JP7046557B2 - Thermoplastic molded products and compositions - Google Patents

Description

The present invention relates to a thermoplastic resin molded product having an excellent appearance such as mechanical strength and surface gloss, a non-slip property, and a tactile sensation having an excellent grip feeling, and a thermoplastic resin composition useful as a molding material thereof. ..

Rubber-reinforced aromatic vinyl-based resins typified by ABS resin are widely used in OA equipment, home appliances, miscellaneous goods, building materials, etc. because they have an excellent balance of physical properties between impact resistance and molding processability and the appearance of molded products. ing.

Of these, OA equipment, home appliances, etc., which are often used or operated by hand, and automobile interior parts such as door trims and glove boxes, which are often touched by the occupant's body, maintain their rigidity. On the other hand, it is required to have good tactile sensation such as cushioning property and tactile sensation.

Some of the above products are manufactured by slash molding or the like by joining a flexible skin material to a rigid core material (Patent Document 1). However, this slash molding has a large number of steps and the raw material is expensive, so that it has been used only for manufacturing a limited number of products.

On the other hand, thermoplastic elastomers are widely used in applications such as building materials, miscellaneous goods, and machine parts as molding materials that provide molded products with excellent flexibility. Specific examples thereof include vinyl chloride, olefins, and urethanes. Examples thereof include various elastomers such as type, styrene type, polyester type and their alloys (Patent Document 2). However, although the molded products obtained from these have high cushioning properties and a soft touch feeling, those having excellent mechanical strength and the appearance of the molded products have not been obtained.

In addition, by blending a thermoplastic elastomer with a rubber-reinforced aromatic vinyl resin whose rubber part is a diene rubber and a silicone rubber or an ethylene / α-olefin rubber, the mechanical strength and the appearance of the molded product are only excellent. It is known that a molded product having an excellent surface tactile sensation can be obtained because the cushioning property and the soft touch feeling are high and the sticky feeling is small (see Patent Documents 3 to 5), but the surface gloss is excellent. Moreover, a molded product that is not slippery and has an excellent grip feeling has not been obtained.

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

An object of the present invention is to provide a thermoplastic resin molded product having an excellent appearance such as mechanical strength and surface gloss, a non-slip property, and a tactile sensation having an excellent grip feeling.

As a result of diligent research to solve the above problems, the present inventors have made a thermoplastic elastomer (thermoplastic elastomer (A) into a rubber-reinforced aromatic vinyl resin (A) containing a predetermined amount of structural units derived from a (meth) acrylic acid alkyl ester compound. A molded product obtained from a thermoplastic resin composition containing B) maintains a MIU value of 0.4 or more, which is an index of slip resistance on the surface of the molded product, while maintaining a high surface gloss. Is suitable as a molded product that is not slippery and requires an excellent tactile sensation, and therefore, it has been found that 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 containing a rubber-reinforced vinyl-based resin (A) containing a rubber portion (a1) and a resin portion (a2), and a thermoplastic elastomer (B). It is a molded product made 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 the structural units constituting the resin portion (a2).
A molded product having a MIU value of 0.4 or more is provided.

Further, the molded product of the present invention can be manufactured by molding using the following thermoplastic resin composition as a molding material.
That is, according to another aspect of the present invention, the thermoplastic resin composition including the rubber reinforced vinyl resin (A) including the rubber portion (a1) and the resin portion (a2) and the thermoplastic elastomer (B). It ’s a thing,
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 the structural units constituting the resin portion (a2).
Provided is a thermoplastic resin composition having a MIU value of 0.4 or more in a molded product when the thermoplastic resin composition is molded.
The thermoplastic resin composition of the present invention, the above-mentioned component (A) and the above-mentioned component (B) may be contained in a ratio sufficient to make the MIU value of the molded product 0.4 or more, but usually, the above-mentioned 5 to 80% by mass of the component (A) and 20 to 95% by mass of the above component (B), preferably 20 to 75% by mass of the above component (A) and 25 to 80% by mass of the above component (B), more preferably. It contains 30 to 70% by mass of the component (A) and 30 to 70% by mass of the component (B) (however, the total amount of the components (A) and (B) is 100% by mass).

According to the present invention, the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound is 50% by mass or more with respect to the total amount of the structural unit constituting the resin portion (a2). Since the thermoplastic elastomer is blended with the resin, the appearance such as surface gloss is superior to that of the molded product obtained from each of the rubber-reinforced aromatic vinyl resin or the thermoplastic elastomer, and the surface gloss is less slippery and the grip feeling is felt. A molded product having an excellent tactile sensation, specifically, a molded product having a MIU value of 0.4 or more, which is an index of slip resistance on the surface of the molded product, 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. , Acrylic and / or methacrylate.

The molded product 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. 1. Rubber-reinforced aromatic vinyl resin (component (A))
The rubber-reinforced aromatic vinyl resin (A) used in the present invention includes 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. include. The rubber portion (a1) is not particularly limited as long as it can achieve the object of the present invention, and may be derived from at least one selected from the group consisting of diene-based rubber and non-diene-based 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) is bonded to the resin portion (a2) to form a composite, and particularly preferably graft-polymerized to form a graft polymer. Therefore, the rubber-reinforced aromatic vinyl-based resin (A) is preferably composed of at least the above-mentioned graft copolymer and the resin portion (a2) that is not graft-polymerized on the rubber portion (a1), and further, the resin. The rubber portion (a1) to which the portion (a2) is not grafted may be contained, or other components such as additives may be contained. The rubber portion (a1) may be rubbery at 25 ° C., that is, has rubber elasticity, and is distinguished from the resin portion (a2) that 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, and acrylonitrile / styrene / butadiene. Styre-butadiene copolymer rubber such as copolymer; styrene / isoprene copolymer rubber such as styrene / isoprene copolymer, styrene / isoprene / styrene copolymer, acrylonitrile / styrene / isoprene copolymer; styrene / isoprene copolymer rubber; natural Examples include rubber. These copolymers may be block copolymers or random copolymers. Further, these copolymers may be hydrogenated (however, the hydrogenation rate is less than 95%). The diene rubber can be used alone or in combination of two or more.

Examples of the non-diene rubber include ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / 1-butene copolymer, ethylene / 1-butene / non-conjugated diene copolymer, and the like. Ethylene / α-olefin copolymer rubber such as ethylene / 1-octene copolymer, ethylene / 1-octene / non-conjugated diene copolymer; acrylic rubber; silicone rubber; silicone / acrylic composite (IPN) Examples thereof include a (co) polymer obtained by hydrogenating a (co) polymer containing a unit composed of rubber and a conjugated diene compound. These can be used alone or in combination of two or more. The hydrogenation rate of the hydrogenated (co) polymer is 95% or more.

In the present invention, the content of the rubber portion (a1) in the rubber-reinforced aromatic vinyl-based resin (A) is preferably 3 to 50% by mass with respect to 100% by mass of the entire rubber-reinforced aromatic vinyl-based resin (A). %, More preferably 5 to 40% by mass, and even more preferably 7 to 30% by mass. When the content of the rubber portion (a1) is within the above range, the impact resistance of the thermoplastic resin molded product of the present invention, the tactile sensation such as grip, and the appearance of the molded product such as surface gloss are more excellent and preferable.

The content of the rubber portion (a1) in the thermoplastic resin composition of the present invention is preferably 100% by mass based on the 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 even more preferably 4 to 25% by mass. When the content of the rubber portion (a1) is within the above range, the impact resistance of the thermoplastic resin molded product of the present invention, the tactile sensation such as grip, and the appearance of the molded product such as surface gloss are more excellent and preferable.

The resin portion (a2) of the rubber-reinforced aromatic vinyl-based resin (A) includes a structural unit derived from an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound, which are a kind of vinyl-based monomer, as essential components. If desired, a structural unit derived from another vinyl-based monomer copolymerizable with the above two vinyl-based 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, and 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. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

Specific examples of the above (meth) acrylic acid alkyl ester compound include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (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 Examples thereof include 2-ethylhexyl and cyclohexyl (meth) acrylate. These compounds can be used alone or in combination of two or more. Of these, methyl acrylate or methyl methacrylate is preferable, and methyl methacrylate is particularly preferable.

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 even 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 even more preferably 65 to 85% by mass (note that the above). The total content ratio of the two types of structural units is 100% by mass). Further, 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 the molded product such as mechanical strength and surface gloss is maintained satisfactorily. Therefore, the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound of the resin portion (a2) shall be 50% by mass or more with respect to the total amount of the structural units constituting the resin portion (a2). Is required, and is preferably 55% by mass or more, more preferably 60% by mass or more, and even more preferably 65 to 85% by mass.

Other vinyl-based compounds that can be copolymerized with the above two vinyl-based monomers include vinyl cyanide compounds, maleimide-based compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, and hydroxyl group-containing unsaturated compounds. Examples thereof include compounds, epoxy group-containing unsaturated compounds, and oxazoline group-containing unsaturated compounds. These can be used alone or in combination of two or more.

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

Specific examples of the above-mentioned maleimide-based compounds include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, and N- ( 4-Methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4) -Hydroxyphenyl) Maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like can be mentioned. These compounds can be used alone or in combination of two or more. As a method for introducing a structural unit derived from a maleimide compound into the rubber-reinforced aromatic vinyl resin (A), in addition to the method for polymerizing the maleimide compound as a raw material, for example, maleic anhydride is not used. It is also possible to use a method of imidizing after performing polymerization using 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, etacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. These compounds can be used alone or in combination of two or more.

Specific examples of the hydroxyl group-containing unsaturated compound include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (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, ( (Meta) Acrylic acid ester having a hydroxyl group such as a compound obtained by adding ε-caprolactone to 2-hydroxyethyl acrylate; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o- Hydroxy-α-methylstyrene, 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-Isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, Examples thereof include trans-4-hydroxy-2-butene and 3-hydroxy-2-methyl-1-propene. 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, and methacrylic glycidyl ether. These compounds can be used alone or in combination of two or more.
Specific examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like.

In the present invention, it is preferable to use a vinyl cyanide compound as the other vinyl-based monomer in order to improve mechanical strength (toughness) and chemical resistance. 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 0 to 36% by mass, based on the total amount of the structural units constituting the resin portion (a2). It is 1 to 25% by mass, 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. Examples thereof include a method of polymerizing (particularly, graft polymerization) a vinyl-based monomer composed of at least an acrylic acid alkyl ester compound. Examples of the polymerization method in this production method include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method in which these are combined. 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, even if the rubbery polymer and the vinyl-based monomer, which are the raw materials, are all added to the reaction system at once and polymerized, the reaction system is divided or continuously. You may carry out polymerization while adding to.

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

As the polymerization initiator, a redox system in which an organic peroxide such as cumenehydroperoxide, diisopropylbenzenehydroperoxide, and paramentanhydroperoxide and a reducing agent such as a sugar-containing pyrophosphate formulation and a sulfoxylate formulation are combined. Initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxymonocarbonate and the like can be mentioned. These may be used alone or in combination of two or more. The amount of the polymerization initiator used is usually 0.1 to 1.5% by mass with respect to the total amount of the vinyl-based monomer. The above-mentioned polymerization initiator can be added to the reaction system collectively or continuously.

Chain transfer agents include octyl mercaptans, n-dodecyl mercaptans, tert-dodecyl mercaptans, n-hexyl mercaptans, n-hexadecyl mercaptans, n-tetradecyl mercaptans, tert-tetradecyl mercaptans and other mercaptans; -Methylstyrene dimer 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-based monomer. The chain transfer agent can be added to the reaction system collectively or continuously.

Examples of the emulsifier include anionic surfactants and nonionic surfactants. Examples of the anionic surfactant include sulfate esters of higher alcohols; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulphate; higher aliphatic carboxylates, aliphatic phosphates and the like. Can be mentioned. Examples of the nonionic surfactant include an alkyl ester type compound of polyethylene glycol, an alkyl ether type compound 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-based monomer.

Emulsion polymerization can be carried out under known conditions depending on the type of vinyl-based monomer, polymerization initiator and the like. The latex obtained by this emulsion polymerization is usually coagulated with a coagulant, and the resin component, that is, the rubber-reinforced aromatic vinyl-based resin (A) is powdered, and then purified by washing with water and drying. Ru. Examples of the coagulant used in this case 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), a graft copolymer in which a (co) polymer of vinyl-based monomers is graft-polymerized on particles of a rubbery polymer and a rubber are usually used. A mixed product of vinyl-based monomers that have not been graft-polymerized on the quality polymer with a (co) polymer can be obtained. In some cases, the mixed product may contain particles of a rubbery polymer in which the (co) polymer has not been graft-polymerized. The rubber-reinforced aromatic vinyl-based resin (A) of the present invention includes a rubber portion (a1) derived from the particles of the rubbery polymer and a resin portion (a2) having a structural unit derived from the vinyl-based monomer. Since it is preferable that the rubber portion (a1) is composed of a graft copolymer in which the resin portion (a2) is graft-polymerized, the graft copolymer and the (co) polymer produced as described above are preferably formed. The mixed product with the rubber-reinforced aromatic vinyl resin (A) can be used as it is.

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

The preferred (co) polymer (A') in the present invention is derived from a structural unit derived from an aromatic vinyl compound, a structural unit derived from a (meth) acrylic acid alkyl ester compound, and optionally a vinyl cyanide compound. Examples thereof include copolymers containing 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, and even more preferably 15 to. It is 35% by mass, and 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 even 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, and particularly preferably 3 to 15%. It is mass% (note that the total content of the above three types of structural units is 100 mass%).

In the present invention, when the (co) polymer (A') is blended with 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 same content ratio of the resin portion (a2) produced in the production of the 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 the structural unit 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 both of the above is 50% by mass or more. When the content ratio of the former and the content ratio of the latter are different, the difference between the two is preferably 10% by mass or less, more preferably 5% by mass or less, and further 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 even more preferably 20 to 100%. When the graft ratio of the rubber-reinforced aromatic vinyl resin (A) is within the above range, the mechanical strength, moldability, and appearance of the molded product of the thermoplastic resin composition of the present invention are further improved.

The graft ratio can be obtained by the following mathematical formula (1).
Graft ratio (% by mass) = ((ST) / T) x 100 ... (1)
In the above formula, S is prepared by adding 1 g of a rubber-reinforced aromatic vinyl resin (A) to 20 ml of acetone, shaking it with a shaker for 2 hours under a temperature condition of 25 ° C, and then shaking it with a shaker for 2 hours, and then under a temperature condition of 5 ° C. It is the mass (g) of the acetone-insoluble matter obtained by centrifuging with a centrifuge (rotation speed; 23,000 rpm) for 60 minutes and separating the acetone-insoluble matter and the acetone-soluble matter, and T is rubber-reinforced. It is the mass (g) of the rubber portion (a1) contained in 1 gram of the aromatic vinyl resin (A). The mass of the rubber portion (a1) can be obtained by a method of calculating from a polymerization formula and a polymerization conversion rate, a method of obtaining by an infrared absorption spectrum, or the like. The acetone insoluble component is 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 in the component (A) of the present invention. It corresponds to the mixture of the free rubber portion (a1), and the acetone-soluble component corresponds to the free resin portion (a2) not bound to the rubber portion (a1) in the component (A) of the present invention.

From this point of view, the components (A) are 5 to 50% by mass of the graft polymer in which the resin portion (a2) is bonded to the rubber portion, and 50 to 95 in the resin portion (a2) not bonded to the rubber portion (a1). It is preferable to contain 8 to 40% by mass of the graft polymer, and more preferably 60 to 92% by mass of the resin portion (a2) not bonded to the rubber portion (a1), and the graft weight is more preferable. It is particularly preferable to contain 10 to 35% by mass of the coalesced portion and 65 to 90% by mass of the resin portion (a2) not bonded to the rubber portion (a1) (however, the total of these two is 100% by mass). .. Here, the graft polymer corresponds to the acetone-insoluble component, and the resin portion (a2) not bonded to the rubber portion (a1) corresponds to the acetone-soluble component.

The graft ratio is, for example, the type and amount of the chain transfer agent used in the graft polymerization in producing the rubber-reinforced aromatic vinyl resin (A), the type and amount of the polymerization initiator, and the monomer component at the time of polymerization. It can be adjusted by appropriately selecting the addition method, addition time, polymerization temperature and the like.

The ultimate 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. It is .07 to 0.8 dl / g, more preferably 0.1 to 0.7 dl / g. When the ultimate viscosity is in the above range, the impact resistance and moldability of the resin composition become better.

The ultimate viscosity [η] can be measured by the following method. First, the acetone-soluble component of the rubber-reinforced aromatic vinyl resin (A) was dissolved in methyl ethyl ketone to prepare 5 pieces having different concentrations. The ultimate viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.

The ultimate viscosity [η] is, for example, the type and amount of the chain transfer agent, polymerization initiator, emulsifier, solvent, etc. used for graft polymerization of the rubber-reinforced aromatic vinyl resin (A), and the monomer at the time of polymerization. It can be adjusted by appropriately selecting the method of adding the component, the addition time, the polymerization temperature, the polymerization time and the like. Further, the rubber-reinforced aromatic vinyl resin (A) is mixed with a (co) polymer (A') having an extreme viscosity [η] different from the extreme viscosity [η] of the acetone-soluble component. Can be done.

In the thermoplastic resin composition of the present invention, the content of the component (A) is preferably 5 to 80% by mass, preferably 20% by mass, assuming that the total amount of the components (A) and (B) is 100% by mass. It is more preferably to 75% by mass, and even more preferably 30 to 70% by mass. When the content of the component (A) is within the above range, the MIU value of the molded product becomes 0.4 or more, and the tactile sensation such as the grip feeling is satisfactorily improved.

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

Specific examples of the thermoplastic elastomer (B) include diene-based elastomers such as styrene-based elastomers and polybutadiene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyvinyl chloride-based elastomers, ester-based elastomers, fluororesin-based elastomers, and ion bridges. Elastomers (ionomers) and the like can be mentioned. These thermoplastic elastomers can be used alone or in combination of two or more.

Specific examples of the styrene-based elastomer include a block copolymer containing one or more of a polymer block A of an aromatic vinyl compound and a 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 type or may be bonded in a radial type. Further, the polymer block B may be a random copolymer containing a small amount of an aromatic vinyl compound as a constituent unit, or a so-called tapered type in which the content of the constituent unit derived from the aromatic vinyl compound gradually increases. It may be a block.

The structure of the block copolymer is not particularly limited, and any of (AB) _n -type, (AB) _n -A type, and (AB) _n -C type can be used. In the formula, A is a polymer block of an aromatic vinyl compound, B is a polymer block of a conjugated diene compound, C is a coupling agent residue, and n is an integer of 1 or more.

As the aromatic vinyl compound which is a constituent unit of the polymer block A of the styrene-based elastomer, all the aromatic vinyl compounds listed as the vinyl-based monomer of the above component (A) can be used, but styrene is preferable. Is used. These aromatic vinyl compounds can be used alone or in combination of two or more. The conjugated diene that is the constituent unit of the polymer block B of the styrene-based elastomer includes 1,3-butadiene, isoprene, 2-methyl-1,3-butadiene, 2,3-diethyl-butadiene, and 2-neopentyl-. 1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and side chain conjugated hexadiene, etc. may be mentioned. 3-butadiene, isoprene and 2-methyl-1,3-butadiene are preferred.

The weight average molecular weight of the styrene-based 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, more preferably 15 to 50% by weight. The block copolymer may be used alone or in combination of two or more having different structures or different contents of structural units derived from aromatic vinyl compounds.

The hydrogenated additive of the styrene-based elastomer can be obtained by hydrogenating the polymer block B of the conjugated diene compound of the styrene-based elastomer obtained above by a known method. Specific methods include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 63-5401, Japanese Patent Application No. 63-285774, and Japanese Patent Application Publication No. 63-285774. There is a method shown in 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, when hydrogen is added non-selectively, ethylene is released from the portion polymerized by the 1,4-vinyl bond. Butylene is generated from the part polymerized by the 2-vinyl bond, styrene-ethylene-butylene-styrene copolymer (SEBS) and the like are generated as a hydrogen additive, and when the 1,2-vinyl bond is selectively hydrogenated. , Styrene-butadiene-butylene-styrene copolymer (SBBS) and the like are produced as hydrogen additives. Commercially available SEBS may be used, and specific examples thereof include Dynaron series (trade name, manufactured by JSR), Lavalon series (trade name, manufactured by Mitsubishi Chemical Corporation), Tough Tech series (trade name, manufactured by Asahi Kasei), and so on. The TPE-SB series (trade name, manufactured by Sumitomo Chemical Corporation) and the like can be mentioned.

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

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 can be mentioned.

Preferred specific examples of the styrene-based elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS), and styrene-butadiene-butylene-styrene copolymer (SBBS). ), Styrene-isoprene-styrene copolymer (SIS) and the like.

As the urethane-based elastomer,
In general, block copolymers having a hard segment block composed of a diisocyanate and a chain extender and a soft segment block composed of a polyol and a diisocyanate as a repeating unit can be mentioned.

Examples of the polyol include polyester polyol, polyester ether polyol, polycarbonate polyol, polyether polyol and the like.

Examples of the polyester polyol include a polyester polyol obtained by a condensation reaction between a dicarboxylic acid or an ester compound thereof or an acid anhydride and a diol; and a polylactone diol obtained by ring-opening polymerization of a lactone monomer such as ε-caprolactone. .. The above-mentioned dicarboxylic acids include 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 naphthalenedicarboxylic acid; hexahydroterephthalic acid. , Hexahydrophthalic acid, Hexahydroisophthalic acid and other alicyclic dicarboxylic acids are used, and the above diols include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol and 1,3-butanediol. , 1,4-Butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 1,3-octanediol, 1,9-nonanediol Etc. are used.

Examples of the polycarbonate polyol include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. One or more polyhydric alcohols such as diol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol and diethylene carbonate, diethyl carbonate Examples thereof include polycarbonate polyol obtained by reacting with and the like. Further, it may be a copolymer of polycaprolactone polyol and polyhexamethylene carbonate.

Further, the polyester ether polyol is a condensation reaction product of the above-mentioned aliphatic dicarboxylic acid, aromatic dicarboxylic acid, alicyclic dicarboxylic acid, or an ester or acid anhydride thereof with glycol such as diethylene glycol or propylene oxide adduct. And so on.

Further, examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol (PTMG) obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran, and copolyethers thereof. ..

Among the various polyols described above, a polyether polyol is preferable from the viewpoint of hydrolysis resistance.

Examples of the isocyanate include tolylene diosocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylylene diisocyanate (NDI), trizine diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate. (IPDI), xylylene diisocyanate (XDI), hydrogenated XDI, triisocyanate, tetramethylxylylene diisocyanate (TMXDI), 1,6,11-undecanetriisocyanate, 1,8-diisocyanate methyloctane, lysine ester triisocyanate, 1, Examples thereof include 3,6-hexamethylene triisocyanate and bicycloheptane triisocyanate. Among these, 4,4'-diphenylmethane diisocyanate (MDI) or dicyclohexylmethane diisocyanate (hydrogenated MDI; HMDI) is preferable.

As the chain extender, a low molecular weight polyol is used, for example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-. Pentandiol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol, glycerin Examples thereof include aliphatic polyols such as 1,4-dimethylolbenzene, 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-1180" and "T-1185" of "T-1000 series" as ester (adipate) series manufactured by DCbayer Polymer Co., Ltd .; "T-2000 series" as ester (lactone) series. "T-2180", "T-2185"; available as an ether type "T-8180", "T-8185" of "T-88000 series", "TP-6580A" of "TP-68000 series", etc. ..

In the thermoplastic resin composition of the present invention, the content of the component (B) is preferably 20 to 95% by mass, preferably 20 to 95% by mass when the total amount of the components (A) and (B) is 100% by mass. It is more preferably to 80% by mass, and even more preferably 30 to 70% by mass. When the content of the component (B) is within the above range, the MIU value of the molded product is 0.4 or more, and the tactile sensation such as the grip feeling is satisfactorily improved.

3. 3. Other formulations

In addition to the above-mentioned components (A) and (B), the thermoplastic resin composition according to the present invention contains, if necessary, a slidability-imparting agent, an antioxidant, a processing stabilizer, an ultraviolet absorber, and the like. Addition of various additives such as light stabilizers, antistatic agents, crystallization nucleating agents, lubricants, plasticizers, metal deactivators, coloring pigments, various inorganic fillers, glass fibers, strengthening agents, flame retardants, mold release agents, foaming agents, etc. The agent can be blended within a range that does not impair the object of the present invention.

4. Method for Producing Thermoplastic Resin Composition of the Present Invention In the thermoplastic resin composition of the present invention, each component is mixed in a predetermined compounding ratio with a tumbler mixer, a henschel mixer, or the like, and then a single-screw extruder, a twin-screw extruder, or the like. 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. A preferred kneader is a twin-screw extruder. Further, when kneading each component, those components may be kneaded all at once, or may be kneaded in multiple stages by dividing and kneading. It can also be pelletized by an extruder after kneading with a Banbury mixer, a kneader or the like. The melt-kneading temperature is usually 180 to 240 ° C, preferably 190 to 230 ° C.

5. Method for Producing Molded Product of the Present Invention The thermoplastic resin composition of the present invention is made into a resin molded product by a known molding method such as injection molding, press molding, sheet extrusion molding, vacuum molding, deformed extrusion molding, foam molding and the like. be able to. The surface of the resin molded product formed from the thermoplastic resin composition of the present invention has an excellent tactile sensation such as a grip feeling, and is suitable as a molding material for various articles such as articles that need to be operated by hand. The grip feeling on the surface of the resin molded product of the present invention is a numerical value based on the MIU value (average friction coefficient) measured on the surface of the molded product using a friction feeling tester KES-SE (trade name: manufactured by Kato Tech Co., Ltd.). Can be transformed into. The molded product of the present invention is less slippery than the conventional molded product and is excellent in tactile sensation such as grip feeling, but the MIU value measured as described above is 0.4 or more, preferably 0.5 or more, and 0. 6.6 to 1.0 is more preferable. Further, the elastic modulus of the molded product of the present invention measured based on ISO 178 is preferably 300 to 1500 MPa, more preferably 400 to 1200 MPa. Further, the Rockwell hardness (hardness scale is R-scale) at room temperature measured based on ISO 2039 of the molded product of the present invention is preferably 20 to 60, more preferably 25 to 50. ..

Since the molded product of the thermoplastic resin composition of the present invention has the above-mentioned tactile sensation, parts for human body contact, for example, automobile interior parts such as shaver handles, door trims, glove boxes, handles, door knobs, handrails, etc. It can be used as a housing, case, cover, etc. for building materials such as mobile phones, mobile music players, smartphones, tablet personal computers, and portable electric products such as laptop computers.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the examples, parts and% are based on mass unless otherwise specified.

1. 1. Ingredient [A]
As raw materials for the rubber-reinforced aromatic vinyl resin, the diene-based rubber-reinforced aromatic vinyl resin (raw material MABS and raw material ABS) obtained in the following Synthesis Examples 1 and 2 and the 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 Synthesis Example 4 below were used.

1-1. Synthesis Example 1 (Synthesis of raw material MABS (diene-based rubber-reinforced aromatic vinyl-based resin))
In a glass flask having an internal volume of 10 liters equipped with a stirrer, 45 parts of polybutadiene (in terms of solid content) having a volume average particle diameter of 300 nm, 0.3 part of sodium dodecylbenzene sulfonate, and 100 parts of ion-exchanged water were charged, and then 100 parts of ion-exchanged water was charged. 3 parts of styrene, 1 part of acrylonitrile, and 11 parts of methyl methacrylate were charged. After raising the temperature to 43 ° C while stirring these mixtures, 0.02 part of ethylenediamine tetrasodium acetate, 0.001 part of ferrous sulfate heptahydrate, 0.08 part of sodium formaldehyde sulfoxylate dihydrate. An aqueous solution consisting of 6 parts of ion-exchanged water and 0.04 part of cumene hydroperoxide were added, and the reaction was continued for 1 hour.

Then, a monomer mixture consisting of 9 parts of styrene, 2 parts of acrylonitrile, 29 parts of methyl methacrylate, 1.2 parts of t-dodecyl mercaptan, 0.1 part of cumene hydroperoxide, and 0.01 part of ethylenediamine 4 sodium acetate. 4 parts of an aqueous solution consisting of 0.001 part of ferrous sulfate heptahydrate, 0.05 part of sodium formaldehyde sulfoxylate dihydrate, 0.3 part of sodium dodecylbenzenesulfonate, and 30 parts of ion-exchanged water. It was added continuously over time and the polymerization reaction was continued. After the addition is completed, 0.003 parts of sodium ethylenediamine tetraacetate, 0.0002 parts of ferrous sulfate, 0.01 parts of sodium formaldehyde sulfoxylate / dihydrate, 0.02 parts of cumenehydroperoxide, and ion exchange After adding 1 part of water and continuing stirring for another 1 hour, the reaction was completed by cooling.

Then, 0.67 parts of the reaction product of p-cresol, dicyclopentadiene, and isobutylene (“SANDWIN-45” manufactured by Toho Chemical Industry Co., Ltd.) and 0.5 part of ethylenediamine 4 sodium acetate were added to the reaction product, and the mixture was 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 graft rate was 52%, and the ultimate viscosity [η] of the acetone-soluble component was 0.24 dl / g (measured at 30 ° C. in methyl ethyl ketone).

1-2. Synthesis Example 2 (Synthesis of raw material ABS (diene-based rubber-reinforced aromatic vinyl-based resin))
In a glass flask equipped with a stirrer, 42 parts of ion-exchanged water, 0.35 parts of potassium rosinate, 0.2 parts of tert-dodecyl mercaptan, and polybutadiene rubber having an average particle diameter of 300 nm (gel content 80%) in a nitrogen stream. ) 100 parts of latex including 45 parts, 11 parts of styrene and 4 parts of acrylonitrile were contained, and the temperature was raised while stirring. When the internal temperature reached 40 ° C., a solution prepared by dissolving 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. .. Then, 0.07 part of cumene hydroperoxide was added to initiate polymerization.
After polymerizing for 30 minutes, 45 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 29 parts of styrene, 11 parts of acrylonitrile, 0.17 parts of tert-dodecyl mercaptan and 0.1 part of cumene hydroperoxide were added for 3 hours. It was added continuously over. Then, the polymerization was continued for another 1 hour, and 0.2 part of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) was added to the reaction system to complete the polymerization.
Then, an aqueous sulfuric acid solution was added to the latex containing the reaction product to solidify the resin component and wash with water. Then, it was washed and neutralized with an aqueous potassium hydroxide solution, further washed with water, and then dried to obtain a diene-based rubber-reinforced aromatic vinyl-based resin (raw material ABS). The polymerization conversion rate is 98%, the graft rate in the graft resin contained in this resin is 50%, and the ultimate viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone-soluble component is 0.35 dl / g. rice field.

1-3. Synthesis Example 3 (Synthesis of raw material MAS (styrene-acrylonitrile-methylmethacrylate 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.

A glass reactor with a capacity of 10 L equipped with a stirrer, a raw material and auxiliary agent addition device, a thermometer, a heating device, etc. is charged with 150 parts of water and 2 parts of sodium dodecylbenzenesulfonate as an emulsifier, and a nitrogen stream is stirred while stirring. Below, the internal temperature was raised to 55 ° C. When the temperature reaches 55 ° C., 0.09 part of ethylenediamine tetraacetic acid / tetrasodium / dihydrate, 0.003 part of ferrous sulfate heptahydrate and sodium formaldehyde are added to the above monomer mixture and 24 parts of water. An aqueous solution in which 0.2 part of sulfoxylate was dissolved was continuously added over 5 hours.

The internal temperature was raised to 67 ° C. within 1 hour from the start of addition of the monomer mixture, and then maintained at 67 ° C. After the continuous addition was completed, 0.05 part of diisopropylbenzene hydroperoxide was added, and the internal temperature was maintained for 1 hour to complete the polymerization reaction. This copolymer latex was coagulated with calcium chloride, washed with water and dried to obtain a powdery copolymer (raw material MAS). The polymerization conversion was 98% and the ultimate 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 synthesizer in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging nitrogen gas into each reactor, in the first reactor, a mixture consisting of 73 parts of styrene, 27 parts of acrylonitrile and 20 parts of toluene, and 0.15 part of tert-dodecyl mercaptan, which is a molecular weight modifier, are added. A solution in which 5 parts of toluene was dissolved and 0.1 part of 1,1'-azobis (cyclohexane-1-carbonitrile) as a polymerization initiator dissolved in 5 parts of toluene were continuously supplied to 110. Polymerization was carried out at ° C. The average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion rate after 2 hours was 56%.
Then, the obtained polymer solution was continuously taken out by a pump provided outside the first reactor and supplied to the second reactor. The amount continuously taken out is the same as the amount supplied to the first reactor. In the second reactor, polymerization was carried out at 130 ° C. for 2 hours, and the polymerization conversion rate after 2 hours was 74%.
Then, the polymer solution was recovered from the second reactor and introduced into a twin-screw, three-stage vented extruder. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatile to recover the styrene / acrylonitrile copolymer (raw material AS). The ultimate viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this styrene / acrylonitrile copolymer was 0.34 dl / g.

2. 2. Ingredient [B]
The following products were used as raw materials for thermoplastic elastomers.

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. The MFR (230 ° C., 21.2N) was 10 g / 10 min. The MFR (200 ° C., 49.0N) was 4 g / 10 min.

3. 3. Ingredient [C]
3-1. Raw material C
ADEKA ADEKA STAB A-60 (trade name) (Tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane). 0.2 parts are mixed at the time of kneading.

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

2. 2. Preparation of Molded Product A resin composition was molded to prepare a test piece having a size of 120 mm × 80 mm × 2 mm. Molding was performed using an injection molding machine IS100GN (trade name: manufactured by Toshiba Machine Co., Ltd.) 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 the molding die, a leather grain die (texture No; TH-894) having unevenness (the depth of the recess is 100 μm) on the inner surface was used.

3. 3. Hardness measurement Based on ISO 2039, Rockwell hardness at room temperature (hardness scale is R-scale) was measured. The test piece was manufactured using an injection molding machine "J110AD-180H" (model name) manufactured by Japan Steel Works, Ltd., in which the set temperature of the cylinder was 220 ° C. and the mold temperature was 50 ° C.

4. Measurement of flexural modulus Based on ISO 178, the flexural modulus was measured using a precision universal testing machine "Autograph AG5000E type" manufactured by Shimadzu Corporation. The unit of the measured value was MPa. The test piece was prepared in the same manner as in 3 (measurement of hardness) above.

5. Evaluation of Appearance of Molded Product 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.
◯: None of (i) flow mark, (ii) peeling, and (iii) bleaching occurs.
Δ: Any of (i) flow mark, (ii) peeling, and (iii) bleaching occurred in a part of the molded product.
X: Any of (i) flow mark, (ii) peeling, and (iii) bleaching occurred on the entire surface of the molded product.

6. Tactile (grip)
The tactile sensation when the textured surface of the molded product prepared in 2 above was traced with a finger at room temperature of 23 ° C. was evaluated according to the following criteria.
○: It is hard to slip.
△: Slightly slippery.
×: Slippery.

7. Measurement of MIU value (KES texture measurement)
The MIU value of the textured surface of the molded product prepared in 2 above was measured using a friction feeling tester KES-SE (trade name: manufactured by Kato Tech Co., Ltd.). The MIU value (average coefficient of friction) is an index of slip resistance, and the higher the value, the more difficult it is to slip.

8. Surface Gloss The gloss when the mirror surface of the molded product prepared in 2 above was visually observed was evaluated according to the following criteria.
○: Glossy, indoor light is reflected ×: No gloss, indoor light is not reflected

9. Bending wrinkle property The molded product prepared in 2 above was bent 20 degrees to the opposite side (glossy surface side) of the grain surface, and the bent side (glossy surface side) was visually observed and evaluated according to the following criteria.
○: No wrinkles ×: Wrinkles occur

The following can be seen from the above table.
In Examples 1 to 5 using the thermoplastic resin composition of the present invention, not only are excellent in hardness, flexural modulus and appearance of the molded product, but also tactile sensation (grip sensation) and slip resistance (MIU value), surface gloss, and so on. It was superior to bending 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. Comparative Example 3 was inferior in tactile sensation (grip sensation) and slip resistance (MIU value).

The molded product of the present invention is excellent in mechanical strength and appearance of the molded product, has a non-slip surface, and has a good tactile sensation such as a grip feeling. It can be suitably used as a necessary article.

Claims (5)

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 the resin portion (a2) is graft-polymerized on the rubber portion (a1). Contains a (co) polymer (A') containing structural units derived from aromatic vinyl compounds and (meth) acrylic acid alkyl ester compounds.
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 the structural units constituting the resin portion (a2).
The component (B) is an elastomer composed of a hydrogenated compound of a block copolymer containing at least one polymer block of an aromatic vinyl compound and one or more polymer blocks of a conjugated diene compound.
The content ratio of the rubber portion (a1) of the rubber-reinforced vinyl-based resin (A) is 3 to 9% by mass with respect to the total of 100% by mass of the rubber-reinforced vinyl-based resin (A) and the thermoplastic elastomer (B). ,
A molded product containing the component (B) in an amount of 20 to 95% by mass with respect to a total of 100% by mass of the components (A) and (B). The molded product according to claim 1, wherein the component (B) is contained in an amount of 25 to 80% by mass with respect to a total of 100% by mass of the components (A) and (B). The molded product according to claim 1 or 2 , which is a part for human body contact. A thermoplastic resin composition containing a rubber-reinforced vinyl-based resin (A) containing 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, and the resin portion (a2) is graft-polymerized on the rubber portion (a1). Contains a (co) polymer (A') containing structural units derived from aromatic vinyl compounds and (meth) acrylic acid alkyl ester compounds.
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 the structural units constituting the resin portion (a2).
The component (B) is an elastomer composed of a hydrogenated compound of a block copolymer containing at least one polymer block of an aromatic vinyl compound and one or more polymer blocks of a conjugated diene compound.
The content ratio of the rubber portion (a1) of the rubber-reinforced vinyl-based resin (A) is 3 to 9% by mass with respect to the total of 100% by mass of the rubber-reinforced vinyl-based resin (A) and the thermoplastic elastomer (B). ,
A thermoplastic resin composition containing the component (B) in an amount of 20 to 95% by mass with respect to a total of 100% by mass of the components (A) and (B). The fourth aspect of the present invention comprises 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.