JP2745625B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention has permanent antistatic properties, excellent mechanical properties such as impact resistance, excellent moldability, excellent surface gloss of molded articles, and The present invention relates to an antistatic resin composition having no delamination (turned up by 1,000 sheets).

2. Description of the Related Art Synthetic polymer materials are used in a wide range of fields due to their excellent properties. If the antistatic property is imparted in addition to the mechanical strength of these materials, their applications can be further expanded. That is, it can be applied to copiers, office automation equipment, various dustproof parts, etc., which are desired to prevent failure due to static electricity.

As a method to improve the antistatic of the synthetic polymer material,
A method of mixing a polyamide elastomer with a modified vinyl polymer having a carboxyl group (Japanese Patent Application Laid-Open No. 60-23535), and a method of mixing a polyamide elastomer with a modified vinyl polymer having a specific amount of a carboxyl group and a graft rubber It discloses that a resin having a semi-permanent antistatic property can be obtained by the method (JP-A-62-241945).

[Problems to be solved by the invention] However, Japanese Patent Application Laid-Open Nos.
In Japanese Patent Application Laid-Open No. 2-241945, a modified vinyl polymer containing a carboxyl group has a problem of impairing the surface gloss of a molded article due to heat history, and is not sufficiently satisfactory.

An object of the present invention is to provide an antistatic thermoplastic resin composition having excellent permanent antistatic properties, mechanical properties represented by impact resistance, moldability, surface gloss of molded articles, and no delamination. It is to provide.

[Means for Solving the Problem] The present invention has the following configuration to achieve the above object.

(A) (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, (b) a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 6000, and ( c) a polyetheresteramide obtained by polymerizing a dicarboxylic acid having 4 to 20 carbon atoms, wherein the polyetherester unit has 90 to 10
(B) 0.1 to 99 parts by weight of a modified vinyl polymer containing a polyalkylene oxide group and / or a derivative thereof (C) 1 to 80 parts by weight of a rubbery polymer And aromatic vinyl monomer and / or (meth) acrylate monomer
100-40% by weight, vinyl cyanide monomer 0-60% by weight
And other vinyl monomers copolymerizable therewith.
0 to 98 parts by weight of a polymerization product obtained by graft polymerization with 99 to 20 parts by weight of a monomer or monomer mixture consisting of 100% by weight (D) an aromatic vinyl monomer and / or (meth) acrylate Monomer or monomer consisting of 100 to 40% by weight of a vinyl monomer, 0 to 60% by weight of a vinyl cyanide monomer and 0 to 60% by weight of another vinyl monomer copolymerizable therewith (Co) polymer of (co) polymerization of mixture (0-98)
Parts by weight of (A) + (B) + (C) + (D) so as to be 100 parts by weight, and the amount of rubbery polymer in the whole
A thermoplastic resin composition blended so as to be less than 10% by weight.

The (A) aminocarboxylic acid or lactam having 6 or more carbon atoms or the salt of diamine and dicarboxylic acid having 6 or more carbon atoms constituting the polyetheresteramide of the present invention is a polyamide-forming component of polyetheresteramide. It is.

As aminocarboxylic acids, ω-aminocaproic acid, ω
-Aminoenanoic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, and 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. Lactams include caprolactam, enantholactam, capryl lactam and laurolactam. Examples of the diamine include hexamethylenediamine, and examples of the dicarboxylic acid include adipic acid, sebacic acid, decanedicarboxylic acid, and isophthalic acid. As a salt of diamine and dicarboxylic acid, used as a salt of diamine and dicarboxylic acid such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-decanedicarboxylate and hexamethylenediamine-isophthalate Can be Among them, caprolactam, 11-aminoundecanoic acid, 12-aminodecanoic acid, and hexamethylenediamine-adipate are particularly preferably used.

Component (a), a salt having 6 or more carbon atoms synthesized from an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a diamine and a dicarboxylic acid is 10 to 90% by weight, preferably 20 to 90% by weight, as a polyetheresteramide structural unit. ~ 80% by weight
If it is less than 10% by weight, the mechanical properties of the polyetheresteramide are inferior, and if it exceeds 90% by weight, the antistatic properties of the resin composition deteriorate, which is not preferable.

(B) Poly (alkylene oxide) glycol, which is a constituent component of (A) polyetheresteramide, includes polyethylene glycol, poly (1,2-propylene oxide) glycol, and poly (1,3-propylene oxide).
Glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran are used. Of these, polyethylene glycol is particularly preferably used because of its excellent antistatic properties. The number average molecular weight of the poly (alkylene oxide) glycol is 200 to 600
0, preferably in the range of 300 to 4000.

If the number average molecular weight is less than 200, the mechanical properties of the obtained polyetheresteramide are inferior, and the number average molecular weight is 6000.
If it exceeds, the antistatic property is insufficient, which is not preferable.

Further, a diol compound having a ring structure represented by the following formulas (I) to (III) can be used in combination with (b) poly (alkylene oxide) glycol.

(Wherein, R ¹ and R ² represent at least one of an ethylene oxide group and a propylene oxide substrate, Y represents a covalent bond, an alkylene group having 1 to 6 carbon atoms, an alkylidene group,
A cycloalkylidene group, an arylalkylidene group, O,
X represents SO, SO ₂ , CO, S, CF ₂ , C (CF ₃ ) ₂ or NH, and X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen group, a sulfonic acid or a metal salt thereof. 1 is O or 1-4
And m and n each represent an integer of 1 to 15. Specific examples include bisphenol A ethylene oxide and / or propylene oxide adducts, 2,2
-Bis (4,4'-hydroxycyclohexyl) propane ethylene oxide and / or propylene oxide adduct, tetrabromobisphenol A ethylene oxide and / or propylene oxide adduct, dimethyl bisphenol A ethylene oxide and / or propylene oxide adduct, Ethylene oxide and / or propylene oxide adduct of methyl bisphenol A, 2,2-bis (4,4'-hydroxyphenyl-3,3 '
-Sodium sulfonate) ethylene oxide and / or propylene oxide adduct of propane, ethylene oxide and / or propylene oxide adduct of bisphenol S, ethylene oxide and / or propylene oxide adduct of cimethyl bisphenol S, ethylene oxide and / or tetramethyl bisphenol S
Or propylene oxide adduct, ethylene oxide of 4,4 ′-(hydroxy) biphenyl and / or propylene oxide adduct, bis (4-hydroxyphenyl)
Ethylene oxide and / or propylene oxide adduct of sulfide, ethylene oxide and / or propylene oxide adduct of bis (4-hydroxyphenyl) sulfoxide, ethylene oxide and / or propylene oxide adduct of bis (4-hydroxyphenyl) 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 adduct, ethylene oxide and / or propylene oxide adduct of 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxy Roxybenzophenone ethylene oxide and / or propylene oxide adduct, hydroquinone ethylene oxide and / or propylene oxide adduct, 1,4-dihydroxycyclohexane ethylene oxide and / or propylene oxide adduct, sodium 1,4-dihydroxybenzenesulfonate An ethylene oxide and / or propylene oxide adduct of dihydroxynaphthalene, an ethylene oxide and / or propylene oxide adduct of dihydroxynaphthalene,
And block copolymers thereof.

Preferred diol compounds are hydroquinone ethylene oxide adducts, bisphenol A ethylene oxide adducts, brominated bisphenol A ethylene oxide adducts, bisphenol S ethylene oxide adducts, dihydroxynaphthalene ethylene oxide adducts, and block polymers thereof. Preferred are ethylene oxide adducts of bisphenol A and block polymers thereof. Further, by using an ethylene oxide adduct of brominated bisphenol A or an ethylene oxide adduct of brominated bisphenol S, the flame retardancy of the resin composition can be improved.

These poly (alkylene oxide) glycols and the diol compounds represented by the general formulas (I) to (III) can be used alone or in combination of two or more as needed. The amount of the diol compound represented by the general formulas (I) to (III) is not particularly limited, but is preferably in the range of 0 to 60% by weight based on polyetherester units obtained by reacting with a dicarboxylic acid.

Further, it can be copolymerized with another diol compound as long as the effects of the present invention are not impaired. In particular,
aromatic diols such as p-xylylene glycol and m-xylylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 1,3-cyclohexanediol
An alicyclic diol compound such as cyclohexanedimethanol can be copolymerized.

(C) 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 dodecanediic acid are preferably used in terms of polymerizability, color tone and physical properties.

The (b) poly (alkylene oxide) glycol and (c) dicarboxylic acid react in a molar ratio of 1: 1 in the reaction, but are supplied at a charging ratio of 1: 1 or appropriately changed depending on the type of dicarboxylic acid used.

The polyetherester derived from the component (b) and the component (c) is a polyetheresteramide constituent unit of 10 to
90% by weight, preferably used in the range of 20-80% by weight,
If the amount is less than 10% by weight, the antistatic property of the resin composition deteriorates,
If it exceeds 90% by weight, the mechanical properties of the polyetheresteramide are inferior and are not preferred.

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 metal salt of titanium oxalate such as titanium 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, lead catalysts such as lead acetate, germanium oxide and the like And the like, and a combination of these catalysts with an antimony-based catalyst such as antimony trioxide is preferably used, but is not particularly limited.

When the color tone fluctuates due to the production conditions, it can be stabilized by adding a small amount of a phosphorus compound, for example, trimethyl phosphate.

The polymerization of the polyetheresteramide of the present invention is not particularly limited. For example, (a) reacting (a) an aminocarboxylic acid or a lactam, or a salt of a dicarboxylic acid having 6 or more carbon atoms with a dicarboxylic acid and (c) a dicarboxylic acid. Both ends make a polyamide prepolymer with carboxylic acid groups. The average molecular weight of the polyamide prepolymer can vary over a wide range, but is preferably from 300 to 15,000, more preferably from 500 to 5,000. (B) reacting a poly (alkylene oxide) glycol with the polyamide prepolymer under vacuum;
(B) Preparation of a carboxylic acid-terminated polyamide prepolymer by charging each compound of the above (a), (b) and (c) into a reaction tank and subjecting them to high-pressure reaction at high temperature in the presence or absence of water Then, the reaction is allowed to proceed under normal pressure or vacuum. (C) The compounds of the above (a), (b) and (c) are charged into a reaction vessel, and heated and stirred under a stream of N ₂ to obtain a transparent and homogeneous solution. Make a mixture. Thereafter, a method of proceeding the reaction under vacuum can be used.

Here, the term "under vacuum" means preferably about 15 mmHg or less, particularly preferably 5 mmHg or less, more preferably 1 mmHg or less.

The modified vinyl polymer (B) containing a polyalkylene oxide group and / or a derivative thereof (hereinafter, referred to as a modified vinyl polymer) used in the present invention refers to at least one kind of vinyl polymer in one molecule. It is a polymer having a polyalkylene oxide group or a derivative thereof.

There is no limitation on the content of these polyalkylene oxide groups or derivatives thereof, and it may be a very small amount,
Further, it may be contained in a large amount as long as the performance as a resin is not impaired. Particularly preferred content of the functional group is 1 to 3 in terms of excellent mechanical properties represented by the impact resistance of the resin composition.
It is in the range of 60% by weight.

(B) The method for introducing a polyalkylene oxide group and / or a derivative thereof into the modified vinyl polymer is not particularly limited. For example, (1) polyalkylene oxide represented by the following formulas (IV) and (V) A method of copolymerizing a vinyl polymer containing a group with a desired vinyl monomer,
(2) a (meth) acrylate-based (co) polymer obtained by copolymerizing a poly (methyl methacrylate) or a (meth) acrylate such as methyl methacrylate or butyl acrylate with a desired vinyl monomer; It contains a carboxyl group obtained by a method of subjecting an alkyl ether polyalkylene oxide glycol to an ester reaction, (3) a method of copolymerizing acrylic acid, methacrylic acid, maleic acid, phthalic acid, etc. with a desired vinyl monomer. A method in which a vinyl-based polymer is subjected to an ester reaction with a polyalkylene oxide glycol having an alkyl ether at one end is exemplified.

(Where R ³ represents hydrogen or an alkyl group having 1 to ⁴ carbon atoms, R ⁴ represents an alkylene group having 2 to 6 carbon atoms, R ⁵ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and n represents 2 to 2 500.) Specific examples include polyethylene glycol acrylate, polyethylene glycol methacrylate, poly (propylene oxide) glycol acrylate, poly (propylene oxide) methacrylate, poly (tetramethylene oxide) glycol acrylate, and 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 (P (Propylene oxide) glycol methacrylate, methoxy poly (tetramethylene oxide) glycol methacrylate, ethoxy polyethylene glycol acrylate, ethoxy polyethylene glycol methacrylate, ethoxy poly (propylene oxide) glycol acrylate, polyethylene glycol acrylamide, polyethylene glycol methacrylamide, poly (propylene oxide) glycol acrylamide, Poly (propylene oxide) glycol methacrylamide, poly (tetramethylene oxide) glycol acrylamide, poly (tetramethylene oxide) glycol methacrylamide, methoxy polyethylene glycol acrylamide, methoxy polyethylene glycol methacrylamide, methoxy poly (pro Lenoxide) glycol acrylamide, methoxy poly (propylene oxide) glycol methacrylamide, methoxy (tetramethylene oxide) glycol methacrylamide, and the like. In particular, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylamide, and methoxy polyethylene glycol methacrylamide It is preferable because of its excellent polymerizability and affinity with the polyetheresteramide (A).

(B) The vinyl monomer used for the polymerization of the modified vinyl polymer is not particularly limited.
Aromatic vinyl monomers such as α-methylstyrene and p-methylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and (meth) acrylic such as methyl methacrylate, ethyl methacrylate and butyl acrylate One or two types of vinyl monomers such as acid ester monomers, maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide;
More than one species can be selected and used according to the purpose.

If necessary, rubbery weights such as polybutadiene, acrylonitrile-butadiene copolymer (NBR), styrene-butadiene copolymer (SBR), polybutyl acrylate and ethylene-propylene-diene terpolymer (EPDM) may be used. The union can be used in combination with the above-mentioned vinyl monomer.

(B) The method for producing the modified vinyl polymer is not particularly limited. For example, when a vinyl monomer containing a polyalkylene oxide group is copolymerized with another vinyl monomer, a bulk polymerization method, a solution, Polymerization method, suspension polymerization method, emulsion polymerization method, bulk-
An ordinary method such as a suspension polymerization method can be used.

In addition, the ester reaction between a (meth) acrylate-based (co) polymer or a carboxyl-containing vinyl-based polymer and a poly (alkylene oxide) glycol having an alkyl ether at one end is carried out at high temperature under normal pressure or vacuum. Can be done at

The poly (alkylene oxide) glycol having an alkyl ether at one end used herein is, for example, methoxypolyethylene glycol, methoxypoly (1,2-propylene oxide) glycol, methoxypoly (1,3-propylene oxide) glycol, methoxypoly (tetramethylene oxide) ) Glycol, methoxy poly (hexamethylene oxide) glycol, methoxy (a block or random copolymer of ethylene oxide and propylene oxide) and methoxy (a block or random copolymer of ethylene oxide and tetrahydrofuran). Ether polyethylene glycol is preferred.

The poly (alkylene oxide) glycol having an alkyl ether at one end has a number average molecular weight of 75 to 20,000.

As the rubbery polymer which is a constituent component of the (C) graft (co) polymer used in the present invention, those having a glass transition temperature of 0 ° C. or lower are suitable, and specifically, polybutadiene, polystyrene-butadiene, polyacrylonitrile -Diene rubbers such as butadiene, acrylic rubbers such as polyisoprene, polychloroprene and polybutyl acrylate, and rubbery polymers such as ethylene-propylene-diene monomer terpolymer can be used. Particularly, polybutadiene or butadiene copolymer is preferable.

(C) Styrene, α-methylstyrene, and aromatic vinyl monomers as constituents of the graft (co) polymer
Examples thereof include vinyltoluene, o-ethylstyrene, and op-dichlorostyrene, and styrene is particularly preferable.

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

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

Other vinyl monomers include maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, acrylamide monomers such as acrylamide and N-methylacrylamide, and maleic anhydride. And unsaturated acid anhydrides such as itaconic anhydride and unsaturated acids such as acrylic acid and methacrylic acid. Among them, N-phenylmaleimide, acrylamide and maleic anhydride are particularly preferable.

(C) The ratio of the aromatic vinyl monomer and / or the (meth) acrylate monomer used in the graft (co) polymer is based on the total vinyl monomer used.
It is 100 to 40% by weight, preferably 100 to 50% by weight.

If the proportion of the aromatic vinyl monomer and / or the (meth) acrylate monomer is less than 40% by weight, the impact resistance of the resin composition is poor, which is not preferable.

In the present invention, the desired physical properties can be obtained by using an aromatic vinyl monomer and / or a (meth) acrylate monomer, but further, a vinyl cyanide monomer or a maleimide monomer can be obtained. Is used in an amount of 60% by weight or less, preferably 50% by weight or less based on all monomers, whereby impact resistance and heat resistance can be further improved.

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

When the proportion of the rubbery polymer in the graft (co) polymer (C) is less than 1 part by weight, the impact resistance of the obtained resin composition is poor, and when it exceeds 80 parts by weight, the rubbery polymer becomes poorly dispersed. This is not preferable because the appearance of the molded article is impaired.

(C) A method for producing a graft (co) polymer is a known polymerization method, for example, emulsification by continuously supplying a monomer or a monomer mixture, a polymerization initiator and an emulsifier in the presence of a rubbery polymer latex. A polymerization method or the like can be used.

As the aromatic vinyl monomer which is a component of the (D) (co) polymer used in the present invention, styrene, α-
Methyl styrene, p-methyl styrene, pt-butyl styrene, o-ethyl styrene, op-chloro styrene and the like are exemplified, and styrene and α-methyl styrene are particularly preferred.

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

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

Other vinyl monomers copolymerizable therewith include maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, N-methyl Examples thereof include acrylamide-based monomers such as acrylamide, and unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, with N-phenylmaleimide and maleic anhydride being particularly preferred.

(D) The proportion of the aromatic vinyl monomer and / or the (meth) acrylate monomer as a component of the (co) polymer is 100 to 40% by weight, preferably 100% by weight, based on all monomers. ~
50% by weight.

If the proportion of the aromatic vinyl monomer and / or the (meth) acrylate monomer is less than 40% by weight, the impact resistance of the resin composition is poor, which is not preferable.

In the present invention, satisfactory physical properties can be obtained by using the above (co) polymer, but furthermore, a vinyl cyanide monomer or a maleimide monomer is not more than 60% by weight based on all monomers, preferably By using it at 50% by weight or less, impact resistance and heat resistance can be further improved.

When the proportion of the vinyl cyanide-based monomer exceeds 60% by weight, the thermal stability of the copolymer deteriorates and the resin composition is significantly colored, which is not preferable.

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

The polymer thus obtained comprises (A) 1 to 40 parts by weight of polyetheresteramide, preferably 5 to 30 parts by weight,
(B) 0.1 to 99 parts by weight, preferably 1 to 95 parts by weight of the modified vinyl polymer; (C) 0 to 98 parts by weight, preferably 0 to 90 parts by weight of the graft (co) polymer; ) Polymer 0
(A) + within 98 parts by weight, preferably within the range of 0 to 90 parts by weight
It is blended so that (B) + (C) + (D) becomes 100 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.

When the content of the modified vinyl polymer (B) is less than 0.1 part by weight, the resin composition cannot be used because of delamination, and when it exceeds 99 parts by weight, the antistatic property of the resin composition is insufficient, which is not preferable.

When the amount of the (C) graft (co) polymer and the amount of the (D) (co) polymer exceed 98 parts by weight, the antistatic properties of the resin composition are insufficient, which is not preferable.

In the resin composition of the present invention, the proportion of the rubbery polymer in the resin composition is 40% by weight or less, preferably 30% by weight or less.

If it exceeds 40% by weight, the resin composition becomes soft and the mechanical properties are poor, which is not preferred.

The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include (A) polyetheresteramide,
It is commercialized by melt-kneading a resin mixture of (B) a modified vinyl polymer, (C) a graft (co) polymer and (D) (co) polymer with a Banbury mixer, roll, extruder, or the like.

The resin composition of the present invention is other thermoplastic polymers compatible with the resin composition of the present invention, for example, polyamide, polybutylene terephthalate, polyethylene terephthalate,
Elastomers such as polycarbonate, polyphenylene ether, vinyl chloride resin, polyglutarimide, hydrogenated and / or non-hydrogenated styrene-butadiene block copolymer, and the like can be mixed to improve the performance as a molding resin. .

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 and plasticizers, glass fibers, metal fibers, and flame retardants can also be added.

[Examples] In order to more specifically describe the present invention, examples and comparative examples will be described below. In addition, after the resin composition finally obtained was molded by an injection molding method, various physical properties were measured by the following test methods.

Izod impact strength: ASTM D256-56A Flexural modulus: ASTM D790 Surface gloss of molded product: Measured at a measurement 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 preventing property of the molded article was determined by bending the molded article, and ：: extremely good, ：: good, and X: the molded article delaminated.

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

Reference Examples (1) (A) Preparation of Polyetheresteramide A-1: 50 parts of caprolactam, 46.0 parts of polyethylene glycol having a number average molecular weight of 1500, and 5.42 parts of terephthalic acid were mixed with "Ilganox" 1098 (antioxidant) 0.2 Parts and an antimony trioxide catalyst together with 0.1 part of an antimony trioxide catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, and heated and stirred for 90 minutes while replacing with nitrogen and flowing a small amount of nitrogen at 240 ° C. to obtain a transparent homogeneous solution. Polymerization was performed for 3 hours under the condition of 0.5 mmHg or less to obtain a viscous and transparent polymer. The polymer was discharged in a gut shape on a cooling belt and pelletized to prepare pellet-like polyetheresteramide (A-1).

A-2: Nylon 6.6 salt (AH salt) 60 parts, number average molecular weight 60
33.8 parts of polyethylene glycol and 8.7 of adipic acid
Of polyetheresteramide (A-2) in exactly the same manner as in (A-1), except that the polymerization time was set to 4 hours.
Was prepared.

A-3: Polyetherester was prepared in the same manner as in (A-1) except that 30 parts of ω-aminodecanoic acid, 14.2 parts of dodecanediic acid, and 58.6 parts of polyethylene glycol having a number average molecular weight of 1000 were used and the polymerization time was 4 hours. The amide (A-3) was prepared.

(2) (B) Preparation of modified vinyl polymer B-1: Suspension polymerization of a monomer mixture of 63% styrene, 24% acrylonitrile, and 13% methoxypolyethylene glycol methacrylate (the average number of ethylene oxide groups is 9) As a result, a bead-shaped modified vinyl polymer (B-1) was prepared. The resulting modified vinyl polymer is methyl ethyl ketone
The intrinsic viscosity of the 0.4% solution measured at 30 ° C. was 0.52.

B-2: A monomer mixture of 66% styrene, 26% acrylonitrile, and 8% methoxypolyethylene glycol methacrylate (the average number of ethylene oxide groups is 4) is suspension polymerized to bead-shaped modified vinyl polymer (B- 2) was prepared. The resulting modified vinyl polymer had an intrinsic viscosity of 0.56 as measured by the same method as in B-1.

B-3: 85 parts of a copolymer composed of 68% of styrene, 24% of acrylonitrile and 8% of methyl methacrylate, and polyethylene glycol 15 having a number-average molecular weight of 1000 and one end of methoxy at one end.
Was charged into a reaction vessel equipped with a helical ribbon stirring blade together with 0.02 part of antimony trioxide, and after purging with nitrogen, the mixture was heated and stirred at 250 ° C. for 60 minutes while passing a small amount of nitrogen to carry out an ester reaction, thereby producing a modified vinyl-based polymer. Combination (B-3) was prepared.

The resulting modified vinyl polymer had an intrinsic viscosity of 0.45 measured by the same method as in B-1.

B-4: 92% styrene, methoxypolyethylene glycol methacrylate (the average number of ethylene oxide groups is 4)
Eight parts of the monomer mixture was subjected to suspension polymerization to prepare a bead-shaped modified vinyl polymer (B-4). The resulting modified vinyl polymer had a limiting viscosity of 0.61 as measured at 30 ° C. in a mixed solution of methyl ethyl ketone / acetone = 1/1, a 0.4% solution.

(3) (C) Preparation of graft (co) polymer C-1: polybutadiene latex (rubber particle diameter 0.25 μm,
Styrene in the presence of 50 parts (solid content conversion) of gel content 80%)
50 parts of a monomer mixture consisting of 70% and acrylonitrile 30% was emulsion-polymerized. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, dried and dried to prepare a powdery graft copolymer (C-1).

C-2: 10 parts of diene NF35A (manufactured by Asahi Kasei Corporation)
After dissolving in 0 parts, bulk polymerization is carried out and the graft polymer (C-
2) was prepared.

C-3: After emulsion polymerization of 85 parts of a monomer mixture composed of 75% of styrene and 25% of acrylonitrile in the presence of 15 parts (in terms of solid content) of the polybutadiene latex used in C-1,
The powdery graft polymer (C-
3) was prepared.

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

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

(4) (D) Preparation of (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 were subjected to suspension polymerization to prepare a copolymer (D-2).

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

Examples 1 to 15 (A) Polyetheresteramide prepared in Reference Example, (B) modified vinyl polymer, (C) graft (co)
The polymer and the (D) (co) polymer were mixed at the compounding ratios shown in Table 1, melt-kneaded and extruded at a resin temperature of 220 ° C. using 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 6 (A) Polyetheresteramide prepared in Reference Example, (B) modified vinyl polymer, (C) graft (co)
The polymer and the (D) (co) polymer were mixed at the compounding ratio shown in Table 1, and each physical property was 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. Each of the resin compositions of the present invention (Examples 1 to 15) is excellent in balance of mechanical properties represented by impact strength and flexural modulus, moldability, and surface gloss of molded articles, and has low volume resistivity. Have a value. In addition, the resistance value hardly changes even when the surface is washed or changes with time, and excellent permanent antistatic properties are exhibited.

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 Example I1), the antistatic property (resistance value) is poor, and when the polyetheresteramide (A) exceeds 40 parts by weight. Comparative Example 2 is inferior in flexural modulus.

When the amount of the modified vinyl polymer (B) is less than 0.1 part by weight (Comparative Example 3), the molded article undergoes delamination, and when the amount exceeds 99 parts by weight (Comparative Example 4), the antistatic properties are inferior. Absent.

When the proportion of the rubbery polymer in the resin composition exceeds 40 parts by weight (Comparative Example 5), the flexural modulus and the surface gloss of the molded product are deteriorated. When the blending amount of the graft (co) polymer (C) exceeds 98 parts by weight (Comparative Example 6), the antistatic property 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 (1)

(57) [Claims] (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 number average molecular weight of 200
(C) a polyetheresteramide obtained by polymerizing (c) a dicarboxylic acid having 4 to 20 carbon atoms, wherein the polyetheresteramide has a polyetherester unit content of 90 to 10% by weight. (B) 0.1 to 99 parts by weight of a modified vinyl polymer containing a polyalkylene oxide group and / or a derivative thereof; (C) 1 to 80 parts by weight of a rubbery polymer and an aromatic vinyl monomer; / Or (meth) acrylate monomer
100-40% by weight, vinyl cyanide monomer 0-60% by weight
And other vinyl monomers copolymerizable therewith.
0 to 98 parts by weight of a polymerization product obtained by graft polymerization with 99 to 20 parts by weight of a monomer or monomer mixture consisting of 100% by weight (D) an aromatic vinyl monomer and / or (meth) acrylate Monomer or monomer consisting of 100 to 40% by weight of a vinyl monomer, 0 to 60% by weight of a vinyl cyanide monomer and 0 to 60% by weight of another vinyl monomer copolymerizable therewith (Co) polymer of (co) polymerization of mixture (0-98)
Parts by weight were blended so that (A) + (B) + (C) + (D) would be 100 parts by weight, and blended so that the amount of the rubbery polymer in the whole was 40% by weight or less. Thermoplastic resin composition.