JP2745572B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention has permanent antistatic properties, and balances mechanical properties represented by impact resistance, moldability, and surface gloss of molded articles. The present invention relates to an antistatic resin composition which is excellent and has no laminar peeling (thousand-sheet turning).

[Prior Art] Synthetic polymer materials are used in a wide range of fields due to their excellent properties. If these materials are provided with antistatic properties in addition to the mechanical strength of the materials, their applications can be further expanded. That is, it can be applied to electronic and electromechanical parts such as copiers and televisions, and various dustproof parts for which failure due to static electricity is to be prevented.
In these fields, the surface gloss of a molded article is important.

As a method for improving the antistatic property of a synthetic polymer material,
Method for graft-polymerizing a vinyl-based monomer or a vinylidene monomer onto a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or / and an acrylic acid ester and a vinyl-based monomer having an alkylene oxide group (Japanese Patent Laid-Open No. 55-
No. 36237), and has achieved practical antistatic properties.

JP-A-60-23435 discloses that a resin having semipermanent antistatic properties is 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. Is disclosed.

[Problems to be Solved by the Invention] However, an antistatic resin obtained by graft-polymerizing a monomer to a hydrophilic rubbery polymer described in JP-A-55-36237 is a special hydrophilic rubber. The use of a state-of-the-art polymer results in a complicated production method and inferior mechanical properties of the obtained resin, which is not satisfactory. In addition, according to Japanese Patent Application Laid-Open No. 60-23435, the antistatic resin contains a large amount of a modified vinyl polymer containing a carboxyl group, so that gelation easily occurs due to heat history and the surface gloss of the molded product is increased. Is significantly worse, and a satisfactory composition cannot be obtained.

Therefore, the present invention has excellent antistatic properties, and has excellent balance of mechanical properties represented by impact resistance and surface gloss of a molded article, regardless of a complicated production method, and delamination. An object of the present invention is to provide a non-static resin composition.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, in order to solve the above problems, a specific polyetheresteramide and a graft (co) polymer contain a specific functional group. The present inventors have found that it is important to incorporate a modified vinyl-based polymer, and have arrived at the present invention.

That is, the present invention provides (A) (a) a salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a dicarboxylic acid with a diamine having 6 or more carbon atoms, (b) a compound represented by the following formulas (I) to (III): Compound shown, ethylene oxide adduct of 2,2-bis (4,4'-hydroxycyclohexyl) propane, propylene oxide adduct of 2,2-bis (4,4'-hydroxycyclohexyl) propane, 1,4-dihydroxy One or more diol compounds selected from ethylene oxide adduct of cyclohexane and propylene oxide adduct of 1,4-dihydroxycyclohexane, (Wherein, R ¹ and R ² each represent at least one of an ethylene oxide group and a propylene oxide group,
Y is a covalent bond, an alkylene group having 1 to 6 carbon atoms, 1 carbon atom
An alkylidene group having from 6 to 6, a cycloalkylidene group having from 7 to 17 carbon atoms, an arylalkylidene group having from 7 to 17 carbon atoms, O,
Represents SO, SO ₂ , CO, S, CF ₂ , C (CF ₃ ) ₂ or NH;
X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen group, sulfonic acid, or a metal salt thereof. l is 0 or 1
And m and n each represent an integer of 1 to 15. ) (C) a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 6,000 and (d) 4 to 20 carbon atoms.
(B) (b1) 1 to 80 parts by weight of a polyetherester amide obtained by copolymerizing dicarboxylic acid of (B2) 100 to 40% by weight of an aromatic vinyl monomer and 0 to 60% by weight of a vinyl cyanide monomer or a monomer mixture 99 to 100 parts by weight
Graft (co) obtained by graft (co) polymerization of 20 parts by weight
2 to 99 parts by weight of a polymer, (C) a modified vinyl polymer containing at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group or a substituted amino group, and a hydroxyl group. 97 parts by weight and (D) 100 to 40% by weight of an aromatic vinyl monomer and / or (meth) acrylate monomer, 0 to 60% by weight of a vinyl cyanide monomer, and 0 to 97 parts by weight of a vinyl (co) polymer obtained by (co) polymerizing a monomer or monomer mixture comprising 0 to 60% by weight of another polymerizable vinyl monomer; + (B) + (C) + (D)
Is 100 parts by weight, and the amount of the rubbery polymer in the whole is 1 to 40% by weight.

 Hereinafter, the present invention will be described specifically.

Examples of the salt of (a) an aminocarboxylic acid having 6 or more carbon atoms or a lactam or a diamine having 6 or more carbon atoms and a dicarboxylic acid, which are constituent components of the polyetheresteramide (A) in the present invention, include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω
-Aminopergonic acid, ω-aminocapric acid and 11-
Aminoundecanoic acid, lactam and hexamethylenediamine-adipate such as aminocarboxylic acid such as 12-aminododecanoic acid or caprolactam, enantholactam, caprylactam, and laurolactam;
Diamine-dicarboxylic acid salts such as hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate are used. Particularly, caprolactam, 12-aminododecanoic acid, and hexamethylenediamine-adipate are preferably used.

(A) A salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms or a dicarboxylic acid with a diamine having 6 or more carbon atoms is a constituent unit of polyetheresteramide and is 10 units.
When the amount is less than 10% by weight, the mechanical properties of the polyetheresteramide are inferior, and when it exceeds 90% by weight, the obtained resin has poor antistatic properties, which is not preferable.

The diol compound (b) which is a constituent component of the polyetheresteramide (A) in the present invention is represented by the formula (I)
A compound represented by (III), an ethylene oxide adduct of 2,2-bis (4,4'-hydroxycyclohexyl) propane, a propylene oxide adduct of 2,2-bis (4,4'-hydroxycyclohexyl) propane, 1 Ethylene oxide adduct of 1,4-dihydroxycyclohexane and 1,4
Propylene oxide adduct of dihydroxycyclohexane.

Specific examples of the compounds represented by the formulas (I) to (III) include ethylene oxide of bisphenol A and / or
Or propylene oxide adduct, ethylene oxide and / or propylene oxide adduct of tetrabromobisphenol A, ethylene oxide and / or propylene oxide adduct of dimethyl bisphenol A,
Ethylene oxide and / or propylene oxide adduct of tetramethylbisphenol A, ethylene oxide and / or propylene oxide adduct of 2,2-bis (sodium 4,4'-hydroxyphenyl-3,3'-sulfonate) propane, bisphenol S Ethylene oxide and / or propylene oxide adduct, dimethyl bisphenol S ethylene oxide and / or propylene oxide adduct, tetramethyl bisphenol S ethylene oxide and / or propylene oxide adduct, 4,4 ′-(hydroxy) biphenyl ethylene oxide and / or Propylene oxide adduct, bis (4-hydroxyphenyl) sulfide ethylene oxide and / or propylene oxide adduct, bis (4-hydroxyphenyl) Ethylene oxide and / or propylene oxide adducts of sulfoxide, bis (4-hydroxyphenyl) ethylene oxide and / or propylene oxide adducts of methane, bis (4-
(Hydroxyphenyl) ether ethylene oxide and / or propylene oxide adduct, bis (4-hydroxyphenyl) amine ethylene oxide and / or propylene oxide adduct, 2,2-bis (4-hydroxyphenyl) ethane ethylene oxide and / or propylene Oxide adducts, ethylene oxide and / or propylene oxide adducts of 1,1-bis (4-hydroxyphenyl) cyclohexane, ethylene oxide and / or propylene oxide adducts of 4,4′-dihydroxybenzophinone, ethylene oxide and / or hydroquinone Or propylene oxide adduct, ethylene oxide and / or propylene oxide adduct of sodium 1,4-dihydroxybenzenesulfonate, dihydroxynaphtha Ethylene oxide and / or propylene oxide adducts of emissions, and the like block copolymers thereof.

Preferred diol compounds include ethylene oxide adducts of hydroquinone, ethylene oxide adducts of bisphenol A, ethylene oxide adducts of bisphenol S, ethylene oxide adducts of dihydroxynaphthalene and block polymers thereof, and especially ethylene oxide adducts of bisphenol A and The block polymer is preferable in terms of polymerizability and economy.

One or two or more of these diol compounds can be used as needed. There is no particular limitation on the amount of copolymerization, but preferably,
It is in the range of 0.1 to 60% by weight.

Further, other diol compounds can be copolymerized within a range that does not impair the effects of the present invention. Specifically, aromatic diols such as p-xylylene glycol and m-xylylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol , 1,3
Alicyclic diol compounds such as cyclohexanedimethanol and the like can be copolymerized;

(C) Poly (alkylene oxide) glycol which is a constituent component of (A) polyetheresteramide includes polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, A (tetramethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran are used. In particular, polyethylene glycol is preferably used from the viewpoint of polymerizability and antistatic properties. . The number average molecular weight of the poly (alkylene oxide) glycol is from 200 to
When the number average molecular weight is less than 200, the obtained polyetheresteramide has poor mechanical properties, and when the number average molecular weight exceeds 6,000, the obtained polyetheresteramide has transparency. Is not preferred because it becomes worse.

(A) The dicarboxylic acid having 4 to 20 carbon atoms, which is a constituent component of the polyetheresteramide, includes terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7-dicarboxylic acid. Acids, diphenyl-4,4'-dicarboxylic acid, aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4 Alicyclic dicarboxylic acids such as 4,4'-dicarboxylic acid and succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanediacid (decanedicarboxylic acid) such as aliphatic dicarboxylic acids, and 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.

(B) Diol compound and (c) poly (alkylene oxide) glycol and (d) dicarboxylic acid
The reaction is carried out at a molar ratio of 1: 1. However, it is usually supplied at a different charging ratio depending on the type of dicarboxylic acid used.

The polyetherester component is used in the range of 90 to 10% by weight as a constituent unit of the polyetheresteramide, and if it exceeds 90% by weight, the mechanical properties of the polyetheresteramide are inferior. Poor prevention is not preferred.

The polymerization method of (A) the polyetheresteramide is not particularly limited. For example, (a) a polyamide prepolymer having a carboxylic acid group at both ends by reacting (a) an aminocarboxylic acid or a lactam with (d) a dicarboxylic acid. And reacting (b) a diol compound with (c) a poly (alkylene oxide) glycol under vacuum.
(B) The compounds (a), (b), (c) and (d) are charged into a reaction vessel and reacted at a high temperature in the presence or absence of water to form a carboxylic acid-terminated polyamide preform. A method of producing a polymer and then proceeding with polymerization under normal pressure or reduced pressure; and (c) the method (a), (b),
The compounds (c) and (d) are charged into a reaction vessel, and heated and stirred under a stream of N ₂ to obtain a transparent homogeneous mixture. Thereafter, a method of proceeding the reaction under vacuum can be used.

Here, the term "under vacuum" refers to about 15 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less.

In the polymerization reaction of the polyetheresteramide of the present invention, a titanium-based catalyst such as a tetraalkyl titanate such as tetrabutyl titanate or a titanium oxalate metal salt such as potassium oxalate, dibutyltin oxide, dibutyltin laurate, and monobutyltin oxide Such as tin catalysts, zirconium tetraalkoxide catalysts such as zirconium tetrabutoxide and zirconium isopropoxide, hafnium tetraalkoxide catalysts such as hafnium tetraethoxide and lead catalysts such as lead acetate, and antimony trioxide One or two or more catalysts selected from antimony oxide-based catalysts and the like are used.

In the present invention, the (B) graft (co) polymer is defined as (b1) a rubbery polymer and (b2) a monomer or monomer mixture composed of an aromatic vinyl monomer and an aromatic vinyl monomer. And those obtained by graft (co) polymerization of a monomer or a monomer mixture selected from a monomer mixture of vinyl cyanide monomers.

As the rubbery polymer (b1) used in the present invention, those having a glass transition temperature of 0 ° C. or lower are preferable, and specifically, diene rubbers such as polybutadiene, polystyrene-butadiene, polyacrylonitrile-butadiene, and polyisoprene. Acrylic rubbers such as polychloroprene and polybutyl acrylate; and rubbery polymers such as ethylene-propylene-diene-based monomer terpolymers can be used.

Particularly, polybutadiene or butadiene copolymer is preferable.

Styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, o-
Alternatively, p-dichlorostyrene and the like can be mentioned, and styrene is particularly preferable.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferable.

If necessary, other vinyl monomers, for example, maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, acrylamide, (meth) acrylic acid and methyl, ethyl, propyl and the like thereof Can be used.

(B) The monomer or monomer mixture of (b2) used in the graft (co) polymer can obtain sufficient physical properties even with an aromatic vinyl monomer alone, but further has a vinyl cyanide monomer , The impact resistance is remarkably improved. The mixing ratio of the mixture of the aromatic vinyl monomer and the vinyl cyanide monomer is 100 to 40% by weight, preferably 100 to 50% by weight of the aromatic vinyl monomer, 0-60% by weight, preferably 0-50% by weight
It is.

If the proportion of the vinyl cyanide-based monomer exceeds 60% by weight, the thermal stability of the graft (co) polymer is remarkably reduced, and a molded article having a poor color tone is not preferable.

(B) The proportion of the rubbery polymer and the monomer or the monomer mixture in the graft (co) polymer is preferably 1 to 80 parts by weight of the rubbery polymer in 100 parts by weight of the total graft (co) polymer. Is 5 to 70 parts by weight, and the monomer or monomer mixture is 99 to 20 parts by weight, preferably 95 to 30 parts by weight.

When the proportion of the rubbery polymer in the (B) graft (co) polymer is less than 1 part by weight, the resulting resin composition has poor impact resistance. When it exceeds 80 parts by weight, the rubbery polymer has poor dispersion. And the appearance of the molded article is impaired, which is not preferable.

(B) The graft (co) polymer is prepared by a known polymerization method, such as a method in which a monomer or a monomer mixture and a polymerization initiator are continuously supplied in the presence of a rubbery polymer latex to carry out emulsion polymerization. Obtainable.

The present invention relates to a modified vinyl polymer (C) containing at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group or a substituted amino group and a hydroxyl group (hereinafter referred to as a modified vinyl polymer). Abbreviation)
By using, the compatibility between the component (A) and the component (B) can be further improved.

The modified vinyl polymer (C) used in the present invention has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers, and has a carboxyl group or an epoxy group in the molecule. At least one selected from the group consisting of an amino group or a substituted amino group and a hydroxyl group
It is a polymer having 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.

Usually, the effect of the present invention can be effectively exhibited if one molecule of the modified vinyl polymer contains at least one or more of the above functional groups substantially on average. (C) The method for introducing a carboxyl group into the modified vinyl polymer is not particularly limited, but may be acrylic acid, methacrylic acid, maleic acid, maleic anhydride,
A method of copolymerizing a vinyl monomer having a carboxyl group or a carboxyl anhydride group such as phthalic acid and itaconic acid with a predetermined vinyl monomer, γ, γ′-azobis (γ-cyanovaleic acid), α, α '-Azobis (α-
A polymerization initiator having a carboxyl group such as (cyanoethyl) -p-benzoic acid and succinic peroxide and / or thioglycolic acid, α-mercaptopropionic acid, β-
Method for (co) polymerizing a predetermined vinyl monomer using a polymerization degree regulator 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 (meth) acrylate-based (co) polymer such as methyl acrylate or butyl acrylate with an alkali can be used.

Although there is no particular limitation on the method of introducing an epoxy group, for example, Wherein R ³ is a hydrogen atom, a lower alkyl group or a lower alkyl group substituted with a glycidyl ester group, and specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate For example, a method of copolymerizing the above with a predetermined vinyl monomer can be used.

The method for introducing an amino group or a substituted amino group is not particularly limited. (Wherein, R 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, A phenyl group, a cycloalkyl group or a derivative thereof is shown.) A vinyl monomer having at least one functional group of an amino group or a substituted amino group is copolymerized with a predetermined vinyl monomer. A method comprising using a chain transfer agent and / or an initiator having at least one functional group selected from the group consisting of amino groups, substituted amino groups and mineral salts thereof represented by the above (V). A method of (co) polymerizing a vinyl monomer can be used.

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

Specific examples of the chain transfer agent having the above functional group include mercaptomethylamine, β-mercaptoethylamine, γ-mercaptopropylamine, N- (β-mercaptoethyl) -N-methylamine, N- (β -Mercaptoethyl) -N-phenylamine, N- (β-mercaptoethyl) -N-cyclohexylamine, bis-
(4-aminophenyl) disulfide, bis- (2-
Aminophenyl) disulfide, bis- (3-aminophenyl) disulfide, p-mercaptoaniline,
Examples thereof include o-mercaptoaniline, m-mercaptoaniline, and hydrochlorides thereof. Specific examples of the initiator include α, α′-azobis (γ-amino-α, γ-dimethylvaleronitrile) and 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.

There is no particular limitation on the method for introducing a hydroxyl group. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
A method of copolymerizing polyethylene glycol methacrylate, polyethylene glycol acrylate, or the like with a predetermined vinyl polymer can be used.

(C) The vinyl monomer used for the polymerization of the modified vinyl polymer is not particularly limited, and examples thereof include aromatic vinyl monomers such as styrene, α-styrene, and vinyl toluene, acrylonitrile, and methacryloyl. Vinyl cyanide monomers such as nitrile, (meth) acrylate monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, butyl acrylate,
One or two of maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, olefin monomers such as ethylene and propylene, and vinyl monomers such as vinyl chloride, vinyl acetate and butadiene. The above can be selected and used according to the purpose. In particular, the mechanical properties of a resin composition that allows the use of 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, rubber-like polymers such as polybutadiene, acrylonitrile / butadiene copolymer (NBR), styrene / butadiene copolymer (SBR), polybutyl acrylate, and ethylene / propylene / diene rubber (EPDM) may be used. Can be used in combination with the vinyl monomer.

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

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

The composition of the present invention further comprises an aromatic vinyl monomer and / or a (meth) acrylate monomer 100 to 4
A monomer or monomer mixture comprising 0% by weight, 0 to 60% by weight of a vinyl cyanide monomer, and 0 to 60% by weight of another vinyl monomer copolymerizable therewith is (co) A vinyl (co) polymer (D) obtained by polymerization may be contained.

Examples of the aromatic vinyl monomer that is a constituent component of the vinyl (co) polymer (D) include styrene, α-methylstyrene, vinyltoluene, and pt-butylstyrene.

Examples of the (meth) acrylate-based monomer include ester compounds such as methyl, ethyl, propyl, n-butyl and i-butyl of acrylic acid and methacrylic acid.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.

Further, as other vinyl monomers copolymerizable with these, maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, ethylene,
Examples include olefin monomers such as propylene, N-vinylpyrrolidone, maleic anhydride, vinyl chloride, and butadiene.

Specific examples of the vinyl (co) polymer (D) include:
Styrene-acrylonitrile copolymer, α-methylstyrene-styrene-acrylonitrile copolymer, α-methylstyrene-methyl methacrylate-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer, styrene-methyl methacrylate-acrylonitrile Copolymer, styrene-methyl methacrylate copolymer, styrene-N-phenylmaleimide-acrylonitrile copolymer, α-methylstyrene-methyl methacrylate copolymer, polystyrene, polymethyl methacrylate, and the like.

This vinyl-based (co) polymer (D) has sufficient physical properties only with a (co) polymer composed of 100 to 40% by weight of an aromatic vinyl-based monomer and / or a (meth) acrylate-based monomer. However, by further containing up to 60% by weight of another vinyl monomer such as a vinyl cyanide monomer and / or a maleimide monomer, remarkable impact resistance and heat resistance are obtained. Characteristics are improved.

When the amount of the vinyl cyanide monomer and / or other vinyl monomer exceeds 60% by weight, problems such as coloring of the resin composition and deterioration of impact resistance occur, which is not preferable.

The polymer thus obtained comprises (A) 1 to 40 parts by weight of polyetheresteramide, preferably 5 to 30 parts by weight,
(B) 2 to 99 parts by weight, preferably 5 to 95 parts by weight of the graft (co) polymer, (C) 0 to 97 parts by weight, preferably 1 to 30 parts by weight of the modified vinyl polymer and vinyl (co) The polymer is blended so that (A) + (B) + (C) + (D) becomes 100 parts by weight within the range of 0 to 97 parts by weight, preferably 0 to 89 parts by weight.

When the amount of the polyetheresteramide (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 has poor mechanical properties, which is not preferable.

If the amount of the (B) graft (co) polymer is less than 2 parts by weight, the impact resistance is insufficient, and if it exceeds 99 parts by weight, the antistatic property is inferior.

Further, (C) the modified vinyl polymer has a concentration of at least one functional group of a carboxyl group, an epoxy group, an amino group or a substituted amino group and a hydroxyl group of the modified vinyl polymer in 100 g of the resin composition. It is preferable to use it in a proportion of 0.5 mol or less. If it exceeds 0.5 mol, the surface gloss of the molded article is reduced.

What is necessary in the resin composition of the present invention is that the proportion of rubber in the resin composition is 1 to 40% by weight, preferably 3 to 30% by weight.

If the amount is less than 1% by weight, the impact resistance of the resin composition is poor, and if it exceeds 40% by weight, the resin composition becomes soft and the mechanical properties are inferior.

The method for producing the resin composition of the present invention is not particularly limited. For example, a resin mixture of (A) a polyetheresteramide, (B) a graft (co) polymer, and (C) a modified vinyl polymer is mixed with a Banbury mixer. It is commercialized by melt-kneading with a roll, extruder or the like. In addition, what mixed the (B) graft (co) polymer and (D) vinyl type (co) polymer beforehand can also be used.

The resin composition of the present invention is another thermoplastic polymer compatible with the resin composition of the present invention, for example, polyamide, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyphenylene ether, vinyl chloride resin, polyglutarimide, hydrogenated. The performance as a molding resin can be improved by mixing an elastomer such as a styrene-butadiene block copolymer to which no hydrogen has been added.

It is also possible to further improve the antistatic property by adding an antistatic agent such as a metal salt of sulfonic acid or an anionic, cationic or nonionic surfactant, and further, if necessary, an oligomer or the like. Various stabilizers such as compatibilizers, antioxidants and ultraviolet absorbers, pigments, dyes, lubricants, plasticizers, glass fibers, flame retardants and the like can also be added. When a modified vinyl polymer having an epoxy group is used, the compatibility of the components (A) and (B) is further improved by adding a sulfonic acid, a tertiary amine and a phosphorus compound. You can also.

[Example] In order to more specifically explain the present invention, an example and a comparative example will be described below. In addition, after the finally obtained resin composition is molded by an injection molding method,
Various physical properties were measured by the following test methods.

Izod impact strength: ASTM D256-56A Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Surface gloss of molded product: Measured at a measuring angle of 60 ° using a square plate of 80 mm × 120 mm × 2 mmt. For the measurement, a digital variable angle gloss meter UGV-5D manufactured by Suga Test Instruments Co., Ltd. was used.

MFR: Measured under the conditions of a nozzle 2 mmφ × 8 mm, a temperature of 220 ° C., and a load of 10 kg.

Volume specific resistance: 2 mmt × 40 mmφ disk, room temperature 23 ℃,
The measurement was performed in a 50% RH atmosphere. A super insulation resistance meter SM-10 manufactured by Toa Denpa Kogyo KK was used for the measurement.

The delamination prevention property of the molded article was determined by bending the molded article and observing the test piece subjected to the pull-up test and the fracture surface. ◎: extremely good, ：: good, ×: the molded article caused delamination,
Was used as a criterion.

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

Reference Examples (1) (A) Preparation of polyetheresteramide A-1: 40 parts of caprolactam, ethylene oxide adduct of bisphenol A (Newpol BPE20, manufactured by Sanyo Chemical Industries, Ltd.) 7.16 parts, number average molecular weight is 1000 44.25 parts of polyethylene glycol and 11.76 parts of terephthalic acid are charged together with 0.2 part of "Irganox" 1098 (antioxidant) and 0.02 part of antimony trioxide in a reaction vessel equipped with a helical ribbon stirring blade, and replaced with N ₂ at 260 ° C. The mixture was heated and stirred for 60 minutes to obtain a transparent homogeneous solution. Next, according to the decompression program, after removing the water in the gas phase part of the reaction vessel by reducing the pressure to 500 Hg, 0.08 parts of zirconium tetrabutoxide was added, and the pressure was reduced again according to the decompression program, 260 ° C., 0.5 mm
Polymerization was conducted for 3 hours and 20 minutes under the condition of Hg or less to obtain a viscous and transparent polymer. Discharge the polymer on the cooling belt in a gut shape,
The pelletized polyetheresteramide (A-1) was prepared by pelletizing.

A-2: 40 parts of ω-aminodecanoic acid, 6.04 parts of 1,4-bis (β-hydroxyethoxy) benzene, and a number average molecular weight of 10
44.25 parts of polyethylene glycol and 13.20 parts of terephthalic acid together with 0.2 part of "Irganox" 1098 and 0.1 part of antimony trioxide were charged into the reaction vessel used in A-1, replaced with N ₂ and heated at 260 ° C. for 60 minutes. After stirring to obtain a clear homogeneous solution, the pressure was reduced according to the pressure reduction program,
Polymerization was performed at 0 ° C. and 0.5 mmHg or less for 4 hours to obtain a viscous and transparent polymer. Thereafter, polyetheresteramide (A-2) was prepared in exactly the same manner as in A-1.

A-3: except that 40 parts of nylon 6.6 salt (AH salt), 6.56 parts of 2,6-bis (β-hydroxyethoxy) naphthalene, 37.74 parts of polyethylene glycol having a number average molecular weight of 400 and 21.33 parts of isophthalic acid were used. Polymerization was carried out in the same manner as in A-2 to prepare a polyetheresteramide (A-3).

A-4: Polymerization was carried out in the same manner as in A-2 except that caprolactam was 50 parts, polyethylene glycol having a number average molecular weight of 1000 was 44.2 parts and terephthalic acid was 7.6 parts, to prepare a polyetheresteramide (A-4).

(2) (B) Preparation of graft (co) polymer B-1: polybutadiene latex (rubber particle type 0.25
μ, gel content 80%) A monomer mixture consisting of 72% styrene and 28% acrylonitrile in the presence of 60 parts (solid content)
40 parts were emulsion polymerized.

The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, dried and dried to prepare a powdery galft copolymer (B-1).

B-2: 10 parts of diene NF35A (manufactured by Asahi Kasei Corporation) are dissolved in 90 parts of styrene, and then the resulting mixture is subjected to bulk polymerization to obtain a graft polymer (B).
-2) was prepared.

B-3: Polybutadiene latex 15 used in B-1
Of a monomer mixture composed of 75% of styrene and 25% of acrylonitrile in the presence of parts (in terms of solid content) of 85 parts by emulsion polymerization, and then in the same manner as B-1, a powdery graft copolymer (B-3) Was prepared.

B-4: AES resin (Uniplite UB-300, manufactured by Sumitomo Nogatack Co., Ltd.) was used.

B-5: AAS resin (Vitax 6100, Hitachi Chemical Co., Ltd.)
Was used.

(3) (C) Preparation of modified vinyl polymer C-1: 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylic acid are subjected to suspension polymerization to form a modified vinyl polymer (C-
1) was prepared.

The resulting modified vinyl polymer (C-1) had an intrinsic viscosity ([η]) of 0.61 as measured at 30 ° C. and 0.4% concentration in methyl ethyl ketone (MEK).

C-2: 71 parts of styrene, 28 parts of acrylonitrile, and 1 part of glycidyl methacrylate were subjected to suspension polymerization to prepare a modified vinyl polymer (C-2).

[Η] of the resulting modified vinyl polymer (C-2) measured by the same method as that of C-1 was 0.56.

C-3: 70 parts of styrene, 27 parts of acrylonitrile and 3 parts of allylamine are subjected to suspension polymerization to obtain a modified vinyl polymer (C-
3) was prepared.

The obtained modified vinyl polymer (C-3) had [η] of 0.49 as measured by the same method as that of C-1.

C-4: A modified vinyl polymer (C-4) was prepared by subjecting 95 parts of styrene and 5 parts of methacrylic acid to suspension polymerization.

The resulting modified vinyl polymer (C-4) is dissolved in toluene
[Η] measured at 30 ° C. and 0.4% concentration was 0.41.

C-5: A modified vinyl polymer (C-5) was prepared by emulsion polymerization of 70 parts of styrene, 24 parts of acrylonitrile, and 6 parts of 2-hydroxyethyl methacrylate. The resulting modified vinyl polymer (C-5) had a [η] of 0.58 as measured by the same method as for C-1.

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

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

D-3: 50 parts of styrene, 30 parts of N-phenylmaleimide,
20 parts of acrylonitrile were emulsion-polymerized. The obtained copolymer latex was coagulated with magnesium sulfate, then secondary aggregated at a high temperature, washed, dried and dried to prepare a powdery copolymer (D-3).

Examples 1 to 14 Table 1 shows (A) polyetheresteramide, (B) graft (co) polymer, (D) vinyl (co) polymer and (C) modified vinyl polymer prepared in Reference Examples. And the mixture was melt-kneaded and extruded at a resin temperature of 220 ° C. with a vented 40 mmφ extruder to produce pellets.

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

The volume specific resistance was measured using a 2 mm-thick injection molded disk under the following conditions.

(1) Immediately after molding, wash with an aqueous solution of detergent "Mama Lemon" (manufactured by Lion Oil & Fats Co., Ltd.), and then sufficiently wash with distilled water to remove water on the surface. The humidity was measured for a period of time. (2) 200% in 50% RH, 23 ℃ after molding
After standing for a day, the residue was washed with an aqueous solution of a detergent “Mama Lemon”, and then sufficiently washed with distilled water to remove moisture on the surface. The humidity was then adjusted at 50% RH at 23 ° C. for 24 hours.

 Table 2 shows the measurement results.

Comparative Examples 1 to 7 Table 1 shows (A) polyetheresteramide, (B) a graft (co) polymer, (D) a vinyl (co) polymer, and (C) a modified vinyl polymer prepared in Reference Examples. And the respective physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

The following is clear from the results in Table 2. All of the resin compositions of the present invention (Examples 1 to 14) are excellent in balance of mechanical properties represented by impact strength and flexural modulus, moldability, and surface gloss of molded articles, and have low volume resistivity. Have a value. 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 blending amount of the polyetheresteramide (A) is less than 1 part by weight (Comparative Examples 1 and 4), the antistatic property (resistance value) is poor, and the polyetheresteramide (A) is less than 40 parts by weight.
When the amount exceeds the weight part (Comparative Example 2), the tensile yield stress and the flexural modulus are inferior.

The ratio of the (b1) rubbery polymer in the resin composition is 1
If it is less than 10% by weight (Comparative Examples 3 and 7), the impact resistance is poor,
When it exceeds 40% by weight (Comparative Example 6), the flexural modulus and the surface gloss of the molded product are deteriorated.

(B) When the polyetheresteramide (A) containing no diol compound is used (Comparative Example 5), the surface gloss of the molded product is inferior.

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

[Effects of the Invention] The thermoplastic resin composition of the present invention has excellent mechanical properties such as permanent antistatic properties and impact resistance, and excellent surface gloss of a molded product.
And there is no delamination.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 71/02 C08L 71/02 77/12 77/12

Claims (4)

(57) [Claims] (A) (A) (a) a salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms or a salt of a dicarboxylic acid with a diamine having 6 or more carbon atoms, (b) the following formulas (I) to (II):
A compound represented by I), an ethylene oxide adduct of 2,2-bis (4,4'-hydroxycyclohexyl) propane,
One kind selected from propylene oxide adduct of 2,2-bis (4,4'-hydroxycyclohexyl) propane, ethylene oxide adduct of 1,4-dihydroxycyclohexane, and propylene oxide adduct of 1,4-dihydroxycyclohexane Two or more diol compounds, (Wherein, R ¹ and R ² each represent at least one of an ethylene oxide group and a propylene oxide group,
Y is a covalent bond, an alkylene group having 1 to 6 carbon atoms, 1 carbon atom
An alkylidene group having from 6 to 6, a cycloalkylidene group having from 7 to 17 carbon atoms, an arylalkylidene group having from 7 to 17 carbon atoms, O,
Represents SO, SO ₂ , CO, S, CF ₂ , C (CF ₃ ) ₂ or NH;
X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen group, sulfonic acid, or a metal salt thereof. l is 0 or 1
And m and n each represent an integer of 1 to 15. ) (C) a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 6,000 and (d) 4 to 20 carbon atoms.
(B) (b1) 1 to 80 parts by weight of a polyetherester amide obtained by copolymerizing the dicarboxylic acid of (A), wherein the polyetheresteramide has 10 to 90% by weight of a polyetheresteramide. (B2) 100 to 40% by weight of an aromatic vinyl monomer and 0 to 60% by weight of a vinyl cyanide monomer or a monomer mixture 99 to 100 parts by weight
Graft (co) obtained by graft (co) polymerization of 20 parts by weight
2 to 99 parts by weight of a polymer, (C) a modified vinyl polymer containing at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group or a substituted amino group, and a hydroxyl group. 97 parts by weight and (D) 100 to 40% by weight of an aromatic vinyl monomer and / or (meth) acrylate monomer, 0 to 60% by weight of a vinyl cyanide monomer, and 0 to 97 parts by weight of a vinyl (co) polymer obtained by (co) polymerizing a monomer or monomer mixture comprising 0 to 60% by weight of another polymerizable vinyl monomer; + (B) + (C) + (D) is blended so as to be 100 parts by weight, and the amount of the rubbery polymer occupying the whole is 1 to 1.
A thermoplastic resin composition formulated to be 40% by weight. (2) 75 to 40% by weight of an aromatic vinyl-based monomer and 25 to 60% by weight of a vinyl cyanide-based monomer, the monomer mixture giving a graft (co) polymer as the component (B). The thermoplastic resin composition according to claim 1, which comprises: 3. The modified vinyl polymer as the component (C) contains at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group or a substituted amino group, and a hydroxyl group. The monomer component is
2. The thermoplastic resin composition according to claim 1, wherein the content is 1% by weight or more based on (C) the modified vinyl polymer. 4. The polyetheresteramide of component (A) is 5 to 30 parts by weight, and the graft (co) of component (B) is
The polymer is 5 to 95 parts by weight, the modified vinyl polymer as the component (C) is 1 to 30 parts by weight, and the vinyl (co) polymer as the component (D) is 0 to 89 parts by weight (here, (A) +
The thermoplastic resin composition according to claim 1, wherein (B) + (C) + (D) is 100 parts by weight).