JP2019073645A - Thermoplastic resin molding and composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin molded product having excellent appearance such as mechanical strength and surface gloss, non-slippery, and excellent tactile sensation. A molded product comprising a rubber-reinforced vinyl-based resin (A) containing a rubber portion (a1) and a resin portion (a2), and a thermoplastic resin composition containing a thermoplastic elastomer (B). , The resin portion (a2) contains a structural unit derived from an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound, and a structural unit derived from the (meth) acrylic acid alkyl ester compound of the resin portion (a2). The content ratio of the resin portion (a2) is 50% by mass or more with respect to the total amount of the structural units constituting the resin portion (a2), and the MIU value of the molded product is 0.4 or more. [Selection diagram] None

Description

  TECHNICAL FIELD The present invention relates to a thermoplastic resin molded article excellent in molded article appearances such as mechanical strength and surface gloss, non-slip, and having a touch feeling excellent in grip feeling, and a thermoplastic resin composition useful as the molding material thereof .

  Rubber-reinforced aromatic vinyl resins represented by ABS resin are widely used for office automation equipment, home appliances, general goods, building materials, etc. because they are excellent in the physical property balance between impact resistance and moldability and molding appearance. ing.

  Among these, office equipment such as OA equipment and home appliances that are often used or operated by hand, and door trims and glove boxes that are frequently touched by the rider's body maintain their rigidity. However, it is required that the cushioning properties and feel such as feel are good.

  The above-mentioned partial product is manufactured by slush molding or the like by bonding a skin material having flexibility to a core material having rigidity (Patent Document 1). However, this slush molding is only used for the production of limited products due to the large number of steps and the expensive raw materials.

  Thermoplastic elastomers, on the other hand, are widely used in applications such as construction materials, general goods, machine parts, etc. as molding materials that give molded articles with excellent flexibility. Specific examples include vinyl chlorides, olefins, urethanes Various elastomers, such as a system, a styrene system, polyester type, and those alloys, are mentioned (patent document 2). However, although the molded products obtained therefrom have high cushioning properties and soft touch feeling, those having excellent mechanical strength and molded product appearance have not been obtained.

  In addition, by blending a thermoplastic elastomer with a rubber-reinforced aromatic vinyl resin in which the rubber portion is composed of a diene rubber and a silicone rubber or an ethylene-α-olefin rubber, the mechanical strength and the appearance of the molded product are excellent. It is known that a molded article excellent in surface touch feeling can be obtained because the cushioning property and soft touch feeling are high and there is little stickiness (see Patent Documents 3 to 5), but the surface gloss is excellent. And, a molded article having a non-slippery feel and an excellent grip feeling has not been obtained.

JP, 2013-159122, A Unexamined-Japanese-Patent No. 2004-238551 JP, 2016-199729, A JP, 2017-8227, A Unexamined-Japanese-Patent No. 2017-109312

  An object of the present invention is to provide a thermoplastic resin molded article which is excellent in appearance of molded articles such as mechanical strength and surface gloss, is not slippery, and has a touch feeling excellent in grip feeling.

  As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic elastomer (A) is a rubber-reinforced aromatic vinyl resin (A) containing a predetermined amount of a structural unit derived from a (meth) acrylic acid alkyl ester compound. The molded article obtained from the thermoplastic resin composition compounded with B) maintains the high surface gloss while maintaining the MIU value, which is an index of the non-slip of the molded article surface, at 0.4 or more. It has been found that it is suitable as a molded article that is required to have a non-slippery feel and an excellent grip feeling, and thus the above object can be achieved, and the present invention has been completed.

Thus, according to one aspect of the present invention, a thermoplastic resin composition comprising a rubber reinforced vinyl resin (A) comprising a rubber portion (a1) and a resin portion (a2), and a thermoplastic elastomer (B) A molded article consisting of
The resin portion (a2) contains a structural unit derived from an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound,
The content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound of the resin portion (a2) is 50% by mass or more with respect to the total amount of structural units constituting the resin portion (a2),
A molded article having an MIU value of 0.4 or more is provided.

Moreover, the molded article of this invention can be manufactured by shape | molding using the following thermoplastic resin composition as a molding material.
That is, according to another aspect of the present invention, a thermoplastic resin composition comprising a rubber reinforced vinyl resin (A) comprising a rubber portion (a1) and a resin portion (a2), and a thermoplastic elastomer (B) The object,
The resin portion (a2) contains a structural unit derived from an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound,
The content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound of the resin portion (a2) is 50% by mass or more with respect to the total amount of structural units constituting the resin portion (a2),
There is provided a thermoplastic resin composition in which the MIU value of a molded article when the thermoplastic resin composition is molded is 0.4 or more.
The thermoplastic resin composition of the present invention, the above component (A) and the above component (B) may be contained in a ratio sufficient to set the MIU value of the molded article to 0.4 or more, but usually the above Component (A) 5-80 mass% and said component (B) 20-95 mass%, Preferably, said component (A) 20-75 mass% and said component (B) 25-80 mass%, More preferably, 30-70 mass% of the said component (A) and 30-70 mass% of the said component (B) (however, the total amount of a component (A) and (B) shall be 100 mass%).

  According to the present invention, the rubber-reinforced aromatic vinyl in which the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound is 50% by mass or more based on the total amount of the structural units constituting the resin portion (a2) Because thermoplastic elastomers are compounded to the epoxy resin, it is superior in appearance such as surface gloss and is less slippery than molded articles obtained from each of rubber reinforced aromatic vinyl resins or thermoplastic elastomers, and has a grip feeling In particular, a molded article having an MIU value of 0.4 or more, which is an index of the slip resistance of the surface of the molded article, can be obtained.

Hereinafter, the present invention will be described in detail.
In the present invention, "(co) polymerization" means homopolymerization and / or copolymerization, "(meth) acrylic" means acrylic and / or methacrylic, and "(meth) acrylate" means , Acrylate and / or methacrylate.

The molded article of the present invention is obtained by molding using a thermoplastic resin composition containing a rubber-reinforced aromatic vinyl resin (A) and a thermoplastic elastomer (B) as a molding material.
1. Rubber-reinforced aromatic vinyl resin (Component (A))
The rubber-reinforced aromatic vinyl resin (A) used in the present invention comprises a rubber portion (a1) and a resin portion (a2) containing a structural unit derived from an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound Including. The rubber portion (a1) is not particularly limited as long as the object of the present invention can be achieved, as long as it is derived from at least one selected from the group consisting of a diene rubber and a non-diene rubber.

  In the rubber reinforced aromatic vinyl resin (A), the rubber portion (a1) and the resin portion (a2) may or may not be bonded to each other, but from the viewpoint of compatibility, the rubber portion ( It is preferable that a1) be combined with the resin portion (a2) to form a complex, and in particular, graft polymerization be performed to form a graft polymer. Therefore, the rubber-reinforced aromatic vinyl resin (A) is preferably at least composed of the above graft copolymer and a resin portion (a2) which is not graft polymerized to the rubber portion (a1), and further, the resin The portion (a2) may comprise the non-grafted rubber portion (a1) or other components such as additives. The rubber portion (a1) is only required to be rubbery at 25 ° C., ie, having rubber elasticity, and is distinguished from the resin portion (a2) which does not exhibit such properties at the same temperature.

  Examples of the diene rubber include homopolymers such as polybutadiene, polyisoprene and polychloroprene; styrene / butadiene copolymer, styrene / butadiene / styrene copolymer, acrylonitrile / butadiene copolymer, acrylonitrile / styrene / butadiene Styrene butadiene copolymer rubber such as copolymer; styrene isoprene copolymer, styrene isoprene styrene copolymer, styrene isoprene copolymer rubber such as acrylonitrile styrene isoprene copolymer; natural Rubber etc. are mentioned. These copolymers may be block copolymers or random copolymers. Moreover, these copolymers may be hydrogenated (however, the hydrogenation rate is less than 95%). The diene rubbers can be used singly or in combination of two or more.

  Examples of the non-diene rubber include ethylene / propylene copolymers, ethylene / propylene / non-conjugated diene copolymers, ethylene / 1-butene copolymers, ethylene / 1-butene / non-conjugated diene copolymers, Ethylene / α-olefin copolymer rubbers such as ethylene / 1-octene copolymer, ethylene / 1-octene / non-conjugated diene copolymer; acrylic rubber; silicone rubber; silicone / acrylic composite (IPN) The (co) polymer etc. which hydrogenate the (co) polymer containing the unit which consists of rubber | gum, a conjugated diene type compound, etc. are mentioned. These can be used singly or in combination of two or more. In addition, the hydrogenation rate of the (co) polymer formed by hydrogenation is 95% or more.

  In the present invention, the content of the rubber portion (a1) in the rubber-reinforced aromatic vinyl resin (A) is preferably 3 to 50 mass based on 100% by mass of the entire rubber-reinforced aromatic vinyl resin (A). %, More preferably 5 to 40% by mass, even more preferably 7 to 30% by mass. When the content of the rubber portion (a1) is in the above-mentioned range, impact resistance of the thermoplastic resin molded article of the present invention, touch such as grip feeling, appearance of molded articles such as surface gloss and the like are further excellent.

  Further, the content of the rubber portion (a1) in the thermoplastic resin composition of the present invention is preferably based on 100% by mass in total of the rubber-reinforced aromatic vinyl resin (A) and the thermoplastic elastomer (B). It is 3 to 35% by mass, more preferably 3.5 to 30% by mass, and still more preferably 4 to 25% by mass. When the content of the rubber portion (a1) is in the above-mentioned range, impact resistance of the thermoplastic resin molded article of the present invention, touch such as grip feeling, appearance of molded articles such as surface gloss and the like are further excellent.

  The resin portion (a2) of the rubber-reinforced aromatic vinyl resin (A) has, as an essential component, a structural unit derived from an aromatic vinyl compound which is a kind of vinyl monomer and a (meth) acrylic acid alkyl ester compound Optionally, structural units derived from other vinyl monomers copolymerizable with the above two vinyl monomers may be provided.

  Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinyl Examples thereof include naphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene and the like. These compounds can be used alone or in combination of two or more. Among these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  Specific examples of the (meth) acrylic acid alkyl ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylate 2-ethylhexyl, cyclohexyl (meth) acrylate and the like. These compounds can be used alone or in combination of two or more. Among these, methyl acrylate or methyl methacrylate is preferred, and methyl methacrylate is particularly preferred.

  In the resin portion (a2), the content ratio of the structural unit derived from the aromatic vinyl compound is preferably 2 to 50% by mass, more preferably 5 to 45% by mass, and still more preferably 15 to 35% by mass. The content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound is preferably 50 to 98% by mass, more preferably 55 to 95% by mass, and still more preferably 65 to 85% by mass. The sum of the content rates of the two types of structural units is 100% by mass). In the thermoplastic resin composition of the present invention, the compatibility between the rubber-reinforced vinyl resin (A) and the thermoplastic elastomer (B) is enhanced, and the appearance of molded articles such as mechanical strength and surface gloss is well maintained. Therefore, the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound of the resin portion (a2) is 50% by mass or more based on the total amount of the structural units constituting the resin portion (a2). Is preferably 55% by mass or more, more preferably 60% by mass or more, and still more preferably 65 to 85% by mass.

  Other vinyl monomers copolymerizable with the above two vinyl monomers include vinyl cyanide compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds A compound, an epoxy group containing unsaturated compound, an oxazoline group containing unsaturated compound etc. are mentioned. These can be used singly or in combination of two or more.

  Specific examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethyl acrylonitrile, α-isopropyl acrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These compounds can be used alone or in combination of two or more. Among these, acrylonitrile is preferred.

  Specific examples of the above maleimide compounds include maleimide, N-methyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-dodecyl maleimide, N-phenyl maleimide, N- (2-methylphenyl) maleimide, N- ( 4-Methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4 And -hydroxyphenyl) maleimide, N-naphthyl maleimide, N-cyclohexyl maleimide and the like. These compounds can be used alone or in combination of two or more. As a method of introducing a structural unit derived from a maleimide-based compound into the rubber-reinforced aromatic vinyl-based resin (A), for example, in addition to the method of polymerization using the maleimide-based compound as a raw material It is also possible to use an imidization method after polymerization using a saturated dicarboxylic acid anhydride as a raw material.

  Specific examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the above-mentioned hydroxyl group-containing unsaturated compound include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- (meth) acrylate Hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, ( (Meth) acrylic acid ester having a hydroxyl group such as a compound obtained by adding ε-caprolactone to 2-hydroxyethyl (meth) acrylate; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o- Hydroxy-α-methyl Styrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenyl Naphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy -2-butene, 3-hydroxy -2- methyl 1-propene etc. are mentioned. These compounds can be used alone or in combination of two or more.

Specific examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether and the like. These compounds can be used alone or in combination of two or more.
As a specific example of the said oxazoline group containing unsaturated compound, a vinyl oxazoline etc. are mentioned.

  In the present invention, in order to improve mechanical strength (toughness) and chemical resistance, it is preferable to use a vinyl cyanide compound as the other vinyl monomer. In the resin portion (a2), the content ratio of the structural unit derived from the vinyl cyanide compound is preferably 0 to 36% by mass, more preferably the total amount of structural units constituting the resin portion (a2). It is 1 to 25% by mass, still more preferably 2 to 20% by mass, and particularly preferably 3 to 15% by mass.

  As a method for producing the rubber-reinforced aromatic vinyl resin (A), for example, an aromatic vinyl compound and (meth) in the presence of a rubbery polymer selected from the group consisting of a diene rubber and a non-diene rubber The method of polymerizing (especially graft polymerization) and manufacturing the vinyl-type monomer comprised at least from an acrylic acid alkylester compound is mentioned. As a polymerization method in this production method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method combining these may be mentioned. In these polymerization methods, known polymerization initiators, chain transfer agents (molecular weight modifiers), emulsifiers and the like can be appropriately used. In the graft polymerization using these polymerization methods, the raw materials rubbery polymer and vinyl monomer as raw materials are divided into all or continuously, even if the entire amount is added to the reaction system at one time and polymerized. The polymerization may be carried out while adding to the

  When the rubber-reinforced aromatic vinyl resin (A) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.

  As a polymerization initiator, a redox system combining an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation Initiators; persulfates such as potassium persulfate; and peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxy laurate, tert-butyl peroxy monocarbonate, and the like. These may be used alone or in combination of two or more. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinyl-type monomer whole quantity. The said polymerization initiator can be added to the reaction system collectively or continuously.

  Chain transfer agents include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; terpinolenes, α -A dimer of methylstyrene and the like can be mentioned. These may be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl monomer. The chain transfer agent can be added collectively or continuously to the reaction system.

  As an emulsifier, anionic surfactant and nonionic surfactant are mentioned. As anionic surfactants, sulfuric acid esters of higher alcohols; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Can be mentioned. Further, examples of the nonionic surfactant include alkyl ester type compounds of polyethylene glycol, alkyl ether type compounds and the like. These may be used alone or in combination of two or more. The amount of the emulsifier used is usually 0.3 to 5.0% by mass with respect to the total amount of the vinyl monomer.

  The emulsion polymerization can be carried out under known conditions depending on the kind of vinyl monomer, polymerization initiator and the like. The latex obtained by this emulsion polymerization is usually solidified by coagulating with a coagulant to powder the resin component, that is, the rubber-reinforced aromatic vinyl resin (A), and then purified by washing with water and drying. Ru. Examples of the coagulant used at this time include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; and organic acids such as acetic acid and lactic acid.

  According to the method for producing the rubber-reinforced aromatic vinyl resin (A), generally, a graft copolymer obtained by graft polymerizing (co) polymers of vinyl monomers with particles of a rubbery polymer, and rubber A mixed product of vinyl monomers which are not graft-polymerized with the (co) polymer of non-graft polymer is obtained. In some cases, the mixed product may comprise particles of rubbery polymer to which the (co) polymer is not graft polymerized. The rubber-reinforced aromatic vinyl resin (A) of the present invention comprises a rubber portion (a1) derived from particles of the rubbery polymer and a resin portion (a2) having a structural unit derived from the vinyl-based monomer And the rubber portion (a1) preferably forms a graft copolymer in which the resin portion (a2) is graft-polymerized, and thus the graft copolymer produced as described above and the (co) polymer And the mixture product thereof can be used as it is as a rubber-reinforced aromatic vinyl resin (A).

  The rubber-reinforced aromatic vinyl resin (A) is composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from another vinyl compound copolymerizable with the aromatic vinyl compound, if desired (co ) The polymer (A ') may be added. The (co) polymer (A ') is a vinyl comprising an aromatic vinyl compound and optionally, another vinyl compound copolymerizable with the aromatic vinyl compound in the absence of the rubbery polymer (a). It can be produced by polymerizing a system monomer. This (co) polymer (A '), when added to the rubber-reinforced aromatic vinyl resin (A), constitutes a resin portion (a2) which is not graft polymerized on the rubber portion (a1). . As the aromatic vinyl compound and the other vinyl-based compound copolymerizable with the aromatic vinyl compound, those described above for the resin portion (a2) can be used.

  Preferred (co) polymers (A ') according to the present invention include structural units derived from aromatic vinyl compounds, structural units derived from (meth) acrylic acid alkyl ester compounds, and optionally vinyl cyanide compounds. And copolymers containing the structural units. In these (co) polymers (A ′), the content ratio of the structural unit derived from the aromatic vinyl compound is preferably 2 to 50% by mass, more preferably 5 to 45% by mass, still more preferably 15 to 5%. The content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound is preferably 50 to 98% by mass, more preferably 55 to 95% by mass, and still more preferably 65 to 85% by mass. The content ratio of the structural unit derived from the vinyl cyanide compound is preferably 0 to 36% by mass, more preferably 1 to 25% by mass, still more preferably 2 to 20% by mass, particularly preferably 3 to 15 It is mass% (In addition, the sum total of content of said 3 types of structural units is made into 100 mass%).

  In the present invention, when the (co) polymer (A ′) is blended in the rubber-reinforced aromatic vinyl resin (A), it is derived from the (meth) acrylic acid alkyl ester compound of the (co) polymer (A ′) The content ratio of the structural unit may be the same as or different from the content ratio of the resin portion (a2) produced when producing the above graft copolymer, and the (meth) acrylic acid alkyl ester of the entire resin portion (a2) If the content ratio of the structural unit derived from the compound is 50% by mass or more with respect to the total amount of structural units constituting the resin portion (a2), the content ratio of the former is 50% by mass or less and the content ratio of the latter May be 50% by mass or more, or vice versa, but it is preferable that the content ratio of the both is 50% by mass or more. When the former content ratio and the latter content ratio are different, the difference between them is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

  The graft ratio of the rubber-reinforced aromatic vinyl resin (A) is usually 10 to 200%, preferably 10 to 150%, more preferably 15 to 120%, and still more preferably 20 to 100%. When the graft ratio of the rubber-reinforced aromatic vinyl resin (A) is in the above-mentioned range, the mechanical strength, the moldability and the appearance of the molded article of the thermoplastic resin composition of the present invention are further improved.

The grafting rate can be determined by the following formula (1).
Graft ratio (mass%) = ((S−T) / T) × 100 (1)
In the above formula, 1 gram of a rubber-reinforced aromatic vinyl resin (A) is charged into 20 ml of acetone, and shaken at 25 ° C. for 2 hours with a shaker, then at 5 ° C. Mass (g) of acetone insolubles obtained by centrifuging for 60 minutes with a centrifuge (rotational speed: 23,000 rpm) and separating acetone insolubles and acetone solubles, T is rubber reinforcement It is mass (g) of the rubber part (a1) contained in 1 gram of aromatic vinyl-type resin (A). The mass of the rubber portion (a1) can be determined by the method of calculating from the polymerization formulation and the polymerization conversion rate, the method of obtaining from the infrared absorption spectrum, or the like. In the component (A) of the present invention, the acetone insolubles are not bonded to the graft polymer and the resin portion (a2) in which the rubber portion (a1) and the resin portion (a2) are bonded by graft polymerization. The acetone solubles correspond to the mixture of the free rubber portion (a1), and the acetone solubles correspond to the free resin portion (a2) not bound to the rubber portion (a1) in the component (A) of the present invention.

  From this viewpoint, the component (A) is 5 to 50% by mass of the graft polymer in which the resin portion (a2) is bonded to the rubber portion, and the resin portion (a2) 50 to 95 not bonded to the rubber portion (a1) It is preferable to contain the mass%, and it is more preferable to contain 8 to 40 mass% of the graft polymer and 60 to 92 mass% of the resin part (a2) not bound to the rubber part (a1), It is particularly preferable to include 10 to 35% by mass of combined and 65 to 90% by mass of resin part (a2) not bound to the rubber part (a1) (however, the total of these two is 100% by mass) . Here, the graft polymer corresponds to the acetone insoluble matter, and the resin portion (a2) not bonded to the rubber portion (a1) corresponds to the acetone soluble matter.

  The grafting ratio is, for example, the kind and amount of chain transfer agent used in graft polymerization when producing a rubber-reinforced aromatic vinyl resin (A), the kind and amount of polymerization initiator, monomer components at the time of polymerization The addition method, the addition time, the polymerization temperature and the like can be appropriately selected.

  The intrinsic viscosity (30 ° C. in methyl ethyl ketone) of the acetone-soluble component of the rubber-reinforced aromatic vinyl resin (A) in the thermoplastic resin composition of the present invention is usually 0.05 to 0.9 dl / g, preferably 0 And preferably from 0.1 to 0.7 dl / g. When the intrinsic viscosity is in the above range, the impact resistance and the moldability of the resin composition become better.

  The measurement of the intrinsic viscosity [η] can be performed by the following method. First, the acetone-soluble component of the rubber-reinforced aromatic vinyl resin (A) was dissolved in methyl ethyl ketone to make five different concentrations. The limiting viscosity [η] was determined from the result of measuring the reduced viscosity at each concentration at 30 ° C. using a Ubbelohde viscosity tube. The unit is dl / g.

  The intrinsic viscosity [η] is, for example, the kind and amount of use of a chain transfer agent, a polymerization initiator, an emulsifier, a solvent, etc. used when graft polymerizing a rubber reinforced aromatic vinyl resin (A), and a monomer at the time of polymerization It can adjust by selecting the addition method and addition time of a component, superposition | polymerization temperature, superposition | polymerization time etc. suitably. In addition, a rubber-reinforced aromatic vinyl resin (A) is mixed with a (co) polymer (A ′) having an intrinsic viscosity []] different from the intrinsic viscosity [η] of the acetone-soluble component. Can.

  The content of the component (A) in the thermoplastic resin composition of the present invention is preferably 5 to 80% by mass, assuming that the total amount of the components (A) and (B) is 100% by mass, 20 It is more preferable that it is -75 mass%, and it is still more preferable that it is 30-70 mass%. When the content of the component (A) is in the above range, the MIU value of the molded article is 0.4 or more, and the tactile sensation such as grip feeling is favorably improved.

2. Thermoplastic Elastomer The thermoplastic elastomer (B) used in the present invention is not particularly limited as long as it is a polymer that can give a molded article having rubber elasticity by heat melting and molding. The thermoplastic elastomer (B) can be molded by heating and melting, but the diene rubber and non-diene rubber used in the component (A) are different in that they can not be molded by heating and molding. The Mooney viscosity (ML _{1 +4} , 100 ° C.) of the thermoplastic elastomer (B) is preferably 30 to 75. Moreover, it is preferable that it is 1-30 g / 10min, and, as for MFR (200 degreeC, 49.0N) of a thermoplastic elastomer (B), 2-20 g / 10min is more preferable.

  Specific examples of the thermoplastic elastomer (B) include styrene elastomers, diene elastomers such as polybutadiene elastomers, olefin elastomers, urethane elastomers, polyvinyl chloride elastomers, ester elastomers, fluorocarbon resin elastomers, ionic crosslinks An elastomer (ionomer) etc. are mentioned. These thermoplastic elastomers can be used alone or in combination of two or more.

  Specific examples of styrenic elastomers include block copolymers containing one or more polymer block A of an aromatic vinyl compound and polymer block B of a conjugated diene compound, and a hydrogenated product thereof. The polymer block A and the polymer block B may be bonded in a linear form or in a radial form. The polymer block B may be a random copolymer containing a small amount of an aromatic vinyl compound as a structural unit, or the so-called tapered type in which the content of the structural unit derived from the aromatic vinyl compound gradually increases. It may be a block.

There is no particular limitation on the structure of the block copolymer, and any of (A-B) _n type, (A-B) _n -A type, or (A-B) _n -C type can be used. In the formula, A represents a polymer block of an aromatic vinyl compound, B represents a polymer block of a conjugated diene compound, C represents a coupling agent residue, and n represents an integer of 1 or more.

  As an aromatic vinyl compound used as a structural unit of polymer block A of a styrene-type elastomer, although all the aromatic vinyl compounds mentioned as a vinyl-type monomer of the said component (A) can be used, Preferably it is styrene Is used. These aromatic vinyl compounds can be used alone or in combination of two or more. Moreover, as a conjugated diene which becomes a structural unit of the polymer block B of a styrene-type elastomer, a 1, 3- butadiene, an isoprene, 2-methyl- 1, 3- butadiene, a 2, 3- diethyl butadiene, 2- neopentyl- 1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and branched conjugated hexadienes, etc. 3-Butadiene, isoprene and 2-methyl-1,3-butadiene are preferred.

  The weight average molecular weight of the styrenic elastomer is preferably 10,000 to 800,000, more preferably 20,000 to 500,000. The content of the aromatic vinyl compound in the polymer block A is preferably 5 to 60% by weight, and more preferably 15 to 50% by weight. The above block copolymers may be used alone or in combination of two or more having different structures or different contents of structural units derived from an aromatic vinyl compound.

  The hydrogenated substance of the styrene-based elastomer can be obtained by subjecting the polymer block B of the conjugated diene compound of the styrene-based elastomer obtained above to a hydrogenation reaction according to a known method. As a specific method, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, Japanese Patent Application No. 63-285774, Japanese Patent Application No. Sho. No. 63-127400.

  In the case of a conjugated diene-based polymer in which the polymer block B is a polymer block of 1,3-butadiene, ethylene is 1, 1 from a portion polymerized by a 1,4-vinyl bond when non-selectively hydrogenated. Butylene is produced from the portion polymerized with 2-vinyl bond, styrene-ethylene-butylene-styrene copolymer (SEBS) etc. is produced as a hydrogen additive, and the 1,2-vinyl bond is selectively hydrogenated Styrene-butadiene-butylene-styrene copolymer (SBBS) etc. are produced as a hydrogen additive. SEBS may use a commercially available product, and specific examples thereof include Dynaron Series (trade name, manufactured by JSR Corporation), Lavaron Series (trade name, manufactured by Mitsubishi Chemical Corporation), Tuftec Series (trade name, manufactured by Asahi Kasei Corporation), TPE-SB series (trade name, manufactured by Sumitomo Chemical Co., Ltd.) and the like can be mentioned.

  The polybutadiene-based elastomer used in the present invention has a 1,2-vinyl bond content of 70% or more, preferably 80% or more, a crystallinity of 5 to 50%, preferably 10 to 35%, and an intrinsic viscosity [η (Measured at 30 ° C. in toluene) is at least 0.5 dl / g, preferably at least 0.6 dl / g. Further, it may be used in combination with 1,2-polybutadiene having different amounts of 1,2-vinyl bond, crystallinity, and intrinsic viscosity [η].

  Other elastomers include, for example, high cis and low cis butadiene rubber (BR), high cis isoprene rubber (IR), emulsion polymerization and solution polymerization styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), ethylene propylene rubber (EPM, EPDM), chloroprene rubber, butyl rubber, natural rubber (NR) and the like.

  Preferred specific examples of the above-mentioned styrene elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-butylene-styrene copolymer (SBBS) And styrene-isoprene-styrene copolymer (SIS).

As said urethane type elastomer,
Generally, a block copolymer comprising a hard segment block consisting of a diisocyanate and a chain extender and a soft segment block consisting of a polyol and a diisocyanate as a repeating unit can be mentioned.

  As a polyol, polyester polyol, polyester ether polyol, polycarbonate polyol, polyether polyol etc. are mentioned.

  Examples of the above-mentioned polyester polyols include polyester polyols obtained by condensation reaction of dicarboxylic acids or their ester compounds or acid anhydrides with diols; polylactone diols obtained by ring-opening polymerization of lactone monomers such as ε-caprolactone etc. . And, as the above dicarboxylic acids, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; hexahydroterephthalic acid And alicyclic dicarboxylic acids such as hexahydrophthalic acid and hexahydroisophthalic acid are used, and as the above-mentioned diol, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol , 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,3-octanediol, 1,9-nonanediol Etc. are used.

  Moreover, as polycarbonate polyol, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Diethylene carbonate, diethyl carbonate, one or more kinds of polyhydric alcohols such as diol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol The polycarbonate polyol etc. which are obtained by making etc. react are mentioned. Also, it may be a copolymer of polycaprolactone polyol and polyhexamethylene carbonate.

  Furthermore, as polyester ether polyols, condensation products of the above-mentioned aliphatic dicarboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, or esters or acid anhydrides thereof and glycols such as diethylene glycol and propylene oxide adducts Etc.

  Furthermore, examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol (PTMG) obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran, and copolyethers of these. .

  Among the various polyols described above, polyether polyols are preferred from the viewpoint of hydrolysis resistance.

  As the isocyanate, tolylene dioxocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthyl diisocyanate (NDI), tolidine diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylene diisocyanate (XDI), hydrogenated XDI, triisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecanetriisocyanate, 1,8-diisocyanatomethyloctane, lysine ester triisocyanate, 1, 3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, etc. are mentioned. Among these, 4,4'-diphenylmethane diisocyanate (MDI) or dicyclohexylmethane diisocyanate (hydrogenated MDI; HMDI) is preferable.

  As chain extenders, low molecular weight polyols are used, for example ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol, glycerin And aliphatic glycols such as 1,4-dimethylol benzene, bisphenol A, ethylene oxide adducts of bisphenol A, and aromatic glycols such as propylene oxide adducts.

  The hardness (Shore A hardness) of the polyurethane elastomer used in the present invention is preferably 70 to 99. Such polyurethane elastomers are "T-1000 series" of "T-1000 series" as "T-1000 series" as an ester (adipate) manufactured by DIAC Bayer Polymer Co., "T-2000" as an ester (lactone) series. "T-2180", "T-2185"; available as ether series "T-8000 series" "T-8180", "T-8185", "TP-6000 series" "TP-6580A", etc. .

  The content of the component (B) in the thermoplastic resin composition of the present invention is preferably 20 to 95 mass%, assuming that the total amount of the components (A) and (B) is 100 mass%, It is more preferable that it is -80 mass%, and it is still more preferable that it is 30-70 mass%. When the content of the component (B) is in the above range, the MIU value of the molded article is 0.4 or more, and the tactile sensation such as the grip feeling is favorably improved.

3. Other ingredients

  In the thermoplastic resin composition according to the present invention, in addition to the above-mentioned component (A) and component (B), as needed, a slidability imparting agent, an antioxidant, a processing stabilizer, an ultraviolet absorber, Various additives such as light stabilizers, antistatic agents, crystallization nucleating agents, lubricants, plasticizers, metal deactivators, color pigments, various inorganic fillers, glass fibers, reinforcing agents, flame retardants, mold release agents, foaming agents, etc. An agent can be blended in the range which does not impair the object of the present invention.

4. Method of Producing Thermoplastic Resin Composition of the Present Invention The thermoplastic resin composition of the present invention is a single screw extruder, a twin screw extruder, etc., after mixing each component with a tumbler mixer or Henschel mixer at a predetermined compounding ratio, It can be produced by melt-kneading under appropriate conditions using a kneader such as a Banbury mixer, a kneader, a roll, or a feeder ruder. The preferred kneader is a twin screw extruder. Furthermore, when kneading each component, those components may be kneaded at once, or may be compounded in multiple stages and divided. In addition, after knead | mixing with a Banbury mixer, a kneader etc., it can also be pelletized with an extruder. The melt-kneading temperature is usually 180 to 240 ° C, preferably 190 to 230 ° C.

5. Method for Producing a Molded Article of the Present Invention The thermoplastic resin composition of the present invention is made into a resin molded article by a known molding method such as injection molding, press molding, sheet extrusion molding, vacuum molding, profile extrusion molding, foam molding and the like. be able to. The surface of a resin molded product formed from the thermoplastic resin composition of the present invention is excellent in touch feeling such as grip feeling, and is suitable as a molding material of various articles such as articles which need to be operated by hand. The grip feeling of the surface of the resin molded article of the present invention is a numerical value by the MIU value (average coefficient of friction) measured on the surface of the molded article using a friction tester KES-SE (trade name: manufactured by Kato Tech Co., Ltd.) Can be The molded article of the present invention is less slippery than conventional molded articles and is excellent in feel such as grip feeling, but the MIU value measured as described above is 0.4 or more, preferably 0.5 or more, 0 .6-1.0 is more preferred. Moreover, it is preferable that it is 300-1500 MPa, and, as for the elasticity modulus measured based on ISO 178 of the molded article of this invention, it is still more preferable that it is 400-1200 MPa. The Rockwell hardness at room temperature (hardness scale: R-scale) measured according to ISO 2039 of the molded article of the present invention is preferably 20 to 60, and more preferably 25 to 50. .

  Since the molded article of the thermoplastic resin composition of the present invention has the above-mentioned touch, parts for human contact, for example, handle of shaver, door trim, glove box, automobile interior parts such as handle, door knob, handrail It can be used as a housing, a case, a cover, etc. of mobile electric products such as building materials such as mobile phones, mobile music players, smartphones, tablet computers, and laptop computers.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples. In the examples, parts and percentages are by mass unless otherwise specified.

1. Component [A]
A diene rubber reinforced aromatic vinyl resin (raw material MABS and raw material ABS) obtained in the following synthesis examples 1 and 2 as a raw material of a rubber reinforced aromatic vinyl resin and a styrene obtained in the following synthesis example 3 -Acrylonitrile-methyl methacrylate copolymer (raw material MAS) and the styrene-acrylonitrile copolymer (raw material AS) obtained in the following synthesis example 4 were used.

1-1. Synthesis example 1 (synthesis of raw material MABS (diene rubber reinforced aromatic vinyl resin))
In a 10-liter glass flask equipped with a stirrer, 45 parts of polybutadiene having a volume average particle diameter of 300 nm (in terms of solid content), 0.3 parts of sodium dodecylbenzene sulfonate, and 100 parts of ion-exchanged water are charged. 3 parts of styrene, 1 part of acrylonitrile and 11 parts of methyl methacrylate were charged. The mixture is heated to 43 ° C. with stirring, then 0.02 part of ethylenediamine tetraacetate sodium, 0.001 part of ferrous sulfate 7-hydrate, 0.08 part of formaldehyde sodium sulfoxylate dihydrate An aqueous solution consisting of 6 parts of ion-exchanged water and 0.04 parts of cumene hydroperoxide were added, and the reaction was continued for 1 hour.

  Thereafter, a monomer mixture comprising 9 parts of styrene, 2 parts of acrylonitrile, 29 parts of methyl methacrylate, 1.2 parts of t-dodecyl mercaptan, 0.1 parts of cumene hydroperoxide, and 0.01 part of sodium ethylenediamine tetraacetate, An aqueous solution consisting of 0.001 part of ferrous sulfate heptahydrate, 0.05 parts of formaldehyde sodium sulfoxylate dihydrate, 0.3 parts of sodium dodecylbenzene sulfonate, and 30 parts of ion exchanged water Add continuously over time and continue the polymerization reaction. After the addition, 0.003 parts of sodium ethylenediamine tetraacetate, 0.0002 parts of ferrous sulfate, 0.01 parts of formaldehyde sodium sulfoxylate dihydrate, 0.02 parts of cumene hydroperoxide, and ion exchange After 1 part of water was added and stirring was continued for further 1 hour, the reaction was terminated by cooling.

  Thereafter, 0.67 parts of a reaction product of p-cresol, dicyclopentadiene and isobutylene ("SANDWIN-45" manufactured by Toho Chemical Co., Ltd.) and 0.5 parts of sodium ethylenediamine tetraacetate are added to the reaction product and coagulated with magnesium sulfate did. The reaction product was thoroughly washed with water, dehydrated and then dried at 80 ° C. for 24 hours to obtain a white powder copolymer (raw material MABS). The polymerization conversion rate was 97.0%, the grafting rate was 52%, and the intrinsic viscosity [.eta.] Of acetone solubles was 0.24 dl / g (measured at 30.degree. C. in methyl ethyl ketone).

1-2. Synthesis Example 2 (synthesis of raw material ABS (diene rubber reinforced aromatic vinyl resin))
In a glass flask equipped with a stirrer, in a nitrogen stream, 42 parts of ion exchanged water, 0.35 parts of potassium rosinate, 0.2 parts of tert-dodecyl mercaptan, polybutadiene rubber with an average particle size of 300 nm (gel content 80% 100 parts of latex containing 45 parts, 11 parts of styrene and 4 parts of acrylonitrile were stored, and the temperature was raised while stirring. When the internal temperature reached 40 ° C, a solution of 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.3 parts of glucose in 8 parts of ion-exchanged water was added . Thereafter, 0.07 parts of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 30 minutes, 45 parts of ion exchanged water, 0.7 parts of potassium rosin acid, 29 parts of styrene, 11 parts of acrylonitrile, 0.17 parts of tert-dodecyl mercaptan and 0.1 parts of cumene hydroperoxide for 3 hours Was added continuously. Thereafter, the polymerization was continued for an additional hour, and 0.2 parts of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) was added to the reaction system to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product to coagulate the resin component and washed with water. Thereafter, the resultant was washed and neutralized using a potassium hydroxide aqueous solution, further washed with water and then dried to obtain a diene rubber reinforced aromatic vinyl resin (raw material ABS). The polymerization conversion rate is 98%, and the grafting rate in the graft resin contained in this resin is 50%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone soluble matter is 0.35 dl / g The

1-3. Synthesis Example 3 (Synthesis of Raw Material MAS (Styrene-Acrylonitrile-Methyl Methacrylate Copolymer))
A monomer mixture was prepared by mixing 21 parts of styrene, 7 parts of acrylonitrile, 72 parts of methyl methacrylate, 0.3 parts of t-dodecyl mercaptan, and 0.2 parts of diisopropylbenzene hydroperoxide.

  150 parts of water and 2 parts of sodium dodecylbenzene sulfonate as an emulsifier are charged into a 10 L glass reactor equipped with a stirrer, raw materials and auxiliary agent addition device, thermometer, heating device, etc., and a nitrogen stream while stirring. Below, internal temperature was heated up to 55 degreeC. When reaching 55 ° C., 0.09 parts of ethylenediaminetetraacetic acid tetrasodium dihydrate, 0.003 parts of ferrous sulfate heptahydrate and sodium formaldehyde in the above monomer mixture and 24 parts of water An aqueous solution in which 0.2 parts of sulfoxylate was dissolved was continuously added over 5 hours.

  The internal temperature was raised to 67 ° C. one hour after the addition start of the monomer mixture, and then maintained at 67 ° C. After completion of the continuous addition, 0.05 part of diisopropylbenzene hydroperoxide was added, and the internal temperature was maintained for 1 hour to complete the polymerization reaction. The copolymer latex was coagulated using calcium chloride, washed with water and dried to obtain a powdery copolymer (raw material MAS). The polymerization conversion rate was 98%, and the intrinsic viscosity [η] was 0.33 dl / g (measured at 30 ° C. in methyl ethyl ketone).

1-4. Synthesis Example 4 (Synthesis of Raw Material AS (Styrene-Acrylonitrile Copolymer))
A jacketed polymerization reactor equipped with a ribbon wing was used with a two-connected synthesis apparatus. After purging nitrogen gas in each reactor, a mixture of 73 parts of styrene, 27 parts of acrylonitrile and 20 parts of toluene in the first reactor, and 0.15 parts of tert-dodecyl mercaptan as a molecular weight modifier And a solution of 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) as a polymerization initiator dissolved in 5 parts of toluene are continuously supplied, The polymerization was carried out at ° C. The average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion after 2 hours was 56%.
Then, the obtained polymer solution was continuously taken out by a pump provided outside the first reactor, and was supplied to the second reactor. The amount taken out continuously is the same as the amount fed to the first reactor. In the second reactor, polymerization was carried out at 130 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
Thereafter, the polymer solution was recovered from the second reactor, and was introduced into the twin screw / three-stage vented extruder. Then, unreacted monomers and toluene (solvent for polymerization) were directly devolatized to recover a styrene-acrylonitrile copolymer (raw material AS). The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this styrene / acrylonitrile copolymer was 0.34 dl / g.

2. Component [B]
The following products were used as a raw material of a thermoplastic elastomer.

2-1. Raw material B-1 (SEBS)
A hydrogenated polymer “DR8903P” (trade name) manufactured by JSR Corporation was used. The styrene / butadiene ratio was 35/65. MFR (230 ° C., 21.2 N) was 10 g / 10 min. MFR (200 ° C., 49.0 N) was 4 g / 10 min.

3. Component [C]
3-1. Raw material C
Adekastab A-60 (trade name) (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane manufactured by ADEKA Corporation). Blended 0.2 parts at the time of kneading.

Examples 1 to 5 and Comparative Examples 1 to 3
1. Preparation of Thermoplastic Resin Composition The components [A] and [B] shown in the following table were mixed at the mixing ratio shown in the same table. Thereafter, the component [C] was blended as described above, and melt-kneaded at a barrel temperature of 220 ° C. using a twin-screw extruder (type name “TEX44, Japan Steel Works”) to pelletize. The obtained resin composition was used for the following measurement and evaluation. The results are shown in the following table.

2. Production of Molded Article The resin composition was molded to produce a test piece of 120 mm × 80 mm × 2 mm. Molding was performed using an injection molding machine IS100GN (trade name: manufactured by Toshiba Machine) under the conditions of a resin temperature of 220 ° C., a mold temperature of 50 ° C., an injection speed of 40 mm / s and an injection pressure of 100 MPa. As a molding die, a leather embossing die (Shibo No; TH-894) having irregularities (the depth of the recess is 100 μm) on the inner surface was used.

3. Hardness Measurement Based on ISO 2039, the Rockwell hardness at room temperature (hardness scale R-scale) was measured. The test piece was produced using an injection molding machine “J110 AD-180H” (type name) manufactured by Japan Steel Works, Ltd., which set the set temperature of the cylinder to 220 ° C. and the mold temperature to 50 ° C.

4. Measurement of flexural modulus Based on ISO 178, flexural modulus was measured using a Shimadzu precision universal testing machine “Autograph AG5000E”. The unit of measurement value was MPa. The test pieces were produced in the same manner as the above 3 (measurement of hardness).

5. Evaluation of Molded Product Appearance Both the textured surface and the mirror surface of the molded product prepared in 2 above were visually observed and evaluated according to the following criteria.
○: Neither (i) flow mark, (ii) peeling, (iii) whitening occurs.
Δ: Any of (i) flow mark, (ii) peeling, and (iii) whitening occurred in part of the molded article.
X: Any of (i) flow mark, (ii) peeling, and (iii) whitening occurred on the entire surface of the molded article.

6. Feeling (grip feeling)
The tactile sensation when the textured surface of the molded article prepared in 2 above was traced with a finger at a normal temperature of 23 ° C. was evaluated based on the following criteria.
○: not slippery.
Δ: Slightly slippery.
X: slippery.

7. Measurement of MIU value (KES texture measurement)
The MIU value of the textured surface of the molded article prepared in 2 above was measured using a friction tester KES-SE (trade name: manufactured by Kato Tech Co., Ltd.). The MIU value (mean friction coefficient) is an indicator of slipperiness, and a higher numerical value means less slippage.

8. Surface Gloss The gloss when the mirror surface of the molded article prepared in 2 above was visually observed was evaluated based on the following criteria.
○: Glossy, indoor light is reflected ×: Non-glossy, indoor light is not reflected

9. The molded product prepared in 2 above was bent 20 degrees to the opposite side (gloss side) of the textured surface, and the bent side (gloss side) was visually observed and evaluated according to the following criteria.
○: no wrinkles occur ×: wrinkles occur

The following can be seen from the above table.
Examples 1 to 5 using the thermoplastic resin composition of the present invention are not only excellent in hardness, flexural modulus and appearance of molded product, but also feel (grip feeling) and slipperiness (MIU value), surface gloss, It had better sex than flexion wrinkles. On the other hand, Comparative Examples 1 and 2 in which the content of the (meth) acrylic acid alkyl ester compound is less than the range of the present invention are inferior in surface gloss and bending wrinkles and do not contain the component (B) of the present invention The comparative example 3 was inferior in touch (grip feeling) and slipperiness (MIU value).

  The molded article of the present invention is excellent in mechanical strength and appearance of the molded article, is not slippery on the surface, and has a good feel such as grip feeling, so that it can not be operated by hand or slipped off easily from the hand It can be suitably used as a necessary item.

Claims (6)

A molded article comprising a thermoplastic resin composition comprising a rubber reinforced vinyl resin (A) comprising a rubber portion (a1) and a resin portion (a2), and a thermoplastic elastomer (B),
The resin portion (a2) contains a structural unit derived from an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound,
The content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound of the resin portion (a2) is 50% by mass or more with respect to the total amount of structural units constituting the resin portion (a2),
A molded article having an MIU value of 0.4 or more.   The component (B) is a styrenic elastomer composed of a block copolymer containing one or more of a polymer block of an aromatic vinyl compound and a polymer block of a conjugated diene compound, and / or a hydrogenated product thereof The molded article according to claim 1, wherein the component (B) is contained in an amount of 7 to 70% by mass with respect to a total of 100% by mass of the components (A) and (B).   The content ratio of the rubber portion (a1) of the rubber-reinforced vinyl-based resin (A) is 3 to 35% by mass with respect to 100% by mass in total of the rubber-reinforced aromatic vinyl-based resin (A) and the thermoplastic elastomer (B) The molded article according to any one of claims 1 to 4, which is   The molded article according to any one of claims 1 to 4, which is a part for human body contact. A thermoplastic resin composition comprising a rubber-reinforced vinyl resin (A) comprising a rubber portion (a1) and a resin portion (a2), and a thermoplastic elastomer (B),
The resin portion (a2) contains a structural unit derived from an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound,
The content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound of the resin portion (a2) is 50% by mass or more with respect to the total amount of structural units constituting the resin portion (a2),
The thermoplastic resin composition whose MIU value of the molded article at the time of shape | molding this thermoplastic resin composition is 0.4 or more.   The composition according to claim 5, containing 5 to 80% by mass of the component (A) and 20 to 95% by mass of the component (B) (provided that the total amount of the components (A) and (B) is 100% by mass). Thermoplastic resin composition.