KR101217582B1 - Thermoplastic resin composition and molded article - Google Patents

Abstract

The following (A) component contains 5-100 mass% and (B) component 95-0 mass%, Comprising: (The sum total of the said (A) component and (B) component is 100 mass%), Furthermore, following (C1 ) 0.5-100 mass parts is contained with respect to a total of 100 mass parts of said (A) component and (B) component, The thermoplastic resin composition characterized by the above-mentioned. (A) component: Styrene-type resin formed by (co) polymerizing an aromatic vinyl compound or another vinyl monomer copolymerizable with an aromatic vinyl compound and an aromatic vinyl compound in presence or absence of a rubbery polymer, (B) component: An olefin type Resin, (C1) component: The block copolymer containing an olefin polymer block (c1-1) and a hydrophilic polymer block (c1-2). The composition provides a molded article excellent in impact resistance, chemical resistance, surface appearance of the molded article, and antistatic or antistatic property.

Description

Thermoplastic composition and molded article {THERMOPLASTIC RESIN COMPOSITION AND MOLDED ARTICLE}

The present invention relates to a thermoplastic resin composition excellent in impact resistance, chemical resistance, surface appearance of a molded article, and antistatic or antistatic property, and a molded article made of the thermoplastic resin composition.

Styrene-based resins such as ABS resins are widely used in electric and electronic fields, OA and home appliances, vehicles, and sanitary fields because of their excellent mechanical strength such as impact resistance, moldability, and rigidity, and excellent surface appearance of molded products. Depending on the intended use, chemical resistance was not sufficient, and further improvement in chemical resistance was required.

On the other hand, since olefin resins such as polypropylene are excellent in chemical resistance, heat resistance, fluidity, and the like, they are widely used in the electric / electronics field, OA / home appliances, vehicle field, and sanitary field like the styrene resins. The impact property was low, and there existed a problem of being easy to generate | occur | produce a curvature and a sink in a molded article. In addition, there was a problem that the change with time such as physical properties and dimensions after molding was large.

For the purpose of improving the above problem, mixing ABS resin and polypropylene is considered, but both materials are poor in compatibility, and only a material which is very easily broken by simple melt mixing is obtained. Although patent document 1 proposes to exist a styrene-butadiene block copolymer rubber when mix | blending a polystyrene resin and a polypropylene resin, there is no description of the example which mix | blended polypropylene with ABS resin, AS resin, etc. Patent Document 2 proposes blending a hydrogenated styrene-butadiene block copolymer when blending a polyolefin-based resin with a polystyrene-based resin, but examples of blending polyolefin-based resins with ABS resins, AS resins and the like are not disclosed. not. Patent Literature 3 proposes a composition composed of a polyolefin resin, a low molecular weight polystyrene, and a styrene-butadiene block copolymer, but an example in which an ABS resin, an AS resin, or the like is blended is not described.

In addition, Patent Document 4 proposes to use a styrene resin modified with an epoxy-modified polypropylene and an unsaturated carboxylic acid or anhydride as a compatibilizer, and Patent Document 5 discloses a polypropylene resin modified with an epoxy group and unsaturated. It has been proposed to use styrene-butadiene-styrene block copolymers modified with carboxylic acid or anhydrides thereof, but the impact resistance and the molded article surface appearance are insufficient. Moreover, the molded article is easy to be charged, and it is difficult to be used for the purpose of causing static interference.

In addition, since both styrene resins such as ABS resins and polyolefin resins such as polypropylene have a property of being easily charged, failures caused by static electricity, such as liquid crystal display devices, plasma displays, peripheral members of semiconductors, Application to various parts, sheets, films, and the like used or handled in clean rooms has been difficult.

In order to improve such a fault, although patent document 9 mix | blended polyamide elastomer with styrene resins, such as ABS resin, there existed a problem that antistatic property was not fully expressed. Similarly, Patent Documents 10 and 11 disclose compositions containing rubber-reinforced styrene resins and polyamide elastomers. Moreover, although it is proposed to mix | blend a specific antistatic agent with polyolefin resin in patent document 6 and patent document 7, there existed a problem, such as lack of antistatic persistence and insufficient antistatic property. In addition, Patent Documents 8 and 12 propose to mix a block copolymer having blocks of polyolefins and hydrophilic polymer blocks such as polyethers in polyolefin resins as a method of maintaining antistatic properties. There was a problem.

Patent Document 1: Japanese Patent Publication No. 52-17055

Patent Document 2: Japanese Patent Application Laid-open No. 56-38338

Patent Document 3: Japanese Patent Application Laid-open No. 56-104978

Patent Document 4: Japanese Patent Application Laid-Open No. 1-174550

Patent Document 5: Japanese Patent Application Laid-Open No. 4-266953

Patent Document 6: Japanese Patent Application Laid-Open No. 4-258647

Patent Document 7: Japanese Patent Application Laid-Open No. 2000-313875

Patent Document 8: Japanese Patent Application Laid-Open No. 2001-278985

Patent Document 9: Japanese Patent Application Laid-Open No. 60-23435

Patent Document 10: Japanese Patent Application Laid-Open No. 4-309547

Patent Document 11: Japanese Patent Application Laid-Open No. 2-292353

Patent Document 12: Japanese Patent Application Laid-Open No. 2002-284880

An object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance, chemical resistance, molded article surface appearance, and antistatic or antistatic property, and a molded article using the thermoplastic resin composition.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, and, as a result, mix | blending a block copolymer containing an olefin polymer block and a hydrophilic polymer block with the thermoplastic resin composition containing a styrene resin and / or an olefin resin, It was found out that a molded article excellent in chemical resistance, molded article surface appearance and antistatic properties could be obtained, and thus the present invention was completed. Furthermore, by further blending a specific antistatic compound and / or a modified molecular weight polymer having a specific block structure or a low molecular weight polyolefin, it has been found that properties such as impact resistance, antistatic property, etc. are improved, and the present invention has been completed.

That is, according to one aspect of the present invention, the composition comprises 5 to 100% by mass of the following (A) component and 95 to 0% by mass of the component (B), provided that the sum of the components (A) and (B) Is 100% by mass),

Moreover, 0.5-100 mass parts of following (C1) components are contained with respect to a total of 100 mass parts of said (A) component and (B) component, The thermoplastic resin composition (henceforth "the first thermoplastic resin composition"). Is provided).

(A) component: Styrene-type resin formed by (co) polymerizing an aromatic vinyl compound or another vinyl monomer copolymerizable with an aromatic vinyl compound in presence or absence of a rubbery polymer,

(B) component: olefin resin,

(C1) component: The block copolymer containing an olefin polymer block (c1-1) and a hydrophilic polymer block (c1-2).

According to a preferred embodiment of the present invention, at least one component selected from the group consisting of the following (C2-1) component, (C2-2) component, (C2-3) component and (C2-4) component The said 1st thermoplastic resin composition which contains 0.001-60 mass parts with respect to a total of 100 mass parts of said (A) component and (B) component is provided.

(C2-1) Component: polyether polyamide and / or polyether polyester

(C2-2) Component: Nonionic antistatic agent,

(C2-3) component: a boron compound,

(C2-4) Component: Lithium salt.

Furthermore, according to another preferred embodiment of the present invention, at least one component selected from the group consisting of the following (D) component, (E) component, (F) component and (G) component is selected from the above-mentioned (A) component and The said 1st thermoplastic resin composition which contains 1-200 mass parts with respect to a total of 100 mass parts of (B) component is provided.

Component (D): a block copolymer (Da) containing a polymer block (d-1) mainly composed of an aromatic vinyl compound and a polymer block (d-2) mainly composed of a conjugated diene compound, and a hydrogenated substance (Db) thereof At least one polymer selected from the group,

(E) component: The graft polymer formed by (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound, and the other vinyl monomer copolymerizable with an aromatic vinyl compound in presence of the said (D) component,

(F) component: The aromatic polycarbonate block copolymer which consists of a polymer block (f-1) which consists of said (D) component, and an aromatic carbonate polymer block (f-2),

(G) Component: Low molecular weight polyolefin modified with unsaturated acid and / or unsaturated acid anhydride.

In the first thermoplastic resin composition, at least one component selected from the group consisting of the (D) component, the (E) component, the (F) component, and the (G) component is the component (C2-1), ( You may use together with at least 1 sort (s) of component chosen from the group which consists of a C2-2) component, (C2-3) component, and (C2-4) component.

Moreover, according to another preferable embodiment of this invention, the said 1st thermoplastic resin composition consists of 5-95 mass% of said (A) component, and 95-5 mass% of (B) component (However, (A) The sum total of a component and (B) component is 100 mass%).

Moreover, according to another situation of this invention, it consists of following 70-97 mass% of (B) components and 30-3 mass% of (C1) components, provided that the said (B) component and (C1) component total Is 100% by mass),

Moreover, 0.01-10 mass parts of following (C2-2) component is contained with respect to a total of 100 mass parts of said (B) component and (C1) component, The thermoplastic resin composition (henceforth "the second thermoplastic resin) Composition "is provided.

(B) component: olefin resin,

(C1) component: The block copolymer containing an olefin polymer block (c1-1) and a hydrophilic polymer block (c1-2),

(C2-2) Component: Nonionic antistatic agent.

The second thermoplastic resin composition comprises at least one component selected from the group consisting of the (C2-1) component, the (C2-3) component and the (C2-4) component with respect to 100 parts by mass of the (B) component. You may contain 0.001-60 mass parts further.

Moreover, according to another situation of this invention, it consists of containing 30-96 mass% of following (B) components, 3-30 mass% of following (C1) components, and 1-40 mass% of following (D) components, provided , The total of the (B) component, (C1) component and (D) component is 100% by mass),

Moreover, 0.01-10 mass parts of following (C2-2) components are contained with respect to a total of 100 mass parts of said (B) component, (C1) component, and (D) component, The thermoplastic resin composition (henceforth, The "third thermoplastic resin composition" is provided.

(B) component: olefin resin,

(C1) component: The block copolymer containing an olefin polymer block (c1-1) and a hydrophilic polymer block (c1-2),

Component (D): a block copolymer (Da) containing a polymer block (d-1) mainly composed of an aromatic vinyl compound and a polymer block (d-2) mainly composed of a conjugated diene compound, and a hydrogenated substance (Db) thereof At least one polymer selected from the group,

(C2-2) Component: Nonionic antistatic agent.

The third thermoplastic resin composition comprises at least one component selected from the group consisting of the (C2-1) component, the (C2-3) component and the (C2-4) component with respect to 100 parts by mass of the (B) component. You may contain 0.001-60 mass parts further.

Each of the second and third thermoplastic resin compositions can be used as a molding material per se, and can also be used as a raw material when producing the first thermoplastic resin composition.

And according to another aspect of this invention, the molded article which consists of at least any one of said 1st-3rd thermoplastic resin composition is provided. This molded article may be a sheet or a film.

Thus, according to still another aspect of the present invention, there is provided a multilayer molded article formed by laminating a sheet or film made of at least one of the first to third thermoplastic resin compositions on at least one surface of a substrate. According to a preferred embodiment, the base material is a sheet or a film made of an olefin resin.

The thermoplastic resin composition of the present invention is characterized in that the block copolymer of the component (C1) is contained in the thermoplastic resin composition containing the styrene resin of the component (A) and / or the olefin resin of the component (B). By containing an antistatic compound and / or a modified polymer of a low molecular weight polyolefin having a specific block structure, a molded article excellent in impact resistance, chemical resistance, molded article surface appearance and antistatic to antistatic properties is obtained.

Hereinafter, the present invention will be described in detail. In addition, in this specification, "(co) polymerization" means homopolymerization and / or copolymerization, "(meth) acryl" means acryl and / or methacryl, and "(meth) acrylate" By acrylate is meant acrylate and / or methacrylate.

[1] the component (A)

The styrene-based resin (A) according to the present invention comprises a vinyl monomer (b) containing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with an aromatic vinyl compound in the presence or absence of the rubbery polymer (a). It is a polymer obtained by (co) polymerization, and it is preferable to contain at least 1 sort (s) of the graft | copolymerized (co) polymerized in presence of a rubbery polymer (a) from the point of impact resistance. Content of a rubbery polymer (a) makes styrene resin (A) 100 mass%, Preferably it is 3-80 mass%, More preferably, it is 5-70 mass%, Especially preferably, it is 10-60 mass%. .

Although it does not specifically limit as said rubbery polymer (a), Polybutadiene, butadiene styrene copolymer, butadiene acrylonitrile copolymer, ethylene propylene copolymer, ethylene propylene non-conjugated diene copolymer, ethylene butene-1 Copolymers, ethylene butene-1, non-conjugated diene copolymers, acrylic rubbers, silicone rubbers, silicone acrylic IPN rubbers, and the like are listed, and these may be used alone or in combination of two or more thereof.

Among these, polybutadiene, butadiene styrene copolymer, ethylene propylene copolymer, ethylene propylene nonconjugated diene copolymer, acrylic rubber and silicone rubber are preferable. As for the butadiene styrene copolymer used here, copolymers other than a block copolymer, especially copolymers other than following (D) component, especially random copolymer are used.

Although the gel content rate of the said rubbery polymer (a) is not specifically limited, When obtaining (a) component by emulsion polymerization, gel content rate becomes like this. Preferably it is 98 mass% or less, More preferably, it is 40-98 mass%. In this range, the thermoplastic resin composition which gives especially the molded article excellent in impact resistance can be obtained.

Moreover, the said gel content rate can be calculated | required by the method shown below. That is, 1 g of a rubbery polymer was added to 100 ml of toluene, and after standing at room temperature for 48 hours, the toluene insoluble content and the wire mesh filtered through a 100 mesh wire mesh (with a mass of ₁ gram W) were vacuum dried at 80 ° C. for 6 hours. It weighs (it is referred to as mass W ₂ grams), and is computed by following formula (1).

Gel content (mass%) = [{W ₂ (g) -W ₁ (g)} / 1 (g)] x 100. (One)

Gel content rate is adjusted by setting suitably the kind and quantity of a molecular weight modifier, superposition | polymerization time, superposition | polymerization temperature, superposition | polymerization conversion ratio, etc. at the time of manufacture of a rubbery polymer.

As an aromatic vinyl compound which comprises the said vinyl monomer (b), styrene, (alpha) -methylstyrene, hydroxy styrene, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Moreover, styrene and (alpha) -methylstyrene are preferable among these.

Other vinyl monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds and other various functional group-containing unsaturated compounds. Preferably, the vinyl monomer (b) has an aromatic vinyl compound as an essential monomer component, and if necessary, one or two selected from the group consisting of vinyl cyanide compounds, (meth) acrylic acid ester compounds and maleimide compounds. The above is used together as a monomer component, and at least 1 type of other various functional group containing unsaturated compounds is used together as a monomer component as needed. Examples of the various functional group-containing unsaturated compounds include unsaturated acid compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, substituted or unsubstituted amino group-containing unsaturated compounds, and the like. Said various functional group containing unsaturated compounds can be used individually by 1 type or in combination of 2 or more types.

Acrylonitrile, methacrylonitrile, etc. are mentioned as a vinyl cyanide compound used here, These can be used individually by 1 type or in combination of 2 or more type. When a vinyl cyanide compound is used, chemical resistance is provided. When using a vinyl cyanide compound, the usage-amount is preferably 1-60 mass% in the (b) component, More preferably, it is 5-50 mass%.

Examples of the (meth) acrylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate, and these may be used alone or in combination of two or more thereof. have. It is preferable to use a (meth) acrylic acid ester compound because the surface hardness is improved. When using a (meth) acrylic acid ester compound, the usage-amount is preferably 1-80 mass% in the (b) component, More preferably, it is 5-80 mass%.

As a maleimide compound, maleimide, N-phenylmaleimide, N-cyclohexyl maleimide, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more type. Moreover, in order to introduce a maleimide unit, you may imidize after copolymerizing maleic anhydride. When a maleimide compound is used, heat resistance is provided. When using a maleimide compound, the usage-amount is preferably 1-60 mass% in the (b) component, More preferably, it is 5-50 mass%.

The unsaturated acid compounds include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and the like, and these may be used alone or in combination of two or more thereof.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and the like, and these may be used alone or in combination of two or more thereof.

The hydroxyl group-containing unsaturated compound is 3-hydroxy-1-propane, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy 2-methyl-1-propane, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N- (4-hydroxyphenyl) maleimide, and the like, and the like, and these are used alone or in combination of two. The above can be used in combination.

Vinyl oxazoline etc. are mentioned as an oxazoline group containing unsaturated compound, These can be used individually by 1 type or in combination of 2 or more type.

Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like, and these may be used alone or in combination of two or more thereof.

Substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, acrylamine and meta Krillamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-amino styrene, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

When using the said other various functional group containing unsaturated compound, when styrene resin and another polymer are mixed, compatibility of both can be improved. Preferred monomers for achieving this effect are epoxy group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds and hydroxyl group-containing unsaturated compounds, more preferably hydroxyl group-containing unsaturated compounds, particularly preferably 2-hydroxyethyl (meth) acrylate. .

As for the usage-amount of the said other various functional group containing unsaturated compound, 0.1-20 mass% is preferable with respect to the whole styrene resin as a total amount of the said functional group containing unsaturated compound used in styrene resin, and 0.1-10 mass% is more preferable.

The amount of the monomer other than the aromatic vinyl compound in the vinyl monomer (b) is preferably 80 mass% or less, more preferably 60 mass% or less, particularly preferably when the total amount of the vinyl monomer (b) is 100 mass%. Is 40 mass% or less. More preferred combinations of monomers constituting the vinyl monomer (b) are styrene / acrylonitrile, styrene / methyl methacrylate, styrene / acrylonitrile / methyl methacrylate, styrene / acrylonitrile / glycidyl methacrylate. , Styrene / acrylonitrile / 2-hydroxyethyl methacrylate, styrene / acrylonitrile / (meth) acrylic acid, styrene / N-phenylmaleimide, styrene / methyl methacrylate / cyclohexylmaleimide, etc. Particularly preferred combinations of monomers polymerized in the presence of (a) are styrene / acrylonitrile = 65/45 to 90/10 (mass ratio), styrene / methyl methacrylate = 80/20 to 20/80 (mass ratio), styrene It is arbitrary in the range of 20-80 mass% of styrene amounts, acrylonitrile, and methyl methacrylate in 20-80 mass% in / acrylonitrile / methyl methacrylate.

(A) component of this invention can be manufactured by well-known polymerization method, such as emulsion polymerization, block polymerization, solution polymerization, suspension polymerization, and the polymerization method which combined these. Among these, the preferable polymerization method of the polymer obtained by (co) polymerizing a vinyl monomer (b) in presence of a rubbery polymer (a) is emulsion polymerization and solution polymerization. On the other hand, the preferable polymerization method of the polymer obtained by (co) polymerizing a vinyl monomer (b) in the absence of a rubbery polymer (a) is block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

When prepared by emulsion polymerization, polymerization initiators, chain transfer agents, emulsifiers and the like can be used, but these can all be known.

Examples of the polymerization initiator include cumene hydroperoxide, p-mentane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, tert-butylhydroperoxide, potassium persulfate, azobisisobutyronitrile, and the like. Listed.

In addition, it is preferable to use a redox system such as various reducing agents, sugar pyrrolate-containing prescription, sulfoxylate prescription, and the like as the polymerization initiator.

Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, and terpinolenes.

Examples of the emulsifier include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, potassium lauryl acid, higher fatty acid salts such as potassium stearate, potassium oleate and potassium palmitate, and potassium rosinate. Rosinates and the like can be used.

Further, in the emulsion polymerization, the method of using the rubbery polymer (a) and the vinyl monomer (b) may be polymerized by adding the vinyl monomer (b) collectively in the presence of the total amount of the rubbery polymer (a), or by dividing or continuous addition. May be polymerized. In addition, a part of rubbery polymer (a) may be added during the polymerization.

After emulsion polymerization, the latex obtained is usually solidified with a coagulant, washed with water and dried to obtain the powder of component (A) of the present invention. At this time, after mixing the latex of 2 or more types of (A) component obtained by emulsion polymerization suitably, you may solidify. As the coagulant used herein, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, or acids such as sulfuric acid, hydrochloric acid, acetic acid, quenoic acid, and malic acid can be used.

The solvent which can be used when preparing component (A) by solution polymerization is an inert polymerization solvent used in normal radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene, toluene, ketones such as methyl ethyl ketone, acetone, aceto Nitrile, dimethylformamide, N-methylpyrrolidone and the like.

Polymerization temperature becomes like this. Preferably it is 80-140 degreeC, More preferably, it is the range of 85-120 degreeC.

A polymerization initiator may be used during the polymerization, or may be polymerized by thermal polymerization without using a polymerization initiator. As the polymerization initiator, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxyester, hydroperoxide, azobisisobutyronitrile and benzoyl peroxide are preferably used.

In addition, when a chain transfer agent is used, mercaptans, terpinolenes, (alpha) -methylstyrene dimer, etc. can be used, for example.

In addition, when prepared by block polymerization or suspension polymerization, polymerization initiators, chain transfer agents and the like described in solution polymerization may be used.

The amount of monomer remaining in the component (A) obtained by each polymerization method is preferably 10,000 ppm or less, and more preferably 5,000 ppm or less.

Moreover, as a polymer component obtained by superposing | polymerizing a vinyl monomer (b) in presence of a rubbery polymer (a), the copolymer which the said vinyl monomer (b) graft-copolymerized with the rubbery polymer (a) and the graft copolymer which are not grafted with rubbery polymer are usually used. Graft components [(co) polymers of the vinyl monomers (b)] are included.

The graft ratio of the above-mentioned (A) component becomes like this. Preferably it is 20-200 mass%, More preferably, it is 30-150 mass%, Especially preferably, it is 40-120 mass%, The graft rate is calculated | required by following formula (2). Can be.

Graft ratio (mass%) = {(T-S) / S} × 100. (2)

In the formula (2), T is added 1 g of component (A) to 20 ml of acetone (however, if the rubbery polymer (a) uses acrylic rubber), 20 ml of acetone is vibrated with a shaker for 2 hours. Centrifuged for 60 minutes in a centrifugal separator (rotation speed: 23,000 rpm) to obtain an insoluble content (g) obtained by separating an insoluble content and a soluble content, and S is the mass (g) of the rubbery polymer contained in 1 g of component (A). )to be.

In addition, the acetone of the component (A) according to the present invention (however, when the rubbery polymer (a) uses an acrylic rubber, acetonitrile) the intrinsic viscosity [η] of the soluble component (methyl ethyl ketone is used as the solvent, Measurement at 30 ° C) is preferably 0.2 to 1.2 mW / g, more preferably 0.2 to 1.0 mW / g, and particularly preferably 0.3 to 0.8 mW / g.

The average particle diameter of the grafted rubbery polymer particles dispersed in the component (A) according to the present invention is preferably 500 to 30,000 mm 3, more preferably 1,000 to 20,000 mm 3, particularly preferably 1,500 to 8,000 mm 3. The average particle diameter can be measured by a well-known method using an electron microscope.

The usage-amount of (A) component which comprises the 1st thermoplastic resin composition of this invention is 5-100 mass% in 100 mass% of total of (A) component and (B) component of this invention, Preferably it is 5-98 mass %, More preferably, it is 10-98 mass%, More preferably, it is 15-95 mass%, More preferably, it is 15-93 mass%, Especially preferably, it is 15-90 mass%, When it is less than 5 mass% There exists a tendency for impact resistance to deteriorate and antistatic property falls.

[2] the component (B)

The olefin resin (B) which concerns on this invention is a polymer containing at least 1 sort (s) of C2-C10 olefins as a structural monomer unit. It is preferable that this olefin resin shows crystallinity at room temperature by X-ray diffraction, More preferably, crystallinity is 20% or more, and has melting | fusing point of 40 degreeC or more. Moreover, this olefin resin needs sufficient molecular weight as resin for shaping | molding at normal temperature.

For example, when propylene is a main component, the melt index measured according to JIS K-6758 is preferably 0.01 to 500 g / 10 minutes, more preferably 0.05 to 100 g / 10 minutes.

Examples of olefins that are constituent monomers of the olefin resins include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, and 3-methylhexene-1. Α-olefins such as these are listed, and preferably ethylene, propylene, butene-1, 3-methylbutene-1 and 4-methylpentene-1. In addition, polymers other than non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and 1,9-decadiene It can be used as part of the component.

As at least a part of the olefin resin (B) used in the present invention, one depolymerized with a polymerization catalyst or one modified with an epoxy group, an amino group, a substituted amino group, a carboxyl group, an acid anhydride group, an oxazoline group, or a hydroxyl group may be used. .

The usage-amount of (B) component which comprises the 1st thermoplastic resin composition of this invention is 0-95 mass% in 100 mass% of total of (A) component and (B) component of this invention, Preferably it is 2-95 mass %, More preferably, it is 5-90 mass%, More preferably, it is 7-90 mass%, Especially preferably, it is 10-85 mass%, When it exceeds 95 mass%, impact resistance will deteriorate and antistatic property will be There is a tendency to decrease.

The usage-amount of (B) component which comprises the 2nd thermoplastic resin composition of this invention is 70-97 mass% in 100 mass% in total of the said (B) component and following (C1) component, Preferably it is 75-96 mass% More preferably, it is 77-96 mass%. If the amount is less than 70% by mass, the chemical resistance is degraded. If the amount is more than 97% by mass, the antistatic property and the molded article surface appearance deteriorate.

The usage-amount of (B) component which comprises the 3rd thermoplastic resin composition of this invention is 30-96 mass% in 100 mass% of total of (B) component, (C1) component, and (D) component, Preferably it is 35-91 Mass%, More preferably, it is 42-91 mass%, Especially preferably, it is 42-85 mass%, When it is less than 30 mass%, chemical resistance will deteriorate, and when it exceeds 96 mass%, antistaticity and the surface appearance of a molded article will deteriorate. .

[3] components (C1)

The component (C1) of the present invention is a block copolymer containing an olefin polymer block (c1-1) and a hydrophilic polymer block (c1-2), and preferably a block copolymer having a structure in which both blocks are alternately bonded to each other. . The block copolymer may be a diblock or a multiblock or more block. The said olefin polymer block (c1-1) is a (co) polymer of said olefins. The number average molecular weight of polystyrene conversion by gel permeation chromatography (GPC) of the olefin polymer block (c1-1) is preferably 800 to 20,000, more preferably 1,000 to 10,000, particularly preferably 1,200 to 6,000.

The block (c1-1) is chemically bonded to the block (c1-2), but the bond is at least one bond selected from an ester bond, an amide bond, an ether bond, a urethane bond, an imide bond, and the like. It has a structure of alternating coupling through the coupling.

For this reason, the both ends of the molecule | numerator of the said block (c1-1) need to be denatured by the functional group which is reactive with the molecular both terminal functional group of the said block (c1-2). These functional groups include a carboxylic acid group, a hydroxyl group, an amino group, an acid anhydride group, an oxazoline group, an epoxy group and the like.

As a method of providing these functional groups, it is preferable to add the (c1-1) component which has a carbon-carbon double bond, and the carbon-carbon unsaturated compound which has the above-mentioned functional group to the molecular terminal obtained by the thermosensitive method.

Examples of the hydrophilic polymer of the block (c1-2) include polyether (c1-2-a), polyether-containing hydrophilic polymer (c1-2-b), and anionic polymer (c1-2-c).

Polyether (c1-2-a) includes polyetherdiol, polyetherdiamine and modified substances thereof.

Examples of the polyether-containing hydrophilic polymer (c1-2-b) include polyetherester amide having a segment of polyetherdiol, polyetheramidoimide having a segment of polyetherdiol, polyetherester having a segment of polyetherdiol, and poly Polyetheramides having segments of ether diamines and polyetherurethanes having segments of polyetherdiols or polyether diamines.

As the anionic polymer (c1-2-c), dicarboxylic acid having a sulfonyl group and polyether (c1-2-a) are essential structural units, and in one molecule, preferably 2 to 80, more preferably Preferred are anionic polymers having 3 to 60 sulfonyl groups.

These may be linear or branched.

Particularly preferred block (c1-2) is polyether (c1-2-a).

Polyether (c1-2-a) of polyether diol with the general formula (I): to _{^{H- (OA 1) n -OE 1}} -O- (A 1 O) n ' represented by -H, and general Formula (II): H- (OA ² ) _m -OE ² -O- (A ² O) _{m '} -H etc. are mentioned.

In the general formula (I), E ¹ is a divalent hydroxyl group-containing moieties other than the hydroxy group in the compound, A ¹ is a carbon number of 2 to 4 alkylene group, n and n 'is the divalent hydroxyl group-containing compound a hydroxyl group per one alkylene oxide It means addition number. n (OA ¹ ) and n '(A ¹ 0) may be the same or different, and in the case where they are composed of two or more oxyalkylene groups, the bonding type may be either block, random, or a combination thereof. . n and n 'are 1-300 normally, Preferably it is 2-250, Especially preferably, it is 10-100. In addition, n and n 'may be same or different.

Examples of the divalent hydroxyl group-containing compound include compounds containing two alcoholic or phenolic hydroxyl groups in one molecule, that is, dihydroxy compounds, and specifically, dihydric alcohols (for example, aliphatic and alicyclic compounds having 2 to 12 carbon atoms). Or aromatic dihydric alcohols), divalent phenols having 6 to 18 carbon atoms, tertiary amino group-containing diols, and the like.

Examples of the aliphatic dihydric alcohols include alkylene glycols such as ethylene glycol and propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,12-dodecanediol and the like.

Examples of the alicyclic dihydric alcohols include 1,2- and 1,3-cyclopentanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like. As aromatic dihydric alcohol, xylenediol etc. are mentioned, for example.

Examples of the dihydric phenol include monocyclic dihydric phenols such as hydroquinone, catechol, resorcin, and ursiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane and di Bisphenol, such as hydroxy biphenyl and dihydroxy diphenyl ether, and condensed polycyclic dihydric phenol, such as dihydroxy naphthalene and vinaphthol, etc. are mentioned.

General formula (II) of, E ² is a residue excluding the hydroxyl group from a divalent hydroxyl group-containing compound described in the general formula (I), A ² is at least partially the general formula (III): -CHR-CHR ' - [ wherein One of R and R 'is a group represented by general formula (IV): -CH ₂ O (A ³ O) _x R ", and the other is H. In general formula (IV), x is an integer of 1-10. , R "is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an acyl group, and A ³ is an alkyl group having 2 to 4 carbon atoms. 2-4 alkylene groups may be sufficient. m (OA ² ) and m '(A ² 0) may be the same or different. It is preferable that m and m 'are 1-300, More preferably, it is 2-250, Especially 10-100 are preferable. In addition, m and m 'may be same or different.

The polyetherdiol represented by the general formula (I) can be produced by addition reaction of an alkylene oxide to a divalent hydroxyl group-containing compound. Alkylene oxides include alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide and 1,3-butyl Len oxides and two or more combinations thereof are used. When using 2 or more types of alkylene oxides together, the bond type may be any of random and / or a block. Preferred as alkylene oxides are block and / or random additions of ethylene oxide alone and in combination with ethylene oxide and other alkylene oxides. The number of additions of the alkylene oxide and the number of hydroxyl groups of the divalent hydroxyl group-containing compound is preferably 1 to 300, more preferably 2 to 250, and particularly preferably 10 to 100.

As a preferable manufacturing method of the polyetherdiol represented by said general formula (II), methods, such as the following (i) and (ii), are mentioned.

(i) General formula (V) using the divalent hydroxyl-containing compound as a starting material:

[Formula (V) of A ⁴ are a carbon number of 2 to 4 alkylene group, p is an integer from 1 to 10, R ¹ is H or C 1 -C 10 alkyl group, an aryl group, an alkylaryl group, an arylalkyl group or an acyl group Is a method of polymerizing or copolymerizing glycidyl ether represented by C2-C4 alkylene oxide.

(ii) A method of passing through a polyether having a chloromethyl group in a side chain by using the divalent hydroxyl group-containing compound as a starting material. More specifically, after addition copolymerization of epichlorohydrin or epichlorohydrin and alkylene oxide, a polyether having a chloromethyl group in the side chain is obtained, the polyether and polyalkylene glycol having 2 to 4 carbon atoms and R ¹ X (R ¹ is the above, X is C1, Br or I) to react in the presence of alkali or the polyether and the C2-C4 polyalkylene glycol monocarbyl ether in the presence of alkali to be.

As the alkylene oxide having 2 to 4 carbon atoms used herein, all of the foregoing may be used.

In addition, the component (C1) of the present invention can be obtained by polymerizing the olefin polymer block (c1-1) and the hydrophilic polymer block (c1-2) by a known method. For example, block (c1-1) and block (c1-2) can be manufactured by performing a polymerization reaction at 200-250 degreeC under reduced pressure. Moreover, a well-known polymerization catalyst can be used at the time of a polymerization reaction.

In addition, although a well-known polymerization catalyst can be used at the time of a polymerization reaction, tin catalysts, such as monobutyl tin oxide, antimony catalysts, such as antimony trioxide and antimony dioxide, titanium catalysts, such as tetrabutyl titanate, and zirconium hydroxide, are preferable. And zirconium-based catalysts such as zirconium oxide and zirconyl acetate, and a group IIB organic acid salt catalyst.

In order to further improve the antistatic or antistatic property which is the object of the present invention, the component (C1) may contain at least one salt (H) selected from the group consisting of alkali metals and alkaline earth metals. These components may be contained before the polymerization of the (C1) component and at the time of the polymerization of the (C1) component, or may be included after the polymerization of the (C1) component. Moreover, what mix | blends when manufacturing the resin composition of this invention can also be contained by the method which combined these.

Salts of the component (H) include organic acids of alkali metals such as lithium, sodium and potassium, and / or organic acids of alkaline earth metals such as magnesium and calcium, salts of sulfonic acids and inorganic acids, halides and the like.

Specific examples of the (H) component include halides of alkali metals such as lithium chloride, sodium chloride, potassium chloride, lithium fluoride, sodium fluoride and potassium fluoride; Inorganic acid salts of alkali metals such as lithium perchlorate, sodium perchlorate and potassium perchlorate; Organic acid salts of alkali metals such as potassium acetate and lithium stearate; Alkali metal salts of alkyl sulfonic acids having 8 to 24 carbon atoms of alkyl groups such as octyl sulfonic acid, dodecyl sulfonic acid, tetradecyl sulfonic acid, stearyl sulfonic acid, tetracosyl sulfonic acid and 2-ethylhexyl sulfonic acid; Alkali metal salts of aromatic sulfonic acids such as phenylsulfonic acid and naphthylsulfonic acid; Alkali metal salts of alkylbenzenesulfonic acids having 6 to 18 carbon atoms in alkyl groups such as octylphenylsulfonic acid, dodecylphenylsulfonic acid, dibutylphenylsulfonic acid and dinonylphenylsulfonic acid; Alkali metal salts of alkylnaphthalenesulfonic acids having 2 to 18 carbon atoms in alkyl groups such as dimethylnaphthylsulfonic acid, diisopropylnaphthylsulfonic acid and dibutylnaphthylsulfonic acid; Alkali metal salts, such as fluorinated sulfonic acids, such as a trifluoromethane sulfonic acid, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. The component (H) is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, still more preferably 0.01 to 3% by mass, particularly preferably 0.01 to the component (C1) of the present invention. It can use in the range of -2 mass%.

The preferable ratio (mass ratio) of the block (c1-1) / block (c1-2) in (C1) component of this invention is the range of 10-90 / 10-90, More preferably, it is 20-80 / 20 -80, Especially preferably, it is the range of 30-70 / 30-70.

Such a block copolymer (C1) can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 2001-278985, Japanese Patent Application Laid-Open No. 2003-48990, and the like. Ltd. It is available as 300, 303, 230 (brand name) etc. of the PELESTAT 300 series of products.

The usage-amount of the (C1) component which comprises the 1st thermoplastic resin composition of this invention is 0.5-100 mass parts with respect to a total of 100 mass parts of said (A) component and (B) component, Preferably it is 0.5-80 mass parts, More preferably, it is 1-60 mass parts, Especially preferably, it is the range of 2-50 mass parts. If the amount is less than 0.5 parts by mass, the antistatic effect is not obtained, the chemical resistance effect is not sufficient, and the impact resistance is deteriorated. When it exceeds 100 mass parts, impact resistance deteriorates.

The usage-amount of the (C1) component which comprises the 2nd thermoplastic resin composition of this invention is 3-30 mass% in 100 mass% of total of the said (B) component and (C1) component, Preferably it is 4-25 mass%, More Preferably it is 4-23 mass%, Especially preferably, it is the range of 5-23 mass%. If it is less than 3 mass%, antistatic property will deteriorate, and if it exceeds 30 mass%, chemical resistance and the surface appearance of a molded article will deteriorate.

The usage-amount of the (C1) component which comprises the 3rd thermoplastic resin composition of this invention is 3-30 mass% in 100 mass% in total of the said (B) component, the said (C1) component, and the following (D) component, Preferably 4-25 mass%, More preferably, it is 4-23 mass%, Especially preferably, it is 5-23 mass%. If it is less than 3 mass%, antistatic property will deteriorate, and if it exceeds 30 mass%, chemical resistance and the surface appearance of a molded article will deteriorate.

[4] (C2) components

In order to further improve antistatic property or antistatic property, the 1st thermoplastic resin composition of this invention has the following (C2-1) component and (C2-2) other than the said (A) component, (B) component, and (C1) component It may further contain at least one component selected from the group consisting of a component, a component (C2-3) and a component (C2-4).

(C2-1) component: polyether polyamide and / or polyether polyester,

(C2-2) Component: Nonionic antistatic agent,

(C2-3) component: a boron compound,

(C2-4) Component: Lithium salt.

The second thermoplastic resin composition of the present invention further contains the component (C2-2) in addition to the component (B) and the component (C1), and the component (C2-1) and the component (C2-3) as necessary. And (C2-4) a component may further contain at least one component selected from the group consisting of.

The third thermoplastic resin composition of the present invention further contains the component (C2-2) in addition to the component (B), the component (C1) and the component (D), and optionally the component (C2-1), ( It may further contain at least one component selected from the group consisting of C2-3) component and (C2-4) component.

[4-1] (C2-1) components

(C2-1) a component of this invention is polyether polyamide and / or polyether polyester.

Polyamides used herein include ethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, 2,3,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4- Diamine components such as aliphatic, alicyclic or aromatic diamines such as bis (aminomethyl) cyclohexane, bis (p-aminohexyl) methane, phenyldiamine, m-xylenediamine, and p-xylenediamine; Obtained by ring-opening polymerization of lactams such as polyamide, caprolactam, lauryllactam derived from aliphatic, alicyclic or aromatic dicarboxylic acids such as acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc. Polyamides derived from aminocarboxylic acids such as polyamides, ω-aminocaproic acid, ω-aminoenanoic acid, aminoundecanoic acid and 1,2-aminododecanoic acid, and copolymerized polyamides thereof, and Mixed polyamides are listed.

The polyether polyamide of the component (C2-1) of the present invention contains a polyether component, but as the polyether component used herein, all of the components (c1-2) described above for the component (C1) can be used. .

The preferable polymerization method of the polyether polyamide of this invention is a hot melt polymerization method, and the preferable specific example is shown below.

(i) A method of polymerizing polyamide, followed by addition of a dicarboxylic acid compound to carboxylate both ends of the polyamide component, followed by addition polymerization of poly (alkylene oxide) glycol to obtain a polyether polyamide.

(ii) polymerizing by excessively adding a dicarboxylic acid compound so that both ends of the molecule are substantially carboxylated at the time of polyamide polymerization, and further adding poly (alkylene oxide) glycol to polymerize. Way.

(iii) A method in which a polyamide producing component, an excess of dicarboxylic acid compound, and poly (alkylene oxide) glycol are added in a prescribed amount in a batch to obtain a polyether polyamide.

In this method, a particularly preferred method is the method of (i) above.

Dicarboxylic acids used for carboxylating the molecular ends of the polyamide component include adipic acid, subric acid, sebacic acid, maleic acid, citraconic acid, maleic anhydride, citraconic anhydride, cyclohexane Dicarboxylic acid, terephthalic acid, isophthalic acid and the like. The number average molecular weight of the polyamide of the present invention is preferably 500 to 20,000, more preferably 500 to 10,000, particularly preferably 500 to 5,000 in terms of achieving the object of the present invention.

The mass ratio (polyamide / polyether) of the polyamide component and the polyether component in the polyether polyamide of the present invention is preferably in the range of 90/10 to 10/90, more preferably 80/20 20/80, Especially preferably, it is 70 / 30-30 / 70.

Although the molecular weight of the polyether polyamide of the present invention is not particularly limited, the reduced viscosity (η _sp / C) (measured at 0.5 g / 100 ml at 25 ° C in formic acid solution) is in the range of 1 to 3 dl / g. It is preferable to exist, More preferably, it is 1.2-2.5 dl / g.

The polyether polyamide of this invention can be used individually by 1 type or in combination of 2 or more types.

As polyester in (C2-1) component of this invention, it is a polymer obtained from (1) C4-C20 dicarboxylic acid and / or its ester formation derivative, and (2) diol component. As said (1) used here, the following are illustrated. Here, carbon number means the total number of carbon which comprises the chain and ring which are directly connected to the carbon of a carboxyl group, and the carbon of a carboxyl group.

Examples of the dicarboxylic acid having 4 to 20 carbon atoms include (a) succinic acid, adipic acid, azelaic acid, sebacic acid, α, ω-dodecane dicarboxylic acid, dodecenyl succinic acid, and octadecenyl dicarboxylic acid. C4-C20 aliphatic dicarboxylic acid, (b) C1-C20 alicyclic dicarboxylic acid, such as 1, 4- cyclohexane dicarboxylic acid, (c) terephthalic acid, isophthalic acid, 1, 4- Aromatic dicarboxylic acids having 8 to 12 carbon atoms such as naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and 2,7-naphthalene dicarboxylic acid, (d C8-C12 substituted aromatic dicarboxylic acid in which sulfonic acid groups, such as 5-sodium sulfo isophthalic acid, 5-potassium sulfoisophthalic acid, and 5-tetrabutyl phosphonium sulfoisophthalic acid, couple | bonded with an aromatic ring, etc. are mentioned. . Moreover, the lower alkyl ester of said (a)-(d) is mentioned as ester formation derivative of C4-C20 dicarboxylic acid. This includes, for example, dimethyl succinate, dimethyl adipic acid, dimethyl azelate, dimethyl sebacin, dimethyl α, ω-dodecanedicarboxylic acid, dimethyl dodecenyl succinic acid, octadecenyldicarboxylic acid dimethyl, 1,4-cyclo Hexanedicarboxylic acid dimethyl, diethyl succinate, diethyl adipic acid, diethyl azelate, diethyl sebacinate, α, ω-dodecanedicarboxylic acid diethyl, dodecenyl succinate diethyl, octadecenyldicar Diethyl acid, 1,4-cyclohexanedicarboxylic acid diethyl, terephthalate dimethyl, terephthalate diethyl, terephthalate di (2-hydroxyethyl), isophthalate dimethyl, isophthalate diethyl, isophthalic acid di (2- Hydroxyethyl), 1,4-naphthalene dicarboxylic acid dimethyl, 1,4-naphthalene dicarboxylic acid diethyl, 2,6-naphthalene dicarboxylic acid dimethyl, 2,6-naphthalene dicarboxylic acid diethyl , 2,7-naphthalene dicarboxylic acid dimethyl, 2,7-naphthale Dicarboxylic acid diethyl, 5-sodium sulfoisophthalic acid dimethyl, 5-potassium sulfoisophthalic acid dimethyl, 5-sodium sulfoisophthalic acid (2-hydroxyethyl), 5-potassium sulfoisophthalic acid (2- Hydroxyethyl) and the like, and these may be used alone or in combination of two or more. In particular, terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 5-sodium sulfoisophthalic acid and ester-forming derivatives thereof are preferred.

Although the polyether polyester of this invention contains the said polyester component and a polyether component, all of the said (C1-2) components can be used as a polyether component used here. The preferable polymerization method of the polyether polyester of this invention is a hot melt polymerization method, and the preferable specific example is shown below.

(i) A method of polymerizing polyester, followed by adding a dicarboxylic acid compound to carboxylate both ends of the polyester component, followed by addition polymerization of poly (alkylene oxide) glycol to obtain a polyether polyester.

(ii) A method of excessively polymerizing a dicarboxylic acid compound so as to substantially carboxylate both ends of the molecule during polyester polymerization, and further polymerizing poly (alkylene oxide) glycol to obtain a polyether polyester.

(iii) A method of obtaining a polyether polyester by subjecting a polyester production component, excess dicarboxylic acid compound, and poly (alkylene oxide) glycol to a prescribed amount batch addition polymerization.

As dicarboxylic acid used when carboxylating the molecular terminal of the said polyester component, adipic acid, a sveric acid, sebacic acid, maleic acid, a citraconic acid, a maleic anhydride, a citraconic acid anhydride, cyclohexane Dicarboxylic acid, terephthalic acid, isophthalic acid, etc., The average molecular weight of the polyester of this invention becomes like this. Preferably it is 300-20,000, More preferably, it is 300-10,000, Especially preferably, it is the range of 500-5,000. It is preferable at the point which achieves the objective of.

The mass ratio (polyester / polyether) of the polyester component and the polyether component in the polyether polyester of the present invention is preferably in the range of 90/10 to 10/90, more preferably 80/20 20/80, It is the range of 70 / 30-30 / 70 which is especially preferable.

Although the molecular weight of the polyether polyester of this invention is not specifically limited, Concentration 1.0g / Pa and 35 degreeC using the mixed solvent of reduced viscosity ((eta) _Sp / C) (phenol / tetrachloroethane = 40/60 mass ratio). Measurement) is preferably 0.3 to 2.5 dl / g, more preferably 0.5 to 2.5 dl / g.

The polyether polyester of this invention can be used individually by 1 type or in combination of 2 or more types.

The polyether polyamide or the polyether polyester which is the component (C2-1) of the present invention is characterized in that the above-mentioned (H) ) Component can be added. As for the quantity of (H) component used here, the range of 0.001-20 mass% is preferable in the (C2-1) component of this invention, More preferably, it is 0.01-15 mass%, Especially preferably, it is 0.1-10 mass%. Range.

In the case of the first thermoplastic resin composition of the present invention, the component (C2-1) is preferably 0.001 to 60 parts by mass, more preferably 0.5 to 50 parts by mass based on 100 parts by mass in total of the component (A) and the component (B). Mass part, More preferably, it is 0.5-40 mass parts, More preferably, it is 1-35 mass parts, Especially preferably, it can be used in the range of 1-30 mass parts. If the amount is less than 0.001 part by mass, the antistatic property and the surface gloss of the molded article deteriorate, and if it exceeds 60 parts by mass, the impact resistance deteriorates.

In the case of the second and third thermoplastic resin compositions of the present invention, the component (C2-1) is preferably 0.001 to 60 parts by mass, more preferably 0.5 to 50 parts by mass, and more preferably 100 parts by mass of the component (B). Preferably it is 0.5-40 mass parts, More preferably, it is 1-35 mass parts, Especially preferably, it can be used in the range of 1-30 mass parts. If the amount is less than 0.001 part by mass, the antistatic property and the surface gloss of the molded article deteriorate, and if it exceeds 60 parts by mass, the impact resistance deteriorates.

It is preferable that the use ratio (C1) / (C2-1) of (C1) component and (C2-1) component of this invention exists in the range of 4-60 / 40-96 by mass ratio, More preferably, it is 6 It is -55 / 45-94, Especially preferably, it is 8-48 / 52-92, The sum total of (C1) component and (C2-1) component is 100 mass%, and the use ratio of (C1) component is 4 mass%. Less than, the area | region exceeding 96 mass% of use ratios of (C2-1) component tends to fall antistatic property, and the usage-amount of (C1) component exceeds 60 mass%, (C2-1) component If the amount of is used is less than 40% by mass, the surface gloss of the molded article tends to be lowered, which is not preferable.

[4-2] (C2-2) component

Examples of the nonionic antistatic agent of the component (C2-2) of the present invention include a (C2-2-1) polyalcohol ester and a nitrogen-containing compound represented by (C2-2-2) a general formula (VI), These can be used individually by 1 type or in combination of 2 or more types.

In general formula, R <^4> is a C8-C22 alkyl group or alkenyl group, X is group represented by following formula X-1 or X-2

Lt;

Y and Z are groups represented by the following formulas Y-1, Y-2 or Y-3, respectively

The two may be the same or different from each other. m + n is an integer of 2-5.

As a (C2-2-1) component, glycerin monostearate, glycerin monomyristate, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monooleate, diglycerol monolaurate, diglycerine monomyri State, diglycerin monopalmitate, diglycerin monostearate, diglycerin monobehenate, diglycerin monooleate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, Sorbitan monobehenate, sorbitan monolaurate, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more type. Particularly preferred are glycerin monostearate, diglycerin monostearate, glycerin monolaurate, diglycerin monolaurate, sorbitan monostearate and (C2-2-1) components containing at least 20% by mass or more thereof.

As a (C2-2-2) component, lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, Amines such as palmityl diisopropanolamine, stearyldiisopropanolamine, oleyldiisopropanolamine, N, N-bishydroxyethylalkyl (12 to 22 carbon atoms of an alkyl group) amine, or lauryl diethanolamide, myristyl diethanol Amides such as amide, palmityldiethanolamide, behenyl diethanolamide, oleyl diethanolamide, lauryldiisopropanolamide, myristyldiisopropanolamide, palmityldiisopropanolamide, stearyldiisopropanolamide, oleyldiisopropanolamide, and the like. These can be used individually by 1 type or in combination of 2 or more types. Preferably it is the said amine compound, More preferably, it is a (C2-2-2) component which contains at least 20 mass% or more of lauryl diethanolamine and stearyl diethanolamine, respectively.

Moreover, a well-known additive can be mix | blended with the said compound in order to improve antistatic performance. Examples thereof include higher alcohols having 12 to 18 carbon atoms, lubricants, silica, calcium silicate, and the like. Moreover, what was masterbatched can also be used for the purpose of improving miscibility.

The nonionic antistatic agent which is the (C2-2) component of this invention can be obtained from a market as ELECTROSTRIPER EA, TS-3B, TS-6B, TS-5, TS-2B (brand name) etc. by Kao Corporation.

In the case of the first thermoplastic resin composition of the present invention, the component (C2-2) is preferably 0.001 to 60 parts by mass, more preferably 0.005 to 50 parts by mass based on 100 parts by mass in total of the component (A) and the component (B). Mass part, More preferably, it is 0.01-30 mass parts, Especially preferably, it is used in 0.05-20 mass parts, Most preferably, it is used in the range of 0.5-10 mass parts, In less than 0.001 mass part, antistatic property deteriorates and 60 mass parts Exceeding the portion deteriorates the chemical resistance and the appearance of the molded article.

In the case of the second thermoplastic resin composition of the present invention, the component (C2-2) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts based on 100 parts by mass in total of the component (B) and the component (C1). A mass part, More preferably, 0.1-5 mass parts is added. If it is less than 0.01 mass part, antistatic property will deteriorate, and when it exceeds 10 mass parts, chemical resistance and the surface appearance of a molded article will deteriorate.

In the case of the 3rd thermoplastic resin composition of this invention, (C2-2) A component becomes like this. Preferably it is 0.01-10 mass parts with respect to 100 mass parts of total of (B) component, (C1) component, and (D) component, More preferably Preferably it is 0.05-8 mass parts, More preferably, 0.1-5 mass parts is added. If it is less than 0.01 mass part, antistatic property will deteriorate, and when it exceeds 10 mass parts, chemical resistance and the surface appearance of a molded article will deteriorate.

[4-3] (C2-3) components

(C2-3) component which concerns on this invention is a boron compound, ie, a compound containing a boron element. This boron compound (C2-3) can be used individually by 1 type or in combination of 2 or more types.

The boron compound (C2-3) is preferably an organoboron polymer compound. As this organoboron high molecular compound, the compound containing the unit represented by following General formula (VII) is preferable.

As a compound containing the unit represented by the said General formula (VII), the semi-polar organoboron high molecular compound represented by the following general formula (VIII), and a tertiary amine with a total of 5-82 carbon atoms which have a hydroxyl group It is preferable that it is a polymer charge transfer type | mold binder which is the reaction product of 1 type, or 2 or more types of, and the ratio of 1 basic nitrogen atom per boron atom.

(Wherein q is 0 or 1 and when q = 1, T is-(T ¹ ) _s- (T ² ) _t- (T ³ ) _u- (where T ¹ and T ³ are the same as each other or Is an oxygen-containing hydrocarbon group having one terminal ether residue and having a total of 100 carbon atoms or less, and T ² is

(However, R ⁹ is a hydrocarbon group having 1 to 82 carbon atoms.)

or,

(Wherein R ¹⁰ is a hydrocarbon group having 2 to 13 carbon atoms), s, t and u are each 0 or 1), and R ⁶ , R ⁷ and R ⁸ are the same or different organic groups. , r is 10 to 1000.)

As R <^6> , R <^7> and R <^{8> in the} said general formula (VIII), a hydrocarbon group, an alkoxy group, a phenoxy group, benzyloxy group, an alkylene glycol group, etc. are mentioned. These groups may have functional groups, such as a hydroxyl group, and may have a substituent.

Examples of the charge transfer type conjugates include those represented by the following formulas (IX) to (XVI). Furthermore, in each of the following chemical formulas, the hydrogen atom or the hydroxyl group is usually bonded to the terminal carbon atom and oxygen atom, respectively.

(Wherein R 'is a residue of polybutene having an average degree of polymerization of 20)

The polymer charge transfer type conjugate may be prepared by the method described in Japanese Patent No. 2573986.

Moreover, a commercial item can be used as a boron compound (C2-3), For example, "Hi-Boron 400N" by Boron International, etc. is preferable.

The boron compound (C2-3) which concerns on this invention may be mix | blended independently at the time of manufacture of a thermoplastic resin composition, and is mix | blended with the mixture (composition) which consists of polymers, such as said (A), (B), (C1) component, etc. You may. Examples of the latter include “Hi-Boron MB400N-8LDPE” (polyethylene matrix masterbatch) manufactured by Boron International.

In the first thermoplastic resin composition of the present invention, the content of the component (C2-3) is preferably 0.001 to 60 parts by mass, when the total of the component (A) and the component (B) is 100 parts by mass. Preferably it is 0.001-50 mass parts, More preferably, it is 0.01-30 mass parts, More preferably, it is 0.05-20 mass parts, Especially preferably, it is 0.05-10 mass parts, Most preferably, it is 0.1-5 mass parts. . If this content is less than 0.001 mass part, antistatic property will tend to deteriorate, while if it exceeds 60 mass parts, surface appearance will tend to deteriorate.

In the 2nd and 3rd thermoplastic resin compositions of this invention, content of (C2-3) component becomes like this. Preferably it is 0.001-60 mass parts with respect to 100 weight part of (B) components, More preferably, it is 0.001--50 mass parts It is 0.01-30 mass parts, More preferably, it is 0.05-20 mass parts, Especially preferably, it is 0.05-10 mass parts, Most preferably, it is 0.1-5 mass parts. If this content is less than 0.001 mass part, antistatic property will tend to deteriorate, while if it exceeds 60 mass parts, surface appearance will tend to deteriorate.

Moreover, the preferable content rate of (C1) component and (C2-3) component is 38-99.9 mass% / 0.2-62 mass%, when these sum total is 100 mass%, More preferably, 67-99.7 mass % / 0.3-33 mass%, More preferably, it is 75-99.2 mass% / 0.8-25 mass%. By setting it as said range, it has further excellent antistatic property.

[4-4] (C2-4) components

Examples of the lithium salt as the (C2-4) component of the present invention include organic acid salts, inorganic acid salts, and halides of lithium, and preferably lithium perchlorate, lithium trifluoromethanesulfonate, and bis (trefluoromethane). At least one compound selected from sulfonyl) imide lithium and tris (trefluoromethanesulfonyl) methane lithium, and more preferably lithium trifluoromethanesulfonate, bis (trefluoromethanesulfonyl) At least one compound selected from imid lithium and tris (trifluoromethanesulfonyl) methane lithium is listed, more preferably bis (trefluoromethanesulfonyl) imide lithium and tris (trefluoromethane At least one compound selected from sulfonyl) methane lithium is listed, particularly preferably tris (terfluoromethanesulfonyl) methane lithium.

Although blending the (C2-4) component of the present invention with the composition of the present invention can improve the antistatic properties and maintains the antistatic properties, the (C2-4) component is added when the (C2-4) component is blended. Although it can mix | blend as it is, mix | blending the (C2-4) component melt | dissolved with the solvent (containing water) etc. can also be used as a masterbatch previously disperse | distributed in high concentration to another polymer.

Particularly preferred as a solvent for dissolving the component (C2-4) is water or a compound represented by the following formula (XVII).

[In general formula (XVII), X is a C2-C8 alkylene group, the bivalent hydrocarbon group containing an aromatic group, or a bivalent alicyclic hydrocarbon group, R is a C1-C9 linear or branched alkyl group each independently. And A each independently represent an alkylene group having 2 to 4 carbon atoms, and n each independently represents an integer of 1 to 7.]

As a compound represented by the said general formula (XVII), it is preferable that R is an alkyl group which does not have a hydroxyl group at the terminal. Especially preferably, it is bis [2- (2 butoxy ethoxy) ethyl] adipate (dibutoxy ethoxy ethyl) or bis (2- butoxy ethyl) phthalate.

The concentration at the time of dissolving the component (C2-4) of the present invention is preferably 0.1 to 80% by mass, more preferably 1 to 60% by mass.

Furthermore, when performing masterbatch which disperse | distributed the (C2-4) component of this invention to another polymer previously, the method of manufacturing by mix | blending melt-kneading with the said polymer and the said solvent as needed, desirable.

Particularly preferred as known polymers used herein are those having ether bonds, which are polyalkylene oxides and / or polyalkylene oxide containing polymers. Specifically, block copolymers composed of polyethylene oxide, polypropylene oxide, polytetramethylene oxide and polyamide, polyester and the polyalkylene oxide, and also the hydrophilic polymer block (c1-2) in the component (C1) of the present invention. What used polyether as a thing can also be used as a polymer which has an ether bond. Therefore, the component (C2-4) of the present invention may be added to the component (C1), or may be added to any one of the components of the present invention.

The amount of the component (C2-4) in the masterbatch in the case of masterbatching the above-mentioned (C2-4) component of the present invention is preferably in the range of 0.5 to 80 mass%, more preferably 1 to 60 mass%, particularly Preferably it is 3-40 mass% of range.

The solution of the component (C2-4) of the present invention described above is Sanko Chemical Industry Co., Ltd. As products of Sankonol 0862-20R, 0862-13T, 0862-10, AQ-50 (trade name), etc., and as masterbatch, Sanko Chemical Industry Co., Ltd. It can obtain as Sankonol TBX-25 (brand name) etc. of a product.

In the case of the 1st thermoplastic resin composition of this invention, (C2-4) A component is 0.001-60 mass parts with respect to 100 mass parts in total of (A) component and (B) component, More preferably, it is 0.005-- 50 mass parts, More preferably, it is 0.01-40 mass parts, More preferably, it is 0.05-25 mass parts, Especially preferably, it is 0.05-15 mass parts, Most preferably, it is used in the range of 0.1-10 mass parts. If it is less than 0.001 mass part, antistatic property will not improve, but if it exceeds 60 mass parts, the persistence and impact resistance of antistatic property will deteriorate.

In the case of the second and third thermoplastic resin compositions of the present invention, the component (C2-4) is preferably 0.001 to 60 parts by mass, and more preferably 0.005 to 50 parts by mass based on 100 parts by mass of the component (B). More preferably, it is 0.01-40 mass parts, More preferably, it is 0.05-25 mass parts, Especially preferably, it is 0.05-15 mass parts, Most preferably, it is used in the range of 0.1-10 mass parts. If it is less than 0.001 mass part, antistatic property will not improve, but if it exceeds 60 mass parts, the persistence and impact resistance of antistatic property will deteriorate.

The first and second thermoplastic resin compositions of the present invention are the components (A), (B) and (C1) in order to further improve impact resistance, chemical resistance, surface appearance of the molded article, or antistatic or antistatic properties. In addition to the component, it may further contain at least one component selected from the group consisting of the following (D) component, (E) component, (F) component and (G) component.

In order to further improve impact resistance, chemical resistance, surface appearance of the molded article, or antistatic or antistatic property, the third thermoplastic resin composition of the present invention contains the following (D) component as an essential component, and if necessary (E ), At least one component selected from the group consisting of (F) component and (G) component.

Component (D): a block copolymer (Da) containing a polymer block (d-1) mainly composed of an aromatic vinyl compound and a polymer block (d-2) mainly composed of a conjugated diene compound, and a hydrogenated substance (Db) thereof At least one polymer selected from the group,

(E) component: The graft polymer formed by (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound, and the other vinyl monomer copolymerizable with an aromatic vinyl compound in presence of the said (D) component,

(F) component: The aromatic polycarbonate block copolymer which consists of a polymer block (f-1) which consists of said (D) component, and an aromatic carbonate polymer block (f-2),

(G) Component: Low molecular weight polyolefin modified with unsaturated acid and / or unsaturated acid anhydride.

In addition, the said (D) component, (E) component, (F) component, and (G) component are said (C2-1) component, (C2-2) component, (C2-3) component, and (C2-4) It may be used in combination with at least one selected from the group consisting of ingredients.

[5] (D) component

Component (D) of the present invention is a block copolymer (Da) containing a polymer block (d-1) mainly composed of an aromatic vinyl compound and a polymer block (d-2) mainly composed of a conjugated diene compound and / or a hydrogenated product thereof (Db), wherein the hydrogenated substance (Db) is mainly hydrogenated at least a part of the carbon-carbon double bond of the conjugated diene compound of the block (d-2).

As the aromatic vinyl compound used herein, all of the above-mentioned ones can be used, but preferably styrene and α-methyl styrene, and particularly preferably styrene.

The conjugated diene compound includes butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like, and preferably butadiene and isoprene. These can be used individually by 1 type or in combination of 2 or more types. The block (d-2) may be a block in which two or more kinds of conjugated diene compounds are used, and in which they are combined in any one of a random shape, a block shape, and a tapered block shape. In addition, the block (d-2) may contain the taper block which an aromatic vinyl compound increases in the range of 1-10, the polymer block etc. from which the vinyl bond content derived from the conjugated diene compound of block (d-2) differs, etc. This may be copolymerized suitably.

Preferable structures of the component (D) of the present invention are polymers represented by the following formulas (XVIII) to (XX) or hydrogenated substances thereof.

(AB) _Y ... (XVIII)

(AB) _Y -X... (XIX)

A- (BA) _Z ... (XX)

(In Structural Formulas (XVIII) to (XX), if A is a polymer block mainly composed of an aromatic vinyl compound, and may be a polymer block composed of an aromatic vinyl compound, some conjugated diene compound may be contained. Preferably, aromatic vinyl A polymer block containing at least 90% by mass of the compound, more preferably at least 99% by mass, B is a homopolymer of a conjugated diene compound or a copolymer of a conjugated diene compound with other monomers such as an aromatic vinyl compound, and X is a couple It is a residue of a ring agent, Y represents an integer of 1-5, Z represents the integer of 1-5, respectively.)

The use ratio of the aromatic vinyl compound and the conjugated diene compound in the component (D) of the present invention is preferably in the range of aromatic vinyl compound / conjugated diene compound = 10 to 70/30 to 90 mass%, more preferably 15 65-35-85 mass%, Especially preferably, it is the range of 20-60 / 40-80 mass%.

Block copolymers composed of aromatic vinyl compounds and conjugated diene compounds are known in the art of anionic polymerization, and are disclosed in, for example, Japanese Patent Application Laid-Open No. 47-28915, Japanese Patent Publication No. 47-3252, and Japanese Patent Publication No. 48- Japanese Patent Application Laid-Open No. 2423 and Japanese Patent Application Laid-Open No. 48-20038. Moreover, about the manufacturing method of the polymer block which has a taper block, it is disclosed by Unexamined-Japanese-Patent No. 60-81217.

The vinyl bond amount (1,2- and 3,4-bond) content derived from the conjugated diene compound of (D) component of this invention becomes like this. Preferably it is the range of 5 to 80%, and of the (D) component of this invention The number average molecular weight is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, particularly preferably 20,000 to 200,000. Among these, it is preferable that the number average molecular weight of A part represented by said Formula (XVIII)-(XX) is 3,000-150,000, and the number average molecular weight of B part is the range of 5,000-200,000.

Adjusting the amount of vinyl bonds of the conjugated diene compound is carried out by amines such as N, N, N ', N'-tetramethylethylenediamine, trimethylamine, triethylamine, diazocyclo (2,2,2) octane, and tetrahydrofuran. And ethers such as diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, thioethers, phosphines, phosphoamides, alkylbenzenesulfonates, alkoxides of potassium and sodium, and the like.

After the polymer is obtained by the above method, a polymer in which the polymer molecular chain is extended or branched through the coupling agent moiety using the coupling agent is preferably included in the component (D) of the present invention. Diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyl trichlorosilicon, tetrachlorotin, butyl trichlorotin, dimethylchlorosilicone, tetrachlorogermanium, 1,2-dibromoethane, 1, 4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized flaxseed oil, tolylene diisocyanate, 1,2,4-benzenetriisocyanate, etc. are mentioned.

Among the block copolymers, the polymer having a tapered block having an increasing number of aromatic vinyl compounds in the block (d-2) in the range of 1 to 10 and a coupling-treated radial block type are preferable in terms of impact resistance.

Moreover, as (D) component, the thing which partially or completely hydrogenated the carbon-carbon double bond of the conjugated diene part of the said block copolymer can be used. As for (D) component, hydrogenation rate is 10 to 100%, More preferably, it is 50 to 100%. In terms of weather resistance of the obtained composition, it is preferable to use a hydrogenated 90% or more. Moreover, it is preferable to use the thing of 50% or more and less than 90% of hydrogenation rate from the point of impact property at low temperature.

The hydrogenation reaction of the polymer composed mainly of the aromatic vinyl compound unit obtained in the above method and the polymer composed mainly of the conjugated diene compound can be carried out by a known method, and by adjusting the hydrogenation rate by a known method. The desired polymer can be obtained. As a specific method, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 63-5401, Japanese Patent Application Laid-Open No. 2- There is a method disclosed in Japanese Patent Laid-Open No. 133406 and Japanese Patent Laid-Open No. 1-297413.

In the case of the 1st thermoplastic resin composition of this invention, the usage-amount of (D) component is 1-200 mass parts with respect to 100 mass parts of total of (A) component and (B) component, More preferably, 5- 170 mass parts, More preferably, it is 10-170 mass parts, Especially preferably, it is the range of 15-150 mass parts. By using in this range, especially the molded article excellent in impact resistance and chemical-resistance can be obtained.

In the case of the 2nd thermoplastic resin composition of this invention, the usage-amount of (D) component is 1-200 mass parts with respect to 100 mass parts of (B) components, More preferably, it is 5-170 mass parts, More preferably, 10-170 mass parts, Especially preferably, it is the range of 15-150 mass parts. By using it in this range, the molded article excellent in impact resistance and chemical-resistance can be obtained especially.

In the case of the 3rd thermoplastic resin composition of this invention, the usage-amount of (D) component is 1-40 mass% in 100 mass% of total of (B) component, (C1) component, and (D) component, Preferably it is 5- 40 mass%, More preferably, it is 5-35 mass%, Especially preferably, it is 10-35 mass%, When less than 1 mass%, the effect which improves antistatic property deteriorates, and when it exceeds 40 mass%, chemical resistance and a molded article are carried out. The surface appearance deteriorates.

[6] (E) ingredients

Component (E) of the present invention is a graft (co) polymer formed by (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with an aromatic vinyl compound in the presence of the component (D), wherein As the aromatic vinyl compound used and other vinyl monomers copolymerizable with the aromatic vinyl compound, all of those described above with respect to the vinyl monomer (b) of component (A) can be used, and a particularly preferred combination of monomers is styrene / acrylonitrile, styrene / Acrylonitrile / methyl methacrylate.

In addition, although all the above-mentioned (D) component used here can be used, Preferably it is hydrogenated the carbon-carbon double bond of a conjugated diene compound unit, More preferably, the carbon- of a conjugated diene compound unit Hydrogenated at least 90% of the carbon double bonds, particularly preferably hydrogenated at least 95%.

Although the (E) component of this invention is obtained by graft-polymerizing the said monomer component in presence of (D) component, the amount of (D) component in (E) component exists in the range of 10-60 mass%, and a graft ratio is 20- It is preferable to exist in 80 mass%.

Such a polymer can be prepared by the solution polymerization, the bulk polymerization, the suspension polymerization and the polymerization method in combination of the above-described components (A). The graft polymer thus obtained usually includes a copolymer obtained by graft copolymerization of the monomer component to component (D) and an ungrafted component ((co) polymer of monomer components) which is not grafted to a rubbery polymer.

In the case of the first thermoplastic resin composition of the present invention, the component (E) is preferably 1 to 200 parts by mass, more preferably 5 to 170 parts by mass based on 100 parts by mass in total of the component (A) and the component (B). Part, More preferably, it is 10-170 mass parts, Especially preferably, it can be used in the range of 15-150 mass parts. By using it in this range, the molded article excellent in impact resistance especially can be obtained.

[7] the component (F)

(F) component of this invention is an aromatic polycarbonate block copolymer which consists of a polymer block (f-1) which consists of (D) component, and an aromatic carbonate polymer block (f-2). Here, it is preferable that the molecular terminal of (D) component has a reactive functional group with aromatic polycarbonate, These functional groups include a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, etc., Preferably it is a hydroxyl group, a carboxyl group, More preferably, it is a hydroxyl group. It is preferable that these functional groups were added to the molecular terminal of aromatic vinyl compound block (d-1). Although there exist both the case which has such a functional group in the both ends of (D) component, and the case where it has in the one end, the one end is preferable at the point of impact resistance. Moreover, it is not necessary for every molecule to have a functional group, It is preferable that it is an average of 0.5 or more per molecule, More preferably, it is the range of 0.7-2.

The method of introducing a functional group at the terminal of a molecule can be performed by a well-known method. For example, the method of superposing | polymerizing an aromatic vinyl compound and a conjugated diene compound in presence of an organic alkali metal compound, and making the compound containing the said functional group react with the active site of the obtained polymer; Adding ethylene oxide and propylene oxide to the terminal of the block copolymer, and then adding active hydrogen compounds such as alcohols, carboxylic acids and water to stop anionic polymerization to introduce hydroxyl groups to the terminal; The method of blowing a carbon dioxide gas at low temperature, stopping anion polymerization, and introducing a carboxylic acid group at the terminal is illustrated.

The component (D) having a functional group at the terminal of the molecule is preferably hydrogenated to a carbon-carbon double bond of a conjugated diene compound unit by a known method, and the hydrogenation is by the known method described above for the component (D). I can do it.

Block (f-2) is an aromatic polycarbonate, obtained by interfacial polycondensation of various hydroxyaryl compounds and phosgene, or transesterification (dissolution polycondensation) of carbonate compounds such as dihydroxyaryl compounds and diphenyl carbonate. All obtained by a well-known polymerization method, such as those obtained by, can be used.

Examples of the dihydroxyaryl compound which is a raw material of the aromatic polycarbonate include bisphenol A, hydroquinone, 2,2-bis (4-hydroxyphenyl) pentane, 2,4-dihydroxydiphenylmethane and bis (2-hydroxy Hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, and the like, and bisphenol A is particularly preferable.

The viscosity average molecular weight of the aromatic polycarbonate used in the present invention is preferably 8,000 to 50,000, more preferably 12,000 to 30,000, particularly preferably 15,000 to 26,000. Moreover, what differs in a viscosity average molecular weight can also be used together suitably.

Further, the viscosity average molecular weight of the aromatic polycarbonate can be calculated by inserting the specific viscosity [η _sp ] measured at a concentration of 0.7 g / 100 ml (methylene chloride) at 20 ° C. using methylene chloride as a solvent, in the following formula (3). have.

Viscosity average molecular weight = ([η] × 8130) ^1.205 . (3)

Here, [η] = [(η _sp x 1.12 + 1) ^1/2 -1] /0.56 C (C represents a concentration.).

(F) component of this invention consists of a block (f-1) of the functional group modified | denatured product of (D) component in which the functional group was introduce | transduced as mentioned above, and the said aromatic carbonate polymer block (f-2), (i) A method of melt kneading block (f-1) and block (f-2), (ii) a method of polymerizing block (f-2) in the presence of block (f-1), (iii) block (f-) Although it can manufacture by the method of adding and reacting block (f-1) at the last stage of superposition | polymerization of 2), the industrially preferable method is the method of said (i).

Moreover, it is preferable that the mass ratio of (D) component / (f-2) component in (F) component exists in the range of 95/5-5/95, More preferably, it is 80/20-20/80 And particularly preferably 70/30 to 30/70.

It is not necessary for both (D) component and (f-2) component of this invention to be a block copolymer, and if the at least 10 mass% or more is a block copolymer, the objective of this invention is achieved.

Such a block copolymer mixture can be produced, for example, by the method described in JP 2001-220506 A. In addition, the (F) component of the present invention is Kuraray Co., Ltd. Industrially available as TM-S4L77, TM-H4L77 (brand name), etc. of the TM polymer series of a product.

In the case of the 1st thermoplastic resin composition of this invention, it is preferable to use the said (F) component in 1-200 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, More preferably Is 5-170 mass parts, More preferably, it is 10-170 mass parts, Especially preferably, it is the range of 15-150 mass parts, In this range, the molded article which was especially excellent in impact resistance can be obtained.

[8] (G) components

The component (G) of the present invention is a low molecular weight polyolefin modified with an unsaturated acid and / or an unsaturated acid anhydride. As a low molecular weight polyolefin used here, it is a low molecular weight among the (B) component of this invention, and among these, a low molecular weight polypropylene or a low molecular weight polyethylene is preferable.

The weight average molecular weight of the low molecular weight polyolefin is preferably 1,000 to 100,000, more preferably 5,000 to 60,000, particularly preferably 8,000 to 50,000. The low molecular weight polyolefin is obtained by a polymerization method or a thermosensitive method of a high molecular weight polyolefin. Preferred from the ease of denaturation to unsaturated acids and / or unsaturated acid anhydrides are those obtained by thermosensitive methods. The low molecular weight polyolefin by the thermosensitivity method is, for example, a method of thermally sensitizing a high molecular weight polyolefin in an inert gas, usually at 300 ° C. to 450 ° C. for 0.5 hour to 10 hours (for example, the method described in JP-A-62804). Etc. can be obtained.

Examples of the unsaturated acid used herein include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid and maleic acid, and these may be used alone or in combination of two or more thereof. In addition, examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, chloro itaconic anhydride, chloro maleic anhydride and citraconic anhydride, and these can be used alone or in combination of two or more thereof. Preferred is maleic anhydride.

(G) component of this invention makes the mass of a low molecular weight polyolefin 100%, Preferably it is 0.5-25 mass%, More preferably, it is 1-20 mass%, Especially preferably, 3-15 mass% unsaturated acid And / or modified with an unsaturated acid anhydride, and can be obtained, for example, by modifying a low molecular weight polyolefin with an unsaturated acid and / or an unsaturated acid anhydride in the presence of an organic peroxide, if necessary, by a solution or melting method. In addition, the material corresponding to (G) component of this invention is Sanyo Chemical Industries, Ltd., for example. The products are available in the market as YOUMEX 1001, 1003, 1010, 100S, 110S, 2000, CA60 (brand name).

In the case of the first thermoplastic resin composition of the present invention, the component (G) is preferably 1 to 200 parts by mass, and more preferably 1 to 50 parts by mass based on 100 parts by mass in total of the component (A) and the component (B). Part, More preferably, it is 1-45 mass parts, Especially preferably, it can be used in the range of 2-40 mass parts, When less than 1 mass part, antistatic property deteriorates, and when it exceeds 50 mass parts, impact resistance and antistatic property This is deteriorated.

The components (D), (E), (F) and (G) of the present invention are effective ingredients for improving the compatibility between components of the thermoplastic resin composition of the present invention and other various properties, and are selected from the respective components. It can use at least 1 type or in combination of 2 or more types. Moreover, you may use it combining 1 type (s) or 2 or more types chosen from (D), (E), (F), and (G) component. When using any 2 or more types of (D), (E), (F), and (G) component together, the total amount of these components is 1 with respect to a total of 100 mass parts of (A) component and (B) component. The range of -200 mass parts is preferable, More preferably, it is 5-150 mass parts, Especially preferably, it is 5-100 mass parts.

In the case where the thermoplastic resin composition of the present invention is mainly composed of an olefin-based polymer, when the above-mentioned (D) component is blended, compatibility between components of the composition is increased, and impact resistance, chemical resistance, surface appearance and antistatic properties of the molded article or It is preferable because the overall antistatic property is improved. When using the said (D) component and the said (G) component together, since the said various characteristic further improves, it is more preferable.

Here, in the case where the olefin polymer is mainly used, the thermoplastic resin composition of the present invention

Expression: {(B) + (C1)} / {(A) + (B) + (C1)} ≥0.4

(In formula, (A), (B), and (C1) represent content (mass basis) of (A) component, (B) component, and (C1) component, respectively.)

If it satisfies.

In the case where the thermoplastic resin composition of the present invention is mainly composed of a styrene-based polymer, blending the (E) component and / or the (F) component is preferable because the antistatic property or the antistatic property is improved.

Here, when the styrene-based polymer is mainly used, the thermoplastic resin composition of the present invention

Expression: {(B) + (C1)} / {(A) + (B) + (C1)} <0.4

(In formula, (A), (B), and (C1) represent content (mass basis) of (A) component, (B) component, and (C1) component, respectively.)

If it satisfies.

The thermoplastic resin composition of the present invention can be prepared by kneading each component by a method such as melt kneading by various extruders, Banbury mixers, kneaders, continuous kneaders and the like. Preferable manufacturing method is a method using an extruder, particularly preferably a method using a multi-screw extruder, or a combination of an extruder, a Banbury mixer, a continuous kneader and the like.

In addition, when kneading each component, these components may be kneaded collectively, or may be kneaded by multistage or divided blending.

A well-known inorganic or organic filler can be mix | blended with the thermoplastic resin composition of this invention. Inorganic fillers used herein include glass fibers, glass pieces, glass fibers, glass beads, hollow glass, carbon fibers, carbon fibers milled fibers, talc, calcium carbonate, calcium carbonate whiskers, wollastonite, Mica, kaolin, montmorillonite, heckrite, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, plate alumina, plate silica and organic treated smectite, aramid fiber, phenolic resin fiber, polyester fiber, etc. It can be used individually or in combination of 2 or more types.

Moreover, in order to improve the dispersibility of the said filler, what was processed with the well-known coupling agent, surface treatment agent, a convergence agent, etc. can also be used, As a well-known coupling agent, a silane coupling agent, titanate coupling agent, aluminum System coupling agents and the like.

The said inorganic or organic filler is used normally in 1-200 mass parts with respect to 100 mass parts of thermoplastic resin compositions of this invention, Preferably it is used in the range of 1-100 mass parts.

In the thermoplastic resin composition of the present invention, known weathering agents, antistatic agents, antioxidants, lubricants, plasticizers, colorants, dyes, crystal nucleating agents, antibacterial agents, fungicides, foaming agents, flame retardants (phosphorus-based flame retardants, nitrogen-based flame retardants, halogens) Flame retardant, silicone flame retardant), flame retardant (antimony oxide compound, chlorinated polyethylene such as PRFE) and the like can be blended.

Moreover, the thermoplastic resin composition of this invention is a polyamide resin, polyester resin, PMMA, methyl methacrylate maleimide compound copolymer, polyphenylene ether, polyoxymethylene, polyphenylene sulfide which are other well-known polymers, Epoxy resins, phenol resins, EVA, EV0H, ENE, LCP, thermoplastic polyurethanes, aromatic polycarbonates, urea resins, phenoxy resins and the like can be suitably blended.

The thermoplastic resin composition of this invention prepared in this way can obtain a molded article by well-known shaping | molding methods, such as injection molding, press molding, sheet molding, film molding, vacuum molding, mold release extrusion molding, and foam molding. In addition, a molded article having the thermoplastic resin composition of the present invention as a surface layer, a polyolefin resin or a styrene resin as a double layer or an intermediate layer may be obtained by multilayer extrusion molding, or a desired molded article may be obtained by vacuum molding the multilayer sheet. . The following are illustrated as molded articles obtained by these molding methods.

Gears, Cases, Sensors, LEP Lamps, Connectors, Sockets, Resistors, Relay Cases, Wafer Cases, IC Trays, Liquid Crystal Trays, Switches, Coil Bobbins, Condensers, Barrier Cases, Optical Pickup Components, Oscillators, Various Terminal Blocks, Transformers, Electrical and electronics represented by plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motor magnetic head bases, power modules, housings, semiconductors, liquid crystal FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer components. part. Home and office represented by VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, sounder parts such as audio / laser discs (registered trademark) and compact discs, lighting parts, refrigerator parts, etc. Electrical appliance parts. Office computer parts, phone equipment parts, facsimile parts, copier parts, cleaning tool parts. Sanitary parts such as toilet bowl, tank cover, casing, kitchen parts, vanity parts and bathroom parts. Housing / Household equipment parts such as window frames, furniture, flooring and wall materials. Parts related to optical and precision instruments such as microscopes, binoculars, cameras and watches. Various valves such as alternator terminals, alternator connectors, IC regulators, exhaust gas valves, fuel valves, exhaust systems, and intake valves. Air Intake Nozzle Snorkel, Intake Manifold, Fuel Pump, Engine Coolant Joint, Carburetor Main Body, Carburetor Spacer, Exhaust Gas Sensor, Coolant Sensor, Oil Temperature Sensor, Brake Pad Wear Sensor, Throttle Position Sensor, Crankshaft Position Sensor, Airflow Meter, Thermostat base for air conditioner, Heating hot air flow control valve, Blush holder for radiator motor, Water pump infeller, Turbine vane, Windshield, Wiper Motor parts, Distributor, Starter switch, Starter relay, Transmission wiper Harness, wind washer nozzle, air conditioner panel switch board, coil bobbin for fuel solenoid valve, fuse connector, horn terminal, electrical component insulation plate, step motor roller, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, Engine oil filter, ignition case. Electrical, such as housings, chassis, relays, switches, case members, trans members, and coil bobbins of storage devices such as PCs, printers, displays, CRT displays, notebook computers, mobile phones, PHS, DVD drives, PD drives, and flexible disk drives. Electronic parts. Exterior materials for vehicles such as bumpers and fenders, and other various applications.

As for the thickness at the time of processing the thermoplastic resin composition of this invention into a sheet | seat and a film, the range of 10 micrometers-100 mm is preferable.

A single layer sheet and a film may be sufficient as the said sheet | seat and the film, and the multilayer molded article formed by laminating | stacking on at least one surface of a base material may be sufficient, and the sheet | seat and film which laminated | stacked the adhesive etc. may be sufficient. Furthermore, a well-known gas barrier film can also be formed in the said sheet | seat and a film.

When using the thermoplastic resin composition of this invention to make a multilayer sheet and a film, the thermoplastic resin composition of this invention can be made into a 2-layer sheet, a film with a base material, a 3-layer sheet which makes a base material an intermediate layer, a film, etc., As the substrate used herein, for example, a sheet or a film made of a known polymer can be used, and a sheet or a film made of the component (A) or the component (B) of the present invention can be preferably used. Sheets or films made of olefinic resins are preferably used. Moreover, what mix | blended the said inorganic and organic filler can also be used for the purpose of improving rigidity and heat resistance.

In the multilayer sheet, the thickness of the thermoplastic resin composition of the present invention is preferably 10 µm or more, more preferably 50 µm or more, particularly preferably 80 µm or more for the purpose of stably expressing antistatic properties. As a method of obtaining such a multilayer sheet and a film, a particularly preferable method is coextrusion by a T-die and coextrusion by inflation. The sheet | seat and film obtained in this way can obtain molded articles, such as a tray, by vacuum molding etc. as needed.

1 shows an example of a multilayer molded article of the present invention, and is a schematic cross-sectional view of a two-layer molded article 1 in which an antistatic layer 12 made of the thermoplastic resin composition of the present invention is disposed only on one surface of a base layer 11.

2 shows another example of the multilayer molded article of the present invention, and schematically shows a three-layer molded article 2 in which antistatic layers 12a and 12b made of the thermoplastic resin composition of the present invention are disposed on both sides of the base layer 11. It is a cross section. In addition, the thickness of the antistatic layer 12a and 12b may mutually be same or different. In addition, the compositions of the antistatic layers 12a and 12b may be the same as or different from each other.

When manufacturing an adhesive sheet and a film, in order to improve adhesiveness with an adhesive or adhesiveness with a primer layer, the surface of the base sheet which consists of a thermoplastic resin composition of this invention, and a base film is various well-known processes, for example, Corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, UV treatment, ion bombard treatment, solvent treatment and the like can be performed. Moreover, these combined processes can be performed as needed.

Moreover, in order to improve the adhesive force of a base sheet, a film, and an adhesive, a primer layer can be formed in a base sheet, a film directly, or on the said surface treatment surface. Specifically, resin such as polyethyleneimine, polyurethane, or acrylic resin is formed into a layer having a thickness of about 0.1 μm to 10 μm, which is very thin. Usually, it can form by applying as a solvent (containing water) solution and drying.

Examples of the pressure-sensitive adhesive include an emulsion type applied by a screen method, a gravure method, a mesh method, and a bar coating method, an organic solvent type, and a hot melt type formed by an extrusion lamination method, a dry lamination method, and a coextrusion method. Can be used. In addition, the thickness of an adhesive is not specifically defined, Usually, it is the range of about 1-100 micrometers.

The molded article thus obtained is a case such as a relay case, a wafer case, a latch crew case, a mask case, a tray such as a liquid crystal tray, a chip tray, a memory tray, a CCD tray, an IC tray, a carrier such as an IC carrier, a polarizing film, and the like. Protective sheet, protective sheet for cutting polarizing film, protective film such as display device and plasma display using liquid crystal, protective film for semiconductor, protective film in clean room, and also for vending machine inner member. Can be.

1 is a schematic cross-sectional view showing a molded article having a two-layer structure in the multilayer molded article of the present invention.

2 is a schematic cross-sectional view showing a molded article having a three-layer structure in the multilayer molded article of the present invention.

*** Brief description of symbols for the main parts of the drawing ***

One; Two-layer molded article, 11; understratum,

12, 12a and 12b; Antistatic layer, 2; 3-layer molded product.

EXAMPLES The present invention will be described in more detail with reference to the following Examples. However, the present invention is not limited to these Examples unless the scope of the present invention is exceeded. In the examples, parts and percentages are based on mass unless otherwise specified. In addition, the various measurements in the Example and the comparative example followed the following method.

[1] evaluation methods

(1) gel content of the rubbery polymer; The method was followed.

(2) average particle diameter of rubbery polymer latex;

The average particle diameter of the rubbery polymer latex used for formation of (A) component was measured by the light scattering method. The measuring instrument was integrated 70 times using the LPA-3100 manufactured by Otsuka Electronics, and used the cumulant method. In addition, it was confirmed by electron microscopy that the particle size of the dispersed grafted rubbery polymer particles in the component (A) was almost the same as that of the latex particle.

(3) graft ratio of (A) component; The method was followed.

(4) Intrinsic viscosity [η] of the acetone soluble component of (A) component; The method was followed.

(5) (D) component (the amount of binding styrene of a polymer, the amount of vinyl bonds, number average molecular weight, and hydrogenation rate);

(5-1) bound styrene amount;

It measured in the polymer before hydrogenation. It was calculated | required from the analytical curve by the infrared method based on absorption of the 699 cm <^-1> phenyl group.

(5-2) number average molecular weight;

It measured in the polymer before hydrogenation. Obtained from gel permeation chromatography (GPC).

(5-3) vinyl bond amount;

It measured in the polymer before hydrogenation. It calculated | required by the infrared method (morelo method).

(5-4) hydrogenation rate;

It measured in the polymer after hydrogenation. Ethylene tetrachloride was used as the solvent and was calculated from the spectral reduction of the unsaturated double bonds in the ¹ H-NMR spectrum at 100 MHz measured at 15% concentration.

(6) Impact resistance

(6-1) impact resistance-1;

In accordance with IS0 Test Method 179, notched Charpy impact strength (N / m ² ) was measured.

(6-2) impact resistance-2;

A plate with a thickness of 2.4 mm was placed on a plate 38 mm in diameter, and the breaking energy (kgf · cm) when the plate was punched at a diameter of 16 mm and a speed of 2.4 m / sec was measured.

(6-3) impact resistance-3;

Fracture energy (kgf · cm) was obtained when a 1.6 mm thick plate was punched at a speed of 2.0 m / sec using a 1/2 inch diameter, rod R1 / 2 inch striking rod.

(7) chemical resistance

(7-1) chemical resistance A;

1% deformation was added to the test piece having a thickness of 3.2 mm x 12.7 mm x 127 mm in length, and the following chemicals were applied, and the surface state of the molded article after being left at 23 ° C. for 48 hours was visually evaluated based on the following evaluation criteria.

○; No change

×; Cracking or breaking

(7-1-1) chemical resistance-A1; Ethyl alcohol

(7-1-2) chemical resistance-A2; Brake fluid

(7-2) chemical resistance B;

1% strain was added to the test piece (length 127mm x width 12.7mm x thickness 1mm), ethanol (Et0H) or methyl ethyl ketone (MEK) was apply | coated to the surface, and it was left to stand at 23 degreeC for 72 hours. Thereafter, the surface state of the test piece was visually evaluated based on the following criteria.

○; No change

×; Crack generation or melting

(7-3) chemical resistance C;

A 1% strain was applied to the test piece using a sheet having a thickness of 1 mm, and the surface condition of the sheet after applying the following chemicals and standing at 23 ° C. for 72 hours was visually evaluated based on the following evaluation criteria.

○; No change,

×; Large cracks or fractures.

(7-3-1) chemical resistance-C1; Methanol.

(7-3-2) chemical resistance-C2; Methyl ethyl ketone.

(8) antistatic

(8-1) antistatic-1;

A disk of 100 mm in diameter and 2 mm in thickness was molded and conditioned at 23 ° C x 50% relative humidity for 7 days, followed by Yokogawa Hewlett-Packard Co. The surface resistivity was measured at an applied voltage of 500V using a 4329A type super insulator.

(8-2) antistatic-2;

A disk 100 mm in diameter and 2 mm thick was molded and condition controlled at 23 ° C. × 30% relative humidity for 1 day. Then, surface resistivity was measured at an applied voltage of 500 V using a High Resistance Meter 4339B manufactured by Agilent-Technologies.

(8-3) antistatic-3;

A disk 100 mm in diameter and 2 mm thick was molded and subjected to condition control at 23 ° C. x 50% relative humidity for 1 day, and the surface resistivity was measured at an applied voltage of 500V using a High Resistance Meter 4339B manufactured by Agilent-TechNOl0gies.

(9) antistatic

(9-1) antistatic agent-1;

Using a sheet having a thickness of 1 mm, the surface resistivity after standing for 24 hours at 23 ° C. and 50% RH was measured at an applied voltage of 500 V using Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation.

(9-2) antistatic agent-2;

Using a sheet having a thickness of 1 mm, the surface resistivity (NO1 surface resistivity) after standing for 24 hours at 23 ° C. and 50% RH was measured at an applied voltage of 100 V using Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation. .

(10) persistence of antistatic;

The sheet having a thickness of 1 mm was immersed in distilled water for 10 days, and then left in a constant temperature and humidity bath at 23 ° C. × 50% RH. The surface specific resistance (NO2 surface specific resistance) in the equilibrium state was obtained by measuring the change with time of surface specific resistance in the method of (9-2).

Persistence was evaluated from the NO1 surface resistivity and the NO2 surface resistivity as follows.

○; NO2 surface resistivity is equal to or lower than NO1 surface resistivity and has persistence.

×; NO2 surface resistivity deteriorates compared to NO1 surface resistivity and persistence deteriorates.

(11) Surface appearance of molded products

(11-1) surface appearance 11;

Visual evaluation was performed based on the following evaluation criteria using a flat molded article having a thickness of 3.2 mm.

◎; Almost no sink, smooth surface condition

○; There is a little sink, but the surface condition of the molded product is smooth, so the problem is high.

×; Problems with high sinks and / or poor surface smoothness of molded parts.

(11-2) surface appearance-2 (glossy);

MURAKAMI COLOR RESEARCH LABORATORY Co., Ltd. 60 degree gloss was measured using the glossmeter GM-26D of the product.

(11-4) surface appearance-3;

The multilayer sheet and the trays were visually evaluated based on the following criteria.

○; The surface is smooth and the shape is stable.

×; Uneven surface or unstable shape.

[2] thermoplastic resin compositions

(1) (A) component

(1-1) Preparation Example 1; ABS resin (A1)

In an internal volume 7L glass flask equipped with a stirrer, 75 parts of ion-exchanged water, 0.5 parts of potassium rosinate, 0.1 parts of tert-dodecyl mercaptan, polybutadiene latex (average particle diameter; 350OPa, gel content; 85) %) 40 parts (solid content), 15 parts of styrene, and 5 parts of acrylonitrile were added, and it heated up stirring. When internal temperature reached 45 degreeC, the solution which melt | dissolved 0.2 part of sodium pyrrolate, 0.01 part of ferrous sulfate heptahydrate, and 0.2 part of glucose in 20 parts of ion-exchange water was added. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After the polymerization for 1 hour, 50 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 parts of tert-dodecyl mercaptan and 0.01 part of cumene hydroperoxide were continuously added over 3 hours. And, after continuing the polymerization for 1 hour, 0.2 part of 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization. The reaction product latex was solidified in an aqueous sulfuric acid solution, washed with water, and dried to obtain a styrene resin A1. The graft ratio of this A1 was 68%, and the intrinsic viscosity [η] of the acetone soluble component was 0.45 dl / g.

(1-2) Preparation Example 2; AS resin (A2)

Two jacketed polymerization vessels with a ribbon wing having an internal volume of 30 L were connected, and after nitrogen replacement, 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reaction vessel. A solution of 0.12 parts of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and a solution of 0.1 parts of 1,1'-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator were continuously fed. The 1st polymerization temperature was adjusted to 110 degreeC, the average residence time was 2.0 hours and the polymerization conversion ratio was 57%. The obtained polymer solution was continuously taken out in the same amount as that of the styrene, acrylonitrile, toluene, molecular weight regulator, and polymerization initiator by a pump placed outside the first reaction vessel, and supplied to the second reaction vessel. The polymerization temperature of the second reaction vessel was carried out at 130 ° C., and the polymerization conversion rate was 75%. The copolymer solution obtained in the second reaction vessel was directly volatilized to remove the unreacted monomer and the solvent by using an extruder having a biaxial three-stage degassing hole, thereby obtaining a styrene resin A2 having an intrinsic viscosity [η] 0.48.

(1-3) Preparation Example 3; Hydroxyl-containing unsaturated compound copolymer AS resin (A3)

In Production Example 1, potassium rosin was replaced with potassium dodecylbenzenesulfonate without using polybutadiene. In addition, styrene / acrylonitrile / 2-hydroxyethyl methacrylate was changed to 22.5 / 7.5 / 3.5 parts as the monomer component in one step. Moreover, all superposed | polymerized by the method of the manufacture example 1 except having changed the continuous addition component into styrene / acrylonitrile / 2-hydroxyethyl methacrylate = 44.7 / 14.9 / 6.9 parts. The reaction product latex was coagulated and washed with an aqueous magnesium sulfate solution and then dried to obtain styrene resin A3. Its intrinsic viscosity [] was 0.44.

(1-4) Preparation Example 4; Carboxyl group-containing unsaturated compound copolymer AS resin (A4)

In Production Example 3, styrene / acrylonitrile / methacrylic acid = 23.7 / 7.9 / 1.7 parts was changed as the monomer component in one step. In addition, all were performed by the method of the manufacture example 1 except having changed the continuous addition component into styrene / acrylonitrile / methacrylic acid = 47.5 / 15.8 / 3.4 parts. Styrene-based resin A4 having an intrinsic viscosity [η] 0.46 was obtained.

(1-5) Preparation Example 5; Epoxy group-containing unsaturated compound copolymer AS resin (A5)

In Production Example 3, styrene / acrylonitrile / glycidyl methacrylate was changed to 23.7 / 7.9 / 1.7 parts as the monomer component in one step. In addition, all were performed by the method of the manufacture example 1 except having changed the continuous addition component into styrene / acrylonitrile / glycidyl methacrylate = 47.5 / 15.8 / 3.4 parts. Styrene-based resin A5 having an intrinsic viscosity [η] 0.42 was obtained.

(2) (B) component;

(2-1) B1; Polypropylene resin

 Block type polypropylene "Novatec BC6C" (trade name) manufactured by Japan Polychem Corporation was used.

(2-2) B2; Polypropylene resin

Homotype polypropylene "Novatec MA1 (trade name)" manufactured by Japan Polychem Corporation was used.

(2-3) B3; Polypropylene resin

Homotype polypropylene "Novatec FY6C" (trade name) from Japan Polychem Corporation was used.

(3) (C1) component;

C1-1; Sanyo Chemical Industries, Ltd. The polypropylene polyether block copolymer "PELESTAT 303" (trade name) of the product was used.

C1-2; Sanyo Chemical Industries, Ltd. Polyethylene polyether block copolymer "PELESTAT 230" (trade name) of the product was used.

(4) (C2-1) a component;

C2-1-1; Sanyo Chemical Industries, Ltd. The polyetherpolyamide "PELESTATM-140" (trade name) of the product was used.

C2-1-2; TAKEMOTO OIL & FAT Co., Ltd. The polyether polyester "TEP-004" (brand name) of the product was used.

(5) (C2-2) a component;

As the component (C2-2) of the present invention, the following nonionic antistatic agent manufactured by Kao Corporation was used.

C2-2-1; ELECTROSTRIPERTS-5 (brand name) glycerin ester antistatic agent,

C2-2-2; ELECTROSTRIPEREA (brand name) diethanolamine type antistatic agent,

C2-2-3; ELECTROSTRIPERTS-3B (brand name) glycerin ester type / diethanolamine type composite antistatic agent.

(6) (C2-3) a component;

As the component (C2-3) of the present invention, "Hi-Boron MB400N-8LDPE (trade name)" manufactured by Boron International was used. This product is a polyethylene masterbatch of Hi-Boron 400N (trade name) (polymeric charge transfer type conjugate) of the company, and the active ingredient as the component (C2-3) is 7%.

(7) (C2-4) a component;

The following were used as (C2-4) component of this invention.

C2-4-1; Sanko Chemical Industry Co., Ltd. Product Sankonol 0862-10T

Content of lithium salt compound 10%,

C2-4-2; Sanko Chemical Industry Co., Ltd. Product Sankonol AQ-50T (brand name)

Content of lithium salt compound 50%.

C2-4-3; Lithium bromide.

(8) (D) component;

(8-1) Preparation Example 6; Partially Hydrogenated Styrene-Butadiene-Styrene Block Copolymer

The autoclave provided with the stirrer and the jacket was dried, nitrogen-substituted, and the cyclohexane solution containing 30 parts of styrene was thrown in. Subsequently, n-butyllithium was added, and it superposed | polymerized at 70 degreeC for 1 hour, and the cyclohexane solution containing 40 parts of butadiene was added, and it superposed | polymerized for 1 hour. A part of the obtained block polymer solution was sampled, 0.3 part of 2,6-di-tert-butylcatechol was added to 100 parts of the block copolymer, and then the solvent was removed by heating. Its styrene content was 60%, the 1,2-vinyl bond amount of the polybutadiene portion was 35%, and the number average molecular weight was 74,000. A solution obtained by reacting titanocene dichloride and triethyl aluminum in cyclohexane was added to the remaining block copolymer solution, and a hydrogenation reaction was performed at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 40 minutes. 0.3 part of 2, 6- di-tert- butyl catechol was added with respect to 100 parts of block copolymers, after that, the solvent was removed and the polymer D1 of 69% of hydrogenation rate was obtained.

(8-2) Preparation Example 7; Fully Hydrogenated Styrene-Butadiene-Styrene Block Copolymer

The autoclave equipped with the stirrer and the jacket was dried, nitrogen-substituted, and the 20 parts solution of cyclohexane and butadiene was thrown in. Next, 0.025 part of n-butyllithium was added and 50 degreeC isothermal polymerization was performed. When the conversion ratio became 100%, 0.75 parts of tetrahydrofuran and 65 parts of butadiene were added, and the temperature rise polymerization was performed from 50 ° C to 80 ° C.

When the conversion ratio reached 100%, 15 parts of styrene was added, and the polymerization reaction was further performed to obtain an A-B1-B2 triblock copolymer before hydrogenation. As a result of sampling and analysis as in Preparation Example 6, 15% (A-block) of styrene block, butadiene block (B1 block) containing 35% of 1,2-vinyl and 10% butadiene block (B2 block) of 1,2-vinyl It was a polymer having a number average molecular weight of 200,000.

In a separate vessel, 1 part of titanocene dichloride was dispersed in cyclohexane and reacted with 0.5 parts of triethylaluminum at room temperature. The obtained homogeneous solution was added to the polymer solution, and hydrogenated at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 2 hours to obtain a hydrogenated polymer D2 having a hydrogenation rate of about 100%.

(8-3) Preparation Example 8; Styrene-butadiene-styrene block copolymer

The autoclave equipped with the stirrer and the jacket was dried and nitrogen-substituted, and 0.08 parts of cyclohexane and tetrahydrofuran were converted in nitrogen stream. Then, when the temperature was raised to 70 ° C by the internal temperature, a cyclohexane solution containing 0.052 parts of n-butyllithium was added, followed by polymerization of 60 minutes by adding 15.5 parts of styrene. Then, a mixture of 3 parts of styrene and 20 parts of butadiene was added to polymerize for 60 minutes (step 2). Further, a mixture of 3 parts of styrene and 20 parts of butadiene was added to polymerize for 60 minutes (3 steps). Further, a mixture of 3 parts of styrene and 20 parts of butadiene was added to polymerize for 60 minutes (step 4), and three tapered blocks were polymerized. Subsequently, 15.5 parts of styrene was added and polymerization was carried out for 60 minutes (step 5). The polymerization conversion rate was 100%.

In addition, it controlled so that internal temperature might become 70 degreeC during superposition | polymerization. After completion of the polymerization, 2,6-di-tert-butylcatechol was added to the polymer solution, and then the solvent was removed by heating to obtain a block copolymer D3 having three tapered blocks in which polystyrene increased in the polybutadiene block portion. . Its number average molecular weight was 128,000, and styrene content was 40%.

(8-4) Preparation Example 9; Styrene-butadiene-radial tereblock copolymer

The autoclave provided with the stirrer and the jacket was dried and nitrogen-substituted, and 2.75 parts of cyclohexane and tetrahydrofuran were prepared in nitrogen stream. 25 parts of styrene were added, and it heated up at 60 degreeC, the cyclohexane solution containing 0.175 parts of n-butyllithium was added, and the polymerization reaction was performed for 60 minutes (1 step). Subsequently, a polymerization reaction was carried out for 60 minutes by adding a mixture of 3 parts of styrene and 20 parts of butadiene (step 2), and a polymerization reaction was performed for 60 minutes by adding a mixture of 3 parts of styrene and 20 parts of butadiene (step 3). Further portions were further polymerized to completion until the conversion was 100%. After adding 0.1 part of silicon tetrachloride as a coupling agent, the coupling reaction was completed. After the end of the polymerization, 2,6-di-tert-butylcatechol was added to the polymer solution, and then the solvent was removed by heating to obtain a coupling type styrene-butadiene block copolymer D4 having a tapered block. Its styrene content was 31%, and the number average molecular weight was 200,000.

(8-5) Styrene-Butadiene-Styrene Block Copolymer

D5; "TR2500" (brand name) of the JSR product was used.

(8-6) Hydrogenated Additives of Styrene-Butadiene Block Copolymer

D6; "DYNAR0N4600P" (trade name) of JSR Corporation was used.

(9) (E) component;

Preparation Example 10; Graft polymer

After nitrogen-substituting the internal volume 10L stainless autoclave with a ribbon wing, 30 parts (solid content), 52.5 parts of styrene, and 52.5 parts of styrene of said polymer D2 which made a homogeneous solution previously using toluene as a solvent in nitrogen stream. 17.5 parts, toluene 120 parts, and tert-dodecyl mercaptan 0.1 part were thrown in, and it heated up stirring. When the internal temperature reached 50 ° C, 0.5 part of benzoyl peroxide and 0.1 part of dicumyl peroxide were added, the temperature was further raised to 80 ° C, and the polymerization reaction was carried out at a constant control at 80 ° C. After 1 hour from the start of the reaction, the temperature was raised to 120 ° C for 1 hour, and the reaction was further performed for 2 hours. The conversion rate was 97%.

After cooling to 100 ° C., 0.2 part of 2,2-methylenebis-4-methyl-6-tert-butylphenol was added, and then the reaction mixture was taken out of the autoclave, and the unreacted substance and solvent were distilled off by steam distillation. , The polymer was pelletized to obtain graft polymer E. The graft ratio of this was 45% and the intrinsic viscosity [η] of the acetone soluble component was 0.45 dl / g.

(10) (F) component;

Kuraray Co., Ltd. TM polymer of the product; TM-S4L77 (trade name of SEPS-aromatic polycarbonate block copolymer) was used.

(11) (G) component;

As the (G) component of the present invention, the following Sanyo Chemical Industries, Ltd. Maleic anhydride modified polyolefin of the product was used.

G1; YOUMEX1001 (product name of maleic anhydride added amount 5%).

G2; YOUMEX1010 (trade name for maleic anhydride added 10% product).

(12) Other Ingredients (H)

(12-1) H1; Aromatic polycarbonate

"NOVAREX 7022PJ" (trade name molecular weight 22,000) from Mitsubishi Engineering-Plastics Corporation was used.

(12-2) H2; Polybutylene terephthalate

Polyplastic Co., Ltd. The product "Duranex XD477 (brand name)" (intrinsic viscosity 1.2 kW / g) was used.

Examples I-1 to I-23, Comparative Examples I-1 to I-3

After mixing with the Henschel mixer at the compounding ratio shown in Table 1a, it melt-kneaded and pelletized using the twin screw extruder (cylinder setting temperature 200 degreeC). After drying the obtained pellet sufficiently, the test piece for evaluation was produced by injection molding (cylinder setting temperature 200 degreeC). This test piece was used to evaluate impact resistance, chemical resistance, molded article surface appearance, and antistatic property by the above-described evaluation method. The evaluation results are shown in Table 1b.

The following becomes clear from the result shown in Table 1b.

The molded articles of Examples I-1 to I-23 of the present invention are excellent in impact resistance, chemical resistance, surface appearance and antistatic properties of the molded article. In addition, although chemical-resistance -A1 and A2 of Examples I-22 and I-23 are all (circle), it is slightly worse than the thing of Examples I-1-I-21.

On the other hand, Comparative Example I-1 is an example in which the amount of the component (A) of the present invention is less than the range of the present invention, and the amount of the component (B) is outside the range of the present invention. Do. Comparative Example I-2 is an example in which the amount of the component (C1) of the present invention is less than the range of the present invention, and the impact resistance, the surface appearance of the molded article, and the antistatic property deteriorate. Comparative Example I-3 is an example in which the amount of the (C1) component of the present invention is used outside the range of the present invention, and the impact resistance and the surface appearance of the molded article deteriorate.

Example I-24

Production of three layer sheet

3-layer sheet (1)

The composition of Example I-19 produced the three-layered sheet whose both surface layers (each thickness is 100 micrometers), and the center layer is B1 component (thickness 800 micrometers). In addition, the sheet was vacuum molded to prepare a tray.

3-layer sheet (2)

Using the composition of Example I-22 and the B1 component, a tray was prepared in a three-layer sheet and vacuum molding in the same manner as above.

3-layer sheet (3)

Using the composition of Example I-22 and ABS (composition consisting of A1 component / A2 component = 40/60%), the composition of Example I-22 is composed of both surface layers (each having a thickness of 100 µm) and the central portion is ABS. A three-layered sheet having a thickness of 800 µm was produced. The tray was prepared by vacuum molding as above.

Examples II-1 to II-15, Comparative Examples II-1 to II-3

After mixing all components by the Henschel mixer in the compounding ratio of Table 2a and 2b, it melt-kneaded and pelletized using the twin screw extruder (cylinder setting temperature 200 degreeC). After drying the obtained pellet sufficiently, the test piece for evaluation was produced by injection molding (cylinder setting temperature 200 degreeC).

Using this test piece, impact resistance, chemical resistance, and antistatic were evaluated by the above-described evaluation method. The evaluation results are shown in Table 2a.

The following becomes clear from the results shown in Tables 2a and 2b.

The molded articles of Examples II-1 to II-15 of the present invention are excellent in all of impact resistance, chemical resistance and antistatic property.

On the other hand, in Comparative Example II-1, the usage-amount of (A) component of this invention is less than the range of invention, and the usage-amount of (B) component is many out of the range of this invention, and impact resistance and antistatic property deteriorate. Comparative Example II-2 is an example in which the amount of the component (C1) of the present invention is less than the range of the invention, and the impact resistance and the antistatic property deteriorate. Comparative Example II-3 is an example in which the amount of the (C1) component of the present invention is used outside the scope of the present invention, and the impact resistance deteriorates.

Examples III-1 to III-18 and Comparative Examples III-1 to III-2

After mixing all the components with the Henschel mixer at the mixing | blending ratio of Table 3a and 3b, it melt-kneaded and pelletized using the twin screw extruder (cylinder setting temperature 220 degreeC). After drying the obtained pellet sufficiently, the test piece for evaluation was produced by injection molding (cylinder setting temperature 220 degreeC).

Using this test piece, impact resistance, chemical resistance, molded article surface appearance and antistatic were evaluated by the above-described evaluation method. The evaluation results are shown in Tables 3A and 3B.

The following becomes clear from the results shown in Tables 3A and 3B.

The molded articles of Examples III-1 to III-18 of the present invention are excellent in chemical resistance and antistatic property, and the molded articles of Examples III-1 to III-17 are also excellent in impact resistance and surface gloss of molded articles.

In Comparative Example III-1, the usage-amount of (A) component of this invention is less than the range of this invention, and the usage-amount of (B) component is many out of the range of this invention, and impact resistance and antistatic property deteriorate. Comparative Example III-2 is an example in which the amount of the component (C1) of the present invention is less than the range of the invention, and the impact resistance and the antistatic property deteriorate.

Example IV-1

Predetermined amounts of the ingredients listed in Table 4 were mixed with a Henschel mixer. Then, melt kneading (cylinder setting temperature 220 degreeC) was performed using the twin screw extruder, and the pelletized thermoplastic resin composition was obtained. As described above, the component (C2-3) contains polyethylene corresponding to the component (B). Thus, the amount of polyethylene is shown in Table 4 as B4.

Next, the component B3 for forming the base layer and the thermoplastic resin composition for forming the antistatic layer on both sides of the base layer are coextruded at a temperature of 210 ° C., and the base layer has a thickness of 800 μm and the thickness of the antistatic layer, respectively. A multilayer sheet having a thickness of 100 mm having a thickness of 100 µm was obtained. The surface resistivity (antistatic property), chemical resistance and surface appearance of the multilayer sheet were evaluated.

In addition, the multilayer sheet was vacuum molded to prepare a tray. This tray was evaluated for surface appearance. The results are shown in Table 4.

Example IV-2 to IV-14

A thermoplastic resin composition, a sheet and a tray were produced in the same manner as in Example IV-1 except that a predetermined amount of the components shown in Table 4 were used, and the surface resistivity and the surface appearance were evaluated. The results are shown in Table 4.

The following becomes clear from Table 4.

Examples IV-1 to IV-14 of the present invention have low surface resistivity, excellent antistatic properties, and excellent chemical resistance and surface appearance.

The antistatic effect which uses together (C1) component and (C2-3) component becomes clear by contrast of Example IV-1 and Example IV-14. That is, the usage-amount of the (C1) component and (C2-3) component in Example IV-1 are 26% and 1.19%, respectively, and the sum total is 27.19%. In addition, the usage-amount of the (C1) component and (C2-3) component in Example IV-14 are 27.19% and 0%, respectively, and the total is 27.19%. Therefore, in Example IV-1 and Example IV-14, even if the total amount of (C1) component and (C2-3) component which impart antistatic property is the same, (C1) component and (C2-3) It can be seen that Example IV-1 using the component is excellent in antistatic property because the surface resistivity is 10 times lower.

Examples V-1 to V-23, Comparative Examples V-1 to V-5

After mixing with the Henschel mixer at the mixing ratios shown in Tables 5a and 5b, the mixture was melt kneaded and pelletized using a twin screw extruder (cylinder set temperature 220 ° C). After drying the obtained pellet sufficiently, the test piece for evaluating the molded product surface appearance was obtained by injection molding (cylinder setting degree 210 degreeC).

A sheet having a thickness of 800 µm of the polymer B3 was used as a core layer, and a three-layer sheet obtained by laminating the resin composition on the front and back with a thickness of 100 µm was produced by coextrusion (temperature 220 ° C.), and the sheet having a thickness of 1 mm. Got. This sheet | seat was cut | disconnected, and it was set as the test piece for antistatic evaluation and the test piece for chemical resistance evaluation.

The evaluation method evaluated the antistatic property, chemical resistance and the surface appearance of the molded article.

Further, the sheets obtained in Examples V-1, V-4, V-5, V-7 to V-9, V-11, V-21 and V-22 were preheated at a temperature of 200 ° C and vacuum forming was performed. The tray molded article was obtained. And the surface specific resistance of the vicinity of the corner of a tray molded article was measured by the method similar to the said antistatic measuring method.

The evaluation results are shown in Tables 5a and 5b.

Examples V-1 to V-4 and Comparative Examples V-1 to V-3 are examples relating to the second thermoplastic resin composition containing the components (B), (C1) and (C2-2) of the present invention as essential components. Examples and Comparative Examples, Examples V-5 to V-8, Comparative Examples V-4 and V-5 are essential components of the components (B), (C1), (C2-2) and (D) of the present invention. Examples and comparative examples relating to the third thermoplastic resin composition. In addition, Examples V-9 to V-23 carry out a first thermoplastic resin composition having the components (A), (B), (C1), (C2-2) and (D) as essential components of the present invention. Yes.

The following becomes clear from the results shown in Tables 5a and 5b.

The molded articles of Examples V-1 to V-23 of the present invention are excellent in antistatic property, chemical resistance and surface appearance of the molded article.

Comparative Example V-1 is an example in which the amount of the component (B) of the present invention is much larger than the range of the present invention, and the amount of the component (C1) is less than the range of the present invention. In Comparative Example V-2, the amount of the component (B) of the present invention is less than the scope of the invention, and the amount of the component (C1) is outside the scope of the invention, whereby the chemical resistance and the appearance of the molded article deteriorate. In Comparative Example V-3, the amount of the (C2-2) component of the present invention is less than the range of the present invention, and the antistatic property is deteriorated. In Comparative Example V-4, the usage-amount of the component (C2-2) of the present invention is outside the scope of the invention, whereby the chemical resistance and the molded article surface appearance deteriorate. Comparative Example V-5 is an example in which the amount of the component (D) of the present invention is used outside the range of the present invention, and the chemical resistance and the appearance of the molded article are deteriorated.

Examples VI-1 to VI-15, Comparative Example VI-1

After mixing with a Henschel mixer at the mixing ratios shown in Table 6, the mixture was melt kneaded and pelletized using a twin screw extruder (cylinder set temperature 220 ° C). After drying the obtained pellet sufficiently, the test piece for impact resistance evaluation was obtained by injection molding (cylinder setting degree 200 degreeC).

Using a sheet having a thickness of 800 μm of the polymer A1 described above as a core layer, a three-layer sheet obtained by laminating the thermoplastic resin composition at a thickness of 100 μm each on its front and back was produced by coextrusion (temperature 200 ° C.) A sheet of 1 mm was obtained. This sheet was cut to obtain a test piece for antistatic evaluation, a test piece for battery property evaluation, and a test piece for chemical resistance evaluation. Various evaluation results are shown in Table 6.

The following becomes clear from the result of Table 6.

The molded articles of Examples VI-1 to VI-15 of the present invention are excellent in antistatic properties, battery properties, chemical resistance and impact resistance, and in particular, the molded articles of Examples VI-1 to VI-14 are excellent in antistatic properties.

On the other hand, in Comparative Example V-1, the usage-amount of the (C1) component of this invention is many examples outside the range of invention, and chemical resistance and impact resistance deteriorate.

The thermoplastic resin composition of the present invention has excellent impact resistance, chemical resistance, surface appearance of molded articles, and antistatic to antistatic properties, and has a high demand for automotive, electric and electronic fields, OA and home appliances. And various parts such as sanitary field.

Claims (12)

5 to 95 mass% of the following (A) component and 95 to 5 mass% of (B) component are contained (However, the sum total of the said (A) component and (B) component is 100 mass%), Moreover, 0.5-100 mass parts of following (C1) components are contained with respect to a total of 100 mass parts of said (A) component and (B) component, The thermoplastic resin composition characterized by the above-mentioned. (A) component: Styrene-type resin formed by (co) polymerizing an aromatic vinyl compound or another vinyl monomer copolymerizable with an aromatic vinyl compound in presence or absence of a rubbery polymer, (B) component: olefin resin, (C1) component: Anionic polymer which makes an olefin polymer block (c1-1), a polyether (c1-2-a), a polyether containing hydrophilic polymer (c1-2-b), and a polyether an essential structural unit A block copolymer containing a hydrophilic polymer block (c1-2) selected from (c1-2-c). The component (A) according to claim 1, wherein at least one component selected from the group consisting of the following (C2-1) component, (C2-2) component, (C2-3) component and (C2-4) component And 0.001 to 60 parts by mass based on 100 parts by mass of the total of the component (B). (C2-1) Component: At least one of polyether polyamide and polyether polyester (C2-2) Component: Nonionic antistatic agent, (C2-3) component: a boron compound, (C2-4) Component: Lithium salt. The at least one component selected from the group consisting of the following (D) component, (E) component, (F) component, and (G) component is a total of 100 of the said (A) component and (B) component of Claim 1 The thermoplastic resin composition comprising 1 to 200 parts by mass relative to the mass parts. (D) component: Comprising a block copolymer (Da) containing the polymer block (d-1) containing an aromatic vinyl compound, and the polymer block (d-2) containing a conjugated diene compound, and its hydrogenated substance (Db) At least one polymer selected from the group, (E) component: The graft polymer formed by (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound, and the other vinyl monomer copolymerizable with an aromatic vinyl compound in presence of the said (D) component, (F) component: The aromatic polycarbonate block copolymer which consists of a polymer block (f-1) which consists of said (D) component, and an aromatic carbonate polymer block (f-2), (G) Component: Low molecular weight polyolefin with a weight average molecular weight of 1,000-100,000 modified | denatured by at least one of unsaturated acid and unsaturated acid anhydride. The at least one component selected from the group consisting of the following (D) component, (E) component, (F) component, and (G) component is a total of 100 of the said (A) component and (B) component of Claim 2 The thermoplastic resin composition comprising 1 to 200 parts by mass relative to the mass parts. (D) component: Comprising a block copolymer (Da) containing the polymer block (d-1) containing an aromatic vinyl compound, and the polymer block (d-2) containing a conjugated diene compound, and its hydrogenated substance (Db) At least one polymer selected from the group, (E) component: The graft polymer formed by (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound, and the other vinyl monomer copolymerizable with an aromatic vinyl compound in presence of the said (D) component, (F) component: The aromatic polycarbonate block copolymer which consists of a polymer block (f-1) which consists of said (D) component, and an aromatic carbonate polymer block (f-2), (G) Component: Low molecular weight polyolefin with a weight average molecular weight of 1,000-100,000 modified | denatured by at least one of unsaturated acid and unsaturated acid anhydride. delete delete delete delete A molded article made of the thermoplastic resin composition according to any one of claims 1 to 4. The molded article according to claim 9, which is a sheet or a film. The multilayer molded article formed by laminating | stacking the sheet | seat or the film which consists of a thermoplastic resin composition in any one of Claims 1-4 on at least one surface of a base material. The multilayer molded article according to claim 11, wherein the substrate is a sheet or a film made of an olefin resin.

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