JP2682056B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention has permanent antistatic properties, excellent mechanical properties typified by impact resistance, and moldability, and exhibits delamination (thousands). The present invention relates to an antistatic resin composition which does not have a flip-flop.

<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 copying machines, various dustproof parts, etc., which are desired to prevent troubles due to static electricity.

As a method for improving the antistatic property of a synthetic polymer material,
Method obtained by graft-polymerizing a vinyl monomer or vinylidene monomer to a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene and / or acrylic acid ester and a vinyl monomer having an alkylene oxide group (JP-A-55
-36237 gazette), etc., and has achieved practical antistatic properties.

Further, JP-A-60-23435 discloses that a resin having semi-permanent antistatic property can be obtained by mixing 5 to 80 parts by weight of polyamide elastomer and 95 to 20 parts by weight of a modified vinyl polymer containing a carboxyl group. Is disclosed.

<Problems to be Solved by the Invention> However, an antistatic resin obtained by graft-polymerizing a hydrophilic rubber-like polymer described in JP-A-55-36237 with a monomer is a special hydrophilic rubber-like polymer. Since a polymer is used, the production method thereof is complicated, and the mechanical properties of the resulting resin are inferior, which is not satisfactory.

Further, since the antistatic resin according to JP-A-60-23435 contains a large amount of a modified vinyl polymer containing a carboxyl group, it easily gels due to heat history and the appearance of the molded product is significantly deteriorated. There's a problem.

Therefore, the present invention has a permanent antistatic property, and is excellent in mechanical properties represented by impact resistance and moldability,
It is an object to provide an antistatic resin that does not cause delamination.

<Means for Solving Problems> The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems.

That is, the present invention provides (A) (a1) an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and a dicarboxylic acid having 6 or more carbon atoms, (a2) a poly (alkylene having a number average molecular weight of 200 to 6,000). Oxide) glycol and (a3) a polyetheresteramide composed of a dicarboxylic acid having 4 to 20 carbon atoms, wherein 1 to 40 parts by weight of a polyetheresteramide having a polyether ester unit of 95 to 10% by weight, (B ) (B1) Rubbery polymer 1 to
80 to 80 parts by weight of (b2) aromatic vinyl-based monomer and / or (meth) acrylic acid ester-based monomer 100 to 40% by weight,
Monomer or monomer mixture consisting of 0 to 60% by weight of vinyl cyanide monomer (provided that the difference between the refractive index of the monomer or the polymer of the monomer mixture and the refractive index of the rubbery polymer is 0.02). 2 to 98 parts by weight of a graft (co) polymer obtained by grafting (co) polymerizing 99 to 20 parts by weight of (C), 0.1 to 40 parts by weight of a modified vinyl polymer (C) containing an epoxy group, and
(D) Aromatic vinyl-based monomer and / or (meth) acrylic acid ester-based monomer 100 to 40% by weight, vinyl cyanide-based monomer 0 to 60% by weight, and other vinyl-based monomer 0
~ 60 wt% monomer or monomer mixture (co)
Polymerized vinyl-based (co) polymer 0 to 96 parts by weight is blended so that (A) + (B) + (C) + (D) is 100 parts by weight, and the rubber weight occupies the whole. The amount of coalescence is 1
It is intended to provide a thermoplastic resin composition formulated so as to be 40% by weight.

 Hereinafter, the present invention will be described specifically.

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

As (a1) the constituent component of the polyether ester amide in the present invention, (a1) an aminocarboxylic acid having 6 or more carbon atoms or a lactam or a salt of a diamine having 6 or more carbon atoms and a dicarboxylic acid is ω-aminocaproic acid,
ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, aminocarboxylic acids such as 12-aminododecanoic acid or caprolactam, enanthlactam,
Capryllactam, and lactams such as laurolactam and salts of diamine-dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate are used, especially caprolactam, 12- Aminododecanoic acid and hexamethylenediamine-adipate are preferably used.

(A1) An aminocarboxylic acid having 6 or more carbon atoms or a lactam or a salt of a dicarboxylic acid having 6 or more carbon atoms and a dicarboxylic acid is a constitutional unit of polyether ester amide and is 5
It is used in an amount of up to 90% by weight, and if it is less than 5% by weight, the mechanical properties of the polyether ester amide are inferior, and if it exceeds 90% by weight, the antistatic property of the obtained resin is inferior, which is not preferable.

Examples of the (a2) poly (alkylene oxide) glycol, which is a constituent component of the polyether ester amide (A), include polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, and poly (1,3-propylene oxide) glycol. (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 20
It is used in the range of 0 to 6,000, preferably 250 to 4,000.
When the number average molecular weight is less than 200, the obtained polyetheresteramide has poor mechanical properties, and the number average molecular weight is 6,000.
If it exceeds, antistatic properties are insufficient, which is not preferable.

Examples of the (a3) dicarboxylic acid having 4 to 20 carbon atoms which is a constituent component of the polyether ester amide include terephthalic acid, isophthalic acid, phthalic acid and naphthalene-2,6-
Aromatic dicarboxylic acids such as dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1 Alicyclic dicarboxylic acids such as 2,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid and succinic acid, oxalic acid, adipic acid,
Aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid may be mentioned, and especially terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid,
Adipic acid and dodecanedioic acid are preferably used in terms of polymerizability, color tone and physical properties.

(A2) Poly (alkylene oxide) glycol and (a
3) Dicarboxylic acid reacts in a 1: 1 molar ratio, but
Usually, the charging ratio is changed according to the type of dicarboxylic acid used.

The polyether ester component is used as a constituent unit of polyether ester amide in the range of 95 to 10% by weight. When it exceeds 95% by weight, the mechanical properties of polyetheresteramide are inferior, and when it is less than 10% by weight, the resin is charged. It is inferior in preventability and is not preferable.

The method for polymerizing (A) polyether ester amide is not particularly limited. For example, (a) (a1) aminocarboxylic acid or lactam and (a3) dicarboxylic acid are reacted to prepare a polyamide prepolymer having carboxylic acid groups at both ends. A method of reacting this with (a2) poly (alkylene oxide) glycol under vacuum, (b) above (a1), (a
2) Charge each compound of (a3) into the reaction layer and react at high temperature in the presence or absence of water to generate a carboxylic acid terminated polyamide prepolymer, and then react under normal pressure or reduced pressure. A publicly known method such as a method for advancing can be used.

The polymerization catalyst is also not limited, and examples include antimony catalysts such as antimony trioxide, tin catalysts such as monobutyltin oxide, titanium catalysts such as tetrabutyl titanate, and zirconate catalysts such as tetrabutyl zirconate. It is also possible to use one kind or two or more kinds.

In the present invention, the (B) graft (co) polymer means (b1) a rubbery polymer and (b2) a monomer comprising an aromatic vinyl monomer and / or a (meth) acrylic acid ester monomer. Or a monomer or monomer selected from a monomer mixture and an aromatic vinyl-based monomer and / or a (meth) acrylic acid ester-based monomer, a vinyl cyanide-based monomer mixture The mixture is graft (co) polymerized.

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.

The (b2) monomer or monomer mixture 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 an aromatic vinyl-based monomer and / or a (meth) acrylic acid ester-based monomer and a vinyl cyanide-based monomer.

Styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, o-
Examples thereof include p-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 i-butyl, with methyl methacrylate being particularly preferable.

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

If necessary, other vinyl-based monomers, for example, maleimide-based monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, acrylamide, and 2-hydroxyethyl (meth) acrylate are used. You can also

The monomer or monomer mixture of (b2) used in the (B) graft (co) polymer has sufficient physical properties even if it is an aromatic vinyl monomer and / or a (meth) acrylic acid ester monomer. However, impact resistance is remarkably improved by further containing a vinyl cyanide-based monomer. The mixing ratio of the mixture of the aromatic vinyl-based monomer and / or the (meth) acrylic acid ester-based monomer and the vinyl cyanide-based monomer is such that the aromatic vinyl-based monomer and / or the (meth) acryl Acid ester monomer 100
-40% by weight, preferably 100-50% by weight, vinyl cyanide-based monomer 0-60% by weight, preferably 0-50% by weight.

When the proportion of the aromatic vinyl-based monomer and / or (meth) acrylic acid ester-based monomer is less than 40% by weight, when the proportion of the vinyl cyanide-based monomer exceeds 60% by weight,
The thermal stability of the graft copolymer is remarkably reduced, resulting in a molded product having a poor color tone, which 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.

If the proportion of the rubber-like polymer in the (B) graft (co) polymer is less than 1 part by weight, the impact resistance of the resulting resin composition is poor, and if it exceeds 80 parts by weight, the rubber-like polymer becomes poorly dispersed. However, the appearance of the molded product 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 modified vinyl polymer containing an epoxy group (C) used in the present invention (hereinafter, abbreviated as modified vinyl polymer) is obtained by (co) polymerizing one or more vinyl monomers. It is a polymer having a structure and having an epoxy group in the molecule.

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

In general, the effect of the present invention is efficiently exhibited when substantially one or more of the above functional groups are contained in one molecule of the modified vinyl polymer.

The method of introducing an epoxy group into the modified vinyl polymer (C) is not particularly limited, but may be represented by the following formula (I). (Wherein R is a hydrogen atom, a lower alkyl group or a lower alkyl group substituted with a lower alkyl group or a glycidyl ester group), and specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, glycidyl itaconate, etc. It is possible to use a method in which is copolymerized with a predetermined vinyl monomer.

(C) The vinyl-based monomer used for the polymerization of the modified vinyl-based polymer is not particularly limited, and examples thereof include aromatic vinyl-based monomers such as styrene and α-methylstyrene,
Vinyl cyanide-based monomers such as acrylonitrile and methacrylonitrile, (meth) acrylate-based monomers such as methyl methacrylate and butyl acrylate, maleimide-based monomers such as maleimide and N-phenylmaleimide, acrylic Α, β-Unsaturated carboxylic acids (anhydrides) such as acids, methacrylic acid, maleic acid, maleic anhydride, olefinic monomers such as ethylene and propylene and vinylic monomers such as vinyl chloride, vinyl acetate and butadiene From the body, one kind or two or more kinds can be selected and used according to the purpose.

In particular, aromatic vinyl-based monomers such as styrene, (meth) acrylic acid ester-based monomers such as methyl methacrylate,
Use of a maleimide-based monomer such as N-phenylmaleimide or a vinyl cyanide-based monomer such as acrylonitrile is preferably used because the 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 used. Can be used in combination with the vinyl monomer.

(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) acrylic acid ester monomer 100.
Vinyl which is obtained by (co) polymerizing a monomer or a mixture of monomers comprising -40% by weight, 0-60% by weight of a vinyl cyanide monomer, and 0-60% by weight of another vinylic monomer. System (co)
The polymer (D) 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.

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

Other vinyl-based monomers that can be copolymerized with these include maleimide-based monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, and N-phenylmaleimide, and olefin-based monomers such as ethylene and propylene. Examples thereof include monomers, 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-methyl methacrylate copolymer, polystyrene, polymethyl methacrylate, and the like.

This vinyl-based (co) polymer is an aromatic vinyl-based monomer and / or a (meth) acrylic acid ester-based monomer.
Sufficient physical properties can be obtained only with a (co) polymer consisting of 0-40% by weight, but 60% by weight of other vinyl-based monomers such as vinyl cyanide-based monomers or maleimide-based monomers
By including up to the above, properties such as impact resistance and heat resistance are remarkably improved.

Further, when the amount of the vinyl cyanide-based monomer or other vinyl-based monomer exceeds 60% by weight, there is a problem that the resin composition is colored, 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) graft (co) polymer 2 to 98 parts by weight, preferably 5 to 94 parts by weight, (C) modified vinyl polymer 0.1 to 40 parts by weight, preferably 1 to 20 parts by weight, and vinyl (copolymer) ) Polymer is blended so that (A) + (B) + (C) + (D) is 100 parts by weight within a range of 0 to 96 parts by weight, preferably 0 to 89 parts by weight.

When the amount of the polyether ester amide (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 the mechanical properties are inferior, 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 98 parts by weight, the antistatic property is deteriorated, which is not preferable.

If the amount of the modified vinyl polymer (C) is less than 0.1 parts by weight, the resin composition will be delaminated and cannot be used. If it exceeds 40 parts by weight, the molding processability will be significantly deteriorated and the surface of the molded article will be free. It is not preferable because it becomes glossy.

On the other hand, when the amount of the vinyl-based (co) polymer (D) exceeds 96 parts by weight, the antistatic property of the resin composition is insufficient, which is not preferable.

What is necessary in the resin composition of the present invention is that the proportion of the rubber substance 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, and examples thereof include (A) polyether ester amide and (B) graft (co) polymer, (C) modified vinyl polymer, and (D) vinyl. It is commercialized by melt-kneading a resin mixture of a system (co) polymer with a Banbury mixer, a roll, an extruder or the like. Note that (D)
When the vinyl-based copolymer is blended, the blending of the (B) graft (co) polymer and the (D) vinyl-based (co) polymer may be independent or may be premixed, and is not particularly limited. .

The resin composition of the present invention is another thermoplastic polymer compatible with the resin composition of the present invention, for example, polyamide, polybutylene phthalate, polyethylene terephthalate, polycarbonate, polyphenylene ether resin, vinyl chloride resin, polyglutarimide, Elastomers such as hydrogenated and / or non-hydrogenated styrene-butadiene block copolymers can be mixed to improve the performance as a molding resin. Further, it is 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, and pigments, dyes, lubricants, plasticizers, glass fibers, flame retardants and the like can be added. Also, sulfonate,
It is possible to further improve the compatibility between the component (A) and the component (B) by adding a tertiary amine and a phosphorus compound.

<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 Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Flammability: Vertical combustion test according to UL94 standard 1/16 "X1
/ 2 "X5" burning test pieces.

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 product is determined by bending the molded product and observing the fracture surface of the test piece subjected to the tensile test.
Very good, ○: Good, X: Delamination of the molded product occurs,
With respect to the appearance of the molded product, ⊚: extremely good appearance, ◯: good, X: poor damage to the surface of the molded product was used as the determination standard.

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

Reference Example (1) Preparation of (A) Polyetheresteramide A-1: 50 parts of caprolactam, 44.2 parts of polyethylene glycol having a number average molecular weight of 1,000 and 7.6 parts of terephthalic acid are added to 0.2 parts of "Irganox" 1098 (antioxidant). And 0.1 parts of antimony trioxide catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, and after nitrogen substitution, the mixture was heated and stirred at 260 ° C for 60 minutes to form a transparent homogeneous solution, and then 260 ° C, 0.5 mmHg.
Polymerization was carried out for 4 hours under the following conditions to obtain a viscous and transparent polymer.

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

A-2: Nylon 6.6 salt (AH salt) 60 parts, number average molecular weight 600
Polyethylene glycol 33.8 parts and adipic acid 8.7
Parts were used to prepare a polyetheresteramide (A-2) by the same method as in (A-1) except that the polymerization time was 4 hours.

A-3: Polyetherester in the same manner as in (A-1) except that 30 parts of ω-aminodecanoic acid, 14.2 parts of dodecanedioic acid and 58.6 parts of polyethylene glycol having a number average molecular weight of 1,000 were used and the polymerization time was set to 3 hours. The amide (A-3) was prepared.

(2) Preparation of (B) Graft (co) polymer B-1: Polybutadiene latex (rubber particle diameter 0.25 μ, gel content 80%) Styrene 70 in the presence of 60 parts (solid content conversion)
%, And 40 parts of a monomer mixture consisting of 30% acrylonitrile was emulsion polymerized.

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-3: Diene NF35A (manufactured by Asahi Kasei Corporation) 10 parts styrene 90
After being dissolved in some parts, it is bulk polymerized and graft polymer (B-3)
Was prepared.

B-4: 75% styrene, acrylonitrile in the presence of 15 parts (solid content equivalent) of the polybutadiene latex used in B-1
After emulsion polymerization of 85 parts of a 25% monomer mixture, B-1
A powdery graft copolymer (B-4) was prepared in the same manner as in.

B-5: Polybutadiene latex used in B1 85 parts (solid content) in the presence of 70% styrene, 30 acrylonitrile
After emulsion-polymerizing 15 parts of a monomer mixture consisting of 10% by weight, a powdery graft copolymer (B-5) was prepared in the same manner as in B-1.

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

B-7: AAS resin (Vitax 6100, manufactured by Hitachi Chemical Co., Ltd.)
Was used. The difference between the refractive index (n _D ²⁰ ° C) of the polymer of the monomer mixture of B-1 to B-7 and the refractive index of the rubber-like polymer was more than 0.02.

(3) Preparation of (C) Modified Vinyl Polymer C-1: 72 parts of styrene, 25 parts of acrylonitrile, and 3 parts of glycidyl methacrylate were subjected to suspension polymerization to prepare a modified vinyl polymer (C-1).

C-2: 73 parts of methyl methacrylate, 25 parts of styrene, and 2 parts of glycidyl methacrylate were subjected to suspension polymerization to prepare a modified vinyl polymer (C-2).

C-3: 97 parts of styrene and 3 parts of glycidyl methacrylate were subjected to suspension polymerization to prepare a modified vinyl polymer (C-3).

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

D-2: 72 parts of methyl methacrylate, 24 parts of styrene, and 4 parts of acrylonitrile were suspension-polymerized 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 to prepare a copolymer (D-3).

Examples 1, 2, 5 to 12 (A) Polyether ester amide prepared in Reference Example, (B) Graft (co) polymer, (C) Modified vinyl-based polymer, and (D) Vinyl-based (co) Polymers were mixed in the compounding ratio shown in Table 1, and the resin temperature was adjusted using a vented 40 mmφ extruder.
Pellets were produced by melt-kneading and extruding at 220 ° C.

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 resistivity value was measured under the following conditions using a 2 mm thick disk injection-molded.

(1) Immediately after molding, wash with an aqueous solution of the detergent "Mama Lemon" (manufactured by Lion Oil and Fats Co., Ltd.), followed by thorough washing with distilled water to remove surface water, and then 24 at 50% RH and 23 ° C. The humidity was measured with time.

(2) After molding, leave at 50% RH and 23 ℃ for 200 days,
After washing with detergent "Mama Lemon" aqueous solution and then with distilled water thoroughly to remove surface moisture, 50% RH, 23 ℃
For 24 hours.

Table 2 shows the measurement results.

Comparative Examples 1 to 9 show (A) polyether ester amides, (B) graft (co) polymers, (C) modified vinyl-based polymers, and (D) vinyl-based (co) polymers prepared in Reference Examples. Mixing was carried out at the compounding ratio shown in No. 1, and each physical property was measured by the same method as in Example 1. The results are also shown in Table 2.

The following is clear from the results in Table 2. The resin compositions (Examples 1 to 12) of the present invention all have excellent mechanical properties represented by tensile properties, flexural modulus and impact strength, and have low volume resistivity values. In addition, the resistance value hardly changes even when the surface is washed or changes with time, and excellent permanent antistatic properties are exhibited. Further, the molded article has no delamination and has an extremely good appearance.

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 wt% (Comparative Examples 3 and 9), the impact resistance is inferior, and
If it exceeds 5% by weight (Comparative Example 6), the flexural modulus, moldability, and appearance of the molded product deteriorate.

The amount of the modified vinyl polymer containing an epoxy group is
When it is less than 0.1 parts by weight (Comparative Example 8), the molded product is delaminated, and when it is more than 40 parts by weight (Comparative Example 7), the moldability is remarkably deteriorated and the appearance of the molded product is impaired, which is not preferable.

When a graft copolymer in which the proportion of the rubbery polymer exceeds 80 parts by weight is used, in 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 has excellent mechanical properties, molding processability, and permanent antistatic property, and has extremely good delamination and appearance of molded articles.

<Effect of the Invention> The thermoplastic resin composition of the present invention is excellent in both permanent antistatic properties, mechanical properties such as impact resistance, and moldability, and
There is no delamination.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08L 77:12 25:08 33:06 101: 06) (C08L 25/08 51:04 77:12 101: 06) ) (C08L 25/08 55:02 77:12 101: 06) (C08L 55/02 77:12 25:08 33:06 101: 06)

Claims (1)

(57) [Claims] 1. (A) (a1) Aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of a diamine and carboxylic acid having 6 or more carbon atoms, (a2) poly (alkylene) having a number average molecular weight of 200 to 6,000. Oxide) glycol and (a3) a polyetheresteramide composed of a dicarboxylic acid having 4 to 20 carbon atoms, wherein 1 to 40 parts by weight of a polyetheresteramide having a polyether ester unit of 95 to 10% by weight, (B ) (B1) 1 to 80 parts by weight of a rubbery polymer (b2) 100 to 40% by weight of an aromatic vinyl-based monomer and / or a (meth) acrylic acid ester-based monomer, a vinyl cyanide-based monomer 0 to 60% by weight of a monomer or a mixture of monomers (however, the difference between the refractive index of the polymer of the monomer or the mixture of monomers and the refractive index of the rubbery polymer exceeds 0.02) 99 to
Graft (co) obtained by graft (co) polymerization of 20 parts by weight
Polymer 2 to 98 parts by weight, (C) Epoxy group-containing modified vinyl polymer 0.1 to 4
0 parts by weight and 100 to 40% by weight of (D) aromatic vinyl-based monomer and / or (meth) acrylic acid ester-based monomer, 0 to 60% by weight of vinyl cyanide-based monomer, and other vinyl A vinyl-based (co) polymer obtained by (co) polymerizing a monomer or a mixture of monomers of 0 to 60% by weight of (A) + (B) + (C ) + (D) is added in an amount of 100 parts by weight, and the total amount of the rubbery polymer is 1%.
A thermoplastic resin composition blended so as to be 40% by weight.