TWI392704B - The thermoplastic resin composition and molded article - Google Patents

Description

Thermoplastic resin composition and molded article

[0001] The present invention relates to a thermoplastic resin composition having excellent impact resistance, chemical resistance, surface appearance of a molded article, antistatic property, and electrical conductivity, and a molded article comprising the thermoplastic resin composition.

[0002] A styrene-based resin such as ABS resin is widely used in electrical and electronic fields, OA, home appliances, and vehicles because of its excellent impact resistance, moldability, rigidity, and other mechanical strengths. In the field, the health field, etc., but some applications cannot fully exert the chemical resistance, and each requirement is to improve the chemical resistance.

On the other hand, olefin-based resins such as polypropylene have excellent chemical resistance, heat resistance, fluidity, etc., and are widely used in electric and electronic fields, OA, home electric appliances, and vehicles, similar to the above-mentioned styrene-based resins. In the field, the sanitary field, and the like, the impact resistance is low, and warpage, burrs, and the like are likely to occur on the molded article. Further, the physical properties and dimensions after molding have time variations.

In order to improve the above problems, although a mixture of ABS resin and polypropylene is considered, the compatibility between the two is poor, and only a very fragile material can be obtained by simple melt mixing; Patent Document 1 mentions that in the polymerization In the case of a styrene resin and a polypropylene resin, a styrene butadiene copolymer block rubber is present, but there is no relevant description of the ABS resin, the AS resin, and the polypropylene; and Patent Document 2 mentions the formulation of a polyolefin resin and a poly In the case of a styrene-based resin, a hydrogen-added styrene-butadiene copolymer is blended, but there is no description of the preparation of the ABS resin, the AS resin, and the polyolefin. Patent Document 3 mentions the blending of a polyolefin resin and a low molecular weight. A composition composed of a polystyrene and a styrene butadiene copolymer block, but there is no relevant description of the ABS resin or the AS resin.

Further, Patent Document 4 mentions that a styrene-based resin which is denatured by an epoxy-modified polypropylene or an unsaturated carboxylic acid or an anhydride is regarded as a compatibilizing agent; it is also mentioned in Patent Document 5, a polypropylene-based resin modified with an epoxy group, and a styrene butadiene copolymerized block which is denatured with an unsaturated carboxylic acid or the anhydride, but has insufficient impact resistance and a surface appearance of the molded article; and the molded article is easily charged. It is difficult to use for applications that cause static electricity.

In addition, styrene resins such as ABS resin and polyolefin resin such as polypropylene all have a property of being easily electrostatically charged, so that it is difficult to be used for a liquid crystal display device, a plasma TV, and a semiconductor periphery which may be hindered by static electricity. Various components, sheets, films, etc. used or operated in components, clean rooms, and the like.

In order to improve the related disadvantages, Patent Document 9 proposes to adjust a polyamine elastomer on a styrene resin such as ABS resin, but has a problem that power generation is not sufficiently found; similarly, Patent Document 10 and Patent Literature There is also a composition which discloses a rubber-reinforced styrene-based resin and a polyamide elastomer. Further, Patent Document 6 and Patent Document 7 propose to formulate a specific antistatic agent on a polyolefin resin, but it is not sustainable. In addition, problems such as insufficient power-generating property are encountered. In addition, the method of continuously exerting the power-generating property is proposed in Patent Documents 8 and 12, and the polyene-based resin is blended with a polyene block and has a poly-polymer. A copolymer block of a hydrophilic block polymer such as ether, but has a problem that power generation property is not sufficiently found.

[Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-56-38338 (Patent Document 3) JP-A-56-104978 (Patent Document 4) Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document No. JP-A-2002-284880] [Patent Document No. JP-A-2002-284880]

Disclosure of invention

An object of the present invention is to provide a thermoplastic resin composition having excellent impact resistance, chemical resistance, surface appearance, antistatic property, and electrical conductivity of a molded article, and a molded article comprising the thermoplastic resin composition. .

In order to achieve the above object, the inventors of the present invention have found that a polyolefin-containing polymer and a hydrophilic resin composition are blended on a thermoplastic resin composition containing a styrene resin and/or an olefin resin. The copolymer of the segment polymer can obtain a molded article having excellent impact resistance, chemical resistance, surface appearance of the molded article, and antistatic property, thereby completing the present invention; and also finding a compound having a specific antistatic property. And/or a polymer of a specific block structure or a low molecular weight polyene metamorphism can improve characteristics such as impact resistance and antistatic property, and thus the present invention has been completed.

In other words, according to the standpoint of the present invention, it is characterized in that it contains 5 to 100% by mass of the following (A) component and 95 to 0% by mass of the component (B) (but the (A) component and (B) The total amount of the ingredients is 100% by mass).

In addition, the total amount of the component (A) and the component (B) is 100 parts by mass, and the following (C1) component contains a thermoplastic resin composition of 5 to 100 parts by mass (hereinafter referred to as "first thermoplastic resin composition") ).

(A) component: a styrene resin which (co)polymerizes an aromatic vinyl compound or a copolymerizable aromatic vinyl compound and another vinyl monomer of an aromatic vinyl compound in the presence or absence of a rubbery polymer; B) Component: an olefinic resin; (C1) component: a block copolymer of an olefin-containing block polymer (c1-1) and a hydrophilic block polymer (c1-2).

Further, according to a preferred embodiment of the present invention, it is provided that the total amount of the component (A) and the component (B) is 100 parts by mass, and at least 0.001 to 60 parts by mass are provided from below (C2). -1) The above first thermoplastic resin composition of one component selected from the group consisting of a component, (C2-2) component, (C2-3) component, and (C2-4) component group.

(C2-1) Ingredients: Polyether Polyamide and/or Polyether Polyester, (C2-2) Ingredients: Nonionic Antistatic Agent, (C2-3) Ingredients: Boron Compound (C2-4) Ingredients: Lithium salt [0010] In addition, according to another preferred embodiment of the present invention, at least 100 parts by mass of the above-mentioned (A) component and (B) component are provided, and at least 1 to 200 mass parts are provided. The first thermoplastic resin composition of the component selected from the group consisting of (D) component, (E) component, (F) component, and (G) component group.

(D) Component: at least a block copolymer containing a block polymer (d-1) mainly composed of an aromatic vinyl compound and a block polymer (d-2) mainly composed of a conjugated diene compound ( D-a) and one component selected from the hydrogen additive (D-b) component group.

(E) component: a graft polymer of (co)polymerized aromatic vinyl compound or copolymerizable aromatic vinyl compound and other vinyl monomer of the aromatic vinyl compound in the presence of the above component (D), (F) Component: an aromatic polycarbonate copolymer composed of the block polymer (f-1) composed of the above component (D) and the aromatic carbonate block polymer (f-2), (G) component A low molecular weight polyolefin which is denatured by an unsaturated acid and/or an unsaturated acid anhydride.

The above-mentioned first thermoplastic resin composition may be used in combination with at least "the component selected from the above (D) component, (E) component, (F) component, and (G) component group". The above-mentioned (C2-1) component, (C2-2) component, (C2-3) component, and (C2-4) component selected from the group of ingredients".

Further, according to another preferred embodiment of the present invention, the first thermoplastic resin composition contains the above-mentioned (A) component in an amount of 5 to 95% by mass, and (B) a component in an amount of 95 to 5% by mass (but this is (A) component and (B) component totaled 100% by mass).

[0012] Further, according to another aspect of the present invention, it is characterized in that it contains 70 to 97% by mass of the following (B) component and 30 to 3% by mass of the (C1) component (but the component (B) and (C1) In the case where the total amount of the component (B) and the component (C1) is 100 parts by mass, the following (C2-2) component contains 0.01 to 10 parts by mass of the thermoplastic resin composition ( Hereinafter, it is referred to as "second thermoplastic resin composition").

(B) Ingredients: olefinic resin, (C1) component: block copolymer of an olefin-containing block polymer (c1-1) and a hydrophilic block polymer (c1-2), (C2-2) component: Non-ionic antistatic agent.

In the second thermoplastic resin composition, the component (B) may have at least 100 parts by mass, and may contain at least the above (C2-1) component, (C2-2) component, (C2). -3) One component selected from the group of ingredients.

[0013] Further, according to another aspect of the present invention, it is characterized in that it contains 30 to 96% by mass of the following (B) component, 3 to 90% by mass of the following (C1) component, and 1 to 40 mass of the following (D) component. % (however, the (B) component, the (C1) component, and the (D) component are 100% by mass in total), and the (B) component, the (C1) component, and the (D) component are collectively 100 mass parts. In other words, a thermoplastic resin composition (hereinafter referred to as "third thermoplastic resin composition") containing 0.01 to 10 parts by mass of the following (C2-2) component.

(B) Ingredients: olefinic resin, (C1) component: block copolymer of an olefin-containing block polymer (c1-1) and a hydrophilic block polymer (c1-2), (D) component: at least a block copolymer (D-a) containing an aromatic vinyl compound-based block polymer (d-1) and a block polymer (d-2) mainly composed of a conjugated diene compound, and the hydrogen One of the components selected from the additive (D-b) component group.

(C2-2) Ingredients: Nonionic antistatic agent.

In the third thermoplastic resin composition, at least 100 parts by mass of the component (B) may be contained in the range of 0.001 to 60 parts by mass from the above (C2-1) component, (C2-3) component, (C2) -) One of the ingredients selected in the group.

The second and third thermoplastic resin compositions may be used not only as a molding material but also as a raw material for producing the first thermoplastic resin composition.

Further, in view of the other aspect of the present invention, there is provided a molded article comprising at least one of the above first to third thermoplastic resin compositions; and the molded article may be a sheet or a film.

Further, in another aspect of the present invention, a sheet or a film comprising at least one of the first to third thermoplastic resin compositions is provided as a base material, and at least one surface has a laminated multilayer molded article; According to a preferred embodiment, the base material is a thin plate or film composed of an olefinic resin.

[0015] The thermoplastic resin composition of the present invention is a styrene resin containing the styrene resin of the above (A) component and/or the component (B) according to the requirements of the block polymer of the above (C1) component. The thermoplastic resin composition contains a polymer having a specific antistatic compound and/or a specific block structure, or a low molecular weight polyene modified product, so that excellent impact resistance, chemical resistance, and surface appearance of the molded article can be obtained. , anti-static properties and even electrical properties.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The contents of the present invention will be described in detail below. Further, "(co)polymerization" as used in the present specification means the meaning of polymerization and/or copolymerization alone; "(partial) propylene" means propylene and/or Or "methacryl"; "(partial) acrylate" means acrylate and / or methacrylate.

[1] (A) The styrene resin (A) related to this issue belongs to, in the presence or absence of the rubbery polymer (a), the (co)polymerizable aromatic vinyl compound may be co-polymerized or The polymer of the ethylene monomer (b) of the polymerized aromatic vinyl compound and the other ethylene monomer of the aromatic vinyl compound is preferably at least 1 in the presence of the rubbery polymer (a) from the viewpoint of the impact resistance. In the case of the content of the rubbery polymer (a), when the styrene resin (A) is regarded as 100% by mass, it is preferably 3 to 80% by mass or 5 to 70. The mass % is also good, but 10 to 60% by mass is better.

[0017] The rubbery polymer (a) is not particularly limited, and examples thereof include polybutadiene, styrene butadiene copolymer, nitrile copolymer, ethylene propylene copolymer, and ethylene propylene non-conjugated diene copolymerization. a product, an ethylene-butene-1 copolymer, an ethylene-butene-1 non-conjugated diene copolymer, a propyl rubber, a silicone rubber, a propyl-based IP rubber, etc., which may be used alone or in combination of two or more. the above.

Among them, polybutadiene, styrene butadiene copolymer, ethylene propylene copolymer, ethylene propylene non-conjugated diene copolymer, propyl rubber, silicone rubber; styrene butadiene copolymer used herein, It can be used for copolymers other than general block polymers, especially copolymers other than the following (D) components, that is, ignoring polymers.

When the component (a) is obtained by emulsion polymerization, the gel content of the rubber polymer is not particularly limited, but the gel content is preferably 98% by mass or less, but 40 to 98% by mass. Preferably, this range provides a thermoplastic resin composition of a molded article excellent in impact resistance.

Further, the above gel content can be obtained by the following formula; in other words, 1 g of the rubbery polymer is put into 100 ml of toluene, and after standing at room temperature for 48 hours, a 100 mesh metal mesh is used (quality is regarded as Wg). After filtration, the portion insoluble in toluene was vacuum-dried at 80 ° C for 6 hours, and weighed (mass W ₂ g), and then calculated from the following formula (1).

[0019] Gel content (% by mass) = [{W ₂ (g) - W ₁ (g)} / 1 (g)] × 100 (1) When manufacturing a rubbery polymer, it is borrowed The gel content is adjusted by appropriately setting the type, amount, polymerization time, polymerization temperature, polymerization conversion ratio, and the like of the molecular weight modifier.

[0020] The aromatic vinyl compound constituting the ethylene monomer (g) may be styrene-α-methylstyrene or hydroxystyrene, and these may be used alone or in combination of two or more. Further, among them, styrene and α-methylstyrene are preferred.

[0021] The aromatic vinyl compound and other copolymerizable ethylene monomers include an acrylonitrile compound, a (partial) acrylate compound, a maleic anhydride imide compound, and other unsaturated compounds containing various functional groups; The ethylene monomer (b) is an aromatic vinyl compound as an essential monomer component, and one or two selected from the group consisting of an acrylonitrile compound, a (meta) acrylate compound, and a maleic anhydride imide compound group can be used as needed. The above combination is used as a monomer component, and at least one other unsaturated compound containing various functional groups may be used as a monomer component as needed; other unsaturated compounds containing various functional groups include unsaturated acid compounds and epoxy groups. An unsaturated compound, a hydrogen-containing unsaturated compound, an oxazoline-containing unsaturated compound, an acid anhydride-containing unsaturated compound, a substituted or non-substituted amino acid unsaturated compound, or the like; the above other unsaturated compound containing various functional groups, which can be used alone One type may be used in combination of two or more types.

[0022] The acrylonitrile compound used herein may be acrylonitrile or methacrylonitrile, and these may be used alone or in combination of two or more. When an acrylonitrile compound is used, chemical resistance is imparted; In the case of the acrylonitrile compound, the amount of the component (b) is preferably from 1 to 60% by mass, but preferably from 5 to 50% by mass.

The (partial) acrylate compound may be a methyl acrylate, an ethyl acrylate, a butyl acrylate, a methacrylic acid, an ethacrylic acid or a butyl acrylate. These may be used alone or in combination of two or more. When the (partial) acrylate compound is used, the surface hardness can be improved; when the (partial) acrylate compound is used, the amount of the component (b) is preferably from 1 to 80% by mass, but from 5 to 80% by mass.

The maleic anhydride imide compound may be, for example, maleic anhydride imide, N-phenyl maleic anhydride imide, N-cyclohexyl maleic anhydride imide, etc., which may be used alone or in combination. Two or more types may be used in combination; in addition, in order to introduce a maleic anhydride imide unit, it may be copolymerized with maleic anhydride to form an imine; and after using maleic anhydride, the heat resistance may be imparted; The amount of the component (b) after the acid anhydride imide compound is preferably from 1 to 60% by mass, more preferably from 5 to 50% by mass.

[0023] Unsaturated acid compounds include acrylic acid, methacrylic acid, Ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, etc., which may be used alone or in combination 2 More than one species to use.

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

[0024] Hydroxy-containing unsaturated compounds are, 3-hydroxy-1 propylene, 4-hydroxy-1 butene, cis-4 hydroxy-2-butene, trans-4-hydroxy-2butene, 3-hydroxyl -2 methyl-1 propylene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N-(4-hydroxyphenyl) maleic anhydride imide, etc., each of which can be used alone It is also possible to combine two or more types and use them.

The oxazoline-containing unsaturated compound may be an oxazoline or the like, and these may be used alone or in combination of two or more.

The acid anhydride-containing unsaturated compound may be used alone or in combination of two or more kinds, and may be used in combination with maleic anhydride, itaconic anhydride, and citraconic anhydride.

The unsaturated compound containing a substituted or non-substituted amino acid is, aminoethyl acrylate, propylene propylaminoethyl, aminopropyl methacrylate, phenylaminoethyl methacrylate, N-ethylene diethylamine, N- Ethylene vinylamine acrylamide, methacrylic acid amine, N-methyl acrylamide, acrylamine, N-methyl propylene hydride, p-amino styrene, etc., which may be used alone or in combination of two or more. reuse.

When the above other unsaturated compounds containing various functional groups are used, the compatibility of the styrene resin with other polymers can be improved, and the optimum monomer for achieving the relevant effect is an epoxy group-containing unsaturated compound. A carboxyl group-containing unsaturated compound or a hydroxyl group-containing unsaturated compound, wherein a hydroxy unsaturated compound is preferred, but a 2-hydroxyethyl (meta) acrylate is more preferred.

The amount of the other functional group-containing unsaturated compound to be used is the total amount of the functional group-unsaturated compound used for the styrene-based resin, and is preferably 0.1 to 20% by mass, but 0.1 to 10%, based on the total amount of the styrene-based resin. The quality % is better.

The amount of the monomer other than the aromatic vinyl compound in the vinyl monomer (b) is preferably 100% by mass or less, and the total amount of the entire ethylene monomer (b) is 100% by mass or less. % is also good, but 40% by mass is better; the best monomer combination constituting the vinyl monomer (b) is styrene/acrylonitrile, styrene/methyl methacrylate, styrene/acrylonitrile/A Methyl acrylate, styrene/acrylonitrile/epoxypropyl methacrylate, styrene/acrylonitrile/2-hydroxyethyl (meta) acrylate/acrylonitrile/(partial) acrylic acid, styrene/N- The best combination of phenol maleic anhydride imide, styrene/methyl methacrylate/cyclohexane maleic anhydride, and the like, which are polymerized in the presence of the rubbery polymer (a), Styrene/acrylonitrile=65/45~90/10 (mass ratio), styrene/methyl methacrylate=80/20~20/80 (mass ratio), styrene/acrylonitrile/methyl methacrylate The amount of styrene is 20 to 80% by mass, and the total amount of acrylonitrile and methyl methacrylate is in the range of 20 to 80% by mass.

The component (A) of the present invention can be produced by a polymerization method known in the art, such as emulsion polymerization, bulk polymerization, solvent polymerization, suspension polymerization, and a combination thereof; wherein, in the presence of the rubbery polymer (a), The optimum polymerization method for (co)polymerizing ethylene monomer (b) is emulsion polymerization and solvent polymerization; on the other hand, (co)polymerization of ethylene monomer (b) in the absence of rubbery polymer (a) The optimum polymerization method obtained is a bulk polymerization, a solvent polymerization, a suspension polymerization, and an emulsion polymerization.

[0027] When it is produced by emulsion polymerization, a starting polymerization agent, an interlocking mobile agent, an emulsifier, or the like can be used, and these can be used.

The starting polymerization agent includes Cumene hydroperoxide, p-mentan hydroperoxide, diisopropyl benzen hydroperoxide, tetra methyl butyl hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, azobisisobutyronitrile, and the like.

Further, it is preferred to use a redox system such as a various reducing agent, a sugar-containing pyrophosphate prescription, or a sulfoxret formulation to start the polymerization agent.

Interlocking mobile agents include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, and onion olefin.

As the emulsifier, an alkylbenzenesulfonate such as sodium dodecylbenzenesulfonate or an aliphatic sulfonate such as sodium lauryl sulfate, potassium laurate, potassium butyrate, potassium oleate or potassium palmitate may be used. A fatty acid salt, rose acid such as potassium oleate, and the like.

[0028] Further, the use of the rubbery polymer (a) and the vinyl monomer (b) in the emulsion polymerization is carried out in the presence of the entire amount of the rubbery polymer (a), and then the ethylene monomer (b) is added at a time. The polymerization may be carried out, or the repolymerization may be carried out separately or continuously; in addition, a part of the rubbery polymer (a) may be added during the polymerization.

[0029] The latex obtained by the emulsion polymerization is solidified by a coagulant, washed with water, and dried to obtain the powder of the component (A1) of the present invention. In this case, two or more kinds of emulsion polymerization may be appropriately mixed (A1). The ingredients are then solidified after the latex. The coagulant used herein may be an inorganic salt such as calcium chloride, magnesium sulfate or magnesium chloride, or sulfuric acid, hydrochloric acid, acetic acid, citric acid, malic acid or the like.

[0030] The solvent usable in the production of the component (A) by solvent polymerization is an inactive polymerization solvent generally used for radical polymerization, such as aromatic hydrocarbons such as ethylbenzene or toluene, ketones such as methyl ethyl ketone and acetone, and acetonitrile. , dimethylformamidine, N-methylpyrrolidone, and the like.

The optimum polymerization temperature range is 80 to 140 ° C, but 85 to 120 ° C is better. The polymerization initiator may be used in the polymerization, and the polymerization may be carried out without using a starting polymerization agent. Thermal polymerization may also be used for the polymerization; the most preferred starting polymerization agent may be a ketone peroxide, a dialkyl peroxide, a dizsil peroxide, a peroxyester, An organic peroxide such as hydroperoxide, azobisisobutyronitrile or benzoquinone peroxide.

Further, when an interlocking mobile agent is used, for example, a mercaptan, an onion olefin, an α-methylstyrene dimer or the like can be used.

When it is produced by bulk polymerization or suspension polymerization, the above-mentioned starting polymerization agent, interlocking mobile agent, etc. can be used for solvent polymerization.

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

Further, in the presence of the rubbery polymer (a), the polymer component obtained by polymerizing the ethylene monomer (b) comprises the grafting of the above ethylene monomer (b) under the rubbery polymer (a). The copolymer after polymerization and the grafting component (copolymer of the above ethylene monomer (b)) which is not grafted in the rubbery polymer.

The graft ratio of the component (A) is preferably from 20 to 200% by mass, preferably from 30 to 150% by mass, more preferably from 40 to 120% by mass, and the graft ratio can be determined from the following formula (2).

[0032] Graft ratio (% by mass) = {(T - S) / S} × 100 (2) T in the above formula (2) is to put 1 g of the component (A) into 20 ml of acetone (but rubber) When the polymer (a) was made of acryl-based rubber, it was acetonitrile), and after vibrating for 2 hours with a vibrating machine, it was centrifuged for 60 minutes using a centrifugal separator (rotation number: 23,000 rpm) to separate insoluble and soluble fractions. The mass (g) of the insoluble portion obtained afterwards; S is the mass (g) of the rubbery polymer contained in 1 g of the component (A).

In addition, the ultimate viscosity "η" of the soluble portion of the (A) component of the present invention (but the rubbery polymer (a) is acetonitrile in the case of a propylene-based rubber) (using methyl ethyl ketone) The ketone is used as a solvent and measured at 30 ° C), preferably 0.2 to 1.2 dl / g, preferably 0.2 to 1.0 dl / g, but more preferably 0.3 to 0.8 dl / g.

The average particle diameter of the grafted rubber polymer particles dispersed in the component (A) of the present invention is preferably 500 to 30,000 A, preferably 1,000 to 20,000 A, but more preferably in the range of 1,500 to 8,000 A; The method is known to measure the average particle size.

The amount of the component (A) constituting the first thermoplastic resin composition of the present invention is 5 to 100% by mass and 5 to 98% by mass based on 100% by mass of the total of the components (A) and (B) of the present invention. It is also better with 10 to 98% by mass, but 15 to 95% by mass is the best; the next is preferably 15 to 93% by mass, and particularly preferably 15 to 90% by mass. If it is less than 5% by mass, it is impact resistant. Poor, antistatic tendency to decline.

[2] (B) Component The related olefinic resin (B) of the present invention is a polymer in which at least one of 2 to 10 carbon atoms is regarded as a monomer unit; the olefinic resin is the most It is preferable that the crystallinity is expressed by room temperature by X-ray diffraction, but the crystallinity of 20% or more is more preferable, and the melting point of 40 ° C or more is obtained. Further, the olefinic resin needs to be sufficient as a molding resin at normal temperature. Molecular weight.

For example, when propylene is used as a main component, the melt flow rate measured according to JIS K-6758 is preferably 0.01 to 500 g/10 min, but is equivalent to a molecular weight of 0.05 to 100 g/10 min.

[0036] Examples of the olefin of the above olefin-based resin constituting monomer include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, and 4-methylpentene. -1, a-olefin such as 3-methylhexene-1, preferably ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1; Non-conjugated 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1-9-decadiene, etc. Diene is considered to be used as part of the polymer component.

At least a part of the olefinic resin (B) used in the present invention is a catalyst for removing a polymerization catalyst, and an epoxy group, an amino group, a substituted amino group, a carboxyl group, an acid anhydride group, an oxazoline group, a hydroxyl group or the like may also be used. Deteriorated substance.

The amount of the component (B) constituting the first thermoplastic resin composition of the present invention is 0 to 95% by mass and 2 to 95% by mass based on 100% by mass of the total of the components (A) and (B) of the present invention. It is preferably 5 to 90% by mass, but 7 to 90% by mass is the best; 10 to 85% by mass is particularly good, and when it exceeds 95% by mass, the impact resistance is poor and the antistatic property tends to decline.

The amount of the component (B) constituting the second thermoplastic resin composition of the present invention is 70 to 97% by mass, preferably 75 to 96% by mass in the total mass of the component (B) and the following (C1) component, but 77 is preferable. ~96 mass% is the best; in terms of the amount, when the amount is less than 70% by mass, the chemical resistance is not good, but when it exceeds 97% by mass, the electric properties and the surface appearance of the molded article are not good.

The amount of the component (B) constituting the third thermoplastic resin composition of the present invention is 30 to 96% by mass, 35 to 91% by mass in the total of 100 masses of the above (B) component and the following (C1) component and (D) component. % and 42 to 91% by mass are also good, but 42 to 85% by mass is the best; when less than 30% by mass, the chemical resistance is not good, but after more than 96% by mass, the electrical properties and the surface appearance of the molded article are not good. .

[0038] The component (C1) of the present invention belongs to a block copolymer comprising an olefin block polymer (c1-1) and a hydrophilic block polymer (c1-2), and has a repeating alternate bond structure in two blocks. The block polymer is optimal; the block polymer may be a diblock or a multiple block of a triblock or more; the above alkyl block polymer (c1-1) is the aforementioned alkene (co)polymer; The number average molecular weight of the polystyrene by gel permeation chromatography (GPC) of the olefin block polymer (c1-1) is preferably 800 to 20,000, preferably 1,000 to 10,000, more preferably 1,200 to 6,000.

[0039] The above block (c1-1) is chemically bonded to the above block (c1-2), but the bond belongs to at least ester bonding, hydrazine bonding, ether bonding, urethane bonding, imino bonding, and the like. One of the combinations is selected, and through these combinations there is a structure in which the alternating combination is repeated.

For this reason, both ends of the above-mentioned block (c1-1) molecule must be deteriorated by a functional group which reacts with the terminal functional groups of the above-mentioned block (c1-2); these functional groups include a carboxyl group, a hydroxyl group, An amino group, an acid anhydride group, an oxazoline group, an epoxy group or the like.

The best method for imparting these functional groups is to add a (c1-1) component having a carbon-carbon double bond and a carbon-carbon unsaturated compound having the above functional group at the end of the molecule obtained by the thermal subtraction method.

[0040] The hydrophilic polymer of the above block (c1-2) includes a polyether (c1-2-a), a polyether-containing hydrophilic polymer (c1-2-b), and an anionic polymer ( C1-2-c).

The polyether (c1-2-a) is a polyether diol, a polyether diamine and these denatured substances. The polyether-containing hydrophilic polymer (c1-2-b) has a polyether ester oxime having a polyether diol segment, a polyether fluorenylene having a polyether diol segment, and a polyether diol. A polyether ester of a segment, a polyether oxime having a polyether diol segment, and a polyether urethane having a polyether diol or a polyether amine segment.

The anionic polymer (c1-2-c) has a dicarboxylic acid having a sulfonyl group and a polyether (c1-2-a) as an essential unit, and preferably has 2 to 80 in one molecule. More preferably an anionic polymer of 3 to 60 sulfonyl groups.

These can be straight locks or divergent.

A particularly preferred block (c1-2) is a polyester (c1-2-a).

[0041] The polyether diol in the polyether (c1-2-a) is given by the general chemical formula (I): H-(OA ¹ )n-O-E ¹ -O(A ¹ O) _{n '} -H It is represented by the general chemical formula (II): H-(OA ² )m-O-E ² -O(A ² O) _{m '} -H.

In the general formula (I), E ¹ is a residue obtained by subtracting a hydroxyl group from a divalent hydroxyl group-containing compound, A ¹ represents an alkylene group having 2 to 4 carbon atoms, and n and n' are each of the foregoing two An additional number of epoxides containing a hydroxyl group of a divalent hydroxy compound; n (OA ¹ ) and n' (A ¹ O) may be the same or different; further, these may be composed of two or more hydroxyalkylene groups. The combination form at the time of constitution may also be a block or a disregard or a composition; n and n' are usually 1 to 300, preferably 2 to 250, and 10 to 100 is particularly preferable; and n and n may be the same. different.

[0042] The above divalent hydroxyl-containing compound is such that there are two alcoholic or phenolic hydroxyl groups in one molecule, in other words, a dihydroxy group, specifically a divalent alcohol (for example, a carbon number of 2 to 12 aliphatic groups). , alicyclic or aromatic divalent alcohol), divalent phenol having 6 to 18 carbon atoms, and amino acid diol having a third order.

Aliphatic divalent alcohols include, for example, alkylene glycols such as ethylene glycol and propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,12-dodecane Alcohol, etc.

The alicyclic divalent alcohols are, for example, 1, 2 and 1, 3-cyclopentane, 1, 2, 1, 3- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol. Etc.; aromatic divalent alcohols, such as xylene glycol.

Divalent phenols include hydroquinone, catechol, resorcinol, Uruciol, monocyclic divalent phenol, bisphenol A, bisphenol F, bisphenol S, 4, 4' dihydroxydiphenyl -2, bisphenol such as 2-butane, dihydroxybiphenyl or dihydroxydiphenyl ether; and condensed polycyclic divalent phenol such as dihydroxynaphthalene or biphenyl.

[0043] E ² in the general chemical formula (II) represents a residue obtained by subtracting a hydroxyl group from the divalent hydroxyl compound described in the general chemical formula (I), and A ² is at least a part, in general Chemical formula (III): -CHR-CHR'- [wherein R, R', general formula (IV): a group represented by -CH ₂ O(A ³ O) _x R", and the others are H; In the general chemical formula (IV), x represents an integer of 1 to 10, R" represents H or an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group or a fluorenyl group having 1 to 10 carbon atoms, and A ³ represents a carbon number of 2~. The substituted alkylene group represented by the alkylene group of 4 may be a carbon number of 2 to 4 alkylene groups; m (OA ² ) and m' (A ² O) may be the same or different; m and m, preferably 1~300, 2~250 is better, but 10~100 is better; in addition, m and m' can be the same or different.

[0044] The polyether diol represented by the above general formula (I) can be produced by adding an epoxide to the divalent hydroxy group-containing compound, and the epoxide has a carbon number of 2 to 4 rings. As the oxide, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, and 1, 3-butylene oxide can be used. And two or more kinds of epoxides are used in combination; and the combination form of two or more kinds of epoxides may be random and/or block; the best epoxide is ethylene oxide alone and epoxy The ethane is further combined with other epoxides and/or random; each of the foregoing epoxides containing a divalent hydroxy compound having a hydroxyl group is preferably 1 to 300, preferably 2 to 250. 10~100 is better.

[0045] The preferred method for producing the polyether diol represented by the above general chemical formula (II) is as follows (a), (b) and the like.

[0046] (a) General chemical formula (V) starting from the aforementioned divalent hydroxyl-containing compound:

Polymerization [A ⁴ in the general chemical formula (V) represents an alkylene group having 2 to 4 carbon atoms, p is an integer of 1 to 10, and R ¹ is H, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkylaryl group. A glycidyl ether represented by an aralkyl group or a fluorenyl group, or an epoxide having a carbon number of 2 to 4.

[0047] (b) a method of using a divalent hydroxy group-containing compound as a starting material and having a chloromethyl group on a side lock via a polyether; specifically, an additional copolymerization of epichlorohydrin, epichlorohydrin and An epoxide having a chloromethyl group on a side lock to obtain a polyether, and reacting the polyether with a carbon number of 2 to 4 polyepoxyglycolic acid and R ¹ X in the presence of a base (R ¹ is the above substance, X is Cl, Br or I), or the polyether is reacted with a carbon number of 2 to 4 polyepoxyglycolic acid monoether in the presence of a base.

[0048] As the carbon number 2 to 4 epoxide used herein, all of the foregoing may be used.

The (C1) component of the present invention can be polymerized by the known method to polymerize the above-mentioned ethylenic block polymer (c1-1) and the hydrophilic block polymer (c1-2); for example, a pressure-decomposing block at 200 to 250 ° C (c1-1) And the block (c1-2) can be produced by performing a polymerization reaction; in addition, a known polymerization catalyst can be used for the polymerization reaction.

[0049] Although a known polymerization catalyst can be used in the polymerization reaction, it is preferably a tin-based catalyst such as a monovalent butyl tin oxide, a ruthenium-based catalyst such as antimony trioxide or ruthenium dioxide, or tetrabutyl titanate. One type or a combination of two or more types selected from the group consisting of a zirconium catalyst such as a titanium catalyst, a zirconium hydroxide, a zirconium oxide, and a zirconium acetate, and a Group IIB organic acid salt catalyst.

[0050] The object of the present invention is to improve the antistatic property or the electrical conductivity, so that the (C1) component contains at least one salt (H) selected from the group consisting of alkaline metals and alkaline earth metal groups; Before the polymerization (C1) component, it may be contained in the polymerization (C1) component, and may be further contained in the polymerization (C1) component; in addition, the formulation in the production of the resin composition of the present invention may also include a combination of these methods. .

(H) Ingredient salts include organic acids such as lithium, sodium, potassium, and the like, and organic acids, sulfonic acids, inorganic acid salts, and halides of alkaline earth metals such as magnesium and calcium.

[0051] Specific preferred (H) components are, for example, lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide and other alkali metal halides; high lithium chloride, high sodium chloride Alkali metal mineral acid salt such as potassium chloride; alkali metal organic acid salt such as potassium acetate or lithium stearate; octyl sulfonic acid, lauryl sulfonic acid, tetradecyl sulfonic acid and stearic acid sulfonic acid An alkali metal salt of an alkyl group having 8 to 24 alkyl sulfonic acids such as tetraalkyl sulfonic acid or 2-ethylhexyl sulfonic acid; an alkali metal salt of an aromatic sulfonic acid such as phenyl sulfonic acid or naphthyl sulfonic acid; The alkyl carbon number of the alkylphenylsulfonic acid, lauryl benzene sulfonic acid, dibutyl phenyl sulfonic acid, dinonyl phenyl sulfonic acid, etc. is an alkali metal salt of 6-18 alkylbenzenesulfonate; dimethyl naphthalene An alkali metal salt having an alkyl carbon number of 2 to 18 alkylnaphthylsulfonic acid such as a sulfonic acid, a diisopropylnaphthylsulfonic acid or a dibutylnaphthylsulfonic acid; a fluorinated sulfonic acid such as trifluoromethanesulfonic acid The alkali metal salt may be used alone or in combination of two or more. The above (H) component is preferably 0.001 to 10% by mass, 0.01 to 5% by mass and 0.01 to 3 by mass of the (C1) component of the present invention. % is also good, but 0.01 to 2% by mass is better.

[0052] The ratio (mass ratio) of the optimum block (c1-1)/block (c1-2) of the component (C1) of the present invention is in the range of 10 to 90/10 to 90, and 20 to 80/20 to 80. Also good, but 30~70/30~70 is better.

The block polymer (C1) can be produced by the method described in JP-A-2001-278985, JP-A-2003-48990, and the component (C) of the present invention can also be obtained from Sanyo Chemical Industry Co., Ltd. 300, 303, 230 (trade name) of the Perestart 300 series.

The amount of the (C1) component constituting the first thermoplastic resin composition of the present invention is 0.5 to 100 parts by mass, preferably 0.50, in the total mass of the component (A) and the component (B) of the present invention. 80 mass parts, 1~60 mass parts are also good, but 2~50 mass parts are the best; when the dosage is less than 0.5 mass parts, anti-static effect can not be obtained, and it is not fully resistant to chemicals, and impact resistance is also Not good; but when it exceeds 100 parts, the impact resistance will be poor.

The amount of the component (C1) constituting the second thermoplastic resin composition of the present invention is 3 to 30% by mass, 4 to 25% by mass, and 4 to 23 in the total mass of the component (B) and the following (C1) component. The mass % is also good, but 5 to 23% by mass is the best; in terms of the amount, the electrical conductivity is not good when the amount is less than 3% by mass, but the chemical resistance and the surface appearance of the molded article are not good after more than 30% by mass.

The amount of the (C1) component constituting the third thermoplastic resin composition of the present invention is 3 to 30% by mass, 4 to 25 mass in the total of 100 masses of the above (B) component and the following (C1) component and (D) component. % and 4 to 23% by mass are also preferable, but 5 to 23% by mass is optimal; when the amount is less than 3% by mass, the power supply property is not good, but when it exceeds 30% by mass, the chemical resistance and the surface appearance of the molded article are not good.

[0054] [4] (C2) component In addition to the above (A) component, (B) component, and (C1) component, in order to improve the antistatic property or electrical conductivity of the first thermoplastic resin composition of the present invention It may contain at least one selected from the group consisting of the following (C2-1) component, (C2-2) component, (C2-3) component, and (C2-4) component group.

(C2-1) Ingredients: Polyether Polyamide and/or Polyether Polyester, (C2-2) Ingredients: Nonionic Antistatic Agent, (C2-3) Ingredients: Boron Compound (C2-4) Ingredients: Lithium salt The second thermoplastic resin composition of the present invention may contain the above (C2-2) component in addition to the above (B) component and (C1) component, and may be selected from the above (C2-1) component, Select at least one component from the (C2-3) component and (C2-4) component group.

The third thermoplastic resin composition of the present invention may contain the above (C2-2) component in addition to the above (B) component, (C1) component, and (D) component, and may be supplied from the above (C2-1). At least one component of the component, (C2-3) component, and (C2-4) component group.

[4-1] (C2-1) Component The component (C2-1) of the present invention is a polyether polyfluorene and/or a polyether polyester. The polyfluorene used herein includes ethylene diamine, tetramethyl diamine, hexamethylene diamine, decanediamine, 2, 3, 4 or 2, 4, 4-trimethylhexamethylenediamine, 1, 3 Or an aliphatic or alicyclic group such as 1, 4-bis(aminomethyl)cyclohexane, bis(p-aminohexyl)methane, phenyldiamine, m-xylenediamine or p-xylenediamine. a diamine component such as an aromatic diamine and adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc., by an aliphatic dicarboxylic acid, an alicyclic group Polyamide, ω-amino-n-hexanoic acid, ω- obtained by ring-opening polymerization of indoleamine such as polydecylamine, caprolactam, lauric acid decylamine or the like formed by the reaction of a dicarboxylic acid or an aromatic dicarboxylic acid Polyamide produced by an aminocarboxylic acid such as aminoheptanoic acid, aminoundecanoic acid or 1,2-aminododecane, and these copolymerized polyamines, and these polyamines are mixed.

[0056] The (C2-1) component of the present invention is a polyether polyether containing a polyether, but the polyether component used herein may be the component (c1-2) described in the component (C1).

The optimal polymerization method of the preferred polyether polyfluorene of the present invention is a heated melt polymerization method, and the best specific examples thereof are as follows: (i) after polymerization polymerization, a dicarboxylic acid oxygen compound is added to carry out both ends of the polyfluorene component. A method of carboxylating and adding poly(epoxide) ethanol to carry out polymerization to obtain a polyether polyfluorene.

(ii) When polymerizing polyfluorene, in order to substantially carboxylate both ends of the molecule, a large amount of a polycarboxylic acid compound is added and polymerized, and poly(epoxide) ethanol is further added to carry out polymerization to obtain a polyether polyfluorene. method.

(iii) A method of obtaining polyether polyfluorene by quantitatively adding a polyfluorene-forming component and a large amount of a dicarboxylic acid oxygen compound, followed by addition of poly(epoxide) ethanol to carry out polymerization.

Among the above methods, the most preferable method is the above (i).

[0057] The dicarboxylic acid used for the carboxylation of the molecular end of the above polyfluorene component is adipic acid, suberic acid, azelaic acid, maleic acid, citraconic acid, maleic anhydride, citraconic anhydride, Cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.; the number average composition of the above polyfluorene of the present invention is preferably 500 to 20000, preferably 500 to 10,000, but the range of 500 to 5000 is the best. Purpose of the invention.

The mass ratio (polyfluorene/polyether) of the polyfluorene component to the polyether component in the polyether polyfluorene of the present invention is preferably in the range of 90/10 to 10/90, and preferably 80/20 to 20/80, but 70 /30~30/70 is better.

Although the molecular weight of the polyether polyfluorene of the present invention is not particularly limited, the reducing viscosity (η _{s p} /C) (0.5 g/100 ml in the formic acid solvent and measured in an environment of 25 ° C) is preferably in the range of 1 to 3 dl/g. But 1.2~2.5dl/g is better.

The polyether polyfluorene of the present invention may be used singly or in combination of two or more.

The polyester in the component (C2-1) of the present invention belongs to (1) a carbon number 4 to 20 dicarboxylic acid and/or a derivative of the ester, and (2) a polymerization obtained from the diol component. The above (1) used herein is as follows; the carbon number as used herein means the total carbon number of a lock or ring constituting a carboxyl group carbon and a direct bond to a carboxyl group.

[0059] The carbon number 4-20 dicarboxylic acid is (a) succinic acid, adipic acid, sebacic acid, sebacic acid, α.ω-dodecanedicarboxylic acid, dodecene succinic acid, ten a carbon number of 4 to 20 aliphatic dicarboxylic acids such as octaenecarboxylic acid, (b) 1,4-cyclohexanedicarboxylic acid, and the like, 8 to 20 alicyclic dicarboxylic acids, (c) terephthalic acid, Carbon 8 to 12 aromatic dicarboxylic acid such as isophthalic acid, 1, 4-naphthalene dicarboxylic acid, 2, 3-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2, 7-naphthalene dicarboxylic acid A sulfonic acid machine such as acid, (d) 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid or 5-tetrabutylphosphonium isophthalic acid is bonded to the carbon number of the aromatic ring 8~ 12, replacing an aromatic dicarboxylic acid or the like; and a dicarboxylic acid ester-forming derivative having 4 to 20 carbon atoms; the lower alkyl ester of the above (a) to (d); for example, dimethyl succinate or Diacid dimethyl, sebacic acid dimethyl, sebacic acid dimethyl, α.ω-dodecanedicarboxylic acid dimethyl, dodecene succinate dimethyl, octadecene carboxylic acid Methyl, 1,4-cyclohexanedicarboxylic acid dimethyl, diethyl succinate, diethyl adipate, diethyl sebacate, diethyl sebacate, α.ω-twel Dicarboxylic acid diethyl, dodecene succinic acid diethyl, octadecene carboxylic acid diethyl, 1,4-cyclohexanedicarboxylic acid diethyl, dimethyl terephthalate, para-benzene Diethyl dicarboxylate, di(2-hydroxyethyl) terephthalate, dimethyl isophthalate, diethyl isophthalate, di(2-hydroxyethyl) isophthalate, 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- Dimethyl naphthalene dicarboxylate, diethyl 2,7-naphthalene dicarboxylate, dimethyl 5-sodium sulfoisophthalate, dimethyl 5-potassium sulfoisophthalate, 5-sodium sulfonate Isophthalic acid (2-hydroxyethyl), 5-potassium sulfoisophthalic acid (2-hydroxyethyl), etc., may be used alone or in combination of two or more; It is terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 5-sodium sulfoisophthalic acid and derivatives of these esters.

[0060] The polyether polyester of the present invention contains the above polyester component and polyether component, and the polyether component used herein can use all of the above (c1-2) components; The preferred polymerization method is a heated melt polymerization method, and the best specific examples thereof are as follows: (i) after polymerizing the polyester, adding a dicarboxylic acid oxygen compound, carboxylating both ends of the polyester component, and adding poly(epoxide) ethanol A method of obtaining a polyether polyester after the polymerization is carried out.

(ii) When polymerizing a polyester, in order to substantially carboxylate both ends of the molecule, a large amount of a polydicarboxylate compound is added and polymerized, and poly(epoxide) ethanol is further added to carry out polymerization to obtain a polyether polyester. method.

(iii) A method of obtaining a polyether polyester by quantitatively adding a polyester-forming component and a large amount of a dicarboxylic acid oxygen compound, followed by addition of poly(epoxide) ethanol to carry out polymerization.

[0061] The dicarboxylic acid used for the carboxylation of the molecular end of the above polyester component is adipic acid, suberic acid, sebacic acid, maleic acid, citraconic acid, maleic anhydride, citraconic anhydride, Cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.; the number average composition of the above polyester of the present invention is preferably from 300 to 20,000, preferably from 300 to 10,000, but the range of 500 to 5,000 is the best. Purpose of the invention.

The mass ratio of the polyester component to the polyether component (polyester/polyether) in the polyether polyester of the present invention is preferably in the range of 90/10 to 10/90, and preferably 80/20 to 20/80, but 70 /30~30/70 is better.

Although the molecular weight of the polyether polyester of the present invention is not particularly limited, the reducing viscosity (η _{s p} /C) (using a phenol/tetrachloroethane = 40/60 mass ratio mixed solvent at a concentration of 1.0 g/dl at 35 ° C) The environment is preferably measured in the range of 0.3 to 2.5 dl/g, but preferably 0.5 to 2.5 dl/g.

The polyether polyester of the present invention may be used alone or in combination of two or more.

[0062] The polyether polyether or polyether polyester of the present invention (C2-1) may be added in the polymerization process (before polymerization, in the initial stage of polymerization, during polymerization, after polymerization), in order to improve the antistatic property (H) The component (H) component used herein has an optimum range of 0.001 to 20% by mass in the component (C2-1) of the present invention, preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass.

The (C2-1) component of the first thermoplastic resin composition of the present invention is preferably used in an amount of 0.001 to 60 parts by mass for the total mass of 100 parts of the component (A) and the component (B). ~50 mass parts, 0.5~40 mass parts and 1~35 mass parts are also good, but 1~30 mass parts are the best; when the dosage is less than 0.001 parts, the antistatic property and the surface gloss of the molded products will be poor, but When it exceeds 60 parts by mass, the impact resistance will also be poor.

The amount of the component (2-1) of the second and third thermoplastic resin compositions of the present invention is preferably in the range of 0.001 to 60 parts by mass and 0.5 to 50 parts by mass for the 100 parts by mass of the component (B). 0.5~40 mass parts and 1~35 mass parts are also good, but 1~30 mass parts are the best; when the dosage is less than 0.001 parts, the antistatic property and the surface gloss of the molded product will be poor, but when it exceeds 60 mass parts Impact resistance will also be poor.

The ratio (C1)/(C2-1) of the component (C1) of the present invention to (C2-1) is preferably in the range of 4 to 60/40 to 96, and preferably 6 to 55/45 to 94. However, it is better to use 8 to 48/52 to 92, and the total ratio of (C1) component to (C2-1) component is regarded as 100% by mass, and the ratio of use of (C1) component is less than 4% by mass, (C2-1 The use ratio of the component in the field of more than 96% by mass has a tendency to decline in antistatic property; the amount of the component (C1) exceeds 60% by mass, and the amount of the component (C2-1) is less than 40% by mass. There is a tendency for the surface gloss of the molded article to decline.

[4-2] (C2-2) component The (C2-2) component of the present invention is a nonionic antistatic agent, respectively having a polyvalent alcohol ester, (C2-2-2) general chemical formula (VI) The nitrogen-containing compound or the like may be used alone or in combination of two or more.

In the general chemical formula, R ⁴ represents an alkyl group or an alkenyl group having a carbon number of 8 to 22, and X is a group represented by the following chemical formula X-1 or X-2.

Y and Z are each a group represented by the following chemical formula Y-1, Y-2 or Y-3

The two may be the same or different; m+n is an integer of 2~5.

[0065] (C2-2-1) components include glyceryl monostearate, glyceryl monomyristate, glyceryl monopalmitate, glyceryl monostearate, glycerol monobehenet, glycerol monoolet, diglycerol Laurate, diglycerin myristate, diglyceryl palmitate, diglyceryl stearate, diglycerin monobehenet, diglycerin monoolet, sorbitan laurate, sorbitan myristate, sorbus The sugar alcoholic acid palmitate, the sorbitan stearate, the sorbitan monobehenet, the sorbitan monoolet, etc., may be used alone or in combination of two or more; the most preferred one is , glyceryl monostearate, diglyceryl stearate, glycerin monoolet, diglycerin monolaurate, sorbitan stearate, and at least 20% by mass of the (C2-2-1) component.

[0066] (C2-2-2) components are, lauryl diethanolamine, myristyl diethanolamine, palmitoyl diethanolamine, stearin diethanolamine, oleyl diethanolamine, lauryl diisopropanolamine, meat Myristyl diisopropanolamine, palm quinone diisopropanolamine, stearin diisopropanolamine, oleyl diisopropanolamine, N, N-bishydroxyethylalkyl (alkyl carbon number 12~ 22) amines such as amines, or lauryl diethanol oxime, myristyl diethanol oxime, palm quinone diethanol oxime, behenyl diethanol oxime, oleyl diethanol oxime, lauryl diisopropanol oxime, nutmeg An anthraquinone such as bismuth isopropoxide, palm ruthenium diisopropylate, stearyl bismuth isopropoxide or oleyl diisopropoxide; these may be used alone or in combination of two or more; The most preferred component is the above-mentioned amine compound, more preferably lauryl diethanolamine or stearin diethanolamine, each containing at least 20% by mass of the (C2-2-2) component.

[0067] In order to improve the antistatic property, the above-mentioned compounds may be formulated with known additives; for example, there are high-grade alcohols, lubricants, strontium, calcium silicate, etc. having a carbon number of 12 to 18; Master batch to improve mixing. The (C2-2) component of the present invention is available as a nonionic antistatic agent, such as Electro Stripper EA, TS-3B, TS-6B, TS-5, TS-2B (trade name) manufactured by Kao Corporation. .

The (C2-2) component of the first thermoplastic resin composition of the present invention is preferably used in an amount of 0.001 to 60 parts by mass for a total of 100 parts by mass of the component (A) and the component (B). ~50 mass parts, 0.01~30 mass parts and 0.05~20 mass parts are also good, but 0.5~10 mass parts are better; when the dosage is less than 0.001 parts, the power supply performance will be poor, but when it exceeds 60 mass parts Chemical resistance and appearance of the molded article may also be poor.

The amount of the (C2-2) component of the second thermoplastic resin composition of the present invention is preferably 0.01 to 10 parts by mass and 0.05 to 8 parts by mass for the 100 parts by mass of the component (B) and the component (C1). It is also good, but the best quality is 0.1~5; when the quality is less than 0.01, the power quality will be poor, but when it exceeds 10 parts, the chemical resistance and the surface appearance of the molded product will be poor.

The amount of the (C2-2) component of the third thermoplastic resin composition of the present invention is preferably 0.01 to 10 parts by mass for the (B) component and the (C1) component and the 100 mass portion of the component (C). 0.5~8 mass parts are also good, but 0.1~5 quality parts are the best; when the quality part is less than 0.01 mass parts, the power quality will be poor, but when it exceeds 10 mass parts, the chemical resistance and the surface appearance of the molded products will be poor.

[0069] [4-3] (C2-3) Component The related (C2-3) component of the present invention is a boron compound, in other words, a boron-containing compound; the boron compound (C2-3) can be used alone. Two or more types can also be combined.

The most preferred boron compound (C2-3) is an organoboron polymer compound; and the organoboron polymer compound preferably contains a compound of the following general formula (VII).

[0070] A compound comprising the unit of the above general chemical formula (VII) is as shown in the following general formula (VIII), and a semipolar organoboron polymer compound having a total of hydroxyl groups of 5 to 82 and a third amine One or two or more kinds of one boron atom to one basic nitrogen atom are required to react with each other - a polymer charge-transfer type combination is preferable.

【化9】

Where q is 0 or 1, and when q=1, T is -(T ¹ ) _s -(T ² ) _t -(T ³ ) _u - (but T ¹ and T ³ are the same or different from each other and possess a terminal ether residue, and an oxygen-containing hydrocarbon group having a total carbon number of 100 or less, T ² is (But R ⁹ is a hydrocarbon number of 1 to 82 carbon atoms.) or (However, R ^{1 0} 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, and r is 10 ~1000. 〕

[0071] R ⁶ , R ⁷ and R ^{8 in} the above general chemical formula (VIII) include a hydrocarbon group, an alkoxy group, a phenoxy group, a benziloxy group, an alkylene glycol group and the like; It may also have a functional group such as a hydroxyl group or a replacement group.

[0072] The charge-transfer-type combination has the combination of the following chemical formulas (IX) to (XVI); further, in the following chemical formulas, the terminal carbon atom and the oxygen atom are usually each bonded to a hydrogen atom or Hydroxyl.

[wherein R' is a residue of polybutene having an average degree of polymerization of 20. 〕

[0073] The above-described polymer charge-transfer type conjugate can be produced by the method described in Japanese Patent No. 2573986.

Further, as the boron compound (C2-3), a commercially available product such as "Hybolon 400N" manufactured by Boron International Co., Ltd., or the like can be used.

[0074] When the thermoplastic resin composition is produced, the related boron compound (C2-3) of the present invention may be separately formulated, and a mixture (composition) composed of a polymer such as the above (A) (B) (C1) component may be blended. In the latter case, "Hybolon 400N-8LDPE" manufactured by Boron International Co., Ltd. (a main compound in which polyethylene is used as a matrix) is used.

The (C2-3) component of the first thermoplastic resin composition of the present invention is preferably 0.001 to 60 parts by mass for the total of 100 parts by mass of the component (A) and the component (B), and secondly, 0.001~50 mass, 0.01~30 mass, 0.05~20 mass, 0.05~10 mass, but 0.1~5 mass is the best; when the content is less than 0.001 mass, antistatic will be poor However, the appearance of the surface will be poor when it exceeds 60 mass parts.

The content of the (2-3) component of the second and third thermoplastic resin compositions of the present invention is preferably 0.001 to 60 parts by mass for the 100 parts by mass of the component (B), and is 0.001 to 50 parts by mass, respectively. 0.01~30 mass part, 0.05~20 mass part and 0.05~10 mass part are also good, but 0.1~5 mass part is the best; when the content is less than 0.001 part, the antistatic property will be poor, but more than 60 mass part The appearance of the surface will also be poor.

In addition, when the total ratio of the (C1) component to the (C2-3) component is 100% by mass, it is preferably 38 to 99.8 mass% and 0.2 to 62 mass%, and the next is 67 to 99.7. The mass %, 0.3 to 33% by mass is also preferable, but 75 to 99.2% by mass / 0.8 to 25% by mass is optimal; and the above range is available to have the best antistatic property.

[4-4] (C2-4) component The lithium salt of the component (C-2) of the present invention is, for example, lithium organic hydrochloric acid, inorganic hydrochloric acid, a halide or the like, and most preferably at least lithium perchlorate, a compound selected from lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonate)imide, and lithium tris(trifluoromethanesulfonate)methane; more preferably at least lithium trifluoromethanesulfonate, double ( a compound selected from lithium trifluoromethanesulfonate) lithium imino and lithium tris(trifluoromethanesulfonate) methane; at least from lithium bis(trifluoromethanesulfonate), and tris(trifluoromethanesulfonate) It is also preferable to select one of the lithium methane compounds, but tris(trifluoromethanesulfonate) methane lithium is more preferable.

[0077] The above (C2-4) component of the present invention is formulated into a composition of the invention, and the electrical conductivity is improved, and the continuity of the electrical properties is also found, but when the component (C2-4) is formulated The component (C2-4) can be directly formulated, but the component (C2-4) dissolved in a solvent (aqueous) or the like can be blended, and other polymers can be dispersed in a high concentration in advance to be used as a main compound.

The solvent most suitable for dissolving the component (C2-4) is water or a compound represented by the following chemical formula (XVII).

[In general formula (XVII), X represents an alkylene group having 2 to 8 carbon atoms, a divalent hydrocarbon group containing an aromatic group, and a divalent alicyclic hydrocarbon group, and R represents an independent carbon number of 1~ 9 is a straight-locked or divalent alkyl group, A represents a carbon number of 2 to 4 alkyl groups, and n represents an integer of 1 to 7 each. 〕

The most preferred compound represented by the above general formula (XVII) is an alkyl group in which R has no hydroxyl group at the terminal; most preferably bis[2-(2-butoxyethoxy)ethyl] adipate (dibutoxyethoxyethyl hexanoate) or bis(2-butoxyethyl) Phthalet.

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

[0080] When the (C2-4) component of the present invention is previously dispersed in another polymer to form a main compound, the (C2-4) component and the solvent as needed are formulated on the known polymer so as to Molten and kneaded to manufacture.

The best known polymers used herein are those having an ether bond, these being polyepoxides and/or polyepoxide-containing polymers; in particular, polyethylene oxides, polypropylene oxides, A polyoxyethylene pentoxide, a poly(fluorene), a block copolymer composed of the polyester and the above polyepoxide, and a hydrophilic polymeric block (C1-2) using the component (C1) of the present invention, a polyether to be used It is considered to be used as a polymer having an ether bond; in other words, the component (C2-4) of the present invention may be added to the above (C1) component, but may be added to any other component of the present invention.

When the (C2-4) component of the present invention is used as the main compound, the amount of the (C2-4) component in the main rubber is preferably in the range of 0.5 to 80% by mass, and preferably 1 to 6% by mass, but 3~ 40% by mass is better.

[0081] The above-mentioned (C2-4) component solution of the present invention can be made from SankonoRL 0862-20R, 0862-13T, 0862-10T, AQ-50T (trade name) manufactured by Sanko Chemical Industry Co., Ltd.; It is purchased from SANKONORL TBX-25 (trade name) manufactured by Chemical Industry Co., Ltd.

The (C2-4) component of the first thermoplastic resin composition of the present invention is preferably 0.001 to 60 parts by mass for the total mass of the components (A) and (B), and secondly, 0.005~50 mass part, 0.01~40 mass part, 0.05~25 mass part, 0.05~15 mass part is also good, but 0.1~10 mass part is the best; when it is less than 0.001 mass part, it can't improve the electric power, but it exceeds At 60 mass parts, the continuity of the electrical properties and the impact resistance are not good.

The content of the (2-4) component of the second and third thermoplastic resin compositions of the present invention is preferably 0.001 to 60 parts by mass for the 100 parts by mass of the component (B), and is 0.005 to 50 parts by mass, respectively. , 0.01~40 mass parts, 0.05~25 mass parts and 0.05~15 mass parts are also good, but 0.1~10 mass parts are the best; when less than 0.001 mass parts, the power can not be improved, but more than 60 mass parts Sexual persistence and impact resistance are not good.

[0083] In order to improve impact resistance, chemical resistance, surface appearance of the molded article, antistatic property or electrical conductivity, the first and second thermoplastic resin compositions of the present invention may be in the above (A) component, (B) The component (C) contains at least one component selected from the group consisting of (D), (E), (F), and (G).

In order to improve impact resistance, chemical resistance, surface appearance of the molded article, antistatic property or electrical conductivity, the third thermoplastic resin composition of the present invention contains the following (D) component which is regarded as an essential component, and may be contained as needed. At least one component selected from the group consisting of (E), (F), and (G).

(D) Component: a block copolymer containing at least an aromatic vinyl compound-based block polymer (d-1) and a conjugated diene compound-based block polymer (d-2) ( D-a) and one component selected from the hydrogen additive (D-b) component group.

(E) component: a graft polymer of (co)polymerized aromatic vinyl compound or copolymerizable aromatic vinyl compound and other vinyl monomer of the aromatic vinyl compound in the presence of the above component (D), (F) Component: an aromatic polycarbonate copolymer composed of the block polymer (f-1) composed of the above component (D) and the aromatic carbonate block polymer (f-2), (G) component A low molecular weight polyolefin which is denatured by an unsaturated acid and/or an unsaturated acid anhydride.

Further, the above (D) component, (E) component, (F) component, and (G) component may be used in combination, at least from the above (C2-1) component, (C2-2) component, (C2-3) component, ( C2-4) Select one component from the group of ingredients.

[5] (D) component The component (D) of the present invention belongs to a block polymer (d-1) mainly composed of an aromatic vinyl compound, and a block polymerization mainly composed of a conjugated diene compound. a block copolymer (D-a) of the material (d-2) and/or the hydrogen additive (D-b), the hydrogen additive (D-b) having at least a part of the above block polymer (d- 2) The carbon-carbon double bond of the conjugated diene compound is added with hydrogen.

Although all of the above-mentioned substances can be used for the aromatic vinyl compound used herein, styrene is preferred, and α-methylstyrene is also preferred, but styrene is most preferred.

Further, the conjugated diene compound is butadiene, isoprene, hexadiene, 2,3-dimethyl, 1,3-butadiene, 1,3-pentadiene, etc. It is preferably butadiene or isoprene; these may be used alone or in combination of two or more; in addition, block (d-2) may be used in two or more kinds of conjugated diene compounds. a block which can be combined in any of a random form, a block shape, or a tapered block shape; in addition, the block (d-2) can also contain an increasing number of aromatic vinyl compounds in a range of 1 to 10 The block may be a copolymer polymer having a different ethylene-binding content from the block (d-2) conjugated diene compound, or may be appropriately copolymerized.

The optimum structure of the component (D) of the present invention is a polymer or a hydrogen additive represented by the following chemical formulas (XIII) to (XX).

(A-B) _Y .........(XVIII) (A-B) _Y -X.........(XIX) A-(B-A) _Z .........(XX)(Structure formula (XVIII)~(XX) Among them, A belongs to a block polymer mainly composed of an aromatic vinyl compound, and may be substantially a block polymer composed of an aromatic vinyl compound, or may contain a partial conjugated diene compound; an optimum aromatic vinyl compound It is a block polymer containing 90% by mass or more, but more preferably 99% by mass or more; B is a single polymer of a conjugated diene compound, or another monomer such as an aromatic vinyl compound and a conjugated diene compound; Copolymer, X is the residue of the coupling agent, Y is an integer from 1 to 5, and Z is an integer from 1 to 5.)

[0087] The optimum use ratio of the aromatic vinyl compound to the conjugated diene compound in the component (D) of the present invention is that the aromatic vinyl compound/conjugated diene compound = 10 to 70/30 to 90% by mass. 15~65/35~85% by mass is also good, but 20~60/40~80% by mass is better.

[0088] The block copolymer of the aromatic vinyl compound and the conjugated diene compound is disclosed in, for example, Japanese Patent Publication No. Sho 47-28915, Japanese Patent Publication No. Sho 47-3252, Japanese Patent Publication No. Sho 48-2423, and Japanese Patent Publication No. 48-20038 discloses an anionic polymerization technique; and a method for producing a block polymer having a tapered block is disclosed in Japanese Patent Publication No. Sho 60-81217.

[0089] The conjugated diene compound derived from the component (D) of the present invention has an ethylene binding amount (1, 2- and 3, 4 bond) content in an optimum range of 5 to 80%, and the component (D) of the present invention The optimum number average molecular weight is 10,000 to 1,000,000, preferably 20,000 to 500,000, but more preferably 20,000 to 200,000; wherein the optimum number average molecular weight of the A portion represented by the above chemical formulas (XVIII) to (XX) is 3,000 to 150,000, B. The optimum number average molecular weight of the part is 5,000 to 200,000.

[0090] N, N, N', N'-tetramethylethylenediamine, trimethylamine, triethylamine, diazocyclooctane (2, 2, 2) and other amines, oxygen dyed cyclopentane, Ethers such as diglyme or diethylene glycol dibutyl ether, thioethers, phosphines, phosphonium phosphates, alkylbenzenesulfonates, potassium or sodium alkoxides, etc. The amount of ethylene bound of the conjugated diene compound.

Although the component (D) of the present invention preferably contains a polymer obtained by the above method, and then a coupling agent is used to cause the polymer molecule to lock through the coupler residue to extend or diverge, the coupling agent used herein has Diethyl adipic acid, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilane, tetrachlorotin, butyl trichlorotin, dimethyldichlorosilane, tetrachloroguanidine, 1,2-dibromoethane, 1, 4-chloromethylbenzene, bis(trichlorosilyl)ethane, epoxidized linseed oil, toluene diisocyanate, 1,2,4-benzene triisocyanate, and the like.

[0091] From the viewpoint of impact resistance, it is preferable that the block polymer has a tapered block polymer having a range of 1 to 10 in which the aromatic vinyl compound is gradually increased on the block (d-2), and/ Or a radial block that has been subjected to coupling processing.

[0092] Further, the (D) component may also be a carbon-carbon double bond of the conjugated diene moiety of the above block copolymer partially or completely added with hydrogen; the optimum hydrogen addition rate of the component (D) is 10 to 100. %, 50~100% is better; from the weather-resistant (light) side of the obtained composition, it is better to use more than 90% of hydrogen-added materials; in addition, from the low-temperature impact surface, it is better to use more than 50% The rate of hydrogen addition is less than 9%.

[0093] The polymer hydrogen-added reaction of the block polymer mainly composed of the aromatic vinyl compound unit obtained by the above method and the block polymer mainly composed of the conjugated diene compound can be carried out by a known method. It is also possible to obtain a target polymer by adjusting the hydrogen addition rate by a known method. The specific method is disclosed in Japanese Patent Publication No. Sho 42-8704, Japanese Patent Publication No. Sho 43-6636, Japanese Patent Publication No. Sho. No. 63-4841, and The method of the Japanese Patent Publication No. 63-5401, Japanese Patent Publication No. Hei 2-133406, and Japanese Patent Publication No. Hei1-297413.

[0094] The (D) component of the first thermoplastic resin composition of the present invention has an optimum range of 1 to 200 mass parts and 5 to 170 masses for a total of 100 parts of the (A) component and the (B) component. The quality of the 10 to 170 parts is also good, but the quality of 15 to 150 is better. When it is used in this range, it can obtain excellent impact resistance and chemical resistance.

The amount of the component (D) of the second thermoplastic resin composition of the present invention is preferably in the range of 1 to 200 parts by mass, 5 to 170 parts by mass, and 10 to 170 parts by mass for the 100 parts by mass of the component (B). Good, but the best quality is 15~150. After using it in this range, it can obtain excellent impact resistance and chemical resistance.

The amount of the component (D) of the third thermoplastic resin composition of the present invention is preferably from 1 to 40% by mass, based on 100 parts by mass of the component (B) and (C1) and (D). 40% by mass and 5 to 35% by mass are also good, but 10 to 35 parts are the best; when less than 1% by mass, the effect of improving the electrical conductivity is not good, but when it exceeds 40% by mass, the chemical resistance and the surface appearance of the molded article It will also be bad.

[6] (E) Component The component (E) of the present invention is a (co)polymerized aromatic vinyl compound, or a copolymerizable aromatic vinyl compound and an aromatic vinyl compound in the presence of the above component (D). A graft copolymer of an ethylene monomer, an aromatic vinyl compound used herein, or a copolymerizable aromatic vinyl compound and another ethylene monomer of an aromatic vinyl compound, an ethylene monomer of the component (A) can be used (b) The best monomer combination for all of the materials described is styrene/acrylonitrile, styrene/acrylonitrile/methyl methacrylate.

[0096] Although the above-mentioned materials can be used for the component (D) used herein, it is preferable to add a carbon-carbon double bond of a hydrogen conjugated diene compound unit, and add hydrogen of 90% or more of a conjugated diene compound unit of carbon. - Carbon double bonding is also good, but more than 95% hydrogen is added.

[0097] The component (E) of the present invention can be obtained by graft polymerization of the above monomer component in the presence of the component (D), but the amount of the component (D) in the component (E) is in the range of 10~ 60% by mass, the graft ratio is preferably from 20 to 80% by mass.

The polymer may be produced by the above solution polymerization, bulk polymerization, suspension polymerization and combined polymerization of the component (A); the graft polymer obtained generally comprises graft copolymerizing the monomer on the component (D). a copolymer of a component, and a ungrafted component (a (co)polymer of a monomer component) which is not grafted on a rubbery polymer.

[0098] The (E) component of the first thermoplastic resin composition of the present invention has an optimum range of 1 to 200 mass parts and 5 to 170 masses for a total of 100 parts of the (A) component and the (B) component. Department, 10~170 quality parts are also good, but 15~150 quality parts are better; after being used in this range, excellent impact resistance molded articles can be obtained.

[0099] [7] (F) component The component (F) of the present invention belongs to the block polymer (f-1) composed of the component (D), and the aromatic carbonate block polymer (f-2) The aromatic polycarbonate block copolymer is composed; the molecular terminal of the component (D) preferably has a functional group reactive with the aromatic polycarbonate, and the functional group has a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, or the like. Among them, the most preferred ones are hydroxyl groups and carboxyl groups, but more preferably hydroxyl groups; these functional groups are preferably attached to the terminal of the aromatic vinyl compound block (d-1); the relevant functional groups are present in (D). The two ends and one end of the component, but one end is better in terms of impact resistance; further, the functional group does not need to have all molecules, and the average of each molecule is preferably 0.5 or more, but 0.7 to 2 ranges are better.

[0100] A method of introducing a functional group into a molecular terminal may be carried out by a known method; for example, by reacting an aromatic vinyl compound with a conjugated diene compound to obtain an active point of a polymer in the presence of an organic alkali metal compound, a method of containing a compound having the aforementioned functional group; and adding ethylene oxide or propylene oxide to the end of the block copolymer, adding an active hydrogen compound such as an alcohol, a carboxylic acid or water to stop anionic polymerization and oxyhydrogen a method of introducing a terminal at the base; and a method of blowing carbon dioxide at a low temperature to stop anionic polymerization and introducing a carboxylic acid group to the terminal.

The (D) component of the functional group at the terminal of the above molecule may be hydrogen-added to the carbon-carbon double bond of the conjugated diene compound unit by a known method, or hydrogen may be added to the component (D) by the aforementioned known method.

[0101] The block polymer (f-2) is an aromatic polycarbonate which can be obtained by interfacial polycondensation between various hydroxyaryl compounds and phosgene (Phosgene); The product obtained by a known polymerization method is obtained by transesterification (melt polycondensation) between a base compound and a carbonate compound such as diphenyl carbonate.

The raw material dihydroxy aryl compound of aromatic polycarbonate is bisphenol A, hydroquinone, 2,2-bis(4-hydroxyphenyl)pentane, 2,4-dihydroxydiphenylmethane, double (2-Hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane, etc., among which bisphenol A is most preferred.

The aromatic polycarbonate used in the present invention has an optimum viscosity average molecular weight of 8,000 to 50,000, preferably 12,000 to 30,000, more preferably 15,000 to 26,000. Further, different viscosity average molecular weights may be suitably used in combination.

[0102] Furthermore, the viscosity average molecular weight of the aromatic polycarbonate is a specific viscosity measured at 20 ° C and a concentration of 0.7 g / 100 ml (methylene chloride) under the condition of methyl chloride. η _{s p} ) is inserted in the following chemical formula (3) for calculation.

Viscosity average molecular weight = ^{_{[(η s p × 8130) 1}} . 2 0 5 ......... (3) In this [[eta]] = _{[(η s p × 1.12 + 1} ) 1/2 -1 ] /0.56C(C Indicative concentration) [0103] The (F) component of the present invention, although useful, introduces a functional group into the terminal (D) component functional group denatured block (f-1), and the above aromatic carbonate block polymer (f- 2) The method of melt-kneading the (i) block (f-1) and the block (f-2), and (ii) the case where the block (f-1) is present, the polymer block (f-2) The method (iii) is carried out by adding a block (f-1) at the final stage of the polymerization block (f-2) to carry out a reaction, etc., but the industrially preferred method is the above (i).

In addition, the optimum mass ratio range of (D) component/(f-2) component of (F) component is 95/5~5/95, 80/20~20/80 is also good, but 70/30~30 /70 is better.

The component (D) and the component (f-2) of the present invention do not need to be a block copolymer, and as long as at least 10% by mass or more is a block copolymer, the object of the present invention is attained.

Such a block copolymer mixture can be produced by a method described in, for example, JP-A-2001-220506. Further, the component (F) of the present invention can be obtained from KURARAY's TM polymer series TM-S4L77, TM. -H4L77 (product name), etc.

[0105] The (F) component of the first thermoplastic resin composition of the present invention has an optimum range of 1 to 200 mass parts and 5 to 170 masses for a total of 100 parts of the (A) component and the (B) component. Department, 10~170 quality parts are also good, but 15~150 quality parts are better; after being used in this range, excellent impact resistance molded articles can be obtained.

[0106] [8] (G) component The component (G) of the present invention belongs to a low molecular weight polyene which is denatured with an unsaturated acid and/or an unsaturated acid anhydride; the low molecular weight polyene used herein is the present invention. (B) A low molecular weight body in the composition, of which the most preferred is a low molecular weight polypropylene, or a low molecular weight polyethylene.

[0107] The weight average molecular weight of the above low molecular weight polyene is preferably from 1,000 to 100,000, preferably from 5,000 to 60,000, but more preferably from 8,000 to 50,000; the low molecular weight polyene can be obtained by thermal reduction of a polymerization method or a high molecular weight polyolefin. Because of the ease of denaturation of unsaturated acids and/or unsaturated anhydrides, it is preferred to use a thermal subtraction method; the low molecular weight polyene by thermal subtraction is such that the high molecular weight polyene is in an inert gas at 300 ° C or even 450 ° C. Under the conditions, a method of heat reduction of 0.5 hours to 10 hours (for example, the method described in JP-A-3-62804) can be obtained.

[0108] The unsaturated acid used herein may be, for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, etc., and these may be used alone or in combination of two or more; Further, as the unsaturated acid anhydride, maleic anhydride, itaconic anhydride, monochloroicic anhydride, monochloromaleic anhydride, citraconic anhydride, etc. may be used alone or in combination of two or more; The best is maleic anhydride.

[0109] The component (G) of the present invention, after considering the quality of the low molecular weight polyolefin as 100%, is preferably 0.5 to 25% by mass, 1 to 20% by mass, but more preferably 3 to 15% by mass. If the acid and/or the unsaturated acid anhydride are denatured, for example, an unsaturated acid and/or an unsaturated acid anhydride organic peroxide is present on the low molecular weight polyene as needed, so as to be obtained by denaturation by a solution method or a melting method; The material which is in accordance with the component (G) of the present invention can be obtained from UMEX 1001, 1003, 1010, 100TS, 110TS, 2000, CA60 (trade name) manufactured by Sanyo Chemical Industries Co., Ltd., and the like.

(01) The (G) component of the first thermoplastic resin composition of the present invention can be used in an optimum range of 1 to 200 mass parts, 1 to 50 for a total of 100 parts by mass of the (A) component and the (B) component. The quality department is better than the 1~45 quality part, but the 2~40 quality part is better. When the quality part is less than 1 part, the antistatic property will be poor. After exceeding 50 parts, the impact resistance and antistatic property will be poor. .

[0111] The components (D)(E)(F) and (G) of the present invention are effective components for improving the compatibility between the components of the thermoplastic resin composition of the present invention and various other characteristics, and may be at least from each component. One or a combination of two or more types may be used, and one or a combination of two or more selected from the group consisting of (D) (E) (F) and (G) may be used. (D) In the case of any of (E) (F) and (G), the total amount of these components is preferably 5 to 100 parts by mass of the component (A) and the component (B).

When the thermoplastic resin composition of the present invention is mainly composed of an ethylenic polymer, the compatibility of the component (D) is improved, and the compatibility with the composition is improved, thereby improving the overall impact resistance, chemical resistance, and formation. The surface appearance, antistatic property and even electrical conductivity of the product; when the above (D) component and the above (G) component are used together, the above characteristics are better improved.

Here, the term "olefinic polymer as a main component" means that the thermoplastic resin composition of the present invention conforms to the following formula: Formula: {(B) + (C1)} / {(A) + (B) + (C1) }≧0.4 ((A)(B)(C1) in the formula each represents (A) component, (B) component, (C1) component content (quality standard). Further, the thermoplastic resin composition of the present invention is benzene. When the ethylene-based polymer is mainly used, when the component (E) and/or the component (F) are blended, the antistatic property and the electrical properties are improved.

Here, the term "styrene-based polymer as a main component" means that the thermoplastic resin composition of the present invention conforms to the following formula: Formula: {(B) + (C1)} / {(A) + (B) + (C1 )}<0.4 ((A)(B)(C1) in the formula each represents (A) component, (B) component, (C1) component content (quality standard) [0112] The thermoplastic resin composition of the present invention, It can be mixed and tempered by various methods such as melting and kneading various components by means of various extruders, Banbury mixers, kneaders, continuous kneading, etc. The best method is to use an extruder, a special method. It is a multi-axis extruder, or a combination extruder, a Banbury mixer, continuous kneading and the like.

In addition, when mixing the ingredients, you can mix these ingredients at the same time, or mix them in multiple stages or splits.

[0113] The thermoplastic resin composition of the present invention may be formulated with a known inorganic or organic filler; the inorganic filler used herein means glass fiber, glass flake, glass fiber MildFiber, glass beads, hollow glass, carbon fiber, Carbon fiber MildFiber, talc, calcium carbonate, calcium carbonate whisker, wollastonite, mica, kaolin, montmorillonite, hectorite, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, alumina plate, seesaw, The montmorillonite, the aromatic polyamine, and the polyester fiber after the organic treatment may be used alone or in combination of two or more.

Further, in order to enhance the dispersibility of the filler, a known compound such as a coupling agent, a surface treatment agent, or a polymerization agent may be used, and a known coupling agent may be a silane coupling agent or a titanate coupling agent. Aluminum coupling agent, etc.

In the mass portion of the thermoplastic resin composition of the present invention, the inorganic or organic filler is generally used in an amount of from 1 to 200 parts by mass, but preferably from 1 to 100 parts by mass.

[0114] The thermoplastic resin composition of the present invention can be formulated with known weathering (light) agents, antistatic agents, antioxidants, lubricants, plasticizers, colorants, dyes, crystal nucleating agents, antibacterial agents, and antifungal agents. , foaming agent, flame retardant (phosphorus flame retardant, nitrogen flame retardant, halogen flame retardant, barium flame retardant), flame retardant aid (yttria compound, PREF, etc., chlorinated polyethylene )Wait.

Further, the thermoplastic resin composition of the present invention is another known polymer, and is also suitably blended with a polyfluorene resin, a polyester resin, a PMMA, a methyl methacrylate, a maleic anhydride imide compound copolymer, Polyphenylene ether, polyepoxymethane, polyphenylene sulfite, epoxy resin, phenol resin, EVA, EVOH, EBE, LCP, thermoplastic polyurethane, aromatic polycarbonate, urea resin, phenoxy resin, etc. .

The thermoplastic resin composition of the present invention prepared by the present invention can be obtained by a molding method such as injection molding, press molding, sheet molding, film molding, vacuum molding, profile extrusion molding, or foam molding to obtain a molded article; The thermoplastic resin composition of the present invention may be regarded as a surface layer, and a molded article in which a polyolefin resin or a styrene resin is regarded as an inner layer or an intermediate layer may be obtained by multi-lamination molding, or a multilayer formed by vacuum forming may be used. A thin plate is obtained to obtain a molded article of interest; the molded article obtained by these molding methods is as follows.

[0117] Various gears, various boxes, sensors, LEP lamps, connectors, sockets, resistors, relay boxes, wafer cassettes, IC trays, liquid crystal trays, switches, coil bobbins, capacitors, variable capacitors Box, optical pickup components, oscillators, various terminal boards, transformers, plugs, printed circuit boards, frequency modulators, amplifiers, microphones, earphones, small motors, magnetic head holders, power modules, housings, semiconductors, Electrical and electronic parts represented by liquid crystal FDD carriers, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc.; VTR parts, TV parts, electric irons, hair dryers, electric cooker parts, microwave oven parts, audio parts , audio laser disc (registered trademark), small disc audio equipment parts, lighting parts, refrigerator parts, etc. represented by the family. OA electrical product parts; OA related parts, telephone related parts, fax machine related parts, photocopying machine related parts, washing utensils related parts; toilet, lid, casing, kitchen parts, washstand related parts, bathroom related parts, etc. Related parts; window frames, furniture, flooring, wall materials, etc., housing related parts; optical equipment, precision equipment related parts represented by microscopes, binoculars, cameras, clocks, etc.; alternator terminals, alternators Connector, IC regulator, exhaust valve, various valves, fuel related, exhaust system, suction system, various valves; intake nozzle snorkel, intake seat, fuel pump, engine cooling water connector, carburetor Main body, carburetor spacer, exhaust sensor, cooling water sensor, oil temperature sensor, brake pad sensor, throttle positioning sensor crankshaft positioning sensor, air flow meter, air conditioner Thermostatic head, heating and temperature control valve, brush holder for radiator motor, water pump impeller, turbine tube, wiper motor related parts, switchboard, start switch, start relay Wiper, transmission window wiper wiring, window nozzle, air conditioning panel switch circuit board, fuel-related solenoid valve coil coil, fuse connector, speaker terminal, padded component insulation board, stepper motor wheel, lamp holder , lamp display, lamp housing, brake piston, spiral bobbin, engine oil filter, ignition box; computer, list machine, display, CRT display, notebook, mobile phone, PHS, DVD player, PD Electrical and electronic equipment parts such as memory devices such as players and floppy disk drives, chassis, relays, switches, housing components, transformer components, and coil bobbins; exterior components for bumpers, fenders, etc. Various uses.

The thickness of the thermoplastic resin composition of the present invention when processed into a sheet or a film is preferably in the range of 10 μm to 100 mm.

The thin plate or the film may be a single-layer thin plate or a film, or may be a multilayer molded article in which at least one side of the base material is laminated, or may be a thin plate or a film such as a build-up adhesive; in addition, the thin plate or the film may be formed. Know the gas protective film.

When a multilayer thin plate or a film is produced from the thermoplastic resin composition of the present invention, the thermoplastic resin composition of the present invention can be used as a three-layered sheet, a film, or the like of an intermediate layer. The base material used herein may be a sheet or a film composed of a known polymer. Among them, a sheet made of the component (A) or the component (B) of the present invention, a film, particularly a sheet made of an olefin resin, is preferably used. The film is optimal; furthermore, in order to improve rigidity and heat resistance, the above-mentioned inorganic or organic filler formulation can also be used.

In order to stably find the electrical conductivity, the thickness of the thermoplastic resin composition of the present invention of the above-mentioned multilayered sheet is preferably 10 μm or more, more preferably 50 μm or more, but more preferably 80 μm or more; and it is preferable to obtain such a multilayer sheet and film. The method is to perform co-extrusion by T Die and co-extrusion by blow molding: a thin plate or a film obtained by this method can be obtained by vacuum forming or the like as a molded article.

1 is a schematic cross-sectional view showing an example of a multilayer molded article of the present invention, which is an antistatic layer 12 composed of a thermoplastic resin composition of the present invention, and a two-layer molded article 1 disposed on one surface of a base layer 11; 2 is a schematic cross-sectional view showing another example of the multilayer molded article of the present invention, which is an antistatic layer 12a and 12b composed of the thermoplastic resin composition of the present invention, and a three-layer molded article 2 disposed on both sides of the base layer 11; Furthermore, the thickness of the antistatic layers 12a and 12b may be the same or different from each other; in addition, the compositions of the antistatic layers 12a and 12b may be identical to each other or may be different from each other.

[0120] In order to improve the adhesion between the adhesives or the adhesion between the primer layers, when manufacturing the adhesive sheets and films, various known treatment methods such as corona discharge treatment, flame treatment, oxidation treatment, and electricity can be used. The surface of the base material sheet and the base material film composed of the thermoplastic resin composition of the present invention are treated by a slurry treatment, a UV treatment, an Ionbombard treatment, a solvent treatment or the like; and a combination treatment may be carried out as needed.

Furthermore, in order to improve the adhesion between the base metal sheet and the film and the adhesive, a primer layer may be formed directly on the base material sheet, the film, or on the surface treatment surface; specifically, the polyethyleneimine is allowed. A resin such as polyurethane or acryl resin forms an extremely thin layer having a thickness of 0.1 μm to 10 μm; usually, a solvent (including water) solution can be applied and formed by drying.

[0121] Adhesives can be classified into a latex type, an organic solvent type, an extrusion lamination method, a dry lamination method, a co-extrusion method, etc. by a screen method, a gravure method, a mesh method, a Bar coating method, and the like. Any of the formed hot melt types and the like can be used; in addition, although the thickness of the adhesive is not particularly specified, it is usually in the range of 1 to 10 μm.

[0122] The obtained molded article can be used for a carrier such as a relay box, a wafer cassette, a Retucule case, an Acth case, a liquid crystal tray, a wafer tray, a memory tray, a CCD tray, an IC tray, or the like, and an IC carrier. The polarizing film protects the thin plate, the protective film when the polarizing film is cut, the protective film such as a liquid crystal display device or a plasma display, a semiconductor-related protective film, a film such as a dust-free indoor protective film, and the internal components of a vending machine.

[Examples]

The present invention will be described in more detail below by way of examples, but the present invention is not limited to the embodiments as long as it does not exceed the gist of the present invention; further, the parts and % in the examples are not indispensable. The discarded material standards; in addition, the various measurements in the examples and comparative examples are based on the following methods.

[0124] [1] Evaluation method (1) rubbery polymer gel content; according to the above method (2) rubbery polymer latex average particle diameter; astigmatism method for forming (A) component rubbery polymerization The average particle size of the latex was measured by the LPA-3100 type manufactured by Otsuka Electronics Co., Ltd., and the cumulative method of 70 times was used. Furthermore, it was confirmed by electron microscopy that the dispersed grafted rubbery substance in the component (A) The particle size of the polymer is almost the same as the particle size of the latex.

(3) The grafting ratio of the component (A); the ultimate viscosity [η] of the acetone-soluble portion of the component (4) according to the above method (4); according to the above method [0125] (5) (D) component (polymer) Binding styrene amount, ethylene amount, number average molecular weight and hydrogen addition rate); (5-1) The amount of bound styrene is measured by the polymer before hydrogen addition; the absorption of 699 cm is determined from the calibration line according to the infrared method ^{- 1} phenyl.

(5-2) The number average molecular weight is measured by a polymer before hydrogen addition; and it is determined by a gel permeation chromatography (GPC) method.

(5-3) The ethylene binding amount was measured by the polymer before hydrogen addition; it was determined by the infrared method (Morelo method).

(5-4) hydrogen addition rate; measured by polymer before hydrogen addition; tetrachloroethylene as solvent, and unsaturated double combination of ¹ H-NMR spectrum of 100 MHz measured at 15% concentration It is calculated from the spectrum of the decrease in the object.

[0126] (6) Impact resistance (6-1) Impact resistance-1; Chaw impact strength (KJ/m ² ) of a built-in notch was measured according to ISO Test Method 179.

(6-2) Impact resistance-2; A 2.4 mm thick flat plate was placed on a tray having a diameter of 38 mm, and the energy (kgf. cm) at the time of punching the flat plate was measured at a striking diameter of 16 mm and a speed of 2.4 m/sec.

(6-3) Impact resistance-3; The energy (kgf. cm) at the time of punching a 1.6 mm flat plate at a speed of 2.0 m/sec with a 1/2 inch diameter and a front end R1/2 打击 bar was obtained.

[0127] (7) Chemical resistance (7-1) Chemical resistance A After adding 1% skew to a test piece having a thickness of 3.2 mm × a width of 12.7 mm × a length of 127 mm, the following drugs were applied, and then based on the following evaluation criteria, visual inspection The surface state of the molded article after being placed in an environment of 23 ° C for 48 hours was evaluated.

○: no change ×: cleft or broken (7-1-1) chemical resistance A1; alcohol (7-1-2) chemical resistance A2; brake oil (7-2) chemical resistance B; test piece (length 127 mm × width 12.7 mm × thickness 1 mm) After adding 1% skew, ethanol (EtOH) or methyl ethyl ketone (MEK) was applied to the surface, and the environment was evaluated visually at 23 ° C based on the following evaluation criteria. The surface condition of the test piece after 72 hours of standing.

○: no change ×: cleft or broken (7-3) chemical resistance C; after adding 1% skew to the test piece with a thickness of 1 mm, the following drugs were applied, and visually evaluated at 23 ° C based on the following evaluation criteria. The surface condition of the sheet after 72 hours of environmental placement.

○: no change ×: cleft or broken (7-3-1) chemical resistance C1; methanol (7-3-2) chemical resistance C2; methyl ethyl ketone [0128] (8) antistatic property (8-1) Antistatic property-1; a circular plate having a diameter of 100 mm and a thickness of 2 mm, adjusted for 7 days in an environment of 23 ° C × 50% relative humidity, and then a 4329A type super insulation resistance meter manufactured by Yokogawa Huret Packard Co., Ltd. The surface intrinsic impedance was measured at an applied voltage of 500V.

(8-2) Antistatic property-2; a circular plate having a diameter of 100 mm and a thickness of 2 mm was adjusted in an environment of 23 ° C × 30% relative humidity for 1 day, and then a High Resistant Meter 4339B type manufactured by Agilent-Technologies Co., Ltd., and The surface intrinsic impedance was measured at an applied voltage of 500V.

(8-3) Antistatic property-3; a circular plate having a diameter of 100 mm and a thickness of 2 mm was adjusted in an environment of 23 ° C × 50% relative humidity for one day, and then Agilent-Technologies Co., Ltd. High Resistant Meter 4339B was used. The surface intrinsic impedance was measured at an applied voltage of 500V.

[0129] (9) Power-supply property (9-1) Power-supply-1; using a thin plate of 1 mm thickness, High Rester UP MCP-HT 450 manufactured by Mitsubishi Chemical Corporation, measured at an applied voltage of 500 V at 23 ° C, 50% RH The surface intrinsic impedance after 24 hours of standing under conditions.

(9-2) Power-generating -2; Surface intrinsic after being placed at 23 ° C, 50% RH for 24 hours with an applied voltage of 100 V using a thin plate of 1 mm thickness and High Rester UP MCP-HT 450 manufactured by Mitsubishi Chemical Corporation impedance.

(10) Persistence of electrical conductivity; immersing a thin plate of 1 mm thickness in distilled water for 10 days, placing it in a constant temperature and humidity chamber at 23 ° C × 50% RH; measuring the time of surface intrinsic impedance by the above method (9-2) Change, and then find the surface intrinsic impedance (NO2 surface intrinsic resistance) of the equilibrium state. The persistence of the intrinsic impedance from the surface of NO1 and the intrinsic impedance of the surface of NO2 was evaluated in accordance with the following.

○; The intrinsic impedance of the surface of NO2 is equivalent or low in persistence compared with the intrinsic impedance of the surface of NO1.

×; The persistence of the intrinsic impedance of the surface of NO2 is inferior to the inherent impedance of the surface of NO1.

(11) Surface appearance of the molded article (11-1) Surface appearance-1; The 3.2 mm-thick flat molded article was visually evaluated based on the following evaluation criteria.

◎; almost no burrs, the surface condition of the molded article is smooth.

○; There are a number of burrs, and the surface condition of the molded article is smooth and has no problem.

×; The raw edges are large and/or the surface state of the molded article is not smooth, and there is a problem.

(11-2) Surface appearance - 2; (gloss) formed flat plate, and 60 degree gloss was measured using the gloss agent GM-26D manufactured by Murakami Color Technology Research Co., Ltd.

(11-3) Surface Appearance-3; Multilayer sheets and trays were visually evaluated based on the following evaluation criteria.

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

×; The surface has irregularities and the shape is unstable.

[0131] [2] Component of thermoplastic resin composition (1) (A) Component (1-1) Production Example 1; ABS resin (A1) was added to a 7 L glass flask containing an internal volume of a stirrer in a nitrogen gas stream 75 parts of ion-exchanged water, 0.5 parts of potassium oleate, 0.1 part of tert-dodecyl mercaptan, 40 parts of polybutadiene latex (average particle size: 3500 A, gel content: 85%) (solid), 15 parts Styrene, 5 parts of acrylonitrile, while stirring, while the internal temperature reached 45 ° C, a solution of 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate 7 hydrate, 0.2 parts of glucose dissolved in 20 parts of ion-exchanged water was added. Thereafter, 0.07 parts of cumene hydroperoxide was added to start polymerization; after 1 hour of polymerization, 50 parts of ion-exchanged water, 0.7 parts of potassium oleate, 30 parts of styrene, 10 parts of acrylonitrile, and 0.05 parts were continuously added for 3 hours. Tert-dodecyl mercaptan and 0.01 parts of cumene hydroperoxide, after further polymerization for 1 hour, add 0.2 part of 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol) The polymerization is completed; the latex of the reaction product is solidified with an aqueous solution of sulfuric acid, and after washing with water, it is dried to obtain a styrene resin A1. This graft ratio A1 68% acetone soluble fraction limit viscosity [[eta]] of 0.45dl / g.

(1-2) Production Example 2; the AS resin (A2) is connected to two polymerization reactors having a spiral belt having an internal volume of 30 liters and a built-in sleeve, and after the nitrogen exchange, the first polymerization is carried out. 75 parts of styrene, 25 parts of acrylonitrile, and 20 parts of toluene were continuously added to the reactor; next, 0.12 parts of tert-dodecanethiol was regarded as a molecular weight modifier, 5 parts of a toluene solution, and 0.1 part of 1 was continuously supplied. , 1'-. azo (cyclohexane-1-Carbonytril) is regarded as starting polymerization agent, and 5 parts of toluene; the first polymerization temperature is controlled to 110 ° C, polymerization is carried out with an average residence time of 2 hours; polymerization conversion After the rate was 57%, from the obtained polymer solvent, the styrene, acrylonitrile, toluene, molecular weight regulator, and the start of the polymerization agent were continuously discharged in the same amount by the pump disposed outside the first polymerization reactor. Thereafter, it is supplied to the polymerization reactor of the second block; the polymerization temperature of the second polymerization reactor is 130 ° C, and the polymerization conversion rate is 75%; next, the polymer is taken from the second polymerization reactor. For the solution, use a 2-axis 3-stage internal venting extruder to remove unreacted monomer and solvent. , Is obtained as the limit viscosity [η] of a styrenic resin A2 0.48.

(1-3) Production Example 3; Hydroxy-Unsaturated Compound Copolymerized AS Resin (A3) Instead of using polybutadiene in Production Example 1, potassium rosinate was changed to dodecylbenzenesulfonate. Potassium acid; in addition, the monomer content of the first paragraph is changed to styrene / acrylonitrile / 2 - hydroxyethyl methacrylate = 22.5 / 7.5 / 3.5 parts; in addition, in addition to the continuous addition of ingredients, benzene Ethylene/acrylonitrile/2-hydroxyethyl methacrylate = 44.7/14.9/6.9 parts, all of which were polymerized by the method of Production Example 1; the latex of the reaction product was solidified with an aqueous solution of magnesium sulfate, washed with water and dried. The styrene resin A3 was obtained; the ultimate viscosity [η] was 0.44.

(1-4) Production Example 4; carboxyl group-containing unsaturated compound copolymerized AS resin (A4) in the first stage monomer component of Production Example 3, changed to styrene/acrylonitrile/methacrylic acid=23.7/7.9 /1.7 parts; further, except that the continuously added components were changed to styrene/acrylonitrile/methacrylate = 47.5/15.8/3.4 parts, all were polymerized by the method of Production Example 1; the ultimate viscosity was obtained. [η] is a styrene resin A4 of 0.46.

(1-5) Production Example 5; Epoxy-containing unsaturated compound copolymerized AS resin (A5) In the first stage monomer component of Production Example 3, changed to styrene/acrylonitrile/epoxypropyl group Acrylate = 23.7 / 7.9 / 1.7 parts; in addition, except that the continuous addition of ingredients was changed to styrene / acrylonitrile / epoxy propyl methacrylate = 47.5 / 15.8 / 3.4 parts, all manufactured The method of Example 1 was carried out; a styrene resin A5 having an ultimate viscosity [η] of 0.42 was obtained.

[0136] (2) (B) component; (2-1) B1; polypropylene resin "Novatec BC6C (trade name)" manufactured by Pochem Co., Ltd., Japan.

(2-2) B2; Polypropylene resin "Novatec MA1 (trade name)" manufactured by Pochem Co., Ltd., Japan was used.

(2-3) B3; Polypropylene resin "Novatec FY6C (trade name)" manufactured by Pochem Co., Ltd., Japan was used.

(3) (C1) Component C1-1; Polyether polyether block copolymer "Pelestart 303 (trade name)" manufactured by Sanyo Chemical Industries, Ltd. was used.

C1-2; Polyether polyether block copolymer "Pelestart 230 (trade name)" manufactured by Sanyo Chemical Industries Co., Ltd. was used.

[0138] (4) (C2-1) Component C2-1-1; a polyether polyether "Pelestart M-140 (trade name)" manufactured by Sanyo Chemical Industries Co., Ltd. was used.

C2-1-2; a polyether polyester "TEP-004 (trade name)" manufactured by Takemoto Oil Co., Ltd. was used.

(5) (C2-2) Component The (C2-2) component of the present invention is the following nonionic antistatic agent manufactured by Kao Corporation. C2-2-1; Electro Stripper TS-5 (trade name) glyceride antistatic agent, C2-2-2; Electro Stripper EA (trade name) diethanolamine antistatic agent, C2-2-3; Electro Stripper TS-3B (trade name) glyceride/diethanolamine composite antistatic agent.

[6140] (6) (C2-3) Ingredients The (C2-3) component of the present invention is "Hybolon MB400N-8LDPE (trade name)" manufactured by Boron International Co., Ltd.; this product belongs to "Hybolon 400N" (trade name) manufactured by the company. The main component of the polyethylene (polymer charge mobile type combination), the active ingredient (C2-3) is 7%.

(7) (C2-4) Component The component (C2-4) of the present invention is as follows.

C2-4-1; SANKONORL 0862-10T (trade name) manufactured by Sanko Kasei Kogyo Co., Ltd., having a lithium chloride compound content of 10%.

C2-4-2; SANKONORL AQ-50T (trade name) manufactured by Sanko Kasei Kogyo Co., Ltd., having a lithium chloride content of 50%.

C2-4-3; lithium bromide.

(8) (D) component (8-1) Production Example 6; styrene-butadiene-styrene block copolymer to which a part of hydrogen was added, and the autoclave of the mixer and the built-in sleeve was dried, and the nitrogen was replaced. Then, a solution of 30 parts of styrene in cyclohexane was further charged; next, n-butyllithium was added, and after polymerization at 70 ° C for 1 hour, a solution of 40 parts of butadiene in cyclohexane was added and polymerization was carried out for 1 hour. After sampling the obtained partial block copolymer, after adding 0.3 part of 2,6-di-tert-p-tert-butyl catechol to 100 parts of the block copolymer, heating to remove the solvent; the styrene content is 60 %, the polybutadiene moiety has a 1,2-ethylene binding amount of 35% and a number average molecular weight of 74,000; and the remaining block copolymerization solution is added to the cyclohexane to react the Titanium Dichloride and the triethylaluminum solution. , performing hydrogenation reaction at 50 ° C, 50 kgf / cm ² hydrogen pressure for 40 minutes; adding 0.3 parts of 2,6-di-tert-p-tert-butyl catechol to 100 parts of the block copolymer, removing the solvent That is, a polymer D1 having a hydrogen addition rate of 69% was obtained.

(8-2) Production Example 7; styrene-butadiene-styrene block copolymer in which hydrogen was completely added. After the autoclave of the mixer and the built-in sleeve was dried, the nitrogen gas was replaced, and 20 parts of the ring was further charged. Alkane and 20 parts of butadiene solution; next, 0.025 parts of n-butyllithium was added, and constant temperature polymerization was carried out at 50 ° C. When the conversion rate reached 100%, 0.75 parts of oxygen-stained cyclopentane and 65 parts were added. Butadiene is heated from 50 ° C to 80 ° C for temperature polymerization; when the conversion rate reaches 100%, after adding 15 parts of styrene, the polymerization reaction is carried out again, and the A-B1-B2 triblock is obtained before hydrogen is added. Copolymer; the same sampling and analysis results as in Production Example 6 were: styrene block 15% (block A), 1, 2-ethylene content of 35% butadiene block (B1 block), 1, 2-ethylene content 10 The number of butadiene blocks (B2 blocks) constitutes a number average molecular weight of 200,000 polymers.

In another container, after dispersing 1 part of Titanium Dichloride in cyclohexane, reacting with 0.5 part of triethylaluminum at room temperature; adding the obtained uniform solution to the above polymerization solution, 50 ° C, 50 kgf / cm ^{Under the} hydrogen pressure, a hydrogenation reaction was carried out for 2 hours, that is, a hydrogen-added polymer D2 having a hydrogen addition rate of almost 100% was obtained.

(8-3) Production Example 8; styrene-butadiene-styrene block copolymer After the autoclave of the mixer and the built-in sleeve was dried, the nitrogen gas was replaced, and 0.08 parts of cyclohexane was converted in a nitrogen stream. After oxygenating with cyclopentane, the temperature is raised. When the internal temperature reaches 70 ° C, cyclohexane containing 0.052 parts of n-butyllithium is added, and then 15.5 parts of styrene is added, followed by polymerization for 60 minutes (paragraph 1); After adding 3 parts of styrene and 20 parts of butadiene mixture, polymerization was carried out for 60 minutes (paragraph 2); in addition, 3 parts of styrene and 20 parts of butadiene mixture were added and polymerized for 60 minutes (paragraph 3); After 3 parts of styrene and 20 parts of butadiene mixture were polymerized for 60 minutes (paragraph 4), 3 cones were polymerized; next, 15.5 parts of styrene was added for polymerization for 60 minutes (paragraph 5); polymerization conversion rate It is 100%.

Furthermore, the internal temperature is controlled at 70 ° C during the polymerization; after the completion of the polymerization, 2,6-di-tert-p-tert-butyl catechol is added to the polymerization solution, and the solvent is removed by heating to obtain polystyrene. The block copolymer D3 having an increasing number of polybutadiene blocks and having three tapered blocks; the number average molecular weight of 128,000 and the styrene content of 40%.

(8-4) Production Example 9; styrene-butadiene radial para-phenylene block copolymer, after drying the autoclave of a stirrer and a built-in sleeve, replacing nitrogen gas, and injecting 2.75 parts of a ring into a nitrogen stream The alkane and oxygen are dyed with cyclopentane; after adding 25 parts of styrene, the temperature is raised to 60 ° C, then 0.175 parts of n-butyl lithium cyclohexane is added and the polymerization reaction is carried out for 60 minutes (the first stage); 3 parts of styrene and 20 parts of butadiene mixture were polymerized for 60 minutes (second stage); in addition, 3 parts of styrene and 20 parts of butadiene mixture were added and polymerization was carried out for 60 minutes (paragraph 3); After the butadiene is polymerized until the conversion rate reaches 100%; after adding 0.1 part of the coupling agent silicon tetrachloride, the coupling reaction is completed; after the polymerization is completed, the 2,6-di-tert-pair is added to the polymerization solution. After the butyl catechol, after heating to remove the solvent, a coupled styrene-butadiene block copolymer D4 having a tapered block was obtained; the styrene content was 31%, and the number average molecular weight was 200,000.

(8-5) A styrene-butadiene-styrene block copolymer D5; "TR2500" (trade name) manufactured by JSR Corporation.

(8-6) The hydrogen-adding material D6 of the styrene-butadiene block copolymer; "DYNARON 4600P" (trade name) manufactured by JSR Corporation.

[9147] (9) (E) component; Production Example 10; Graft polymer A stainless steel autoclave having a spiral-type stirring blade and an internal volume of 10 liters was subjected to nitrogen replacement, and then toluene was previously introduced in a nitrogen stream. After considering the solvent, 30 parts of the above-mentioned polymer D2 solution (solid), 52.5 parts of styrene, 17.5 parts of acrylonitrile, 120 parts of toluene, 0.1 part of tert-dodecyl mercaptan were charged, and the temperature was raised while stirring; When the internal temperature reached 50 ° C, 0.5 parts of phenylhydrazine peroxide and 0.1 part of dicumyl peroxide were added, and then the temperature was raised to 80 ° C, and then the polymerization was carried out while controlling at a constant temperature of 80 ° C; It takes about 1 hour to raise the temperature to 120 ° C from the hour, and then ends after 2 hours of reaction; the conversion rate is 97%.

After cooling to 100 ° C, after adding 0.2 part of 2,2-methylenedi-4-methyl-6-tert-butylphenol, the reaction mixture was taken out from the autoclave, and the unreacted product was distilled off by steam distillation. Simultaneously with the solvent, the polymer was formed into a spherical shape to obtain a graft polymer E; the graft ratio was 5%, and the ultimate viscosity [η] of the acetone-soluble portion was 0.45 dl/g.

[0148] (10) (F) component; TM polymer manufactured by KURARAY Co., Ltd.; TM-S4L77 (SEPS-aromatic polyphthalate block copolymer trade name).

[0149] (11) (G) component; (G) component of the present invention, the following maleic anhydride-modified polyene manufactured by Sanyo Chemical Industries Co., Ltd. was used.

G1; YUMEX 1001 (maleic anhydride additional 5% product name) G2; YUMEX 1010 (maleic anhydride additional amount 10% product name) [0150] (12) other ingredients (H) (12-1) H1; "Novalex 7022PJ (trade name)" (viscosity average molecular weight 2,200) manufactured by Mitsubishi Engineering Plastic Co., Ltd., an aromatic polycarbonate.

(12-2) H2; "PBT XD477 (trade name)" (intrinsic viscosity: 1.2 dl/g) manufactured by Poly Plastics, Polybutylene terephthalate.

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

The formulation ratios shown in Table 1-1 were mixed by a Henshell mixer, and then subjected to melt-kneading using a two-axis extruder (cylinder set temperature: 240 ° C) to form pellets; after the obtained pellets were sufficiently dried, Then, an evaluation test piece was prepared by injection molding (cylinder set temperature: 230 ° C); the test piece was used to evaluate impact resistance, chemical resistance, surface appearance and antistatic property of the molded article by the above evaluation method; -2 is shown.

From the evaluation results shown in Table 1-2, the following items were clarified.

The molded articles of Examples I-1 to I-23 of the present invention all have excellent impact resistance, chemical resistance, surface appearance and antistatic property of the molded article; further, the chemical resistance of Examples I-22 and I-23 Both sex-A1 and A2 are marked with ○ printed, but slightly inferior to Examples I-1 to I-21.

On the other hand, Comparative Example I-1 belongs to the amount of the component (A) of the present invention, which is less than the scope of the invention, and the amount of the component (B) is out of the scope of the invention, so that the impact resistance and the surface appearance of the molded article are exhibited. Poor; Comparative Example I-2 is an amount of the component (C1) of the present invention, which is inferior to the scope of the invention, so that impact resistance, surface appearance and antistatic property of the molded article are poor; Comparative Example I-3 is the present invention ( The amount of the component of the component C1 is out of the range of the invention, so that the impact resistance and the surface appearance of the molded article are inferior.

Example I-24 Manufacturing three-layer sheet Three-layer sheet (1)

Two skin layers (each having a thickness of 100 μm) were produced using the composition of Example I-19, and a three-layered sheet was produced using the B1 component (thickness: 800 μm) in the center layer. Further, the sheet was vacuum-formed to manufacture a tray.

Three-layer sheet (2)

Using the composition of Example I-22 and the component B1, a three-layered sheet and a vacuum forming tray as described above were produced.

Three-layer sheet (3)

Using the composition of Example I-22 and ABS (A1 component / A2 component = 40/60% composition), Example I-22 was fabricated into two skin layers (each thickness was 100 μm), and the center layer was ABS. A three-layer sheet was produced by the composition (thickness: 800 μm); and the tray was produced by vacuum forming in the same manner as described above.

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

According to the formula ratios shown in Tables 2-1 and 2-2, the mixture was mixed by a Henshell mixer, and then subjected to melt-kneading using a two-axis extruder (cylinder set temperature: 200 ° C) to form pellets; the obtained pellets were obtained. After sufficiently drying, a test piece for evaluation was produced by injection molding (cylinder set temperature: 200 ° C).

Using this test piece, the impact resistance, chemical resistance, and antistatic property were evaluated by the aforementioned evaluation methods; the evaluation results are shown in Table 2-1.

From the evaluation results shown in Tables 2-1 and 2-2, the following items were clarified. The molded articles of Examples II-1 to II-15 of the present invention all have excellent impact resistance, chemical resistance and antistatic property.

On the other hand, Comparative Example II-1 belongs to the amount of the component (A) of the present invention, which is less than the scope of the invention, and the amount of the component (B) is out of the scope of the invention, so that the impact resistance and the antistatic property are poor. Comparative Example II-2 is an amount of the component (C1) of the present invention, which is inferior to the range of the invention, so that the impact resistance and the antistatic property are poor; Comparative Example II-3 is the amount of the component (C1) of the present invention. It is out of the scope of the invention, and the impact resistance is poor.

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

According to the formula ratios shown in Tables 3-1 and 3-2, all the components were mixed by a Henshell mixer, and then melted and kneaded by a two-axis extruder (cylinder set temperature: 220 ° C) to obtain pellets; After the pellets were sufficiently dried, a test piece for evaluation was produced by injection molding (cylinder set temperature: 220 ° C).

Using this test piece, the impact resistance, the chemical resistance, the surface appearance of the molded article, and the antistatic property were evaluated by the aforementioned evaluation methods; the evaluation results are shown in Tables 3-1 and 3-2.

From the evaluation results shown in Tables 3-1 and 3-2, the following items were clarified. The molded articles of Examples III-1 to III-18 of the present invention all have excellent impact resistance and chemical resistance; and the molded articles of Examples III-1 to III-17 have excellent impact resistance and surface gloss of the molded article. .

Comparative Example III-1 is an example of the amount of the component (A) of the present invention, which is out of the scope of the invention, and the amount of the component (B) is out of the scope of the invention, so that the impact resistance and the antistatic property are poor; The use of the component (C1) of the present invention in Example III-2 is out of the range of the invention, and the impact resistance and the antistatic property are inferior.

After mixing the predetermined amount of the components described in Table 4 with a Henshell mixer, and then performing a melt-kneading using a two-axis extruder (cylinder set temperature: 220 ° C), a pelletized thermoplastic resin composition can be obtained; Since the component of C2-3) contains polyethylene equivalent to the component (B), the amount of the polyethylene is described in Table 4 as B4.

Next, the above-mentioned component B3 for forming a base layer and the above-mentioned thermoplastic resin composition for forming an antistatic layer on both surfaces of the base layer are pressed together at a temperature of 210 ° C, thereby obtaining a base layer thickness of 800 μm, an antistatic layer thickness of 100 μm each, and a thickness. 1 mm multi-layer sheet; for this multi-layer sheet, the intrinsic resistance (antistatic property), chemical resistance, and surface appearance of the surface were evaluated.

Further, the above-mentioned multilayer sheet was vacuum-formed to produce a tray; the evaluation results of evaluating the surface appearance of the tray are shown in Table 4.

Example IV-2~IV-14

Thermoplastic resin compositions, sheets, and trays were prepared in the same manner as in Example IV-1 except for the amounts specified in Table 4 to evaluate the surface specific resistance and surface appearance. The evaluation results are shown in Table 4. Show.

The following items can be clarified from Table 4.

Low surface intrinsic impedance and excellent power generation of Embodiments IV-1 to IV-14 of the present invention Sex, chemical resistance and surface appearance.

From the comparison of Example IV-1 and Example IV-14, the antistatic effect by the combination of the (C1) component and the (C2-3) component can be clarified; in other words, in the embodiment IV-1 ( The amount of the component (C2-3) and the component (C2-3) are each 26% and 1.19%, respectively, and the total amount is 27.1%; on the other hand, the amount of the component (C1) and the component (C2-3) in the embodiment IV-14 are used. Each of 27.19% and 0%, the total is 27.19%; in other words, in Example IV-1 and Example IV-14, even if the antistatic property (C1) component and (C2-3) component are combined In Example IV-1 having the same amount and using the (C1) component and the (C2-3) component, the surface specific resistance was also 10 times or less and excellent in antistatic property.

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

According to the formula ratios shown in Tables 5-1 and 5-2, the mixture was mixed by a Henshell mixer, and then melted and kneaded by a two-axis extruder (cylinder set temperature: 220 ° C) to form pellets; After drying, a test piece for evaluating the surface appearance of a molded article was obtained by injection molding (cylinder set temperature: 210 ° C).

The core layer was a sheet of the above polymer B3 having a thickness of 800 μm, and the surface layer and the bottom layer were each formed by using the above-mentioned resin composition having a thickness of 100 μm, and co-extrusion (temperature: 220 ° C) to make a laminated three-layer sheet, and a thickness of 1 mm was obtained. Thin sheet; the sheet is cut for use as a test piece for electric property evaluation and a test piece for evaluation of chemical resistance.

The electroforming property, the chemical resistance, and the surface appearance of the molded article were evaluated by the aforementioned evaluation methods. Further, the above-mentioned thin 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 then vacuum formed. That is, a tray molded article was obtained; next, the surface specific impedance in the vicinity of the corner of the tray molded article was measured in the same manner as the above-described power measuring method.

The evaluation results are shown in Table 5-1 and Table 5-2.

Examples V-1 to V-4 and Comparative Examples V-1 to V-3 belong to a second thermoplastic resin composition in which the components (B), (C1) and (C2-2) of the present invention are regarded as desired components. Related Examples and Comparative Examples; Examples V-5 to V-8 and Comparative Examples V-4 to V-5 belong to the components (B), (C1), (C2-2) and (D) of the present invention. Related Examples and Comparative Examples of Third Thermoplastic Resin Composition of Desirable Ingredients; Further, Examples V-9 to V-23 belong to the components (A), (B), (C1), (C2-) of the present invention. 2) and (D) related examples of the first thermoplastic resin composition regarded as the desired component.

The following items can be clearly identified from the results in Tables 5-1 and 5-2.

In the examples of the present invention, the molded articles of V-1 to V-23 have excellent electric properties, 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 out of the scope of the invention, and the amount of the component (C1) is out of the range of the invention, so that the electrical conductivity and the surface appearance of the molded article are poor; V-2 is an example of the amount of the component (B) of the present invention, which is out of the scope of the invention, and the amount of the component (C1) is out of the scope of the invention, so that the chemical resistance and the surface appearance of the molded article are poor; Comparative Example V- 3 The amount of the component (C2-1) of the present invention is out of the scope of the invention, so that the electroforming property is inferior; the comparative example V-4 is an example in which the amount of the component (C2-2) of the present invention is out of the scope of the invention. Therefore, the chemical resistance and the surface appearance of the molded article were inferior; the comparative example V-4 was an example in which the amount of the component (D) of the present invention was out of the scope of the invention, so that the chemical resistance and the surface appearance of the molded article were inferior.

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

The mixture ratio shown in Table 6 was mixed by a Henshell mixer, and then subjected to melt-kneading using a two-axis extruder (cylinder set temperature: 220 ° C) to form pellets; after the obtained pellets were sufficiently dried, they were sprayed. Forming (cylinder setting temperature: 210 ° C) A test piece for evaluation of impact resistance was obtained.

The core layer was obtained by using the above-mentioned polymer A1 sheet having a thickness of 800 μm, and the surface layer and the bottom layer were each formed by using the above-mentioned thermoplastic resin composition having a thickness of 100 μm, and co-extrusion (temperature: 220 ° C) to obtain a laminated three-layer sheet. A sheet having a thickness of 1 mm; the sheet was cut for use as a test piece for evaluation of electrical continuity of test pieces for electric power evaluation, and a test piece for evaluation of chemical resistance; Table 6 shows various evaluation results.

From the results described in Table 56, the following matters were clarified.

The molded articles of the embodiments VI-1 to VI-15 of the present invention have excellent electric properties and system Electrical durability, chemical resistance, and impact resistance, especially in the molded articles of Examples VI-1 to VI-14, have excellent electrical properties.

On the other hand, Comparative Example V-1 is an example in which the amount of the component (C1) of the present invention is out of the range of the invention, so that the electrical conductivity and the surface appearance of the molded article are inferior.

[Industrial Applicability]

The thermoplastic resin composition of the invention has excellent impact resistance, chemical resistance, surface appearance of the molded article, antistatic property and electric property, and can be applied to vehicles, electrical, electronic, OA, which require high performance. Various components such as home appliances and health care.

1‧‧‧2 layer molded products

11‧‧‧ grassroots

12, 12a and 12b‧‧‧charged prevention layer

2‧‧‧3 layer molded products

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

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

1. . . 2-layer molded product

11. . . Grassroots

12. . . Charge prevention layer

Claims (8)

A thermoplastic resin composition containing 5 to 95% by mass of the following (A) component and 95 to 5% by mass of the component (B) (but the component (A) and the component (B) are 100% by mass in total), In addition, in the case where the (A) component and the (B) component are 100 parts by mass in total, the following (C1) component contains 0.5 to 100 parts by mass, and the thermoplastic resin composition having the above characteristics; (A) component: The styrene resin is a styrene resin obtained by polymerizing ethylene monomer (b) in the presence or absence of a rubbery polymer. However, the above ethylene monomer (b) is selected from the following: An aromatic vinyl compound derived from at least one of a group consisting of styrene, α-methylstyrene, and hydroxystyrene as an essential monomer component; here, if necessary, from a vinyl cyanide compound or a (partial) acrylate One or more selected from the group consisting of a compound and a maleimide compound, used as a monomer component; and further, if necessary, at least one of unsaturated compounds containing various other functional groups, as a monomer component And use;; (B) Ingredients: Ethylene resin contains 2 to 10 carbons (olef) Ate) at least one of an olefinic resin as a constituent monomer unit; (C1) component: a block copolymer containing an alkyl block polymer (c1-1) and a hydrophilic block polymer (c1- 2) block copolymer "However, the above-mentioned olefin block polymer (c1-1) is a block formed of the olefin (co)polymer constituting the above (B) component; the aforementioned hydrophilic block polymer ( C1-2) a polyether (c1-2-a), a polyether-containing hydrophilic polymer (c1-2-b), or an anion containing the above polyether (c1-2-a) as an essential constituent unit Polymer (c1-2-c). The thermoplastic resin composition according to the first aspect of the invention, wherein the composition of the (A) component and the (B) component in total of 100 parts by mass contains at least 0.001 to 60 parts by mass (C2- 1) one component selected from the component, (C2-2) component, (C2-3) component, and (C2-4) component group; (C2-1) Ingredients: Polyether Polyamide and/or Polyether Polyester, (C2-2) Ingredients: Nonionic Antistatic Agent, (C2-3) Ingredients: Boron Compound, (C2-4) Ingredients : Lithium salt. The thermoplastic resin composition according to the first aspect of the invention, wherein the component (A) and the component (B) have a total mass of 100 parts by mass, and at least one of the following components (D) a component selected from the group consisting of (E) component, (F) component, and (G) component group; (D) component: a block polymer (d-1) containing at least an aromatic vinyl compound, And a block copolymer (Da) of the block polymer (d-2) mainly composed of a conjugated diene compound and a component selected from the hydrogen additive (Db) component group, (E) component: a graft polymer of (co)polymerized aromatic vinyl compound or copolymerizable aromatic vinyl compound and other vinyl monomer of the aromatic vinyl compound in the presence of the above component (D), (F) component: D) an aromatic polycarbonate copolymer composed of a block polymer (f-1) composed of a component and an aromatic carbonate block polymer (f-2), (G) component: an unsaturated acid And/or low molecular weight polyene denatured with an unsaturated acid anhydride. The thermoplastic resin composition according to the second aspect of the invention, wherein the component (A) and the component (B) have a total mass of 100 parts by mass, and at least 1 to 200 parts by mass. (D) component, (E) component, (F) component, (G) component selected from one component; (D) component: at least aromatic vinyl compound-based block polymer (d-1), And a block copolymer (Da) of the block polymer (d-2) mainly composed of a conjugated diene compound and a component selected from the hydrogen additive (Db) component group, (E) component: In the presence of the above component (D), (co)polymerized aromatic vinyl compound, or copolymerizable aromatic vinyl compound and aromatic a graft polymer of another ethylene monomer of a vinyl compound, (F) component: a block polymer (f-1) composed of the above component (D), and an aromatic carbonate block polymer (f-2) The aromatic polycarbonate copolymer block composed of (G) component: a low molecular weight polyene which is denatured by an unsaturated acid and/or an unsaturated acid anhydride. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin composition is a molded article. The thermoplastic resin composition according to claim 5, wherein the molded article is a sheet or a film. The thermoplastic resin composition according to any one of claims 1 to 4, which is a multilayered article obtained by laminating a thin plate or a film as a base material and having at least one surface. The thermoplastic resin composition according to claim 7, wherein the base material is a thin plate or a film composed of an olefinic resin.