JPH01163250A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition with permanent antistaticity, outstanding in impact resistance, molding process ability, etc., also free from lamellar debonding, by blending each specified amount of specific polyetheresteramide, graft (co)polymer, modified vinyl polymer, etc. CONSTITUTION:The objective composition can be obtained by blending (A) 1-40 pts.wt. of a polyetheresteramide containing 95-10wt.% of polyetherester unit, produced from A1: 6C-amino carboxylic acid or lactam, etc., A2: poly(alkyleneoxide)glycol with a number-average molecular weight of 200-6000 and A3: 4-20C dicarboxylic acid, (B) 2-98 pts.wt. of a graft (co)polymer produced from B1: 1-80 pts.wt. of a rubbery polymer and B2: 99-20 pts.wt. of a monomer (mixture) comprising aromatic vinyl monomer, etc., (C) 0.1-40 pts.wt. of a modified vinyl polymer containing epoxy group, and (D) 0-96 pts.wt. of a vinyl (co)polymer produced from aromatic vinyl monomer and/or (meth)acrylic ester monomer, etc., so that the content of the component B1 fall between 1 and 40wt.%.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention has permanent antistatic properties, excellent mechanical properties such as impact resistance, and excellent moldability, and is free from delamination (delamination). The present invention relates to an antistatic resin composition that does not cause sheet peeling.

<Prior Art> Synthetic polymer materials are used in a wide range of fields due to their excellent properties. These materials can be used in a wider range of applications if they are provided with antistatic properties in addition to their mechanical strength. In other words, it is possible to expand the application to copying machines and various dustproof parts where it is desired to prevent failures due to static electricity.

One way to improve the antistatic properties of synthetic polymer materials is to add vinyl to a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and/or acrylic ester with a vinyl monomer having an alkylene oxide group. A method of obtaining monomers or vinylidene monomers by graft polymerization (JP-A-55
38237), which have achieved practical antistatic properties.

Furthermore, JP-A-60-23435 discloses that a resin having semi-permanent antistatic properties is produced by mixing 5 to 80 parts of a polyamide elastomer and 95 to 20 parts by weight of a modified vinyl polymer containing a carboxyl group. Disclose what you will get.

<Problems to be Solved by the Invention> However, the antistatic resin obtained by graft polymerizing a monomer to a hydrophilic rubber-like polymer described in JP-A-55-36237 has a special hydrophilic rubber-like structure. Since a polymer is used, the production method is complicated and the resulting resin has poor mechanical properties, so it is not fully satisfactory.

Furthermore, since the electrically conductive resin disclosed in JP-A No. 60-23435 contains a large amount of modified vinyl polymer containing carboxyl groups, it easily gels due to heat history, resulting in a markedly poor appearance of the molded product. There's a problem.

Therefore, an object of the present invention is to provide an antistatic resin that has permanent antistatic properties, has excellent mechanical properties such as impact resistance, and moldability, and is free from delamination.

Means for Solving the Problems〉 As a result of intensive study by the present inventors to solve the above problems,
We have arrived at the present invention.

That is, the present invention provides (A) (a1) a salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a diamine and a dicarboxylic acid having 6 or more carbon atoms; (a2) a polyester having a number average molecular weight of 200 to 6,000; A polyether ester amide composed of (alkylene oxide) glycol and (a3) dicarboxylic acid having 4 to 20 carbon atoms, with a polyether ester unit content of 95 to 10% by weight.
1 to 40 parts by weight of polyether ester amide, (
B) (b1) 1 to 80 parts by weight of rubbery polymer (b2)
Monomer or monomer mixture consisting of 100 to 40% by weight of aromatic vinyl monomer and/or (meth)acrylic acid ester monomer and 0 to 60% by weight of vinyl cyanide monomer 99 to 99% 2 to 98 parts by weight of a graft (co)polymer obtained by grafting (co)polymerizing 20 parts by weight, (C) 0.1 to 40 parts by weight of a modified vinyl polymer containing an epoxy group, and (D) 100 to 40% by weight of aromatic vinyl monomer and/or (meth)acrylic acid ester monomer,
A vinyl (co)polymer obtained by (co)polymerizing a monomer or monomer mixture consisting of 0 to 60% by weight of vinyl cyanide monomer and 0 to 60% by weight of other vinyl monomers. 0
~96 parts by weight (A) + (B) + (C) + (D)
The purpose of the present invention is to provide a thermoplastic resin composition in which the amount of the rubbery polymer is 100 parts by weight, and the amount of the rubbery polymer is 1 to 40% by weight.

The present invention will be specifically explained below.

The thermoplastic resin composition of the present invention comprises (A) polyether ester amide, (B) graft (co)polymer and (C)
Made of modified vinyl polymer.

Examples of the salts of (a1) aminocarboxylic acids or lactams having 6 or more carbon atoms or diamines and dicarboxylic acids having 6 or more carbon atoms, which are the constituent components of (A) polyetheresteramide in the present invention, include ω-aminocaproic acid;
Aminocarboxylic acids such as ω-aminoenantoic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, 12-aminododecanoic acid or caprolactam, enantholactam, capryllactam, and lauro lactams such as lactams and hexamethylenediamine-adipates,
Salts of diamine-dicarboxylic acids such as hexamethylene diamine-sebacate and hexamethylene diamine-isophthalate are used, especially caprolactam, 12-
Aminododecadiic acid and hexamethylene diamine adipate are preferably used.

(a1) Salts of aminocarboxylic acids or lactams having 6 or more carbon atoms or diamines and dicarboxylic acids having 6 or more carbon atoms are the constituent units of polyether ester amide with 5
If the amount is less than 5% by weight, the mechanical properties of the polyether ester amide will be poor, and if it exceeds 90% by weight, the resulting resin will have poor antistatic properties, which is not preferred.

(A) Constituent component of polyether ester amide (
a2) Poly(alkylene oxide) glycol includes polyethylene glycol, poly(1゜2-propylene oxide) glycol, 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. Among these, polyethylene glycol is particularly preferably used because of its excellent antistatic properties. The number average molecular weight of poly(alkylene oxide) glycol is 2
00 to 6,000, preferably 250 to 4,000.

If the number average molecular weight is less than 200, the mechanical properties of the resulting polyether ester amide will be poor;
If it exceeds 000, it is not preferable because the antistatic property is insufficient.

(A) Constituent component of polyether ester amide (
a3) Dicarboxylic acids having 4 to 20 carbon atoms include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,
Aromatic dicarboxylic acids such as 6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid , 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanedioic acid, etc. In particular, terephthalic acid, isophthalic acid, 1°4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

(a2) Poly(alkylene oxide) glycol and (a
3) Dicarboxylic acids are reacted at a molar ratio of 1:1, but the charging ratio is usually changed depending on the type of dicarboxylic acid used.

The polyether ester component is a structural unit of polyether ester amide and is used in an amount of 95 to 10% by weight.
If it exceeds 5% by weight, the mechanical properties of the polyether ester amide will be poor, and if it is less than 10% by weight, the antistatic properties of the resin will be poor, which is not preferred.

(A) There are no particular limitations on the polymerization method for polyether ester amide. For example, (a) (a1) aminocarboxylic acid or lactam and (a3) dicarboxylic acid are reacted to form a polyamide prepolymer having carboxylic acid groups at both ends. (b) a method of reacting (a2) poly(alkylene oxide) glycol with the above (a1) under vacuum;
), (a2), and (a3) into the reaction layer,
Known methods such as a method in which a carboxylic acid-terminated polyamide prepolymer is produced by reacting at high temperature in the presence or absence of water and then proceeding with the reaction under normal pressure or reduced pressure can be used.

Furthermore, there are no restrictions on the polymerization catalyst; for example, one type of polymerization catalyst may be used, such as an antimony catalyst such as antimony dioxide, a tin catalyst such as monobutyltin oxide, a titanium catalyst such as tetrabutyl titanate, or a zirconate catalyst such as tetrabutyl zirconate. Alternatively, two or more types can also be used.

In the present invention, (B) graft (co)polymer means (b1) rubbery polymer, (b2) aromatic vinyl monomer and/or (meth)
A monomer or monomer mixture consisting of an acrylic acid ester monomer, and a monomer consisting of an aromatic vinyl monomer and/or a (meth)acrylic acid ester monomer, and a vinyl cyanide monomer Graph the monomer or monomer mixture selected from the monomer mixture.
co)polymerized.

The rubbery polymer (b1) used in the present invention is preferably one having a glass transition temperature of 0°C or lower, and specifically, diene rubbers such as polybutadiene, polystyrene-butadiene, polyacrylonitrile-butadiene, polyisoprene, etc. , polychloroprene, acrylic rubbers such as polybutyl acrylate, and rubbery polymers such as ethylene-propylene-diene monomer terpolymers can be used.

Particularly preferred are butadiene or butadiene copolymers.

The monomer or monomer mixture (b2) used in the present invention is a monomer or monomer mixture consisting of an aromatic vinyl monomer and/or a (meth)acrylic acid ester monomer, and It is selected from a monomer mixture consisting of aromatic vinyl monomers and/or (meth)acrylic acid ester monomers and vinyl cyanide monomers.

Aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, 0-ethylstyrene, op
-dichlorostyrene, etc., and styrene is particularly preferred.

(Meth)acrylic acid ester monomers include acrylic acid and methacrylic acid methyl, ethyl, propyl, n
-butyl, i-butyl, etc., and methyl methacrylate is particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, and acrylonitrile is particularly preferred.

If necessary, other vinyl monomers such as maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, acrylamide, (meth)
2-hydroxyethyl acrylate and the like can also be used.

(B) Monomer or monomer body temperature of (b2) used in the graft (co)polymer. The compound can obtain sufficient physical properties with just the aromatic vinyl monomer and/or (meth)acrylic acid ester monomer, but by further containing the vinyl cyanide monomer, the properties are significantly improved. Improves impact resistance. Aromatic vinyl monomer and/or (meth)
The blending ratio of the mixture consisting of an acrylic ester monomer and a vinyl cyanide monomer is 1 part aromatic vinyl monomer and/or (meth)acrylic ester monomer
00-40% by weight, preferably 100-50% by weight, 0-60% by weight of the entire cyanide vinyl spinning wheel, preferably 0-60% by weight
It is 50% by weight.

When the proportion of aromatic vinyl monomer and/or (meth)acrylic acid ester monomer is less than 40% by weight, and when the proportion of vinyl cyanide monomer exceeds 60% by weight, grafting This is not preferred because the thermal stability of the copolymer is significantly reduced and molded products with poor color tone are produced.

(B) The proportion of the rubbery polymer and monomer or monomer mixture in the graft (co)polymer is 1 to 80 parts by weight, preferably 1 to 80 parts by weight of the rubbery polymer in 100 parts by weight of the entire 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.

If the proportion of the rubbery polymer in this graft (co)polymer (B) is less than 1 part by weight, the resulting resin composition will have poor impact resistance, and if it exceeds 80 parts by weight, the rubbery polymer will be poorly dispersed. , which is undesirable because it impairs the appearance of the molded product.

(B) The graft (co)polymer is produced by a known polymerization method, such as a method of emulsion polymerization by continuously supplying a monomer or a monomer mixture and a polymerization initiator in the presence of a rubbery polymer latex. Obtainable.

(C) The modified vinyl polymer containing an epoxy group (hereinafter abbreviated as modified vinyl polymer) used in the present invention is obtained by (co)polymerizing one or more vinyl monomers. It is a polymer with a structure and an epoxy group in the molecule.

The content of these epoxy groups is not particularly limited, and may be contained in a very small amount, or may be contained in a large amount as long as the performance as a resin is not impaired.

Usually, the effects of the present invention can be efficiently exhibited if substantially one or more of the above-mentioned functional groups are contained on average in one molecule of the modified vinyl polymer.

(C) There is no particular restriction on the method of introducing an epoxy group into the modified vinyl polymer, but for example, the following formula (I) CH2=C-COCH2CHCH2 1II \ / ROO ... (I) (in the formula, R 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, glycidyl itaconate, etc. A method such as copolymerization with a monomer can be used.

(C) There are no particular restrictions on the vinyl monomer used in the polymerization of the modified vinyl polymer, such as styrene,
Aromatic vinyl monomers such as α-methylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, (meth)acrylic acid ester monomers such as methyl methacrylate and butyl acrylate, maleimide , maleimide monomers such as N-phenylmaleimide,
α,β-unsaturated carboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, maleic acid, and maleic anhydride; olefinic monomers such as ethylene and propylene; and vinylic monomers such as vinyl chloride, vinyl acetate, and butadiene. One or more types can be selected and used depending on the purpose.

In particular, aromatic vinyl monomers such as styrene, (meth)acrylic acid ester monomers such as methyl methacrylate, N
- Maleimide monomers such as phenylmaleimide and vinyl cyanide monomers such as acrylonitrile are preferably used because the resulting resin composition has excellent mechanical 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 added to the above. It can also be used in combination with vinyl monomers.

(C) There are no particular restrictions on the method for producing the modified vinyl polymer, including bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization,
Conventional methods such as bulk-suspension polymerization methods can be used.

The composition of the present invention further contains 100% of an aromatic vinyl monomer and/or (meth)acrylic acid ester monomer.
~40% by weight, vinyl cyanide monomer 0-60% by weight
A vinyl (co)polymer (D) obtained by (co)polymerizing a monomer or a monomer mixture consisting of , and other vinyl monomers in an amount of 0 to 60% by weight may be included.

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

(Meth)acrylic acid ester monomers include acrylic acid and methyl, ethyl, propyl, n
Examples include ester compounds such as -butyl and i-butyl. Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile.

Other vinyl monomers that can be copolymerized with these include maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, and N-phenylmaleimide, and olefin monomers such as ethylene and propylene. mer, N-vinylpyrrolidone, acrylamide, maleic anhydride, vinyl chloride, butadiene, and the like.

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-methacrylic acid Examples include methyl copolymer, polystyrene, and polymethyl methacrylate.

This vinyl (co)polymer contains 10% of aromatic vinyl monomer and/or (meth)acrylic acid ester monomer.
Sufficient physical properties can be obtained with only a (co)polymer consisting of 0 to 40% by weight, but additionally 60% by weight of other vinyl monomers such as vinyl cyanide monomers or maleimide monomers. By containing up to 100% of the content, properties such as impact resistance and heat resistance are significantly improved.

Furthermore, if the content of vinyl cyanide monomer or other vinyl monomer exceeds 60% by weight, problems such as coloring of the resin composition occur, which is not preferable.

The thus obtained polymer contains (A) 1 to 40 parts by weight, preferably 5 to 30 parts by weight of polyether ester amide;
(B) Graft (co)polymer 2 to 98 parts by weight, preferably 5 to 94 parts by weight, (C) Modified vinyl polymer 0.1 to 98 parts by weight
(A) + (B) + (C) + within the range of 40 parts by weight, preferably 1 to 20 parts by weight, and 0 to 96 parts by weight, preferably 0 to 89 parts by weight of the vinyl (co)polymer. (D
) is blended in an amount of 100 parts by weight.

If the polyether ester amide (A) is less than 1 part by weight, the antistatic properties of the resin composition will be insufficient, and if it exceeds 40 parts by weight, the resin composition will become flexible and have poor mechanical properties, which is not preferred.

If the amount of the graft (co)polymer (B) is less than 2 parts by weight, the impact resistance will be insufficient, and if it exceeds 98 parts by weight, the antistatic property will be poor, which is not preferable.

(C) If the modified vinyl polymer is less than 0.1 part by weight, the resin composition will cause delamination and cannot be used. If it exceeds 40 parts by weight, the molding processability will be significantly deteriorated and the surface of the molded product will be This is not preferable because it becomes matte.

Furthermore, if the amount of the vinyl (co)polymer (D) exceeds 96 parts by weight, the antistatic properties of the resin composition will be insufficient, which is not preferable.

What is required 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 it is less than 1% by weight, the impact resistance of the resin composition will be poor, and if it exceeds 40% by weight, the resin composition will become flexible and have poor mechanical properties, which is not preferable.

There are no particular limitations on the method for producing the resin composition of the present invention; for example, (A) polyetheresteramide and (B)
) graft (co)polymer, (C) modified vinyl polymer,
The product is produced by melt-kneading a resin mixture of (D) vinyl-based (co)polymer using a Banbury mixer, roll, extruder, or the like. In addition, when blending (D) a vinyl-based copolymer, the (B) graft (co)polymer and (D) vinyl-based (co)polymer may be blended independently or may be mixed in advance. Well, no particular restrictions.

The resin composition of the present invention may contain other thermoplastic polymers that are compatible with the resin composition of the present invention, such as polyamide, polybutylene phthalate, polyethylene terephthalate, polycarbonate, polyphenylene ether resin, vinyl chloride resin, polyglutarimide, The performance as a molding resin can be improved by mixing elastomers such as hydrogenated and/or non-hydrogenated styrene-butadiene block copolymers. It is also possible to further improve the antistatic property by adding antistatic agents such as metal salts of sulfonic acid and anionic, cationic, or nonionic surfactants, and if necessary, oligomers, etc. Compatibilizers, antioxidants, various stabilizers such as ultraviolet absorbers, pigments, dyes, lubricants, plasticizers, glass fibers, flame retardants, etc. can also be added. Also, sulfonate, 3
Component (A) and (
It is also possible to further improve the compatibility of component B).

EXAMPLES In order to explain the present invention more specifically, Examples and Comparative Examples will be given below. In addition, after the finally obtained resin composition was molded by injection molding, various physical properties were measured by the following test methods.

Izot impact strength: ASTM D256-56A Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Flammability: A vertical combustion test was conducted on a 1/16" x 1/2" x 5" flame test piece according to UL94 standards.

MFR: Measured under the conditions of nozzle size 2mmφX8mm+, temperature 220°C, and load 10kg.

Volume resistivity value: Measured using a 2 mmt×40+n+aφ disk at a room temperature of 23° C. and a 50% R11 atmosphere.

Toa Radio for measurement Super insulation resistance meter 5M manufactured by Kogyo Co., Ltd. A type 10 was used.

The delamination prevention property of the molded product was determined by bending the molded product and observing the fracture surface of a tensile test specimen. ◎: Very good, O: Good, X: The molded product causes delamination.
The criteria for the appearance of the molded product were ◎: Very good appearance, O: Good, and X: The surface of the molded product was damaged and was defective.

In addition, parts and percentages in the examples indicate parts by weight and percentage of polymerization, respectively.

Reference example (1) (A) Preparation of polyether ester amide A-
1: 50 parts of cabrolactam, number average molecular weight is 1.000
44.2 parts of polyethylene glycol and 7.6 parts of terephthalic acid were charged together with 109 g of "Irganox" (antioxidant) 0.2 part and antimony dioxide catalyst 0.1 part into a reaction vessel equipped with a helical ribbon stirring blade. After purging with nitrogen and heating and stirring at 260°C for 60 minutes to obtain a transparent homogeneous solution, the solution was heated to 260°C and 0. Polymerization was carried out for 4 hours under conditions of 5 mm and 11 g or less to obtain a viscous and transparent polymer.

Pelletized polyether ester amide (A-1) was prepared by discharging the polymer onto a cooling belt and pelletizing it.

A-2: Except that 60 parts of nylon 6.6 salt (AH salt), 33.8 parts of polyethylene glycol with a number average molecular weight of 600 and 8.7 parts of adipic acid were used, and the polymerization time was 4 hours. Polyether ester amide (A-2) was prepared in exactly the same manner as in ).

A-3: 30 parts of ω-aminodecanoic acid, 14 parts of dodecanedioic acid
．． Polyether ester amide (A-3) was prepared in the same manner as (A-1) except that the polymerization time was 3 hours using 2 parts and 58.6 parts of polyethylene glycol with a number average molecular weight of ff1,000. .

(2) (B) Preparation of graft (co)polymer B-1 = 70% styrene in the presence of 60 parts (solid content) of polybutadiene latex (rubber particle size 0.25μ, gel content 80%) , 40 parts of a monomer mixture consisting of 30% acrylonitrile was subjected to emulsion polymerization.

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

B-2: 7 parts of methyl methacrylate in the presence of 40 parts of the polybutadiene latex used in B-1 (calculated as solid content)
After emulsion polymerization of 60 parts of a monomer mixture consisting of 2% styrene, 24% styrene, and 4% acrylonitrile, a powdery graft copolymer (B-2) was prepared in the same manner as B-1.

B-3 A graft polymer (B-3) was prepared by dissolving 10 parts of Nidiene NF35A (manufactured by Asahi Kasei Corporation) in 90 parts of styrene, and then performing bulk polymerization.

B-4: Polybutadiene latex 1 used in B-1
After emulsion polymerizing 85 parts of a monomer mixture consisting of 75% styrene and 25% acrylonitrile in the presence of 5 parts (solid content), a powdery graft copolymer (B-4) was prepared in the same manner as B-1. ) was prepared.

B-5: After emulsion polymerization of 15 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile in the presence of 85 parts (solid content equivalent) of the polybutadiene latex used in B-1, B-1 and A powdery graft copolymer (B-5) was prepared in the same manner.

B-6: AES resin (Unibrite UB-300, manufactured by Sumitomo Naugatac Co., Ltd.) was used.

B-7: AAS resin (Pitax 6100, manufactured by Hitachi Chemical Co., Ltd.) was used.

(3) (C) Preparation of modified vinyl polymer C-1 = Modified vinyl polymer (C-1
) was prepared.

C-2 = 73 parts of methyl methacrylate, 25 parts of styrene,
A modified vinyl polymer (C-2) was prepared by suspension polymerization of 2 parts of glycidyl methacrylate.

C-3: A modified vinyl polymer (C-3) was prepared by suspension polymerization of 97 parts of styrene and 3 parts of glycidyl methacrylate.

(4) (D) Preparation of vinyl (co)polymer D-1 = A copolymer (D-1) was prepared by suspension polymerization of 72 parts of styrene and 28 parts of acrylonitrile.

D-2 = 72 parts of methyl methacrylate, 24 parts of styrene,
A copolymer (D-2) was obtained by suspension polymerization of 4 parts of acrylonitrile.
) was prepared.

D-3: 50 parts of styrene, 30 parts of N-phenylmaleimide
part, and 20 parts of acrylonitrile were emulsion polymerized to form a copolymer (
D-3) was prepared.

Examples 1 to 12 (A) polyether ester amide prepared in Reference Example,
(B) Graft (co)polymer, (C) Modified vinyl polymer, and (D) Vinyl (co)polymer were mixed at the compounding ratio shown in Table 1, and the mixture was heated to resin temperature using a vented 40 mmφ extruder. Pellets were produced by melt-kneading and extrusion at 220°C.

Next, a test piece was molded using 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 resistivity value was measured using an injection molded disk with a thickness of 2 mm under the following conditions.

(1) Immediately after molding, wash with an aqueous solution of the detergent "Mama Lemon" (manufactured by Lion Yushi Co., Ltd.), then thoroughly wash with distilled water to remove surface moisture, and then clean with a 50% R11, 23°C
The humidity was adjusted for 24 hours and measured.

(2) 50% after molding After being left in RH 123℃ for 200 days, washed with detergent "Mama Lemon" aqueous solution, then thoroughly washed with distilled water to remove surface moisture, then 50%
The humidity was adjusted at RH and 23° C. for 24 hours.

The measurement results are shown in Table 2.

Comparative Examples 1 to 9 (A) polyether ester amide prepared in Reference Example,
(B) the graft (co)polymer, (C) the modified vinyl polymer, and (D) the vinyl (co)polymer were mixed in the blending ratio shown in Table 1, and the mixture was prepared in the same manner as in Example 1. Each physical property was measured. The results are shown in Table 2.

The following is clear from the results in Margin Table 2 below. The resin compositions of the present invention (Examples 1 to 12) all have excellent mechanical properties represented by tensile properties, flexural modulus, and impact strength, and have low volume resistivity values. Moreover, the resistance value hardly changes even after surface cleaning or changes over time, and it exhibits excellent permanent antistatic properties. Furthermore, the molded product has no delamination and has an extremely good appearance.

On the other hand, the blending amount of polyether ester amide (A) is 1
When the amount is less than 40 parts by weight (Comparative Example 1.4), the antistatic property (resistance value) is poor, and the polyether ester amide (A) is less than 40 parts by weight.
When the amount exceeds parts by weight (Comparative Example 2), the tensile yield stress and flexural modulus are poor.

The ratio of the rubbery polymer (b1) in the resin composition is 1
If it is less than % by weight (Comparative Examples 3 and 9), the impact resistance is poor;
If it exceeds 40% polymerization (Comparative Example 6), the flexural modulus, moldability and appearance of the molded product will deteriorate.

The amount of modified vinyl polymer containing epoxy groups is 0.
．． If the amount is less than 1 part by weight (Comparative Example 8), the molded product will delaminate, and if it exceeds 40 parts by weight (Comparative Example 7), the molding processability will be significantly deteriorated and the appearance of the molded product will be impaired, which is not preferable.

When a graft copolymer containing more than 80 parts by weight of the rubbery polymer is used (Comparative Example 5), the graft copolymer is poorly dispersed, the impact resistance is poor, and the appearance of the molded product is impaired.

That is, the resin composition of the present invention is a composition that has excellent mechanical properties, moldability, and permanent antistatic properties, and also exhibits extremely good delamination and appearance of molded products.

<Effects of the Invention> The thermoplastic resin composition of the present invention has excellent mechanical properties such as permanent antistatic property and impact resistance, and moldability, and is free from delamination.

Claims (1)

Scope of Claims: (A) (a1) An aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms, (a2) having a number average molecular weight of 200 to 6,000; 1 to 40 parts by weight of a polyether ester amide composed of poly(alkylene oxide) glycol and (a3) dicarboxylic acid having 4 to 20 carbon atoms, the polyether ester unit being 95 to 10% by weight. , (B) (b1) 1 to 80 parts by weight of the rubbery polymer, and (b2) 100 to 100 parts of the aromatic vinyl monomer and/or (meth)acrylic acid ester monomer.
Graft (co)polymers 2 to 9 obtained by grafting (co)polymerizing 99 to 20 parts by weight of a monomer or monomer mixture consisting of 40% by weight and 0 to 60% by weight of a vinyl cyanide monomer.
8 parts by weight, (C) modified vinyl polymer containing epoxy group 0.1
~40 parts by weight and (D) 100-40% by weight of aromatic vinyl monomer and/or (meth)acrylic acid ester monomer, 0-60% by weight of vinyl cyanide monomer, and other Vinyl (co)polymer 0 to 96 obtained by (co)polymerizing a monomer or monomer mixture consisting of 0 to 60% by weight of vinyl monomer
Blend so that (A) + (B) + (C) + (D) is 100 parts by weight, and the amount of rubbery polymer in the whole is 1 to 40% by weight. thermoplastic resin composition.