JP2003213060A - Resin composition and its molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having excellent antistatic performances, transparency and impact strength and a molded product prepared by injection molding the resin composition. <P>SOLUTION: This resin composition is prepared by adding a polyetherester- amide and a surfactant to a resin component composed of a styrene resin and a rubber-modified styrene resin having specific constituent monomer units and specific constituent amounts. The resultant resin composition has excellent physical properties balance and transparency and persistent antistatic performances as compared with those of a conventional antistatic resin. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition excellent in antistatic performance, transparency and impact strength, and a molded article obtained by injection molding the resin composition.

[0002]

2. Description of the Related Art Generally, a styrene resin represented by ABS resin is widely used for electric, electronic equipment parts, OA equipment, pachinko parts, etc., and is particularly used for functions and designs which require transparency. For this, transparent ABS is used. On the other hand, styrene-based resin has a high electric resistivity value, so dust may adhere to the molded product, and in electronic equipment, there is a problem that electrostatic charge such as malfunction due to electrified electricity may occur, and antistatic performance is required. Has been done. Therefore,
As these antistatic methods, generally known is a method in which an antistatic agent, carbon black, and metal powder are kneaded into a resin.

The method of kneading an antistatic agent into a resin is effective as a method of imparting antistatic performance, but has a drawback that the antistatic effect is not continuous. On the other hand, the method in which carbon black or metal powder is kneaded has a problem of reducing the appearance, molding processability, and impact strength, although it has a long-lasting antistatic effect. It cannot be used because it loses its characteristic transparency.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a resin composition having excellent antistatic performance, transparency and impact strength, and a molded article obtained by injection molding the resin composition.

[0005]

Means for Solving the Problems In the styrene resin, the present inventors have conducted extensive studies to solve the above problems, and as a result, by adding a specific additive to a specific rubber-modified styrene resin composition. The present invention has been accomplished by finding a resin composition having excellent impact strength without impairing transparency and excellent antistatic performance.

That is, the present invention provides the following (A) component 82.
8 to 94% by mass, (B) component 4 to 17% by mass, and
(C) component characterized by containing 0.2 to 3 parts by mass
Resin composition to be used and injection molding formed by molding the composition
It is a form. Component (A): (I) Styrene-based monomer unit 20 to 80 parts
%, (Meth) acrylic acid ester-based monomer unit 80 to
20% by weight and other vinyls copolymerizable with these monomers
Styrene-based resin consisting of 0 to 10 mass%
40-95 parts by mass of the continuous phase of (II) Styrene-based monomer
20-80% by mass of body unit, (meth) acrylic acid ester
80 to 20 mass% of system monomer units and co-polymerization with these monomers
From 0 to 10% by mass of another polymerizable vinyl monomer unit
20 to 90 parts by mass of the graft branch of the copolymer
Graft copolymerization with 10-80 parts by mass of elastic material
60 to 5 parts by mass of the dispersed phase of the body, and further the dispersed phase
Has a volume average particle diameter of 0.1 to 0.6 μm, and
The difference in the refractive index between the continuous phase and the dispersed phase is 0.05 or less.
Styrene modified resin composition Component (B): (B1) aminocarbo having 6 or more carbon atoms
Acid or lactam, or diamid having 6 or more carbon atoms
Salt of carboxylic acid and dicarboxylic acid, (B2) following formulas (1) to (3)
One or more diol compounds selected from
(However, in the formula, R₁Is an ethylene oxide group, R₂Is ethylene
An oxide group or a propylene oxide group is shown. Y is shared
The bond has an alkylene group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms.
Rukylidene group, cycloalkylidene having 7 to 17 carbon atoms
Group, arylalkylidene group having 7 to 17 carbon atoms, O, S
O, SO₂, CO, S, CF₂, C (CF ₃)₂Or NH
X is hydrogen, an alkyl group having 1 to 6 carbon atoms, halogen
Group, sulfone group or a metal salt thereof. X_LL is 0 or
Is an integer of 1 to 4, m and n are each an integer of 16 or more.
Indicates. )

[Chemical 4]

[Chemical 5]

[Chemical 6] And (B3) a polyetheresteramide (C) component obtained by copolymerizing a dicarboxylic acid having 4 to 20 carbon atoms:
Anionic surfactant and / or non-amine nonionic surfactant

In particular, as component A, (A1) styrene-based monomer unit 20 to 80% by mass, (meth) acrylic acid ester-based monomer unit 80 to 20% by mass, and copolymerizable with these monomers 40 to 95 parts by mass of a styrene-based resin composed of 0 to 10% by mass of another vinyl-based monomer unit, (A2) 20 to 80% by mass of a styrene-based monomer, and 80 of a (meth) acrylic acid ester-based monomer. To 20 to 90% by mass and 20 to 90% by mass of a monomer mixture consisting of 0 to 10% by mass of another vinyl-based monomer copolymerizable with these monomers.
Rubber-modified styrenic resin 5 comprising a polymer polymerized in the presence of ˜80 parts by mass, and having a volume-average dispersed particle diameter of a soft component mainly composed of a rubber-like elastic body of 0.1-0.6 μm. It is preferable to use a rubber-modified styrene-based resin composition consisting of -60 parts by mass and further having a difference in refractive index of 0.05 or less between the styrene-based resin (A1) and the rubber-modified styrene-based resin (A2). .

The component (A1) (A1) is a styrene-based monomer, a (meth) acrylic acid ester-based monomer, and optionally other vinyl-based monomer copolymerizable with these monomers. A styrene resin obtained by copolymerizing a monomer mixture consisting of a monomer is preferable, and (A2) is a styrene monomer in the presence of a rubber-like latex, (meth)
It is preferable to use a rubber-modified styrene resin obtained by emulsion graft polymerization of a monomer mixture consisting of an acrylic acid ester monomer and another vinyl monomer copolymerizable with these monomers. The present inventors have found out.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The styrene resin constituting the continuous phase of the component (A) of the present invention includes a styrene monomer unit, a (meth) acrylic acid ester monomer unit, and another vinyl copolymerizable with these monomers. It is a copolymer composed of system monomer units. The graft copolymer constituting the dispersed phase means a styrene-based monomer unit, a (meth) acrylic acid ester-based monomer unit, and another vinyl-based monomer copolymerizable with these monomers. It is a copolymer obtained by grafting a copolymer composed of units on a rubber-like elastic material.

The styrenic monomer used as the component (A) of the present invention includes styrene, α-methylstyrene, p
-Methyl styrene, o-methyl styrene, m-methyl styrene, ethyl styrene, pt-butyl styrene, chloro styrene, bromo styrene and the like can be mentioned, but preferably styrene and α-methyl styrene, particularly preferably styrene. Is. These styrenic monomers are
They may be used alone or in combination of two or more.

The (meth) acrylic acid ester-based monomer used in the present invention means a methacrylic acid ester such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, methyl acrylate, ethyl acrylate,
Examples thereof include acrylic acid esters such as n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate and octyl acrylate, with methyl methacrylate and n-butyl acrylate being preferred. These (meth) acrylic acid ester-based monomers may be used alone or in combination of two or more kinds.

Other vinyl-based monomers used as other vinyl-based monomers copolymerizable with these monomers as required include acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, fumaronitrile. , Maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. Preferably methacrylic acid,
Acrylonitrile and N-phenylmaleimide.

The rubber-like elastic material used in the present invention includes polybutadiene, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene random copolymer, styrene-isoprene random copolymer and the like. Is mentioned.

The component (A) of the present invention can be copolymerized with 20 to 80% by mass of styrene-based monomer units, 80 to 20% by mass of (meth) acrylic acid ester-based monomer units, and these monomers. 40 to 95 parts by mass of a continuous phase of a styrene resin composed of 0 to 10% by mass of other vinyl-based monomer units, 20 to 80% by mass of styrene-based monomer units, and a (meth) acrylic acid ester-based monomer 20 to 90 parts by mass of a graft branch of a copolymer composed of 80 to 20% by mass of a body unit and 0 to 10% by mass of another vinyl-based monomer unit copolymerizable with these monomers is a rubber-like elastic body 10. A rubber-modified styrenic resin composition comprising 5 to 60 parts by weight of a dispersed phase of a graft copolymer grafted to -80 parts by weight (however, the total amount is 100 parts by weight). The total amount of the continuous phase and the dispersed phase is 100 parts by mass. When the ratio of each monomer unit is out of this range, the transparency of the obtained resin composition is lowered, which is not preferable. Further, when the rubber-like elastic material in the graft copolymer is less than 10 parts by mass, good impact strength cannot be obtained, and when it exceeds 80 parts by mass, transparency is lowered, which is not preferable. Similarly, if the dispersed phase in the rubber-modified styrene-based resin composition is less than 5 parts by mass, good impact strength cannot be obtained, and if it exceeds 60 parts by weight, transparency is lowered, which is not preferable.

Further, the volume average particle diameter of the dispersed phase is from 0.1 to 10.
The thickness of 0.6 μm is preferable for obtaining good transparency and impact strength of the resin composition. Volume average particle size is 0.1
If it is less than μm, the impact strength is lowered, and if it exceeds 0.6 μm, the transparency is lowered, which is not preferable.

Further, the component A of the resin composition of the present invention is
A styrene resin (A1) comprising a styrene monomer unit, a (meth) acrylic acid ester monomer unit and another vinyl monomer unit copolymerizable with these monomers; Rubber-modified styrene obtained by polymerizing a monomer mixture of a monomer, a (meth) acrylic acid ester-based monomer, and another vinyl-based monomer copolymerizable with these monomers in the presence of a rubber-like elastic body. It is preferable to use a rubber-modified styrene-based resin composition containing a resin (A2).

The ratio of the monomer units constituting (A1) is
Styrene-based monomer units 20 to 80% by mass, (meth) acrylic acid ester-based monomer units 80 to 20% by mass, and other vinyl-based monomer units 0 to 20 copolymerizable with these monomers.
It is 10% by mass. When the ratio of each monomer unit is out of this range, the transparency of the resin composition obtained is lowered, which is not preferable.

(A2) is a unit amount consisting of a styrene-based monomer, a (meth) acrylic acid ester-based monomer, and another vinyl-based monomer copolymerizable with these in the presence of a rubber-like elastic material. It is a rubber-modified styrene resin obtained by copolymerizing a body mixture. In this case, (A2) may be a graft copolymer in which each monomer is completely grafted on a rubber-like elastic material, or may be a mixture of a graft copolymer and an ungrafted copolymer. .

The ratio of the monomer units constituting (A2) is
Styrene-based monomer unit 20 to 80% by mass, (meth) acrylic acid ester-based monomer unit 20 to 80% by mass, and other vinyl-based monomer unit 0 to 0, which is copolymerizable with these monomers.
It is 10% by mass. When the ratio of each monomer unit is out of this range, the transparency of the obtained resin composition is lowered, which is not preferable.

The amount of the rubber-like elastic material used in (A2) is 1 in 100 parts by mass of the rubber-modified styrene resin (A2).
It is 0 to 80 parts by mass. If the rubber-like elastic body is less than 10 parts by mass, good impact strength cannot be obtained, and if it exceeds 80 parts by mass, the transparency is lowered, which is not preferable.

In order to obtain good transparency and impact strength of the resin composition, the volume average particle diameter of the dispersed particles of the soft component containing the rubber-like elastic material as the main component is 0.1 to 0.6 μm. Is preferred. If the volume average particle diameter is less than 0.1 μm, the impact strength is lowered, and if it exceeds 0.6 μm, the transparency is lowered, which is not preferable.

The volume average particle size of the dispersed phase is N, N-
It is a volume-based median diameter measured by a light-scattering type particle size distribution analyzer by dispersing the rubber-modified styrene resin composition (A) in dimethylformamide (DMF). The dispersed particle size of the soft component containing the rubber-like elastic body of the rubber-modified styrene resin (A2) as the main component can be measured in the same manner. When the component (A2) is produced by the emulsion graft polymerization method, the particle size distribution, the graft ratio of the styrene resin to the rubber-like elastic body, the gelling degree of the rubber-like elastic body, and the control of characteristics such as swelling degree are controlled. The rubber-modified styrene-based resin (A2) obtained by the emulsion graft polymerization method is used as the rubber-modified styrene-based resin composition (A (A), the dispersed particle diameter of (A) may be replaced by the dispersed particle diameter of the soft component containing the rubber-like elastic body (A2) as a main component.

The mixing ratio of (A1) / (A2) of the component (A) used in the present invention is (A1) / (A2).
= 40/60 to 95/5 mass ratio. (A1) / (A
2) When the mass ratio exceeds 95/5, the impact strength of the obtained resin composition decreases, and the (A1) / (A2) mass ratio is 40 /.
When it is less than 60, the moldability of the obtained resin composition is lowered, which is not preferable. Further, in order to maintain good transparency of the obtained resin composition, the difference between the refractive index of the component (A1) and the refractive index of the component (A2) is preferably 0.05 or less, particularly preferably 0.03 or less.

The method for producing the rubber-modified styrenic resin composition of the present invention is not particularly limited, but the styrenic resin (A
In the production of 1), a bulk polymerization method, a suspension polymerization method, a bulk-suspension polymerization method, a solution polymerization method, and a rubber-modified styrene resin (A
For the production of 2), an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, a bulk-suspension polymerization method, a solution polymerization method or the like can be used, but the emulsion polymerization method can be preferably used. Further, either a batch polymerization method or a continuous polymerization method can be used. When the styrene-based resin (A1) and the rubber-modified styrene-based resin (A2) are used, the separately manufactured products may be mixed in advance as the component (A), or (A) /
You may melt-mix at the time of manufacture of the resin composition of (B) / (C) component. Further, the rubber-modified styrene resin composition of the component (A) of the present invention may be produced by known techniques such as bulk polymerization method, suspension polymerization method, bulk-suspension polymerization method, solution polymerization method and emulsion polymerization method. Good.

In these polymerization methods, azo compounds such as azobisbutyronitrile and azobiscyclohexanecarbonitrile as a polymerization initiator, benzoyl peroxide,
t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxide, dicumyl peroxide, ethyl-3,3
An organic peroxide such as -di- (t-butylperoxy) butyrate can be used. Further, t-dodecyl mercaptan, n-dodecyl mercaptan and 4-methyl-2,4-diphenylpentene-1 were used as molecular weight regulators.
As a plasticizer, diisobutyl adipate, butylbenzyl phthalate, or the like may be added if necessary.

Next, the polyether ester amide (B) used in the present invention will be described. (B1)
Is selected from aminocarboxylic acids or lactams having 6 or more carbon atoms, or salts of diamines and dicarboxylic acids having 6 or more carbon atoms. The aminocarboxylic acid having 6 or more carbon atoms is preferably ω-aminocaproic acid, ω-aminocaprylic acid, ω-aminoenanthic acid or 1,2aminododecanoic acid, and the lactan is preferably caprolactam, enanthlactam or capryllactam. . As the salt of diamine having 6 or more carbon atoms and dicarboxylic acid, hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalate and the like are preferable. Especially caprolactam, 1,2
Aminododecanoic acid and hexamethylenediamine-adipate are preferred.

The diol compound (B2) is represented by the following formulas (1) to (3).

[Chemical 7]

[Chemical 8]

[Chemical 9]

(In the formula, R ₁ is an ethylene oxide group,
R ₂ represents an ethylene oxide group or a propylene oxide group. Y is a covalent bond and is an alkylene group having 1 to 6 carbon atoms, an alkylidene group having 1 to 6 carbon atoms, a cycloalkylidene group having 7 to 17 carbon atoms, an arylalkylidene group having 7 to 17 carbon atoms, O, SO, SO ₂ , CO, S, CF ₂ , C (C
F ₃₎ shows a ₂ or NH, X represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen group, a sulfonic group or a metal salt thereof. _L of XL represents 0 or an integer of 1 to 4, and m and n each represent an integer of 16 or more. )

Specific examples thereof include ethylene oxide and / or propion oxide adducts of bisphenol A, ethylene oxide and / or propylene oxide adducts of 2,2-bis (4,4'-hydroxycyclohexyl) propane, and dimethylbisphenol A. Ethylene oxide and / or propylene oxide adduct, tetramethylbisphenol A ethylene oxide and / or propylene oxide adduct, 2,2-bis (4,4′-)
Hydroxyphenyl-3,3'-sodium sulfonate) propane ethylene oxide and / or propylene oxide adduct, bisphenol S ethylene oxide and / or propylene oxide adduct, 4,4 '-(hydroxy) biphenyl ethylene oxide and / or propylene Oxide adduct, ethylene oxide and / or propylene oxide adduct of bis (4-hydroxyphenyl) sulfide, ethylene oxide and / or propylene oxide adduct of bis (4-hydroxyphenyl) methane, ethylene oxide of bis (4-hydroxyphenyl) amine And / or propylene oxide adduct, ethylene oxide and / or propylene oxide adduct of bis (4-hydroxyphenyl) ether, 1,1-bis (4-hydroxyphenyl) Yl) ethylene oxide and / or propylene oxide adducts of Scicli hexane, 1,
4-dihydroxycyclohexane ethylene oxide and / or propylene oxide adduct, hydroquinone ethylene oxide and / or propylene oxide adduct, dihydroxynaphthalene ethylene oxide and / or
Alternatively, propylene oxide adducts and block copolymers thereof may be mentioned.

Preferred diol compounds are ethylene oxide adducts of hydroquinone, ethylene oxide adducts of bisphenol A, ethylene oxide adducts of bisphenol S, ethylene oxide adducts of dihydroxynaphthalene and block polymers thereof, and particularly ethylene oxide adducts of bisphenol A. And block polymers thereof are preferred.

The dicarboxylic acid component (B3) is preferably a dicarboxylic acid having 4 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid and naphthalene-2,6.
-Dicarboxylic acids, aromatic dicarboxylic acids such as naphthalene-2,7-dicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid, and succinic acid, oxalic acid, adipic acid ,
Sebacic acid, adipic acid and 1,4-cyclohexanedicarboxylic acid are preferred.

The proportions of (B1), (B2) and (B3) used are 25 to 85 parts by mass of (B1) and 15 to 7 of (B2).
0 parts by mass and (B3) are preferably 5 to 60 parts by mass.

The polyether ester amide (B) can be polymerized by, for example, reacting (B1) aminocarboxylic acid or lactam with (B3) dicarboxylic acid to prepare a polyamide prepolymer having carboxylic acid groups at both ends. (B
2) A method of reacting a diol compound under vacuum, or charging each of the compounds (B1), (B2) and (B3) into a reaction tank and reacting at a high temperature to form a dicarboxylic acid-terminated polyamide prepolymer, and then A method of proceeding the polymerization under normal pressure or reduced pressure can be used.

Next, the surfactant (C) used in the present invention will be described. (C) is an anionic surfactant and / or a non-amine nonionic surfactant. When an amine-based nonionic surfactant having each structure of primary amine, secondary amine, and tertiary amine is contained in the resin composition, the resin composition exhibits a yellow hue, resulting in poor appearance and reduced commercial value. Not preferable.

Examples of the anionic surfactant used in the present invention include alkyl sulfonate, alkyl benzene sulfonate, and alkyl sulfate, and the alkyl sulfonate is preferably used. More preferably, it is an alkyl sulfonate having 10 to 14 carbon atoms.

The non-amine nonionic surfactants used in the present invention include polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters such as polyoxyethylene fatty acid esters, monofatty acid glycerin esters, difatty acid glycerin esters, monofatty acid diesters. Examples thereof include glycerin fatty acid esters such as glycerin ester and difatty acid diglycerin ester. Among them, glycerin fatty acid ester is preferably used.

The surfactant used in the present invention may be used alone or in a plurality thereof, but the anionic surfactant / non-amine nonionic surfactant = 0.5 / 99.
It is preferable to use it in a ratio of 5 to 15/85 (mass ratio) in order to obtain excellent antistatic performance.

Next, the resin composition of the present invention will be described. The resin composition of the present invention is (A) component 82.8-9.
4% by mass, component (B) 4 to 17% by mass, component (C) 0.
If it is 2 to 3 mass%, and the component (B) is less than 4 mass%, excellent antistatic performance cannot be obtained, and if it exceeds 17 mass%, the resin composition exhibits a yellow hue, resulting in poor appearance and commercial value. It is not preferable because it is lowered. Further, when the content of the component (C) is less than 0.2% by mass, excellent antistatic performance cannot be obtained, and when it exceeds 3% by mass, the transparency is lowered, which is not preferable. There are no particular restrictions on the method of mixing the components (A), (B) and (C), but for example, after premixing with a known mixing device such as a Henschel mixer or a tumbler mixer, a single screw extruder or By performing melt-kneading using an extruder such as a twin-screw extruder, uniform mixing can be achieved.

Additives may be added to the resin composition of the present invention as needed. For example, a plasticizer, a lubricant, silicone oil and the like can be added to improve fluidity and releasability. Further, in order to impart weather resistance, a light stabilizer or an ultraviolet absorber can be added. In addition, antioxidants, colorants and the like can be added.

Since the resin composition of the present invention is excellent in transparency, impact strength and durable antistatic performance, a translucent game board, a center cover, a protective case, a pachinko machine part such as ball roll, a lighting device.・ Covers for ice makers, printers, shredders, cases such as copying machine trays and cassettes, household goods such as daily sundries and toys, game machines, mobile phones, shavers, radio-cassettes, interiors such as refrigerators and coolers Molded products, ice cream cups, confectionery containers, caps for aerosol products, artificial dialysis parts, lenses,
Suitable for injection molded products such as stationery, nameplates, partition plates, food trays, egg containers, blister packs, insulating plates, IC related magazine rails, IC carrier tapes, lenticular sheets, and other keranders, and (variant) extrusion molded products. .

[0041]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.
All parts and ratios described in the present invention are based on mass unless otherwise specified.

First, the rubber-modified styrene resin compositions (A) and (B) polyether ester amide (B) used in Examples and Comparative Examples are shown. Production of rubber-modified styrene resin composition (A) (1) Styrene resin (A1) Styrene resin (A1) -1 Styrene 25 in a 200 liter capacity autoclave.
0 Kg, methyl methacrylate 75 Kg monomer mixture, benzoyl peroxide 80 as polymerization initiator
g, t-dodecyl mercaptan 150 as a chain transfer agent
After adding g and heating with stirring at a temperature of 95 ° C. for 6 hours and further at a temperature of 130 ° C. for 2 hours, the suspension polymerization was stopped by cooling. After completion of the reaction, washing, dehydration and drying were carried out to obtain a bead-shaped styrene resin (A1) -1. Styrene resin (A
The composition of 1) -1 is shown in Table 1.

Styrenic resin (A1) -2 Bead-like styrene resin (A1) -in the same manner as the styrene resin (A1) -1, except that 23 kg of styrene, 73 kg of methyl methacrylate and 4 kg of acrylonitrile were used. Got 2. Styrene resin (A1)-
The composition of No. 2 is shown in Table 1.

(2) Rubber-modified styrene-based resin (A2) Rubber-modified styrene-based resin (A2) -1 In a 200-liter capacity autoclave, butadiene 6 was added.
5kg, pure water 150kg, potassium oleate 0.5k
g, t-butyl hydroper-oxide 130 g, Rongalit 30 g, ferrous sulfate 2 g, ethylenediaminetetraacetic acid sodium salt 3 g, sodium pyrophosphate 10
0 g and 1 kg of t-dodecyl mercaptan were charged, and polymerization was carried out at a temperature of 45 ° C. for 17 hours. The volume average particle diameter of the obtained butadiene rubber latex was 0.08 μm. To this latex, 5 g of sodium sulfosuccinate was added and stabilized. In addition to this latex,
By adding an aqueous solution of hydrogen chloride under stirring, the latex particles are coagulated and enlarged, and the volume average particle diameter is 0.2 μm.
m rubber latex was obtained. To this latex, 8.4 kg of styrene, 26.6 kg of methyl methacrylate, 40 g of divinylbenzene and 80 g of t-butyl hydroperoxide were added, and polymerization was carried out at a temperature of 60 ° C. for 6 hours. After adding 500 g of t-butylphenol and 500 g of dilaurylthiopropionate to this latex, a copolymer is precipitated with hydrochloric acid, neutralized, washed and dehydrated and dried to obtain a powdery copolymer (A2) -1. Obtained. The composition of the rubber-modified styrene resin (A2) -1 is shown in Table 1.

Rubber-modified styrene resin (A2) -2,
3, 4, 5 Rubber modified with dispersed particles having a volume average particle diameter of 0.12 μm by changing only the aggregation conditions of the rubber latex in the same manner as in the production of the rubber modified styrene resin (A2) -1. Styrene resin (A2) -2, 0.4 μm
Rubber-modified styrenic resin (A2) having dispersed particles of
Rubber-modified styrene-based resin (A2) -4 having dispersed particles of 3, 0.08 μm and rubber-modified styrene-based resin (A2) -5 having dispersed particles of 0.8 μm were obtained. Table 1 shows the compositions of the rubber-modified styrene resin (A2) -2, 3, 4, and 5.

(3) Rubber-modified styrenic resin composition (A) The styrene-based resin (A1) obtained by the above method and the rubber-modified styrene-based resin (A2) were mixed with a Henschel mixer at the compounding ratio shown in Table 2. After mixing, they were melt-kneaded using a twin-screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd., cylinder temperature 220 ° C.) to prepare pellets, and A-1 to 8 were obtained.

(4) Polyether ester amide (B) 50 parts by mass of caprolactam, 35 parts by mass of adduct of ethylene oxide with 32 mol of bisphenol A, and adipic acid 1
Polyether ester amide B was obtained from 5 parts by mass.
The refractive index of this polyether polyamide is 1.520.
Met.

(5) Surfactant (C) -1,2 Dodecyl sulfonate is added to anionic surfactant (C)-
It was set to 1. Diglycerin monostearate was used as the anionic surfactant (C) -2.

Examples 1 to 6 and Comparative Examples 1 to 6 A-1 to 8 obtained by the above method, polyether ester amide B, and surfactant C-1 and C2 at the compounding ratio shown in Table 3. After mixing with a Henschel mixer, a twin-screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd., cylinder temperature 220)
(° C) to melt-knead and prepare pellets to obtain a resin composition. Then, the pellets were injection-molded with a 2-ounce in-line screw injection molding machine (SN-51B manufactured by Niigata Iron Works Co., Ltd., cylinder temperature: 220 ° C.), and physical properties, transparency, and hue were measured using the obtained molding specimen. It was The measured values are shown in Tables 3 and 4.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

The styrene resin (A
1), various measured values constituting the rubber-modified styrene-based resin (A2) and the rubber-modified styrene-based resin composition (A), and the measurement methods and evaluation criteria of the respective physical property values performed will be described below. (1) Amount of rubber-like elastic material in rubber-modified styrenic resin (A2): Measured by an infrared absorption spectrum method generally used for rubber-modified polystyrene. That is, the mass ratio of styrene and butadiene of the rubber-like elastic body is measured in advance by the infrared absorption spectrum method, and then the mass ratio of butadiene of the rubber-modified styrene resin (A2) is measured by the infrared absorption spectrum method. The amount of the rubber-like elastic material in the rubber-modified styrene resin (A2) was determined from both measured values. The infrared absorption spectrum measuring device used was FTS-575C manufactured by Nippon Bio-Rad Laboratories.

(2) Structural unit of the continuous phase in the rubber-modified styrene resin (A2): rubber-modified styrene resin (A2)
Is dissolved in toluene and then centrifuged, and the supernatant is separated and methanol is added to precipitate the styrene polymer. This precipitate was dried, dissolved in deuterated chloroform to prepare a 2% solution, and FT-NMR was used as a measurement sample.
(FX-90Q type manufactured by JEOL Ltd.) was used for 13 C measurement, and calculated from the peak areas of styrene and methyl methacrylate. The styrene-based resin (A1) monomer was also subjected to 13C measurement using FT-NMR (FX-90Q type manufactured by JEOL Ltd.) and calculated from the peak areas of styrene, methyl methacrylate and acrylonitrile.

(3) Method of measuring graft ratio: The precipitate obtained by the above centrifugal separation operation was dried by a vacuum dryer to obtain an insoluble content X. Further, the mass Y of styrene and the mass Z of methylmethacrylate quantified by pyrolysis gas chromatography using the sample of this insoluble matter were determined, and the graft ratio (%) = 100 × (Y + Z) / {X− (Y + Z) } It calculated from the formula of.

(4) Volume average particle diameter of dispersed particles containing rubber-like elastic material as a main component: rubber-modified styrene resin (A2)
About 1 g of N, N-dimethylformamide (DMF) 10
The mixture is stirred in 0 g for 24 hours, added with DMF, diluted to an appropriate concentration, measured with a light scattering type particle size distribution measuring device (LS230 type, manufactured by COULTER), and shown as a volume-based median diameter.

(5) Measurement of refractive index: styrene resin (A
1) A 0.5 mm-thick test piece was prepared using a press molding machine, and a digital refractometer RX-2000 (manufactured by ATAGO) was used.
Was measured at a temperature of 25 ° C. A saturated aqueous solution of potassium iodide was used as the contact liquid. Further, the polyether ester amide B was measured in the same manner. Further, since it is difficult to measure the refractive index of the rubber-modified styrene resin composition (A) and the rubber-modified styrene resin (A2), the composition ratio of the monomer units constituting (A2) is measured by composition analysis. Then, the refractive index is calculated by using the following equation 1. n = X _A × n _A + X _B × n _B + X _C × n _C + ··· Formula 1 That is, the composition of the monomer unit constituting the rubber-modified styrene resin (A2) is Am monomer: X _A , Bm monomer:
X _B and Cm monomer: When composed of X _C (however, in mass ratio X _A + X _B + X _C = 1), n _A is the refractive index of the polymer composed of the Am monomer, and n _B is the Bm monomer. , N _C is the refractive index of the polymer composed of the Cm monomer, and the refractive index of the styrene monomer, the methyl methacrylate monomer, the acrylonitrile monomer, and the butadiene monomer are respectively represented. , 1.595, 1.494, 1.516,
It was set to 1.518.

(6) IZOD impact strength:
According to ASTM D256, 12.7 × 64 × 6.
Make a notch with a depth of 2.54 mm in a 4 mm thick test piece,
The impact speed was measured at 3.46 m / sec.

(7) Haze: Measured in accordance with ASTM D1003 using a test piece having an injection molded body of 30 × 90 × 2 mm thickness.

(8) Total light transmittance: ASTM D100
In accordance with No. 3, the measurement was performed using a test piece having an injection molded body of 30 × 90 × 2 mm thickness.

(9) YI (yellowness): JIS-K710
In accordance with No. 3, the measurement was performed using a test piece having an injection molded body of 30 × 90 × 2 mm thickness. Table 5 shows the relationship between YI and hue.

[0063]

[Table 5]

(10) Antistatic effect: The antistatic effect is
An injection-molded square plate having a thickness of 2 mm was used to evaluate the surface specific resistance value measured under the following two conditions. (A) Immediately after molding: The rectangular plate immediately after molding was washed in pure water for 1 minute, sufficiently dried, and then conditioned at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours in accordance with JIS K-6911. The surface specific resistance value was measured. (B) Immediately after being left for 300 days: the formed square plate is heated to 23 °
After leaving it in a humidity of 50% RH for 300 days, in pure water 1
After washing for a minute and thoroughly drying, JIS K-6911
In accordance with the above, the surface specific resistance value was measured by controlling the humidity at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours. The surface specific resistance (Ω) in the present invention is a level at which the antistatic effect is extremely excellent, and the target was 10 ¹⁰ or less. Therefore, the resin composition of the present invention and the molded article thereof are suitably used for materials that require stricter antistatic performance.

[0065]

According to the present invention, a polyether ester amide and a surfactant are mixed with a resin component composed of a styrene resin having a specific constituent monomer unit and a constituent amount and a rubber-modified styrene resin. Thus, it is possible to obtain a resin composition having excellent physical property balance and transparency as compared with a conventional antistatic resin and having a durable antistatic property.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/00 C08K 5/00 C08L 51/04 C08L 51/04 // (C08L 25/14 77:12 77 : 12) (72) Inventor Kazuyoshi Ebe No. 6 Goi Minamikaigan, Ichihara, Chiba Denki Kagaku Kogyo Co., Ltd. Chiba factory F term (reference) 2C088 BC63 4F071 AA10 AA22 AA22X AA33 AA33X AA57 AA77 AC10 AC14 AE10 AF23 AF30 AF31Y AF38 AF39Y AH16 AH19 BA01 BB05 BC07 BC10 4J001 DA04 DB02 DB05 DC03 DC05 DC14 EA02 EA06 EA14 EA15 EA17 EB03 EB04 EB06 EB08 EB14 EB35 EB36 EB37 EB46 EC08 ED24 ED34 ED36 ED45 ED46 ED47 ED48 ED49 ED50 ED64 ED65 EE30E EE72E FA01 FA03 FB01 FB03 FB06 FC01 FC03 FD01 GA12 GB14 HA01 JA01 JA07 JB22 JB36 JB38 JB41 JB42 JC02 4J002 BC07W BG04W BG05W BN16X CH024 CL083 EH056 EV246 FD314 FD316 GC00 GG00 GQ00 4J026 AA68 AC 10 AC11 AC16 AC32 BA05 BA06 BA07 BA25 BA27 BA31 BA38 BB03 BB04 DA04 DA07 DA12 DA15 DA16 DB04 DB08 DB12 DB15 DB26 FA03 FA07 GA09

Claims (8)

[Claims] 1. The following component (A), 82.8 to 94 mass%,
(B) component 4 to 17% by mass, and (C) component 0.2 to 3
A resin composition characterized by containing mass%. Component (A): (I) Styrene-based monomer unit 20 to 80 parts
%, (Meth) acrylic acid ester-based monomer unit 80 to
20% by weight and other vinyls copolymerizable with these monomers
Styrene-based resin consisting of 0 to 10 mass%
40-95 parts by mass of the continuous phase of (II) Styrene-based monomer
20-80% by mass of body unit, (meth) acrylic acid ester
80 to 20 mass% of system monomer units and co-polymerization with these monomers
From 0 to 10% by mass of another polymerizable vinyl monomer unit
20 to 90 parts by mass of the graft branch of the copolymer
Graft copolymerization with 10-80 parts by mass of elastic material
60 to 5 parts by mass of the dispersed phase of the body, and further the dispersed phase
Has a volume average particle diameter of 0.1 to 0.6 μm, and
The difference in the refractive index between the continuous phase and the dispersed phase is 0.05 or less.
Styrene modified resin composition Component (B): (B1) aminocarbo having 6 or more carbon atoms
Acid or lactam, or diamid having 6 or more carbon atoms
Salt of carboxylic acid and dicarboxylic acid, (B2) following formulas (1) to (3)
One or more diol compounds selected from
(However, in the formula, R₁Is an ethylene oxide group, R₂Is ethylene
An oxide group or a propylene oxide group is shown. Y is shared
The bond has an alkylene group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms.
Rukylidene group, cycloalkylidene having 7 to 17 carbon atoms
Group, arylalkylidene group having 7 to 17 carbon atoms, O, S
O, SO₂, CO, S, CF₂, C (CF ₃)₂Or NH
X is hydrogen, an alkyl group having 1 to 6 carbon atoms, halogen
Group, sulfone group or a metal salt thereof. X_LL is 0 or
Is an integer of 1 to 4, m and n are each an integer of 16 or more.
Indicates. ) [Chemical 1] [Chemical 2] [Chemical 3] , And (B3) a dicarboxylic acid having 4 to 20 carbon atoms.
Polymerized polyetheresteramide (C) anio
Surfactant and / or non-amine nonionic surfactant
Agent 2. The component (A) comprises (A1) 20 to 80% by mass of a styrene-based monomer unit, 80 to 20% by mass of a (meth) acrylic acid ester-based monomer unit, and these monomers. 40 to 95 parts by mass of a styrene-based resin composed of 0 to 10% by mass of another polymerizable vinyl-based monomer unit, (A2) 20 to 80% by mass of a styrene-based monomer, and a (meth) acrylic acid ester-based monomer. 20 to 90 parts by mass of a monomer mixture consisting of 80 to 20% by mass of a monomer and 0 to 10% by mass of another vinyl-based monomer copolymerizable with these monomers is added to the rubber-like elastic material 10 to
A rubber-modified styrenic resin 5 comprising a polymer polymerized in the presence of 80 parts by mass and having a volume-average dispersed particle diameter of a soft component mainly composed of a rubber-like elastic body of 0.1 to 0.6 μm. And a rubber-modified styrene-based resin composition having a difference in refractive index of 0.05 or less between the styrene-based resin (A1) and the rubber-modified styrene-based resin (A2). The resin composition according to claim 1. 3. The component (A2) (A2) can be copolymerized with a styrene monomer unit, a (meth) acrylic acid ester monomer unit and these monomers in the presence of a rubber latex. The resin composition according to claim 2, which is a rubber-modified styrene-based resin obtained by emulsion-grafting a monomer mixture containing another vinyl-based monomer unit. 4. The difference between the refractive index of the rubber-modified styrenic resin composition as the component (A) and the refractive index of the component (B) is within 0.05, which is any one of claims 1 to 3. The resin composition according to item 1. 5. The component (C) is an anionic surfactant /
Non-amine nonionic surfactant = 0.5 / 99.5-
It is a ratio of 15/85 (mass ratio), The resin composition of any one of Claims 1-4 characterized by the above-mentioned. 6. The component (C), wherein the anionic surfactant is an alkyl sulfonate having 10 to 14 carbon atoms, and the non-amine nonionic surfactant is a glycerin fatty acid ester. The resin composition described. 7. The surface specific resistance value obtained by injection molding the resin composition according to claim 1 is 10 ⁹
A molded body having a resistance of 10 ¹⁰ Ω. 8. A pachinko machine base component formed by injection molding according to claim 7.