JPH072884B2 - Molded product with antistatic properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention is a molded article having excellent mechanical properties and appearance, and having permanent antistatic property, such as dropout of light or magnetic recording due to static electricity or electrostatic charge. The present invention relates to a housing of a recording medium that prevents disturbance of signals, sounds, and images.

<Prior Art> As a housing material of a recording medium substrate, synthetic polymers such as ABS resin and polypropylene are often used. These synthetic polymer materials generally have high volume resistivity,
Since it is easily charged, there are problems such as noise during recording and reproduction, and dust easily adhering.

Known methods for imparting antistatic properties to a molded product include a method of kneading an antistatic agent and a metal filler in a resin, and a method of applying metal plating.

On the other hand, JP-A-60-23435 discloses that a resin having semipermanent antistatic property is obtained by mixing 5 to 80% by weight of polyamide elastomer and 95 to 20% by weight of a modified vinyl polymer containing a carboxyl group. Is disclosed.

<Problems to be Solved by the Invention> However, in the method of kneading an antistatic agent, the antistatic property greatly depends on the environment, and when a metal filler is contained, a lightweight molded article having a good appearance cannot be obtained. If the molded product is metal-plated, conductivity can be obtained, but there are problems such as high manufacturing cost and restrictions on the appearance, and the reality is that there is no satisfactory housing for the recording medium substrate. .

Further, the antistatic resin according to JP-A-60-23435 has a reactivity between a modified vinyl polymer containing a carboxyl group (hereinafter referred to as a modified vinyl polymer) and a polyetheresteramide. In addition, since the amount of the modified vinyl polymer blended is large, there are problems that molding processability is extremely poor and physical properties cannot be obtained with good reproducibility.

It is an object of the present invention to provide a housing of a recording medium substrate and an IC card case which have a permanent antistatic property, a high mechanical strength, a low specific gravity, and a bright color and a good appearance at a low cost.

<Means for Solving the Problems> As a result of intensive studies to solve the above-mentioned object, the present inventors have found that a specific polyamide elastomer, a styrene-based thermoplastic resin, and a modified vinyl-based polymer are used as materials for a housing of a recording medium. The present inventors have found that the above objects can be effectively achieved by using a thermoplastic resin composition in which a specific amount of is blended, and have reached the present invention.

That is, the present invention includes (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, and 5 to 30 parts by weight of a polyetheresteramide having a polyether ester unit of 75 to 40% by weight, B) 55 to 94 parts by weight of a graft (co) polymer-containing material containing the following graft (co) polymer, (b) (b1) 1 to 80 parts by weight of a rubbery polymer (b2) (b2-1) A monomer or a mixture of monomers comprising an aromatic vinyl monomer and / or a (meth) acrylic acid ester monomer, and (b2-2) an aromatic vinyl monomer and / or (meth)
Grafting 99 to 20 parts by weight of a monomer or a monomer mixture selected from a monomer mixture consisting of 99 to 40% by weight of an acrylate monomer and 1 to 60% by weight of a vinyl cyanide monomer ( Copolymerized graft (co) polymer and (C) carboxyl group-containing modified vinyl polymer 1
To 15 parts by weight of (A) + (B) + (C) are added in an amount of 100 parts by weight, and the total amount of the rubber-like polymer is 1-40% by weight, and poly (alkylene) is used. Oxide) glycol unit in an amount of 4 to 18% by weight of the thermoplastic resin composition, which is used as an optical disk jacket, video floppy, digital audio cassette, TV gun, video game software, video cassette, video disk, and Provided is a molded article having an antistatic property, which is molded in a housing of a light or magnetic recording medium selected from the group of IC cards.

The present invention will be specifically described below.

(A1) Aminocarboxylic acid having 6 or more carbon atoms or a lactam or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms, which is a constituent component of the polyether ester amide (A) in the present invention, 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 laurolactam Salts of diamine-dicarboxylic acids such as lactams and hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate are used, especially caprolactam, 12-aminododecanoic acid, hexamethylenediamine. -Adipate is preferably used.

(A1) Aminocarboxylic acid having 6 or more carbon atoms or lactam or a salt of dicarboxylic acid having 6 or more carbon atoms and dicarboxylic acid is a constituent unit of polyether ester amide with 25 to
Used in the range of 60% by weight, preferably 30-55% by weight,
If it is less than 25% by weight, the mechanical properties of the polyether ester amide are inferior, and if it exceeds 60% by weight, the antistatic property 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 property. 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.
If the number average molecular weight is less than 200, the mechanical properties of the obtained molded product will be poor, and if the number average molecular weight exceeds 6,000, the antistatic property will be 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 (a3)
The dicarboxylic acid reacts at a molar ratio of 1: 1 in terms of the reaction, but the charging ratio is usually changed depending on the kind of the dicarboxylic acid used.

The polyether ester component is a constituent unit of polyether ester amide and is 75 to 40% by weight, preferably 70 to 45% by weight.
If it exceeds 75% by weight, the mechanical properties of the molded product will be poor, and if it is less than 40% by weight, the antistatic property of the molded product will be poor, which 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. Make up,
A method of reacting this with (a2) poly (alkylene oxide) glycol under vacuum, (b) the above (a1), (a2),
A method in which each compound of (a3) is charged in a reaction layer and reacted at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, and thereafter polymerization is recommended under normal pressure or reduced pressure and (C) The above (a1),
It is possible to use a known method such as a method in which the compounds (a2) and (a3) are simultaneously charged in a reaction layer, melt-mixed, and then polymerization is carried out all at once under high vacuum.

In the present invention, the (b) graft (co) polymer in the (B) graft (co) polymer-containing material is (b1) a rubbery polymer (b2) (b2-1) an aromatic vinyl monomer and / Or a monomer or a mixture of monomers consisting of (meth) acrylic acid ester type monomer (b2-2) aromatic vinyl type monomer and / or (meth)
It is obtained by graft (co) polymerizing a monomer or a monomer mixture selected from a monomer mixture consisting of an acrylate ester monomer and a vinyl cyanide monomer.

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 and polyacrylonitrile-butadiene, and polyisoprene. Acrylic rubbers such as polychloroprene and polybutyl acrylate, and rubbery polymers such as ethylene-propylene-diene monomer terpolymers can be used.

Polybutadiene or a butadiene copolymer is particularly preferable.

As the aromatic vinyl-based monomer, styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, op
-Dichlorostyrene and the like can be mentioned, but styrene is particularly preferable.

Examples of the (meth) acrylic acid ester-based monomer include acrylic acid and methacrylic acid methyl, ethyl, propyl, and n.
-Butyl, i-butyl and the like can be mentioned, but methyl methacrylate is 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 the like can be used.

(B) The blending 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 used in the graft (co) polymer is the aromatic vinyl-based monomer. System monomer and / or (meth)
Acrylic ester monomer 99 to 40% by weight, preferably
90 to 50% by weight, vinyl cyanide monomer 1 to 60% by weight,
It is preferably 10 to 50% by weight.

If the proportion of the vinyl cyanide-based monomer is less than 1% by weight, the effect of improving the impact resistance due to the inclusion of the vinyl cyanide-based monomer does not remarkably appear, which is not preferable. On the other hand, if it exceeds 60% by weight, the thermal stability of the graft copolymer is remarkably deteriorated and a molded product having a poor color tone is obtained, which is not preferable.

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

If the proportion of the rubbery 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 rubbery polymer becomes poorly dispersed. However, the appearance of the molded product is deteriorated, which is not preferable.

(B) The graft (co) polymer is prepared by a known polymerization method, for example, a method of continuously supplying a monomer or a mixture of monomers and a polymerization initiator in the presence of a rubbery polymer latex to carry out emulsion polymerization. Obtainable.

In the present invention, the (B) graft (co) polymer-containing material is required to contain the above graft (co) polymer, and the amount of the rubbery polymer in the resin composition is 1 to 1.
If it is 40% by weight, only the graft (co) polymer may be used.

Examples of the other (co) polymer in the (B) graft (co) polymer-containing material include styrene-acrylonitrile copolymer, α-methylstyrene-styrene-acrylonitrile copolymer, α-methylstyrene-methacrylic acid. Methyl-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer, styrene-methyl methacrylate-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-N-phenylmaleimide-acrylonitrile copolymer, α -Methylstyrene-methylmethacrylate copolymer, polystyrene, polymethylmethacrylate, etc. may be mentioned.

Preferable examples include (co) polymers of aromatic vinyl monomers and / or (meth) acrylic acid ester monomers, aromatic vinyl monomers and /
Alternatively, it is a copolymer of a (meth) acrylic acid ester-based monomer and a vinyl cyanide-based monomer.

Particularly, aromatic vinyl-based monomer and / or (meth) acrylic acid ester-based monomer 100 to 40% by weight, preferably 100
The most preferable example is a (co) polymer composed of ˜50 wt% and vinyl cyanide monomer 0-60 wt%, preferably 0-50 wt%.

In this (co) polymer, if the ratio of the aromatic vinyl-based monomer and / or the (meth) acrylic acid ester-based monomer is too small, the affinity with the polyether ester amide is deteriorated and delamination occurs. Since there is a tendency, it is preferable to use 40% by weight or more.

The modified vinyl polymer containing a carboxyl group (C) used in the present invention (hereinafter, abbreviated as modified vinyl polymer) is obtained by polymerizing or copolymerizing one or more vinyl monomers. It is a polymer having a structure obtained by the above and having a carboxyl group in the molecule.

The carboxyl group may be an anhydrous carboxyl group. The content of these carboxyl groups is not 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.

Usually, the effect of the present invention is efficiently exhibited when substantially one average of one or more carboxyl groups is contained in one molecule of the modified vinyl polymer.

The method for introducing a carboxyl group into the modified vinyl polymer (C) is not particularly limited, but is a carboxyl group or a carboxyl anhydride such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid. A method for copolymerizing a vinyl monomer having a group with a desired vinyl monomer, γ, γ'-azobis (γ-cyanovaleic acid), α, α '-(α-cyano) ethyl-
Polymerization initiator having a carboxyl group such as p-benzoic acid and persuccinic acid and / or thioglycolic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, α-mercapto-isobutyric acid and 2, 3 or 4- A desired vinyl monomer (co) is prepared by using a polymerization degree regulator having a carboxyl group such as mercaptobenzoic acid.
A method of polymerizing, a method of saponifying a (meth) acrylate (co) polymer such as methyl methacrylate or butyl acrylate with an alkali, and the like can be used.

There is no particular limitation on the vinyl-based monomer used in the polymerization of the (C) modified vinyl-based polymer, and for example, 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, malein One or two of α, β-unsaturated carboxylic acid (anhydride) such as acid and maleic anhydride, olefinic monomer such as ethylene and propylene and vinylic monomer such as vinyl chloride, vinyl acetate and butadiene. More than one species 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, N
The use of a maleimide-based monomer such as 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. The vinyl-based monomer can also be used together.

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

The polymer thus obtained is (A) polyether ester amide 5 to 30 parts by weight, preferably 8 to 25 parts by weight,
55-94 parts by weight, preferably 60-90 parts by weight of (B) graft (co) polymer-containing material and (C) modified vinyl polymer 1
Within the range of 15 parts by weight, preferably 2 to 13 parts by weight (A)
Blend so that + (B) + (C) is 100 parts by weight.

If the amount of (A) polyether ester amide is less than 5 parts by weight, the antistatic property of the molded product is insufficient, and if it exceeds 30 parts by weight,
It is not preferable because the rigidity of the molded product is lowered and the molded product is easily deformed.

If the content of the (B) graft (co) polymer is less than 55 parts by weight, the impact resistance is insufficient, and if it exceeds 94 parts by weight, the antistatic property is deteriorated, which is not preferable.

When the amount of the modified vinyl polymer (C) is less than 1 part by weight, the compatibility of the resin composition is deteriorated and the appearance of the molded product is impaired.
If it exceeds 15 parts by weight, the moldability is deteriorated and the surface of the molded product becomes matte, which is not preferable.

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

If it 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, which is not preferable.

It is also necessary that the amount of poly (alkylene oxide) glycol units is 4-18% by weight, preferably 5-15% by weight. If it is less than 4% by weight, the antistatic property of the molded product is insufficient, and if it exceeds 18% by weight, the molded product becomes flexible, which is not preferable.

The method for producing the resin composition used in the present invention is not particularly limited, and includes, for example, a resin mixture of (A) polyether ester amide, (B) graft (co) polymer-containing material and (C) modified vinyl polymer. Can be produced by melt-kneading with a Banbury mixer, roll, extruder or the like. When only the graft (co) polymer is not used in (B), the graft (co) polymer is used.
The blending of the polymer and the (co) polymer may be independent or may be premixed and is not particularly limited.

The resin composition used in the present invention is another thermoplastic polymer compatible with the resin composition, for example, vinyl chloride resin, polyolefin resin, polyamide, polybutylene terephthalate, polyethylene terephthalate, polycarbonate,
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 also possible to further improve the antistatic property by adding an antistatic agent such as a metal salt of sulfonic acid or anionic or cationic surfactant, and further, if necessary, a compatibilizer such as an oligomer, Various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants, and plasticizers, flame retardants, hydrotalcites, etc. can also be added.

The resin composition thus obtained can be used for injection molding, extrusion molding, vacuum molding, press molding, or any other commonly used molding method to produce an optical disk jacket, a video floppy,
Molded into a housing for optical or magnetic recording media selected from the group of digital audio cassettes, TV guns, video game software, video cassettes, video discs, laser discs and IC cards.

The housing of the recording medium in the present invention refers to a main body molded product that holds the recording medium, or a case that houses the main body molded product.

As the housing of a new recording medium, the above-mentioned molded article is strongly required to protect the function of the medium from the electrification of resin. At the same time, it must be lightweight and have high mechanical strength, and a good appearance and bright color as a housing are also essential. The molded product of the present invention has all of these characteristics, and is the first molded product made of a synthetic polymer to have antistatic properties, light weight, bright color, strength, low cost, and good appearance.

By using the molded article of the present invention, not only noise due to charging and static electricity of the resin is reduced, but also weight reduction of the product and arbitrary coloring / cost reduction are possible.

The resin composition used in the present invention is particularly suitable for use in the molded article of the present invention, but since it has an excellent physical property balance as a thermoplastic resin, it can be used for purposes other than the present invention. is there.

<Examples> In order to more specifically describe the present invention, examples and comparative examples will be described below.

In the examples, parts and% mean parts by weight and% by weight. The physical properties of the materials were measured by the following methods.

Volume resistivity value: 2t × 40 ^φ disk, room temperature 23 ℃, humidity 5
It was measured in a 0% RH atmosphere. A super insulation resistance meter SM-10 type manufactured by Toa Denpa Kogyo Co., Ltd. was used for the measurement.

Flame retardance: Vertical combustion test according to UL94 standard 1/16 ″ × 1 /
2 ″ × 5 ″ combustion test pieces were used.

Izod impact strength: ASTM D-256-56A Flexural modulus: ASTM D790 (1) (A) Preparation of polyetheresteramide A-1: 50 parts of caprolactam, 45 parts of polyethylene glycol having a number average molecular weight of 1000 and adipic acid 7.0 Part of "Irganox" 1098 (antioxidant) and 0.1 part of antimony trioxide catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, and the atmosphere was replaced with nitrogen. After the solution, it was polymerized for 4 hours at 260 ° C. and 0.5 mmHg or less to obtain a viscous and transparent polymer.

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

A-2: Nylon 6.6 salt (AH salt) 50 parts, number average molecular weight 60
41.1 parts polyethylene glycol with 0 and 1 terephthalic acid
(A- except that 1.8 parts was used and the polymerization time was 4 hours).
Polyamide elastomer (A-
2) was prepared.

A-3: ω-aminoundecanoic acid 30 parts, dodecanoic acid 14.2 parts and polyethylene glycol 58.6 having a number average molecular weight of 1000
(A-1) except that the polymerization time was changed to 3 hours by using 1 part.
A polyamide elastomer (A-3) was prepared by the same method as described above.

(2) Preparation of (B) (b) Graft (Co) polymer B-1: Polybutadiene Latex (Rubber Particle Diameter 0.25 μ,
Styrene in the presence of 60 parts (gel content 80%) (solid content conversion)
Monomer mixture 40 consisting of 55% and 45% methyl methacrylate 40
Part 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-2: 60 parts of a monomer mixture consisting of 75% of methyl methacrylate and 25% of styrene was emulsion polymerized in the presence of 40 parts of the polybutadiene latex used in B-1 (in terms of solid content), and then B-1 Similarly, a powdery graft copolymer (B-2) was prepared.

B-3: Diene NF35A (manufactured by Asahi Kasei Corporation) 10 parts styrene 9
After dissolving in 0 part, bulk polymerization was carried out and the graft polymer (B-
3) was prepared.

B-4: Emulsion polymerization of 15 parts of a monomer mixture consisting of 45% styrene and 55% methyl methacrylate in the presence of 85 parts of the polybutadiene latex used in B-1 (as solid content) was carried out, and then B-1 Similarly, a powdery graft copolymer (B-4) was prepared.

B-5: Polybutadiene latex (rubber particle diameter 0.25 μ,
Styrene in the presence of 60 parts (gel content 80%) (solid content conversion)
40 parts of a monomer mixture consisting of 70% and 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-5).

(3) Preparation of (B) (b ') (co) polymer b-1: 55 parts of methyl methacrylate and 45 parts of styrene were copolymerized to prepare a copolymer (b-1).

b-2: 72 parts of styrene and 28 parts of acrylonitrile were copolymerized to prepare a copolymer (b-2).

b-3: Copolymer (b-3) obtained by copolymerizing 50 parts of styrene, 30 parts of N-phenylmaleimide and 20 parts of acrylonitrile.
Was prepared.

(4) Preparation of (C) carboxyl group-containing modified vinyl polymer C-1: Modified vinyl polymer in the form of beads obtained by suspension polymerization of 45 parts of styrene, 50 parts of methyl methacrylate and 5 parts of methacrylic acid. (C-1) was prepared.

C-2: 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylic acid were suspension-polymerized to prepare a bead-shaped modified vinyl polymer (C-2).

C-3: 70 parts of methyl methacrylate, 24 parts of styrene, 4 parts of acrylonitrile, and 2 parts of acrylic acid were suspension-polymerized to prepare a bead-shaped modified vinyl polymer (C-3).

Examples 1 to 9 (A) Polyether ester amide prepared in Reference Example,
(B) (b) Graft copolymer, (b ') (co) polymer and (C) modified vinyl polymer were mixed in the compounding ratio shown in Table 1, and a resin temperature of 220 was used with a vented 40 mmφ extruder. Pellets were produced by melt-kneading and extruding at ℃.

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

The volume resistivity value uses a 2 mm thick disc molded by injection molding,
The measurement was performed under the following conditions.

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

(2) After molding, leave it in 50% RH, 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 ℃
The humidity was measured for 24 hours.

The measurement results of the physical properties of the raw material resin are summarized in Table 2.

The pellets produced as described above were molded by an injection molding machine at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C. to mold the molded products shown in Table 2, and evaluated for antistatic property, appearance, and characteristics as a housing of recording medium.

The results are shown in Table 3.

The following is clear from the results of Tables 2 and 3. The molded articles of the present invention all have mechanical properties typified by impact strength and flexural modulus, and high permanent antistatic properties. In addition, it is lightweight, has a clear and good appearance, and can provide desired antistatic properties even in a thin molded product. That is, the molded product of the present invention has excellent mechanical properties, permanent antistatic property, light weight, bright color / good appearance, and low cost.

Comparative Examples 1 to 9 (A) Polyether ester amide prepared in Reference Example,
(B) (b) Graft (co) polymer, (b ') (co) polymer, (C) Modified vinyl polymer were mixed in the compounding ratio shown in Table 1 and the same method as in Example 1 Each physical property was measured by.

The results of measuring the physical properties of the raw material resin are shown in Table 2, and the properties of the molded product are shown in Table 3.

When the proportion of the rubbery polymer (b1) in the resin composition is less than 1% by weight (Comparative Example 1), the impact resistance is poor, and when it exceeds 40% by weight (Comparative Example 2), the rigidity of the molded product is high. Is low and the antistatic property is also poor.

When the compounding amount of the modified vinyl polymer (C) containing a carboxyl group is less than 1 part by weight (Comparative Example 3), flow marks are generated in the molded product, and when it exceeds 15 parts by weight (Comparative Example). In the case of 4), moldability and appearance are deteriorated. When the amount of the poly (alkylene oxide) glycol unit is less than 4% by weight (Comparative Example 5), the antistatic property of the molded product is insufficient, and when it exceeds 18% by weight (Comparative Example 6), the rigidity is poor.

When a graft copolymer in which the proportion of the rubber-like polymer exceeds 80 parts by weight is used, (Comparative Example 7) has a poor dispersion of the graft copolymer and impairs the appearance of the molded article.

In addition, a method using a conventional metal or antistatic agent (Comparative Example 8,
In 9), the external appearance, specific gravity, and permanent antistatic property deteriorate.

<Effects of the Invention> The molded product of the present invention has features such as permanent antistatic property, mechanical properties, appearance, lightness, dimensional stability, and low cost.

Claims (2)

[Claims] 1. (A) (a1) 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) 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, and 5 to 30 parts by weight of a polyetheresteramide having a polyether ester unit of 75 to 40% by weight, B) 55 to 94 parts by weight of a graft (co) polymer-containing material containing the following (b) graft (co) polymer, (b) (b1) 1 to 80 parts by weight of a rubbery polymer (b2) (b2) -1) A monomer or a mixture of monomers comprising an aromatic vinyl-based monomer and / or a (meth) acrylic acid ester-based monomer, and (b2-2) an aromatic vinyl-based monomer and / or (Meta)
Grafting 99 to 20 parts by weight of a monomer or monomer mixture selected from a monomer mixture consisting of 99 to 40% by weight of an acrylate monomer and 1 to 60% by weight of a vinyl cyanide monomer. Copolymerized graft (co) polymer and (C) carboxyl group-containing modified vinyl polymer 1
To 15 parts by weight of (A) + (B) + (C) are added in an amount of 100 parts by weight, and the total amount of the rubber-like polymer is 1-40% by weight, and poly (alkylene) is used. Oxide) glycol unit in an amount of 4 to 18% by weight of the thermoplastic resin composition, which is used as an optical disk jacket, video floppy, digital audio cassette, TV gun, video game software, video cassette, video disk, and Molded product with antistatic property, which is molded in the housing of optical or magnetic recording medium selected from the group of IC cards. 2. The graft (co) polymer-containing material (B) according to claim 1, the graft (co) polymer and the aromatic vinyl-based monomer and / or (meth) acrylic acid ester-based material. The antistatic molded article according to claim 1, which is a mixture with a (co) polymer consisting of 100 to 40% by weight of a monomer and 0 to 60% by weight of a vinyl cyanide monomer.