly H
I-PS resin, ABS resin, AES resin, AAS resin,
ACS resin, MBS resin and the like are preferably used. In that case, the rubbery polymer is 40% by weight or less, preferably 30% by weight or less in the resin composition. If it exceeds 40% by weight, the resin composition becomes soft, which is not preferable.

The method for producing the styrene resin (E) is not limited, and a usual method such as a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method or a bulk-suspension polymerization method can be used.

The proportions of the (A) polyamide elastomer, (B) polyphenylene ether, (C) polyamide resin, (D) modified vinyl polymer and (E) styrene resin in the present invention are as follows: ) Component, (C) component, (D) component and (E) component in total of 100 parts by weight, the component (A) is 1 to 40 parts by weight, preferably 5 to
30 parts by weight, component (B) is 95-1 parts by weight, preferably 90-5 parts by weight, component (C) is 1-60 parts by weight, preferably 5-40 parts by weight, component (D) is 0.1 parts by weight. To 50 parts by weight, preferably 1 to 30 parts by weight, and the component (E) is 0 to 95 parts by weight.
Parts by weight, preferably 1 to 80 parts by weight. However,
The total of (A) + (B) + (C) + (D) + (E) is 10
0 parts by weight.

When the content 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 mechanical properties are inferior. If the polyphenylene ether (B) exceeds 95 parts by weight, the antistatic property is insufficient, and if it is less than 5 parts by weight, the heat resistance is poor, which is not preferable. If the amount of the (C) polyamide resin is less than 1 part by weight, the antistatic property is not improved,
If it exceeds 60 parts by weight, the impact resistance is poor and it is not preferable. When the modified vinyl polymer (D) is 0.1 part by weight, the impact resistance and the delamination preventive property are poor, and when it exceeds 50 parts by weight, the impact resistance and the appearance of the molded product are deteriorated and the product cannot be used.
If the amount of the styrene resin (E) exceeds 95 parts by weight, the antistatic property is deteriorated, which is not preferable.

In the present invention, the above resin composition contains an alkali metal,
When an inorganic metal salt (F) selected from an alkaline earth metal, a transition metal, and an aluminum metal (hereinafter abbreviated as an inorganic metal salt) is blended, rigidity, antistatic property, and metal corrosion resistance are improved.

The metals of the inorganic metal salt (F) in the present invention include Li, Na, K, Rb, Cs, Be, Mg and C.
a, Sr, Ba, Ti, Zr, Mn, Fe, Co, N
Examples thereof include i, Cu, Zn, Al and the like. Especially Li, N
Preferred are a, K, Ca, Mg, Zn and Al.

On the other hand, as the group forming a salt with the above metal, nitric acid, sulfuric acid, chlorine salt, perchloric acid, thiocyanic acid, carbonic acid, oxalic acid, silicic acid, phosphoric acid, boric acid, cyanic acid, halogen, Hydroxy, oxygen, etc. are mentioned, and of these,
Perchloric acid, thiocyanic acid, hydroxide, oxygen, carbonic acid, silicic acid,
Halogen is preferred. Specifically, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate,
Sodium perchlorate, potassium perchlorate, lithium perchlorate, sodium carbonate, potassium carbonate, lithium carbonate,
Sodium iodide, potassium iodide, and lithium iodide are preferable because they are excellent in improving antistatic properties.

Calcium hydroxide, magnesium hydroxide, aluminum hydroxide, zinc hydroxide, calcium oxide, magnesium oxide, aluminum oxide, zinc oxide,
Examples thereof include calcium carbonate, basic calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminum carbonate, zinc carbonate, potassium silicate, sodium silicate, calcium silicate, magnesium silicate and hydrotalcite. Among them, calcium hydroxide. , Magnesium hydroxide, calcium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, and hydrotalcite are particularly preferable in terms of excellent corrosion resistance of metals.

Here, hydrotalcite is a general formula

[Chemical 4] Is a compound represented by. Among them, Mg _4.5 is preferable.
Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O, Mg _4.5 Al
₂ (OH) ₁₃ CO ₃ .

The hydrotalcite-like compound can be synthesized by various methods as described in US Pat. No. 3,539,306.

Generally, synthetic hydrotalcites can be produced by co-precipitation of a solution of a cationic component and a solution of an anionic component. The most readily available hydrotalcite would be magnesium-aluminum hydroxycarbonate hydrate. A preferred hydrotalcite is Mg _4.5 Al ₂ (OH) ₁₃ by the manufacturer.
Commercial name DH characterized as CO ₃ · 3.5H ₂ O
Magnesium aluminum hydroxyhydrate available as T-40.

The above inorganic metal salts may be used alone or in combination of two or more.

The amount of the (F) inorganic metal salt added in the present invention is (A) polyamide elastomer, (B) polyphenylene ether, (C) polyamide resin, (D) modified vinyl polymer and (E) styrene resin. Of the total amount ((A) + (B) + (C) + (D) + (E) = 100 parts by weight) of 0 to 10 parts by weight, preferably 0.01 to
It is in the range of 5 parts by weight.

If the amount of the inorganic metal salt (F) added exceeds 10 parts by weight, the impact resistance is deteriorated, which is not preferable.

The method for producing the resin composition of the present invention is not particularly limited. For example, (A) polyamide elastomer, (B) polyphenylene ether, (C) polyamide resin, (D) modified vinyl resin, (E) styrene. It is commercialized by melt-kneading a mixture of a system resin and, if necessary, (F) an inorganic metal salt with a Banbury mixer, a roll, a uniaxial or biaxial extruder, or the like.

The resin composition of the present invention is mixed with another thermoplastic resin compatible with the composition of the present invention, for example, polycarbonate, polyglutarimide, polycyclohexanedimethylene terephthalate, etc. to obtain impact resistance and heat resistance. Of polyolefin, polybutylene terephthalate,
It is also possible to improve the chemical resistance by mixing with polyethylene terephthalate or the like, and improve the flame resistance by mixing with vinyl chloride resin, halogen-containing polystyrene or the like. Also,
A metal salt of sulfonic acid and polystyrene containing the compound,
It is also possible to further improve the antistatic property by adding an antistatic agent such as an anionic, cationic, or nonionic surfactant, and if necessary, various kinds of antioxidants, ultraviolet absorbers, etc. Stabilizers, pigments, dyes, lubricants and plasticizers, flame retardants and the like can also be added.

[0066]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below. The finally obtained resin composition was molded by the injection molding method, and then the physical properties were measured by the following test methods.

Izod impact strength: ASTM D256-56A Flexural modulus: ASTM D790 Heat distortion temperature: ASTM D648 (18.56 kg / cm ²
Load) Surface resistivity: 2mm ^t x 40mm ^φ disk, room temperature 2
The measurement was performed at 3 ° C. and a humidity of 50% RH. A super insulation resistance meter SM-10E type manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement. Delamination prevention property: A molded product immediately after injection molding was bent and observed by observing the surface. ⊚: extremely good, ◯: good, ×: delamination of the molded product was used as a criterion.

The parts and% in the examples mean parts by weight and% by weight, respectively.

Reference Example (1) Preparation of (A) Polyamide Elastomer A-1: Caprolactam 40.0 parts, number average molecular weight 1
500 parts of polyethylene glycol 55.2 parts and 6.4 parts of terephthalic acid were added together with 0.2 parts of "Irganox" 1098 (antioxidant) and 0.1 part of antimony trioxide catalyst into a reaction vessel equipped with a helical ribbon impeller. After charging, the atmosphere was replaced with nitrogen, and the mixture was heated and stirred at 260 ° C. for 60 minutes to form a transparent homogeneous solution, which was then polymerized for 3 hours under the conditions of 260 ° C. and 0.5 mmHg or less to obtain a viscous and transparent polymer.

The polymer was discharged onto a cooling belt in a gut form and pelletized to prepare a pelletized polyether ester amide (A-1).

A-2: Polyethylene glycol having a number average molecular weight of 4000 was reacted with acrylonitrile, and hydrogenation reaction was further carried out to obtain polyethylene glycol diamine having amino groups at both ends. This is subjected to a salt reaction with terephthalic acid by a conventional method to obtain 40% of polyethylene glycol diammonium terephthalate.
A solution was obtained.

120 parts of the 40% aqueous solution of polyethylene glycol diammonium terephthalate in a concentrated canister,
16 parts of 40% hexamethylene diammonium adipate aqueous solution was added, and the internal temperature was reduced to about 2 at normal pressure until the internal temperature reached 110 ° C.
Heated for hours and concentrated to 80% concentration. Subsequently, the above concentrated solution was transferred to the polymerization canister, and heating was started while flowing nitrogen into the polymerization canister.

When the internal temperature reached 120 ° C., a predetermined amount of sodium dodecylbenzenesulfonate and 1,3,5
10 parts of -trimethyl-2,4,6-tri (3,5-di-t-butylhydroxybenzyl) benzene were added, stirring was started, and the internal temperature was raised to 245 ° C. 24
The polymerization was completed by heating at 5 ° C. for 18 hours.

Thereafter, pelletized polyetheramide (A-2) was prepared in the same manner as in A-1.

(2) Preparation of (B) polyphenylene ether B-1: CPX-100L (manufactured by Mitsubishi Gas Chemical Co., Inc.) was used. B-2: 3 parts of maleic anhydride was mixed with 100 parts of polyphenylene ether, and the mixture was melt-kneaded and extruded at a resin temperature of 300 ° C. with a vented 30 mmφ twin-screw extruder, and pelletized modified polyphenylene ether (B-
2) was prepared. 10 g of the obtained pellets were made into a fine powder by a grinder, and then Soxhlet extraction was carried out using 100 ml of methanol. When the extracted sample was analyzed by NMR, the content of maleic anhydride was 2.3%.

(3) Preparation of (C) Polyamide Resin C-1: CM-1021 (nylon-6, Toray Industries, Inc.)
Manufactured) was used. C-2: CM-3001 (nylon-66, Toray Industries, Inc.)
Manufactured) was used.

(4) Preparation of (D) Modified Vinyl Polymer D-1: A modified vinyl polymer (D-1) was prepared by suspension polymerization of a mixture of 96% styrene and 4% methacrylic acid. .. D-2: A modified vinyl polymer (D-2) was prepared by suspension polymerization of a mixture of 80% styrene, 15% acrylonitrile and 5% methacrylic acid. D-3: 95% styrene and 5% 2-hydroxyethyl methacrylate were subjected to suspension polymerization to obtain a modified vinyl polymer (D-
3) was prepared. D-4: Styrene 99.5% and glycidyl methacrylate 0.5% are subjected to suspension polymerization to obtain a modified vinyl polymer (D-
4) was prepared. D-5: 95% styrene and 5% 2-vinyl-2-oxazoline were solution-polymerized, and then the solvent was removed to prepare a modified vinyl polymer (D-5). D-6: "Dailark" 232 (manufactured by ARCO) was used.

(5) (E) Preparation of styrene resin E-1: 10 parts of diene NF35A (manufactured by Asahi Kasei Co., Ltd.) was dissolved in 90 parts of styrene and 0.05 part of t-butylperoxybenzoate, and then bulk polymerization was carried out. Then, a graft polymer (E-1) was prepared. E-2: Polybutadiene latex (rubber particle size 0.3
50 parts of a monomer mixture consisting of 76% styrene and 24% acrylonitrile was emulsion-grafted in the presence of 50 parts (solid content) of 1 μm and gel content 88%. The resulting graft copolymer is solidified with sulfuric acid and neutralized with caustic soda,
It was washed, filtered and dried to prepare a powdery graft copolymer (E-2). E-3: 76 parts of styrene and 24 parts of acrylonitrile were suspension-polymerized to prepare a copolymer (E-3).

(6) (F) Preparation of Inorganic Metal Salt F-1: Magnesium silicate (Hytron A, manufactured by Takehara Chemical Co., Ltd.) was used. F-2: Potassium thiocyanate (Katayama Chemical Co., Ltd.) was used.

Examples 1 to 18 Polyamide elastomer (A) prepared in Reference Example,
(B) Polyphenylene ether, (C) Polyamide resin, (D) Modified vinyl polymer, (E) Styrene resin and (F) Inorganic metal salt were mixed at the compounding ratio shown in Table 1 and 40 mmφ extrusion with vent Machine, melt kneading at 280 ℃,
Pellets were produced by performing extrusion. Then, an injection molding machine was used to mold a test piece at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and each physical property was measured. For the surface resistivity, a 2 mm thick disc molded by injection molding was used.

(1) Immediately after molding, the product was washed with an aqueous solution of a detergent "Mama Lemon" (manufactured by Lion Corporation), followed by sufficient washing with distilled water to remove surface water, and then 50% RH,
The humidity was measured at 23 ° C for 24 hours.

(2) After molding, 1 at 50% RH and 23 ° C.
After leaving it to stand for 00 days, it was washed with a detergent "Mama Lemon" aqueous solution, then thoroughly washed with distilled water, to remove water from the surface, and then conditioned at 50% RH and 23 ° C. for 24 hours for measurement.

The measurement results are shown in Table 2.

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[Table 1]

[0085]

[Table 2]

Comparative Examples 1 to 10 (A) Polyamide elastomer prepared in Reference Example,
(B) Polyphenylene ether, (C) Polyamide resin, (D) Modified vinyl polymer, (E) Styrene resin were mixed at the compounding ratio shown in Table 1, and each physical property was measured by the same methods as in the examples. did. The measurement results are shown in Table 2.

From the results of Table 2, the following is clear. All of the resin compositions of the present invention (Examples 1 to 18) have excellent balance between mechanical strength represented by impact strength and flexural modulus and heat resistance, and have low surface resistivity. .. Moreover, the resistance value hardly changes even when the surface is washed or changes with time, and excellent permanent antistatic property is exhibited. That is, the resin composition of the present invention has excellent mechanical properties, heat resistance and permanent antistatic property, and is excellent in delamination prevention property.

On the other hand, when the compounding amount of the polyamide elastomer (A) is less than 1 part by weight (ratio 1), the resistance value is high and the antistatic property is poor, and when it exceeds 40 parts by weight (comparative example 2).
Is inferior in flexural modulus and heat resistance, which is not preferable.

When the compounding amount of the polyphenylene ether (B) exceeds 95 parts by weight (Comparative Example 3), the antistatic property is inferior, and when it is less than 5 parts by weight (Comparative Example 4), the heat resistance is poor and it is not preferable.

When the content of the polyamide resin (C) is less than 1 part by weight (Comparative Example 5), the antistatic property is not improved, and when it exceeds 60 parts by weight (Comparative Example 6), the heat resistance is poor and it is not preferable.

The amount of the modified vinyl polymer (D) blended was 0.
If it is less than 1 part by weight (Comparative Examples 7 and 9), the impact resistance is poor, and the molded product delaminates and cannot be used. If it exceeds 50 parts by weight (Comparative Example 8), the heat resistance and antistatic property are poor. Not preferable.

If the styrene resin (E) exceeds 95 parts by weight (Comparative Example 10), the heat resistance and antistatic property are poor, which is not preferable.

[0093]

The thermoplastic resin composition of the present invention exhibits excellent permanent antistatic properties, impact resistance, mechanical properties such as rigidity, heat resistance, and excellent delamination prevention properties.

According to the present invention, a permanent antistatic resin excellent in mechanical properties can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 77/00 LQS 9286-4J LQV 9286-4J 101/02 LSY 7242-4J

Claims (1)

[Claims] 1. A polyamide elastomer having 1 to 40 parts by weight of a soft component (A) is a polyalkylene glycol containing polyethylene glycol as a main component, (B) 95 to 1 parts by weight of polyphenylene ether, and (C) a polyamide resin 1
To 60 parts by weight, (D) carboxyl group, epoxy group, amino group, hydroxyl group, polyalkylene oxide group,
A total amount of 0.1 to 50 parts by weight of a modified vinyl polymer containing at least one functional group selected from oxazoline groups and 0 to 95 parts by weight of (E) styrene resin ((A) + (B ) + (C) + (D) + (E) = 100 parts by weight), (F) 0 to 10 parts by weight of an inorganic metal salt selected from an alkali metal, an alkaline earth metal, a transition metal, and an aluminum metal. A blended thermoplastic resin composition.