JP6714356B2 - Laminate - Google Patents

Description

The present invention, at least a portion of the base layer (II), excellent in mechanical strength and appearance of the molded article, and good tactile feel, such as the feel of the surface, such as adhesion to the base layer (II). The present invention relates to a laminate having a skin layer (I) which is also excellent in moldability.

BACKGROUND ART Automotive interior parts such as door trims and glove boxes are often touched by the body of a passenger, and it is required that the parts have good cushioning properties and tactile sensations while maintaining rigidity. Many of the automobile interior parts described above are conventionally manufactured by slush molding or the like by joining a core material having rigidity to a skin material made of urethane resin or the like having flexibility (Patent Document 1).

On the other hand, thermoplastic elastomers are widely used in building materials, miscellaneous goods, machine parts, etc. as molding materials that give molded articles with excellent flexibility. Specific examples include vinyl chloride-based, olefin-based, urethane Examples thereof include various elastomers such as type, styrene type, polyester type and alloys thereof (Patent Document 2).

In addition, rubber-reinforced aromatic vinyl resins represented by ABS resins are widely used for office automation equipment, home appliances, miscellaneous goods, building materials, etc. because of their excellent balance of impact resistance and molding processability and excellent appearance of molded products. It's being used.

Therefore, in order to obtain a part having a good cushioning property and a tactile sensation while maintaining the rigidity, a laminate obtained by coextrusion or heat fusion of the thermoplastic elastomer and the rubber-reinforced aromatic vinyl resin is produced. However, there is a problem in that the production is complicated and the cost is high, and further, when the surface formed from the thermoplastic elastomer is touched with a hand, it has a sticky feeling, and a tactile feeling such as a tactile feeling is bad. ..

Further, a thermoplastic resin composition in which a rubber-reinforced aromatic vinyl-based resin is mixed with a thermoplastic elastomer is conventionally known (see Patent Documents 3 and 4), but a part having a good cushioning property and a touch feeling such as a feeling of touch. It was not intended to obtain the goal, and the problem was not solved.

JP, 2013-159122, A JP, 2004-238551, A JP-A-2000-309675 JP, 2006-124523, A

The object of the present invention is to provide at least a part of the base material layer (II) with excellent mechanical strength and appearance of a molded article, and having a good tactile sensation such as a touch on the surface, and adhesion to the base material layer (II). Another object of the present invention is to provide a laminate having a skin layer (I) which is excellent in moldability and the like.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a skin obtained from a thermoplastic resin composition (X) in which a thermoplastic elastomer (B) is blended with a rubber-reinforced aromatic vinyl resin (A). By laminating the layer (I) on at least a part of the base material layer (II), an MIU value of 0.4 or less, which is an index of the stickiness of the surface, is shown, and an index of the soft touch feeling of the surface. Since it has an LC value of 0.9 or less, it is suitable for applications where good tactile sensation is required, and further, a laminate having excellent moldability such as adhesion to the base material layer (II) can be obtained. The inventors have found that the object can be achieved, and have completed the present invention.

Thus, according to one aspect of the present invention, a laminate comprising a skin layer (I) on at least a part of the base material layer (II),
The skin layer (I) is a rubber-reinforced aromatic vinyl resin (A) containing a rubber portion (a1) and a resin portion (a2) containing a constitutional unit derived from an aromatic vinyl compound, and a thermoplastic resin. There is provided a laminate comprising the thermoplastic resin composition (X) containing the elastomer (B), wherein the skin layer (I) has an MIU value of 0.4 or less and an LC value of 0.9 or less.

According to the present invention, the skin layer (I) provided on at least a part of the base material layer (II) is formed from a thermoplastic resin composition (X) in which a thermoplastic elastomer is mixed with a rubber-reinforced aromatic vinyl resin. Therefore, the texture of the surface is improved as compared with the laminated body in which the skin layer is formed of each of the rubber-reinforced aromatic vinyl-based resin or the thermoplastic elastomer. Specifically, it is an index of the sticky feeling of the surface of the laminated body. The MIU value is 0.4 or less, and the LC value, which is an index of the soft touch feeling of the surface of the laminate, is 0.9 or less, the tactile feeling is excellent, and the adhesion to the base material layer (II) is further improved. It is possible to obtain a laminate excellent in moldability and the like.

It is sectional drawing which shows an example of the laminated body of this invention. It is a perspective view showing an example (cover for smart phones) of a layered product of the present invention.

Hereinafter, the present invention will be described in detail.
In the present invention, “(co)polymerization” means homopolymerization and/or copolymerization, “(meth)acryl” means acryl and/or methacryl, and “(meth)acrylate” means , Acrylate and/or methacrylate.

The skin layer (I) of the laminate of the present invention is formed by using the thermoplastic resin composition (X) containing the rubber-reinforced aromatic vinyl resin (A) and the thermoplastic elastomer (B) as a molding material. It is obtained by

1. Rubber-reinforced aromatic vinyl resin (component (A))
The rubber-reinforced aromatic vinyl-based 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. The rubber part (a1) is not particularly limited as long as it can achieve the object of the present invention, but from the viewpoint of the feel of the skin layer (I), the silicone rubber (a1-2) or the ethylene/α-olefin rubber ( It is preferable to contain at least a1-3). More preferably, the rubber portion (a1) has a diene rubber (a1-1) of 0 to 90 mass% and a silicone rubber (a1-2) of 10 to 60 mass% or an ethylene/α-olefin rubber (a1-3). ) 10 to 100 mass% (the total of the component (a1-1) and the component (a1-2) or (a1-3) is 100 mass%). Even more preferably, the rubber portion (a1) is composed of 40 to 90% by mass of the diene rubber (a1-1) and 10 to 60% by mass of the silicone rubber (a1-2) (the component (a1-1). ) And the component (a1-2) are 100% by mass), or 0 to 90% by mass of the diene rubber (a1-1) and 15 to 100% by mass of the ethylene/α-olefin rubber (a1-3). % (The total of the component (a1-1) and the component (a1-3) is 100% by mass). When the blending ratio of the above components (a1-1), (a1-2) and (a1-3) is out of the above range, the appearance of the skin layer (I) is inferior, and in some cases, the moldability is inferior. The surface of the skin layer (I) may become sticky, resulting in a poor feel such as touch.

In the rubber-reinforced aromatic vinyl-based 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, it is preferably graft-polymerized to form a graft polymer. Therefore, the rubber-reinforced aromatic vinyl resin (A) is preferably composed of at least the above graft copolymer and the resin portion (a2) not graft-polymerized to the rubber portion (a1). The part (a2) may contain a rubber part (a1) which is not grafted, or other components such as an additive. The rubber portion (a1) may be any material that is 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 (a1-1) include homopolymers of polybutadiene, polyisoprene, polychloroprene, etc.; styrene/butadiene copolymers, styrene/butadiene/styrene copolymers, acrylonitrile/butadiene copolymers, acrylonitrile/ Styrene/butadiene copolymer rubber such as styrene/butadiene copolymer; styrene/isoprene copolymer such as styrene/isoprene copolymer, styrene/isoprene/styrene copolymer, acrylonitrile/styrene/isoprene copolymer Rubber; natural rubber and the like can be mentioned. These copolymers may be block copolymers or random copolymers. Further, these copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%). The diene rubbers can be used alone or in combination of two or more.

The silicone rubber (a1-2) is not particularly limited as long as it is a polyorganosiloxane-based rubber having a polymerizable unsaturated bond (for example, carbon-carbon double bond), and among them, it is represented by the following general formula (1). A modified polyorganosiloxane rubber obtained by co-condensing at least one kind of the organosiloxane (i) having the structural unit with the graft crossing agent (ii) is preferably used.
R ¹ _n SiO _(4-n)/2 (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and n is an integer of 0 to 3. When n is 2 to 3, R ^1's may be the same or different. May be.)

In the general formula (1), R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; an aryl group such as a phenyl group or a tolyl group; an alkenyl group such as a vinyl group or an allyl group; A group in which a part of hydrogen atoms bonded to carbon atoms of the group is substituted with a halogen atom, a cyano group or the like; a group in which at least one hydrogen atom of an alkyl group is substituted with a mercapto group or the like.

The organosiloxane (i) may be linear, branched or cyclic, and is preferably cyclic. Specific examples of the organosiloxane (i) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, Examples include octaphenylcyclotetrasiloxane. These can be used alone or in combination of two or more.
The organosiloxane (i) is, for example, a polycondensed product having a weight average molecular weight (Mw) of about 500 to 10,000, which has been condensed in advance by using one or more compounds represented by the general formula (1). It may be an organosiloxane. The end of the molecular chain of this polyorganosiloxane may be sealed with a functional group such as a hydroxyl group, an alkoxy group, a trimethylsilyl group, or a methyldiphenylsilyl group.

As the graft crossing agent (ii), vinylmethyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, 1-(p-vinylphenyl)methyldimethylisopropoxysilane, 2-(p-vinylphenyl)ethylenemethyldimethoxysilane, 3 -(P-Vinylphenoxy)propylmethyldiethoxysilane, 1-(o-vinylphenyl)-1,1,2-trimethyl-2,2-dimethoxydisilane, allylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane And the like, a compound having a carbon-carbon unsaturated bond and an alkoxysilyl group; a silane compound having a mercapto group (thiol group) such as γ-mercaptopropylmethylmethyldimethoxysilane; a silane compound having an amino group; tetravinyltetra Examples thereof include methylcyclosiloxane. When the organosiloxane (i) contains a polymerizable unsaturated bond, the graft crossing agent (ii) may or may not have a polymerizable unsaturated bond.

The above-mentioned modified polyorganosiloxane rubber is produced by a method in which the organosiloxane (i) and the graft crossing agent (ii) are shear-mixed by using a homomixer or the like in the presence of an emulsifier such as alkylbenzene sulfonic acid, and condensed. be able to. The upper limit of the amount of the graft crossing agent (ii) used is preferably 50% by mass, more preferably 10% by mass, when the total amount of the organosiloxane (i) and the graft crossing agent (ii) is 100% by mass. It is preferably 5% by mass.
In the production of the modified polyorganosiloxane rubber, a crosslinking agent may be added to improve impact resistance. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. When a crosslinking agent is used, the upper limit of the amount used is usually 10% by mass, preferably 5% by mass, when the total amount of the organosiloxane (i) and the graft crossing agent (ii) is 100% by mass.
The weight average molecular weight (Mw) of the modified polyorganosiloxane rubber is preferably 30,000 to 1,000,000, more preferably 50,000 to 300,000. Within this range, the composition of the present invention is provided with good impact resistance and fluidity. The volume average particle diameter of the modified polyorganosiloxane rubber is preferably 20 to 500 nm, more preferably 50 to 400 nm, still more preferably 150 to 350 nm, from the viewpoint of impact resistance.

The ethylene/α-olefin rubber (a1-3) is a copolymer rubber containing a structural unit derived from ethylene and a structural unit derived from α-olefin. As the α-olefin, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1- Eikosen etc. are mentioned. These α-olefins can be used alone or in combination of two or more. The number of carbon atoms of the α-olefin is preferably 3 to 20, more preferably 3 to 12, and further preferably 3 to 8 from the viewpoint of impact resistance. The mass ratio of ethylene:α-olefin in the ethylene/α-olefin rubber is usually 5 to 95:95 to 5, preferably 50 to 95:50 to 5, and more preferably 60 to 95:40 to 5. When the mass ratio of ethylene:α-olefin is within the above range, the resulting molded article has further excellent impact resistance, which is preferable. The ethylene/α-olefin rubber may include a structural unit derived from a non-conjugated diene, if necessary. Examples of the non-conjugated diene include alkenyl norbornenes, cyclic dienes, and aliphatic dienes, preferably 5-ethylidene-2-norbornene and dicyclopentadiene. These non-conjugated dienes can be used alone or in admixture of two or more. The ratio of the non-conjugated diene to the total amount of the rubbery polymer is usually 0 to 10% by mass, preferably 0 to 5% by mass, more preferably 0 to 3% by mass.

In the present invention, it is preferable to use an ethylene/α-olefin rubber (a1-3) having a melting point (Tm) of 0 to 130°C. The Tm (melting point) of the ethylene/α-olefin rubber is more preferably 0 to 120°C, still more preferably 10 to 90°C, and particularly preferably 20 to 80°C. The fact that the ethylene/α-olefin rubber has a melting point (Tm) means that the rubber has crystallinity. Therefore, by using the ethylene/α-olefin rubber having such a melting point (Tm), it is possible to easily improve the feel of the skin layer (I).

The Mooney viscosity (ML1+4, 100° C.; according to JIS K 6300) of the ethylene/α-olefin rubber (a1-3) is usually 5 to 80, preferably 10 to 65, and more preferably 10 to 45. When the Mooney viscosity is within the above range, the molding processability is excellent, and the impact strength and appearance of the skin layer (I) are excellent, which is preferable.

From the viewpoint of improving the feel of the skin layer (I), the ethylene/α-olefin rubber (a1-3) is preferably an ethylene/α-olefin copolymer containing no non-conjugated diene component. -Propylene copolymer, ethylene/1-butene copolymer and ethylene/1-octene copolymer are more preferable, and ethylene/propylene copolymer is particularly preferable.

In the present invention, the content of the rubber portion (a1) in the rubber-reinforced aromatic vinyl-based resin (A) is preferably 10 to 90 mass with respect to 100% by mass of the rubber-reinforced aromatic vinyl-based resin (A) as a whole. %, more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass. When the content of the rubber portion (a1) is within the above range, the laminate of the present invention is more excellent in impact resistance, the feel of the skin layer (I), the appearance of the skin layer (I), and the like, which is preferable.

The content of the rubber part (a1) in the thermoplastic resin composition (X) of the present invention is 100% by mass with respect to the total amount of the rubber-reinforced aromatic vinyl resin (A) and the thermoplastic elastomer (B). , 5 to 40% by mass, preferably 7 to 35% by mass, more preferably 10 to 30% by mass, and further preferably 12 to 25% by mass. When the content of the rubber portion (a1) is less than 5% by mass, the feel of the skin layer (I) (cushioning property or soft touch) is poor, and when it exceeds 40% by mass, the feel of the skin layer (I) ( Smoothness) is inferior.

The resin portion (a2) of the rubber-reinforced aromatic vinyl-based resin (A) includes a constitutional unit derived from an aromatic vinyl compound, which is one of vinyl-based monomers, as an essential component, and, if desired, the aromatic vinyl compound. A constitutional unit derived from another vinyl-based monomer copolymerizable with 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 and fluorostyrene. 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.

When the resin portion (a2) has a constitutional unit derived from another vinyl-based monomer copolymerizable with the aromatic vinyl compound, the usage ratio of the aromatic vinyl compound and the other vinyl-based monomer is From the viewpoint of mechanical strength and molding appearance, when these totals are 100% by mass, respectively, preferably 50 to 95% by mass and 5 to 50% by mass, more preferably 60 to 90% by mass and 10 to 40%, respectively. It is% by mass.

Other vinyl monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds, (meth)acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, and hydroxyl groups. Examples thereof include a group-containing unsaturated compound, an epoxy group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound. These may be used alone or in combination of two or more.
In the present invention, the other vinyl-based monomer is preferably a vinyl cyanide compound because it has excellent mechanical strength (toughness) and chemical resistance. In this case, the lower limit of the ratio of the total amount of the structural units derived from the aromatic vinyl compound and the vinyl cyanide compound contained in the resin part (a2) is preferably 100% by mass of the resin part (a2). Is 5% by mass, more preferably 10% by mass, still more preferably 15% by mass.

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

Specific examples of the (meth)acrylic acid ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 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)acrylic acid 2 -Ethylhexyl, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate and the like can be mentioned. These compounds can be used alone or in combination of two or more.

Specific examples of the maleimide compounds include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, 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 -Hydroxyphenyl)maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These compounds can be used alone or in combination of two or more. As a method of introducing a constitutional unit derived from a maleimide compound into the rubber-reinforced aromatic vinyl resin (A), other than a method of polymerizing the maleimide compound as a raw material, for example, a maleic anhydride compound may be used. It is also possible to use a method of performing imidation after performing 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 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 (meth)acrylic acid 3-. 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-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 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 methacryl 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.

As described above, in the rubber-reinforced aromatic vinyl-based resin (A) of the present invention, the rubber portion (a1) is a portion (a1-1) made of a diene rubber and a portion (a1-) made of a silicone rubber. 2) or ethylene/α-olefin rubber (a1-3) in some cases. Examples of the method for producing the rubber-reinforced aromatic vinyl-based resin (A) including a plurality of types of rubber parts include, for example, the presence of both a diene-based rubber and a silicone rubber or an ethylene/α-olefin-based rubber, In addition to a method of producing (in particular, graft-polymerizing) a vinyl-based monomer composed of at least an aromatic vinyl compound, a vinyl-based monomer containing at least an aromatic vinyl compound in the presence of a diene rubber. Rubber-reinforced aromatic vinyl resin produced by polymerizing (particularly, graft polymerization) a vinyl compound, and a vinyl monomer at least composed of an aromatic vinyl compound in the presence of silicone rubber or ethylene/α-olefin rubber Can be obtained by a method of mixing with a silicone rubber reinforced aromatic vinyl resin produced by polymerizing (particularly, graft polymerization). The polymerization method in this production method may be emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these. 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 diene rubber and the silicone rubber or the ethylene/α-olefin rubber and the vinyl monomer, which are the raw materials, may be added to the reaction system all at once and polymerized. The polymerization may be carried out while being dividedly or continuously added to the reaction system.

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

As the polymerization initiator, a redox system in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, or paramenthane hydroperoxide is combined with a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation. Initiators: Persulfates such as potassium persulfate; Benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, peroxides such as tert-butyl peroxymonocarbonate. 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 mass% with respect to the total amount of the vinyl-based monomer. The above polymerization initiator can be added to the reaction system all at once or continuously.

As the chain transfer agent, 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 -Methylstyrene dimer and the like. 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 mass% with respect to the total amount of the vinyl monomer. The chain transfer agent can be added to the reaction system all at once or continuously.

Examples of emulsifiers include anionic surfactants and nonionic surfactants. 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. Are listed. Examples of nonionic surfactants include polyethylene glycol alkyl ester type compounds and alkyl ether type compounds. 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 mass% with respect to the total amount of the vinyl monomer.

Emulsion polymerization can be carried out under known conditions depending on the type of vinyl monomer, polymerization initiator and the like. The latex obtained by this emulsion polymerization is usually coagulated with a coagulant to give a resin component, that is, the rubber-reinforced aromatic vinyl resin (A) in the form of powder, which is then purified by washing with water and drying. It 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; organic acids such as acetic acid and lactic acid.

According to the method for producing the rubber-reinforced aromatic vinyl resin (A), the (co)polymer of vinyl monomers is usually a rubber such as a diene rubber, a silicone rubber, and an ethylene/α-olefin rubber. Formation of a graft copolymer graft-polymerized on the particles of a polymer and a (co)polymer of vinyl monomers that are not graft-polymerized on either silicone rubber or other rubber polymers The thing is obtained. In some cases, the mixed product may contain particles of a rubbery polymer of a diene rubber, a silicone rubber or an ethylene/α-olefin rubber in 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 the particles of the rubbery polymer and a resin portion (a2) having a constitutional unit derived from an aromatic vinyl compound. Since the rubber part (a1) preferably forms a graft copolymer in which the resin part (a2) is graft-polymerized, the graft copolymer and the (co)polymer produced as described above are The mixed product can be used as it is as the rubber-reinforced aromatic vinyl-based resin (A).

The rubber-reinforced aromatic vinyl resin (A) comprises a constitutional unit derived from an aromatic vinyl compound and, if desired, a constitutional unit derived from another vinyl compound which is copolymerizable with the aromatic vinyl compound (copolymerization). ) The polymer (A′) may be added. This (co)polymer (A') is a vinyl consisting of an aromatic vinyl compound and, if desired, another vinyl compound which is 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-based resin (A), it forms a resin portion (a2) that is not graft-polymerized with the rubber portion (a1). .. As the aromatic vinyl compound and the other vinyl-based compound copolymerizable with the aromatic vinyl compound, those described above with respect to the resin portion (a2) can be used.

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%, still more preferably 20 to 100%. When the graft ratio of the rubber-reinforced aromatic vinyl resin (A) is within the above range, the thermoplastic resin composition of the present invention has better mechanical strength, moldability, and appearance of a molded product.

The graft ratio can be calculated by the following mathematical formula (1).
Graft ratio (mass %)=((S−T)/T)×100 (1)
In the above formula, S is 1 g of the rubber-reinforced aromatic vinyl-based resin (A) added to 20 ml of acetone, shaken for 2 hours at a temperature of 25° C. with a shaker, and then at a temperature of 5° C. And is a mass (g) of acetone insoluble matter obtained by separating the acetone insoluble matter and the acetone soluble matter by centrifuging for 60 minutes with a centrifuge (rotation speed; 23,000 rpm), and T is rubber-reinforced. It is the mass (g) of the rubber part (a1) contained in 1 gram of the aromatic vinyl resin (A). The mass of the rubber portion (a1) can be determined by a method of calculating from the polymerization prescription and the polymerization conversion rate, a method of determining from an infrared absorption spectrum, or the like. The acetone-insoluble matter is not bound to the graft polymer and the resin portion (a2) in which the rubber portion (a1) and the resin portion (a2) are bound by graft polymerization in the component (A) of the present invention. It corresponds to the mixture of the free rubber part (a1), and the above acetone-soluble component corresponds to the free resin part (a2) which is not bonded to the rubber part (a1) in the component (A) of the present invention.

From such a viewpoint, when the rubber part (a1) contains the diene rubber (a1-1) and the silicone rubber (a1-2), the component (A) is a rubber part derived from the diene rubber (a1-1). 10 to 60% by mass of the first graft polymer having the resin portion (a2) bonded thereto, and the second graft polymer 2 to 25 having the resin portion (a2) bonded to the rubber portion derived from the silicone rubber (a1-2). It is preferable to contain 25% to 85% by mass of the resin part (a2) which is not bonded to the rubber part (a1), 14 to 55% by mass of the first graft polymer, and 4% of the second graft polymer. To 20% by mass and 30 to 80% by mass of the resin part (a2) not bonded to the rubber part (a1), more preferably 19 to 50% by mass of the first graft polymer and the second graft. It is particularly preferable to contain 6 to 20% by mass of the polymer and 35 to 75% by mass of the resin part (a2) not bonded to the rubber part (a1) (however, the total of these three parts is 100% by mass). ). When the rubber portion (a1) contains the ethylene/α-olefin rubber (a1-3) and optionally the diene rubber (a1-1), the component (A) is added to the diene rubber (a1-1). 0-60% by mass of the first graft polymer in which the resin portion (a2) is bonded to the rubber portion derived therefrom, and the resin portion (a2) is bonded to the rubber portion derived from the ethylene/α-olefin rubber (a1-3). 5 to 70% by mass of the third graft polymer and 10 to 80% by mass of the resin part (a2) not bonded to the rubber part (a1), and the first graft polymer 5 to 55 It is more preferable that the first graft polymer contains 20% by mass of the second graft polymer, 10-65% by mass of the second graft polymer, and 20-75% by mass of the resin part (a2) not bonded to the rubber part (a1). It is particularly preferable to contain 10 to 50% by mass, the second graft polymer 15 to 60% by mass, and the resin part (a2) 30 to 70% by mass not bonded to the rubber part (a1) (however, these The total of the three is 100% by mass). Here, the first, second and third graft polymers correspond to the acetone insoluble matter, and the resin portion (a2) not bonded to the rubber portion (a1) corresponds to the acetone soluble matter.

The graft ratio is, for example, the type and amount of the chain transfer agent used in the graft polymerization when 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 intrinsic viscosity (in methyl ethyl ketone, 30° C.) 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. 0.07 to 0.8 dl/g, more preferably 0.1 to 0.7 dl/g. When the intrinsic viscosity is within the above range, impact resistance and moldability of the resin composition will be better.

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

The intrinsic viscosity [η] is, for example, the type and amount of a chain transfer agent, a polymerization initiator, an emulsifier, a solvent, etc. used in the graft polymerization of the rubber-reinforced aromatic vinyl-based resin (A), a monomer used in the polymerization. It can be adjusted by appropriately selecting the addition method and addition time of the components, 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 intrinsic viscosity [η] different from the intrinsic viscosity [η] of the acetone-soluble component to prepare the mixture. You can

In the thermoplastic resin composition (X) of the present invention, the content of the component (A) is 30 to 93 mass% when the total amount of the components (A) and (B) is 100 mass %. It is more preferably 40 to 92% by mass and even more preferably 45 to 90% by mass. When the content of the component (A) is within the above range, the feel of the molded product is improved satisfactorily.

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 article having rubber elasticity by heating and melting and molding. The thermoplastic elastomer (B) can be melted and molded by heating, but the diene rubber (a1-1), the silicone rubber (a1-2) and the ethylene/α-olefin rubber (a1) used in the component (A) are used. -3) is different in that it cannot be molded by being melted by heating. 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 elastomers such as styrene elastomers and polybutadiene elastomers, olefin elastomers, urethane elastomers, polyvinyl chloride elastomers, ester elastomers, fluororesin elastomers, and ion crosslinks. An elastomer (ionomer) etc. are mentioned. These thermoplastic elastomers can be used alone or in combination of two or more kinds. Among them, from the viewpoint of improving the feel of a molded article, when the rubber part (a1) of the component (A) contains a diene rubber (a1-1) and a silicone rubber (a1-2), a styrene elastomer And a polybutadiene-based elastomer is preferable, and when the rubber portion (a1) of the component (A) contains an ethylene/α-olefin-based rubber (a1-3), a urethane-based elastomer is preferable.

Specific examples of the styrene-based elastomer include a block copolymer containing at least one polymer block A of an aromatic vinyl compound and one polymer block B of a conjugated diene compound and a hydrogenated product thereof. The polymer block A and the polymer block B may be linearly bonded or may be radially bonded. Further, the polymer block B may be a random copolymer containing a small amount of an aromatic vinyl compound as a constitutional unit, or a so-called taper type in which the content of the constitutional unit derived from the aromatic vinyl compound is gradually increased. 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 residue of a coupling agent, and n is an integer of 1 or more.

As the aromatic vinyl compound serving as the constitutional unit of the polymer block A of the styrene elastomer, all the aromatic vinyl compounds listed as the vinyl monomer of the above component (A) can be used, but preferably styrene. Is used. These aromatic vinyl compounds can be used alone or in combination of two or more. Further, as the conjugated diene which is a constituent unit of the polymer block B of the styrene elastomer, 1,3-butadiene, isoprene, 2-methyl-1,3-butadiene, 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 side chain conjugated hexadienes, and the like. 3-Butadiene, isoprene and 2-methyl-1,3-butadiene are preferred.

The weight average molecular weight of the styrene elastomer is preferably 10,000 to 800,000, more preferably 20.000 to 500,000. Further, 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 above block copolymers may be used alone or in combination of two or more having different structures or different content of constituent units derived from an aromatic vinyl compound.

The hydrogenated product 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 No. 63-285774. There is a method shown in No. 63-127400.

When the polymer block B is a conjugated diene polymer, which is a polymer block of 1,3-butadiene, when non-selectively hydrogenated, ethylene is added from the portion polymerized by 1,4-vinyl bond, Butylene is produced from the portion polymerized by the 2-vinyl bond, and styrene-ethylene-butylene-styrene copolymer (SEBS) is produced as a hydrogenated product, and when the 1,2-vinyl bond is selectively hydrogenated. , Styrene-butadiene-butylene-styrene copolymer (SBBS) and the like are produced as hydrogenated products. SEBS may be a commercially available product, and specific examples thereof include Dynaron series (trade name, manufactured by JSR Corporation), Lavalon series (trade name, manufactured by Mitsubishi Chemical Corporation), Tuftec series (trade name, manufactured by Asahi Kasei Corporation), Examples thereof include TPE-SB series (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

The polybutadiene 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 in toluene at 30° C.) is 0.5 dl/g or more, preferably 0.6 dl/g or more. In addition, a combination of 1,2-polybutadiene having different 1,2-vinyl bond amounts, crystallinity, and intrinsic viscosity [η] may be used.

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.

Specific preferred examples of the styrene elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-butylene-styrene copolymer (SBBS). ), a styrene-isoprene-styrene copolymer (SIS), and the like.

As the urethane elastomer,
Generally, a block copolymer having a repeating unit of a hard segment block composed of a diisocyanate and a chain extender and a soft segment block composed of a polyol and a diisocyanate can be mentioned.

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

Examples of the above-mentioned polyester polyol include a polyester polyol obtained by a condensation reaction of a dicarboxylic acid or its ester compound or acid anhydride with a diol; a polylactone diol obtained by ring-opening polymerization of a lactone monomer such as ε-caprolactone. .. And as the above-mentioned dicarboxylic acid, 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 Alicyclic dicarboxylic acids such as hexahydrophthalic acid and hexahydroisophthalic acid 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, neopentyl glycol, 1,3-octanediol, 1,9-nonanediol Etc. are used.

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

Further, as the polyester ether polyol, a condensation reaction product of the above aliphatic dicarboxylic acid, aromatic dicarboxylic acid, alicyclic dicarboxylic acid, or ester or acid anhydride thereof and 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, the polyether polyol is preferable from the viewpoint of hydrolysis resistance.

As the isocyanate, tolylene diosocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylene diisocyanate (XDI), hydrogenated XDI, triisocyanate, tetramethyl xylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, 1,8-diisocyanate methyl octane, lysine ester triisocyanate, 1, 3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate and the like can be mentioned. 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, and 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 the like, and aromatic glycols such as 1,4-dimethylolbenzene, bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct.

The polyurethane elastomer used in the present invention preferably has a hardness (Shore A hardness) of 70 to 99. Such polyurethane elastomers are manufactured by DIC Bayer Polymer Ltd. as an ester (adipate) type "T-1000 series" "T-1180", "T-1185"; as an ester (lactone) type "T-2000 series". "T-2180", "T-2185"; available as ether series as "T-8180", "T-8185" of "T-8000 series", "TP-6580A" of "TP-6000 series" and the like. ..

In the thermoplastic resin composition (X) of the present invention, the content of the component (B) is 7 to 70 mass% when the total amount of the components (A) and (B) is 100 mass %. It is more preferably from 8 to 60% by mass, even more preferably from 10 to 55% by mass. When the content of the component (B) is within the above range, the tactile sensation of the skin layer (I) is favorably improved. If it is less than 7% by mass, a soft touch feeling cannot be obtained. When the content of the component (B) exceeds 70% by mass, the smoothness of the skin layer (I) is lost, that is, a sticky feeling appears. When the rubber portion (a1) of the component (A) contains a diene rubber (a1-1) and a silicone rubber (a1-2) and the component (B) is a styrene elastomer and a polybutadiene elastomer, the component (B). The content of is preferably 7 to 45% by mass, more preferably 8 to 40% by mass, and even more preferably 10 to 30% by mass. When the rubber portion (a1) of the component (A) contains an ethylene/α-olefin rubber (a1-3) and optionally a diene rubber (a1-1), and the component (B) is a urethane elastomer, a component The content of (B) is preferably 25 to 70% by mass, more preferably 28 to 60% by mass, and even more preferably 30 to 55% by mass.

3. Other compounding agents The thermoplastic resin composition (X) according to the present invention preferably contains a silicone oil in order to make the effect of reducing the sticky feeling on the surface of the molded article more remarkable.

The silicone oil is not particularly limited as long as it has a polyorganosiloxane structure. Specific examples of silicone oils include unmodified silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, as well as modified silicone oils having various organic groups introduced into the polyorganosiloxane structure. However, unmodified silicone oil is preferable from the viewpoint of the effect. These silicone oils can be used alone or in combination of two or more kinds.

The kinematic viscosity of the silicone oil at 23° C. is preferably 60 to 500.000 cSt, more preferably 80 to 350,000 cSt. The kinematic viscosity of the silicone oil is measured by an Ubbelohde viscometer according to ASTM D445-46T (JIS8803 is also acceptable).

The content of the silicone oil is preferably 0.2 with respect to 100 parts by mass of the thermoplastic resin composition (X) of the present invention, that is, 100 parts by mass in total of the above component (A) and the above component (B). To 6 parts by mass, and more preferably 0.5 to 5 parts by mass. When the blending amount of the silicone oil is within the above range, the effect of reducing the sticky feeling on the surface of the skin layer (I) can be sufficiently obtained.

In the thermoplastic resin composition (X) according to the present invention, in addition to the above-mentioned component (A), component (B) and silicone oil, if necessary, a slidability-imparting agent, antioxidant, processing stability Agents, ultraviolet absorbers, light stabilizers, antistatic agents, crystallization nucleating agents, lubricants, plasticizers, metal deactivators, color pigments, various inorganic fillers, glass fibers, reinforcing agents, flame retardants, release agents, Various additives such as a foaming agent can be added within a range that does not impair the object of the present invention.

4. Method for producing thermoplastic resin composition (X) of the present invention The thermoplastic resin composition (X) of the present invention comprises a uniaxial extruder after mixing the components at a predetermined mixing ratio in a tumbler mixer, a Henschel mixer, or the like. It can be produced by melt-kneading under suitable conditions using a kneader such as a twin-screw extruder, a Banbury mixer, a kneader, a roll or a feeder-ruder. A preferred kneader is a twin-screw extruder. Further, when the respective components are kneaded, the components may be kneaded at once, or may be kneaded in multiple stages in a divided manner. In addition, after kneading with a Banbury mixer, a kneader, or the like, pelletization can be performed with an extruder. The melt-kneading temperature is usually 180 to 240°C, preferably 190 to 230°C.

5. Method for Producing Laminate of the Present Invention The laminate of the present invention comprises a base material layer (II) and a skin layer (I) made of the thermoplastic resin composition (X) on at least a part of the base material layer (II). ). The skin layer (I) may be formed on part or all of at least one surface of the base material layer (II). The material (Y) forming the base material layer (II) preferably exhibits easy adhesion with the thermoplastic resin composition (X). The skin layer (I) and the base material layer (II) are preferably laminated with each other, and it is more preferable that both layers are laminated so as to form an interface. Since the thermoplastic resin composition (X) contains the thermoplastic elastomer (B), a pretreatment for molding can be omitted at the time of molding the laminate of the present invention, and the skin layer can be satisfactorily satisfactorily heated only at the time of molding. (I) and the base material layer (II) form an interface having high peel strength.

The material (Y) forming the base material layer (II) exhibits easy adhesion to the thermoplastic resin composition (X) when the base material layer (II) made of the material (Y) is a thermoplastic resin composition. It means that it can be bonded to (X) with a sufficient adhesive force.

The material (Y) is preferably a plastic material, more preferably a thermoplastic resin, from the viewpoint of adhesiveness between the base material layer (II) and the skin layer (I) and moldability. Preferred thermoplastic resins include acrylonitrile-butadiene-styrene copolymer (ABS) resin, polycarbonate (PC) resin, polyamide (PA) resin, polyester resin, polyvinyl chloride (PVC) resin, PC/ABS alloy, PA/ At least one resin selected from ABS alloy, polybutylene terephthalate (PBT)/ABS alloy and PP/ABS alloy can be mentioned, more preferably ABS resin, PC resin, PC/ABS alloy, PA/ABS alloy, PBT/ABS. At least one resin selected from alloys and PP/ABS alloys.

The thermoplastic resin composition (X) of the present invention does not require a pre-molding treatment at the time of molding such as injection molding, and can form an interface having a high peel strength with the resin satisfactorily only by heat during molding. it can.

The method for producing the laminate of the present invention includes T-die laminate molding method, co-extrusion molding method, blow molding method, insert injection molding method, two-color injection molding method, core back injection molding method, sandwich injection molding method, injection press molding. Various molding methods such as a method can be used.

Among the above molding methods, the insert injection molding method means that after the base material layer (II) shaped by injection molding or the like is inserted into the mold, the base material layer (II) and the mold In this method, the thermoplastic resin composition (X) is injection-molded in the voids so that the skin layer (I) is laminated on the base material layer (II). In addition, the two-color injection molding method uses two or more injection molding machines to perform injection molding of the base material layer (II), and then the mold is rotated or moved so that the cavity of the mold is formed. After the replacement, a gap is formed between the base material layer (II) and the mold, and the thermoplastic resin composition (X) is injection-molded therein to form the base material layer (II) and the skin layer (I). It is a method of molding so as to be laminated. Further, the core-back injection molding method uses one injection molding machine and one mold to injection-mold the base material layer (II), and then expands the cavity volume of the mold to produce the base material. The thermoplastic resin composition (X) is injection-molded in the space between the layer (II) and the mold to form the base material layer (II) and the skin layer (I) so that they are laminated. is there. In the laminating mode, the base material layer (II) and the skin layer (I) are laminated so as to form an interface.

The base material layer (II) according to the present invention may be molded by using a normal injection molding method or may be molded by gas injection molding.

The two-color extrusion molding method is a resin composition that forms a base material layer (II) and a skin layer (I) in each of the channels in the heating cylinders of two different extruders. The present invention, in which the resin forming the base material layer (II) and the skin layer (I) are formed by supplying the material (X) and rotating the screw in each flow path separately in a non-interlocked manner. The thermoplastic resin composition (X) of (1) is plasticized and melted in each channel, and continuously extruded from the tip opening of each channel while being extruded from a die hole to form a base material layer (II). And the skin layer (I) are laminated.

FIG. 1 is a sectional view of a laminated body according to an embodiment of the present invention. This laminated body 1 comprises a skin layer (I) 2 formed of a thermoplastic resin composition (X), and a base material layer (I) formed of a resin having an adhesive property with the thermoplastic resin composition (X). II) 3 is laminated.

The surface of the skin layer (I) of the laminate of the present invention has a cushioning property or a soft touch feeling, is smooth with less sticky feeling on the surface, has a good tactile feeling such as a touch feeling, and is in contact with the human body, particularly the skin or the human body. It is suitable as various articles such as articles inevitable and articles that require manual operation. The surface of the skin layer (I) of the laminate of the present invention has a cushioning property or a soft touch feeling. The hardness of the surface can be quantified by an LC value (compression hardness) measured by a handy compression tester KES-G5 (trade name: manufactured by Kato Tech Co., Ltd.). The surface of the skin layer (I) of the laminate of the present invention has a low stickiness or smoothness, and the surface of the skin layer (I) of the above laminate can be measured by the friction tester KES-SE (trade name: Kato). It can be digitized by the MIU value (average friction coefficient) measured by using Tech Co., Ltd.). The skin layer (I) of the laminate of the present invention has a higher cushioning property or soft touch feeling than conventional molded products, has less sticky feeling on the surface, is smooth, and is excellent in tactile sensation. The value is preferably 0.9 or less, more preferably 0.2 to 0.8, further preferably 0.3 to 0.7, and the MIU value measured as described above is 0.4 or less. It is preferably 0.05 to 0.35, more preferably 0.1 to 0.3. The elastic modulus of the skin layer (I) of the laminate of the present invention measured according to ISO 178 is preferably 500 MPa or more, more preferably 600 to 1500 MPa. Further, Rockwell hardness (hardness scale, R-scale) at room temperature, measured based on ISO 2039 of the skin layer (I) of the laminate of the present invention, is preferably 40 to 85, and 50 to 80. Is more preferable.

Since the laminate of the present invention has the above-mentioned excellent touch, it is used for automobile interior parts such as door trims, glove boxes, handles, building materials such as door knobs, mobile phones, portable music players, smartphones, tablet computers, and laptop computers. It can be used as a casing, a case, a cover, etc. of portable electric products such as

Hereinafter, the present invention will be described more specifically 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. Ingredient [A]
As raw materials for the rubber-reinforced aromatic vinyl-based resin, the diene-based rubber-reinforced aromatic vinyl-based resins (raw materials A1-1 to A1-2) obtained in the following Synthesis Examples 1 and 2 and the synthesis example 3 below were obtained. The obtained silicone rubber-reinforced aromatic vinyl-based resin (raw material A2), the ethylene-propylene (EP) rubber-reinforced aromatic vinyl-based resin (raw-material A3) obtained in Synthesis Example 4 below, and Synthesis Example 5 below. The obtained styrene-acrylonitrile copolymer (raw material A4) was used.

1-1. Synthesis example 1 (synthesis of raw material A1-1 (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 part of potassium rosinate, 0.2 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle size of 300 nm (gel content 80% ) 100 parts of latex containing 40 parts, 13 parts of styrene and 7 parts of acrylonitrile were housed and heated with stirring. When the internal temperature reached 40°C, a solution prepared by dissolving 0.2 part of sodium pyrophosphate, 0.01 part of ferrous sulfate heptahydrate and 0.3 part 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, 30 parts of styrene, 10 parts of acrylonitrile, 0.17 parts of tert-dodecyl mercaptan and 0.1 part of cumene hydroperoxide are used for 3 hours. And added continuously. Then, the polymerization was further continued for 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 coagulate the resin component, followed by washing 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 rubber-reinforced aromatic vinyl resin. The graft ratio of the graft resin contained in this resin was 50%, and the content of ungrafted (co)polymer (hereinafter referred to as "acetone-soluble component") was 40%. The viscosity [η] (in methyl ethyl ketone, 30°C) was 0.40 dl/g.

1-2. Synthesis Example 2 (Synthesis of Raw Material A1-2 (Diene Rubber Reinforced Aromatic Vinyl Resin))
In a polymerization vessel equipped with a stirrer, 280 parts of water and 60 parts of polybutadiene latex having a weight average particle size of 0.26 μm and a gel fraction of 90% (as solid content), sodium formaldehyde sulfoxylate 0.3 parts, ferrous sulfate 0. After charging 0025 parts and 0.01 part of disodium ethylenediaminetetraacetate, the mixture was deoxygenated, heated to 60° C. with stirring in a nitrogen stream, and then 10 parts of acrylonitrile, 30 parts of styrene, 0.2 part of t-dodecyl mercaptan, A monomer mixture consisting of 0.3 part of cumene hydroperoxide was continuously added dropwise at 60° C. over 5 hours. After the dropping was completed, the polymerization temperature was raised to 65° C. and stirring was continued for 1 hour, and then the polymerization was terminated to obtain a latex of a graft copolymer. The polymerization conversion rate was 98%. Then, 0.2 part of 2,2'-methylene-bis(4-ethylene-6-t-butylphenol) was added to the obtained latex, calcium chloride was added to coagulate, and washing, filtration and drying steps were carried out. After that, a powdery diene rubber-reinforced aromatic vinyl resin was obtained. The graft ratio of the obtained resin is 40%, the content of ungrafted (co)polymer (hereinafter referred to as "acetone-soluble component") is 16%, and the intrinsic viscosity [η] of the acetone-soluble component is Was 0.38 dl/g.

1-3. Synthesis Example 3 (Synthesis of Raw Material A2 (Silicone Rubber Reinforced Aromatic Vinyl Resin))
A mixture of 1.5 parts of p-vinylphenylmethyldimethoxysilane and 98.5 parts of octamethylcyclotetrasiloxane was added to 300 parts of an aqueous solution prepared by dissolving 2.0 parts of dodecylbenzenesulfonic acid in distilled water, and a homomixer was used. It was emulsified and dispersed by stirring for 3 minutes. The emulsified dispersion was transferred to a separable flask equipped with a condenser, a nitrogen gas inlet and a stirrer, heated under stirring at 90° C. for 6 hours to cause a condensation reaction, and cooled at 5° C. for 24 hours to complete the reaction. It was As a result, a latex containing a modified polyorganosiloxane rubber with a condensation rate of 93% was obtained. Then, an aqueous sodium carbonate solution was added to this latex to neutralize it to pH 7. The volume average particle size of the modified polyorganosiloxane rubber was 280 nm.
Next, in a glass flask equipped with a stirrer, 40 parts of the modified polyorganosiloxane rubber, 100 parts of ion-exchanged water, 1.5 parts of sodium dodecylbenzenesulfonate, 0.1 part of tert-dodecylmercaptan, 15 parts of styrene and Acrylonitrile (5 parts) was contained, and the temperature was raised to 45°C with stirring. Thereafter, an activator aqueous solution consisting of 0.1 part of sodium ethylenediamine tetraacetate, 0.003 part of ferrous sulfate, 0.2 part of formaldehyde sodium sulfoxylate dihydrate and 15 parts of deionized water, and diisopropylbenzene. Hydroperoxide (0.1 part) was added to initiate polymerization. Then, 1 hour later, an incremental polymerization consisting of 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.1 part of tert-dodecyl mercaptan, 0.2 part of diisopropyl hydroperoxide, 30 parts of styrene and 10 parts of acrylonitrile. The ingredients were added continuously over 3 hours to continue the polymerization. After the addition was completed, stirring was continued for 1 hour.
Thereafter, 0.2 part of 2,2-methylene-bis(4-ethylene-6-tert-butylphenol) was added to terminate the polymerization, and a latex containing a silicone-based rubber-reinforced resin was obtained. Then, 2 parts of calcium chloride was added to the latex to coagulate the resin component, followed by washing with water and drying (75° C., 24 hours) to recover a white powder (silicone rubber-reinforced aromatic vinyl resin). The graft ratio was 84%, the content of ungrafted (co)polymer (hereinafter referred to as "acetone-soluble component") was 26.4%, and the intrinsic viscosity [η] of acetone-soluble component (in methyl ethyl ketone) , 30° C.) was 0.47 dl/g.

1-4. Synthesis example 4 (synthesis of raw material A3 (ethylene/propylene (EP) rubber-reinforced aromatic vinyl-based resin))
An ethylene/propylene copolymer rubber (ethylene/propylene = 78/22 (%), Tm: 40°C, glass transition temperature: was added to a stainless steel autoclave equipped with a ribbon-type stirrer blade, a continuous additive addition device, a thermometer, and the like. -50°C, Mooney viscosity (ML1+4,100°C): 20) 30 parts, styrene 52.5 parts, acrylonitrile 17.5 parts, toluene 120 parts were charged, the internal temperature was raised to 70°C, and the contents of the autoclave were heated. Was stirred for 1 hour to form a uniform solution. After that, 0.5 part of tert-butyl peroxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 100° C., while maintaining this temperature, the stirring reaction speed was set to 100 rpm to carry out the polymerization reaction. went. Four hours after the initiation of the polymerization reaction, the internal temperature was raised to 120° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization reaction. Then, the internal temperature was cooled to 100° C., and 0.2 part of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenol)-propionate was added. Then, the reaction solution was extracted from the autoclave, and unreacted materials and the solvent were distilled off by steam distillation. Then, a 40 mmφ vented extruder (cylinder temperature: 220° C., vacuum degree: 760 mmHg) was used to substantially degas the volatile components, and pelletized to obtain an ethylene/α-olefin rubber-reinforced aromatic vinyl resin. The graft ratio in the graft resin contained in this resin was 55%, and the content of ungrafted (co)polymer (hereinafter referred to as "acetone-soluble component") was 53.5%. The intrinsic viscosity [η] (in methyl ethyl ketone, 30° C.) was 0.3 dl/g.

1-5. Synthesis example 5 (synthesis of raw material A4 (styrene-acrylonitrile copolymer))
A synthesis apparatus in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging nitrogen gas into each reactor, a mixture of 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene, and 0.15 part of tert-dodecyl mercaptan, which is a molecular weight modifier, were added to the first reactor. Was dissolved in 5 parts of toluene, and a solution of 0.1 part of 1,1′-azobis(cyclohexane-1-carbonitrile), which is a polymerization initiator, dissolved in 5 parts of toluene was continuously supplied. 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 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 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 volatilized to recover the styrene/acrylonitrile copolymer. The styrene-acrylonitrile copolymer had an intrinsic viscosity [η] (in methyl ethyl ketone, 30°C) of 0.51 dl/g.

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

2-1. Raw material B-1 (SBS)
A styrene-butadiene thermoplastic elastomer "TR2000" (trade name) manufactured by JSR Corporation was used. The styrene/butadiene ratio was 40/60. MFR (200 degreeC, 49.0N) was 13 g/10min. MFR (190°C, 21.2N) was 3g/10min.

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

2-3. Raw material B-3 (SIS)
A styrene/isoprene thermoplastic elastomer "SIS5250" (trade name, styrene/isoprene block copolymer) manufactured by JSR Corporation was used. The styrene/isoprene ratio was 20/80. MFR (200°C, 49.0N) was 12g/10min. MFR (190°C, 21.2N) was 3g/10min.

2-4. Raw material B-4 (TPU)
Urethane elastomer "T1190N" (trade name) manufactured by DIC Bayer Polymer was used.

3. Ingredient [C]
3-1. Raw material C-1 (silicone oil)
A dimethyl silicone oil "KF-96SS" (trade name) manufactured by Shin-Etsu Silicone Co., Ltd. was used. The kinematic viscosity at 25° C. was 100 cSt.

4. Ingredient [D]
4-1. Raw material D-1 (glass fiber)
The glass fiber "RES03-TP89Z" (trade name) manufactured by Nippon Sheet Glass Co., Ltd. was used.

Examples 1-11 and Comparative Examples 1-6
1. Preparation of thermoplastic resin composition (X) The raw materials [A], [B], [C] and [D] shown in the following table were mixed in the mixing ratio shown in the same table. Then, using a twin-screw extruder (model name “TEX44, Japan Steel Works”), the mixture was melt-kneaded at a barrel temperature of 220° C. to form pellets. The thermoplastic resin composition (X) thus obtained was used for the following measurements and evaluations. The results are shown in the table below.

2. Preparation of Laminated Body The above thermoplastic resin composition (X) was molded to prepare a 120 mm×80 mm×1 mm test piece for the skin layer (I). Molding was performed using an injection molding machine IS100GN (trade name: manufactured by Toshiba Machine) under the conditions of a resin temperature of 190°C to 220°C, a mold temperature of 30°C, an injection pressure of 110 MPa, and an injection speed of 40 mm/s. As the molding die, a leather embossing die (texture No; TH-894) having irregularities (concave depth 100 μm) on the inner surface was used.
The test piece for the skin layer (I) obtained above was inserted into an injection molding die, and the ABS resin "Techno ABS130" for the base material layer (II) (trade name: Techno Polymer Co., Ltd.) Was subjected to insert injection molding to perform two-color molding, and the skin layer (I) and the base material layer (II) were fused together to obtain a laminate in which both layers were laminated. The injection molding of the ABS resin was performed under the conditions of a resin temperature of 220° C., a mold temperature of 50° C., an injection pressure of 100 MPa, and an injection speed of 40 mm/s.

3. Hardness measurement Based on ISO 2039, Rockwell hardness at room temperature (hardness scale is R-scale) was measured. The hardness of the skin layer (I) was measured using the laminate prepared in the above 2 as a test piece.

4. Evaluation of appearance of molded product The surface of the skin layer (I) of the laminate prepared in 2 above was visually observed and evaluated according to the following criteria.
◯: None of (i) flow mark, (ii) peeling, and (iii) whitening occurred.
Δ: Any of (i) flow mark, (ii) peeling, and (iii) whitening occurred on a part of the molded product.
X: Any of (i) flow mark, (ii) peeling, and (iii) whitening occurred on the entire surface of the molded product.

5. Evaluation of Molding Workability The following two criteria evaluated the workability at the time of two-color molding of the skin layer (I) of the above-mentioned laminated body 2.
Good: The molded product or sprue runner did not adhere to the mold, and the adhesion between the base material layer (II) and the skin layer (I) and the mold releasability were good.
X: The molded product or sprue runner adheres to the mold, and the adhesion between the base material layer (II) and the skin layer (I) or the mold releasability is poor.

6. Touch (stickiness)
The feel of the surface of the skin layer (I) of the laminate prepared in the above 2 when traced with a finger at room temperature of 23° C. was evaluated according to the following criteria. When the stickiness becomes remarkable, the smoothness of the surface of the skin layer (I) of the laminate decreases, and the touch becomes poor.
○: No stickiness is felt.
Δ: A little sticky is felt.
X: Remarkable stickiness is felt.

7. Touch (soft touch)
The feel of the surface of the skin layer (I) of the laminate prepared in the above 2 when traced with a finger at room temperature of 23° C. was evaluated according to the following criteria.
○: Feels soft △: Feels slightly soft ×: Feels hard

8. KES texture measurement
8-1. Measurement of MIU value (average friction coefficient) (smoothness, stickiness)
The MIU value of the surface of the skin layer (I) of the laminate prepared in the above 2 was measured using a friction tester KES-SE (trade name: manufactured by Kato Tech Co., Ltd.).
8-2. Measurement of LC value (compression hardness) (cushioning property, soft touch feeling)
The LC value of the surface of the skin layer (I) of the laminate prepared in the above 2 was measured using a handy compression tester KES-G5 (trade name: manufactured by Kato Tech Co., Ltd.).
8-3. Measurement of SMD Value (Surface Roughness: Unit: μm) The SMD value of the surface of the skin layer (I) of the laminate prepared in 2 above was measured using a friction tester KES-SE (trade name: manufactured by Kato Tech Co., Ltd.). It was measured.

The following can be seen from the above table.
Examples 1 to 11 in which the skin layer (I) is formed using the thermoplastic resin composition (X) of the present invention are not only excellent in molding processability such as adhesion between layers and the appearance of the molded article, but also a laminate The surface of the skin layer (I) had a high cushioning property and a soft touch feeling, and there was little stickiness, and it was smooth and excellent in touch. Moreover, when the cover (thickness 2 mm) for the smartphone shown in FIG. 2 was molded using the thermoplastic resin compositions (X) of Examples 1 to 11, the cushioning property and the soft touch feeling of the cover surface were good. Met.

On the other hand, the amount of the part composed of the silicone rubber (a1-2) or the ethylene/α-olefin rubber (a1-3) in the rubber part (a1) of the component (A) in the skin layer (I) is small. The laminates of Comparative Examples 1 and 6 had a sticky feeling on the surface of the skin layer (I) of the laminate and were inferior in touch. The laminates of Comparative Examples 2 and 4 in which the content of the component (B) in the skin layer (I) was high, the moldability was poor, the surface of the skin layer (I) of the laminate had a sticky feeling, and the touch was poor. In the laminate of Comparative Example 2, flow marks were further generated on the surface of the skin layer (I), and the appearance was inferior. The laminates of Comparative Examples 3 and 5 in which the content of the component (B) in the skin layer (I) was small, the soft touch feeling of the surface of the skin layer (I) of the laminate was poor and the touch was poor.

The laminate of the present invention is excellent in mechanical strength and appearance of the molded article of the skin layer (I), and has a good tactile sensation such as a touch feeling of the surface of the skin layer (I), so that it often comes into contact with the human body. Suitable for use as a body.

Claims (3)

A laminate comprising a skin layer (I) on at least a part of the base material layer (II),
The skin layer (I) is a rubber-reinforced aromatic vinyl resin (A) containing a rubber portion (a1) and a resin portion (a2) containing a constitutional unit derived from an aromatic vinyl compound, and a thermoplastic resin. It is composed of a thermoplastic resin composition (X) containing an elastomer (B), and the rubber portion (a1) of the component (A) is 40 to 90 mass% of a diene rubber (a1-1) and a silicone rubber (a1-). 2) 10 to 60% by mass (the total amount of the above component (a1-1) and the above component (a1-2) is 100% by mass), and the above component (B) is the weight of the aromatic vinyl compound. A styrene elastomer composed of a block copolymer containing one or more polymer blocks of a conjugated diene compound and /or a hydrogenated product thereof , wherein the thermoplastic resin composition (X) is The component (B) is contained in an amount of 7 to 45% by mass based on 100% by mass of the total of the components (A) and (B), the MIU value of the skin layer (I) is 0.4 or less, and the LC value is The laminated body which is 0.9 or less. A laminate comprising a skin layer (I) on at least a part of the base material layer (II),
The skin layer (I) is a rubber-reinforced aromatic vinyl resin (A) containing a rubber portion (a1) and a resin portion (a2) containing a constitutional unit derived from an aromatic vinyl compound, and a thermoplastic resin. It is composed of a thermoplastic resin composition (X) containing an elastomer (B), and the rubber portion (a1) of the component (A) comprises 0 to 90% by mass of a diene rubber (a1-1) and ethylene/α-olefin. 10 to 100% by mass of the system rubber (a1-3) (the total amount of the component (a1-1) and the component (a1-3) is 100% by mass), and the component (B) is urethane. The thermoplastic resin composition (X) contains the component (B) in an amount of 25 to 70% by mass based on 100% by mass of the components (A) and (B), and the skin layer. A laminate having an MIU value of (I) of 0.4 or less and an LC value of 0.9 or less. The layered product according to claim 1 or 2 which is a part for human contact.

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