JP2007001086A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate including a layer excellent in scratch resistance, abrasion resistance, flexibility, etc. <P>SOLUTION: In the laminate, a surface layer (a) is laminated on a polymer composition layer (b). The layer (a) is mainly made of a polymer. The layer (b) is made of a thermoplastic polymer composition containing (I) 100 pts.mass of at least one block copolymer (I) selected from an α-methyl styrene block copolymer having a polymer block (A) mainly comprising an α-methyl styrene unit and a polymer block B mainly comprising a conjugated diene unit and its hydrogenation product, (II) 200 pts.mass or below of a softening agent for a non-aromatic rubber, and (III) 10-200 pts.mass of at least one thermoplastic resin selected from an acrylic resin, polystyrene resin, polycarbonate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyester resin, and polyamide resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminate in which a surface layer is provided on a thermoplastic polymer composition layer.

  For the purpose of imparting further functions to materials such as resin as a base material, a plurality of materials are laminated in multiple layers, and these laminates are automobile parts, home appliance parts, building materials, furniture, toys, It is used in a wide range of fields such as sports equipment and daily necessities. Examples of the material used for these laminates include soft vinyl chloride resins that are inexpensive and have good surface properties such as scratch resistance and abrasion resistance, and flexibility. However, the soft vinyl chloride resin has a plasticizer that exudes to the surface, the plasticizer is suspected of being an endocrine disrupting chemical, and is highly corrosive gas such as hydrogen chloride and extremely toxic during incineration. There are problems such as easy generation of dioxins, and there are problems in terms of safety and environmental pollution. Therefore, in recent years, polyolefin-based thermoplastic elastomers and styrene-based thermoplastic elastomers that do not contain halogen or plasticizer and are excellent in flexibility have been used as alternative materials for soft vinyl chloride resins. However, these thermoplastic elastomers are inferior in scratch resistance and abrasion resistance as compared with soft vinyl chloride.

  Therefore, for the purpose of improving scratch resistance and wear resistance, the surface of the thermoplastic elastomer is coated with a urethane resin paint or an acrylic resin paint. However, even if a low-polarity polyolefin-based thermoplastic elastomer or styrene-based thermoplastic elastomer is coated with a highly polar urethane-based resin paint or acrylic-based resin paint, sufficient adhesive strength cannot be obtained, and the coating layer may peel off. Prone to occur. Therefore, conventionally, a method has been proposed in which a surface treatment is performed by applying a urethane resin paint or an acrylic resin paint to the surface of the thermoplastic elastomer as described above, followed by priming with a primer such as chlorinated polyolefin or acid-modified polyolefin. (Patent Documents 1 and 2).

  On the other hand, examples of the thermoplastic elastomer having excellent scratch resistance and abrasion resistance include polyurethane-based thermoplastic elastomers, which comprise a polymer composition layer comprising a polyurethane-based thermoplastic elastomer as a component and a urethane-based resin coating surface layer. A method for producing a laminate is disclosed (for example, Patent Document 3).

JP-A-63-272547 JP 2004-136602 A JP 2003-136647 A

  However, the laminates described in Patent Documents 1 and 2 require a step of applying a primer, which makes the manufacturing process complicated. In addition, the laminate described in Patent Document 3 requires a primer to be adhered to the polyurethane thermoplastic elastomer using a primer when an olefin-based material is used for the base material layer of the laminate, and the manufacturing process is complicated. It is. In addition, due to the lack of hydrolysis resistance and weather resistance of polyurethane-based thermoplastic elastomers, there are also problems such as performance deterioration such as discoloration and poor flexibility.

  Therefore, the object of the present invention is to solve such a conventional problem, and includes a layer having excellent scratch-resistant surname, wear-resisting surname, flexibility, and the like, and further requires a complicated process such as applying a primer. The object of the present invention is to provide a laminate that can be easily manufactured.

According to the present invention, the above object is
[1] A laminate in which the surface layer (a) / polymer composition layer (b) are laminated in this order;
The surface layer (a) is a layer mainly composed of a polymer; and
The polymer composition layer (b)
(I) At least one block selected from an α-methylstyrene block copolymer having a polymer block A mainly composed of α-methylstyrene units and a polymer block B mainly composed of conjugated diene units and a hydrogenated product thereof For 100 parts by mass of copolymer (I),
(II) 200 parts by mass or less of non-aromatic rubber softener (II),
(III) At least one heat selected from the group consisting of acrylic resins, polystyrene resins, polyphenylene ether resins, polycarbonate resins, polyvinyl chloride resins, polyvinyl acetate resins, polyester resins and polyamide resins. A laminate which is a layer made of a thermoplastic polymer composition containing 10 to 200 parts by mass of the plastic resin (III);
[2] The laminate of [1], wherein the surface layer (a) is a coating layer made of a polyurethane-based or acrylic polymer;
[3] The polymer block A in the block copolymer (I) is a polymer block mainly composed of α-methylstyrene units and having a number average molecular weight of 1,000 to 50,000, and the polymer block B is a polymer block b1 described below. b2 and the block copolymer (I) has the formula:
A-b1-b2
(Wherein A is polymer block A,
b1 is a polymer block having a number average molecular weight of 1,000 to 30,000, mainly consisting of conjugated diene units, wherein the 1,4-bond amount of the conjugated diene units is less than 30%;
(b2 represents a polymer block having a number average molecular weight of 10,000 to 400,000, which is mainly composed of conjugated diene units, and the 1,4-bond amount of the conjugated diene units is 30% or more)
A laminated body according to [1] or [2], which comprises a structure represented by:
[4] Further, a thermoplastic polymer foam layer (c) is laminated in the order of surface layer (a) / polymer composition layer (b) / thermoplastic polymer foam layer (c) [1] ] To any one of [3],
The thermoplastic polymer foam layer (c) comprises an olefin resin, an olefin thermoplastic elastomer, a polystyrene thermoplastic elastomer, a polyester thermoplastic elastomer, a polyamide thermoplastic elastomer, and a polyurethane thermoplastic elastomer. A laminate formed by using at least one selected from;
[5] Furthermore, the material layer (d) made of at least one selected from the group consisting of thermoplastic resin, metal, fabric, leather, glass and wood is a surface layer (a) / polymer composition layer (b). [1] to [1] to [layer] which are laminated in the following order: / material layer (d) or surface layer (a) / polymer composition layer (b) / thermoplastic polymer foam layer (c) / material layer (d) 4] any laminate;
Is achieved by providing

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which contains the layer excellent in scratch resistance, abrasion resistance, a softness | flexibility etc., and can be manufactured easily without requiring complicated processes, such as apply | coating a primer, is provided.

The present invention is described in detail below.
The laminate of the present invention is a laminate that is laminated in the order of surface layer (a) / polymer composition layer (b). Materials used for the surface layer (a) located on the surface side of the laminate of the present invention are polyester resin, polyurethane resin, acrylic resin, silicone resin, vinyl acetate resin, ethylene / vinyl acetate resin, chloride Mainly composed of polymers such as vinyl resins, phthalic resins, fluorine resins, melamine resins, phenol resins, alkyd resins, and synthetic rubber resins. Among these, the surface layer (a) is a coating layer formed from a polyurethane polymer, an acrylic polymer or a mixture thereof, and has hydrolysis resistance, discoloration resistance, abrasion resistance, and scratch resistance. It is preferable because of excellent properties such as toughness and good adhesion between the surface layer (a) and the polymer composition layer (b). As the polyurethane-based or acrylic-based coating agent for forming the surface layer (a), any conventionally known ones such as a one-component coating agent and a two-component coating agent can be used.

  Examples of polyurethane-based coating agents preferably used for forming the surface layer (a) include high and medium molecular weight polyols such as polyester polyols, polyether polyols, and polycarbonate polyols; 4,4′-diphenylmethane diisocyanate, toluene diisocyanate, p- Aromatic diisocyanates such as phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate and / or aliphatic or cycloaliphatic diisocyanates such as hydrogenated 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate; 1,4-butanediamine; Polyures using chain extenders such as hydrazine, aliphatic diamines such as hexamethylene diamine, and low molecular weight diols. Mention may be made of the emissions-based coating agent. Among them, a polyurethane coating agent using a polycarbonate polyol and / or a polyether polyol, an aliphatic diisocyanate and an aliphatic diamine chain extender is preferably used because of its excellent hydrolysis resistance and discoloration resistance. .

  Examples of the acrylic coating agent include a coating agent comprising a methyl methacrylate homopolymer or a copolymer obtained by copolymerizing methyl methacrylate as a main component and another copolymerizable monomer. Examples of other copolymerizable monomers include acrylic acid or a metal salt thereof; methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate, t-butyl acrylate, acrylic acid 2 -Acrylic esters such as ethylhexyl; methacrylic acid or metal salts thereof; ethyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacrylic acid Methacrylic acid esters such as cyclohexyl; Vinyl acetate; Aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; Maleic anhydride; Maleimides such as N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide Compounds etc. It is below. When these are copolymerized with methyl methacrylate, they may be used alone or in combination of two or more compounds.

  The block copolymer (I), which is a constituent component of the polymer composition layer (b) constituting the laminate of the present invention, comprises a polymer block A mainly composed of α-methylstyrene units and a polymer composed mainly of conjugated diene units. It is at least one block copolymer selected from an α-methylstyrene block copolymer having a combined block B and a hydrogenated product thereof.

  The polymer block A of the block copolymer (I) comprises 90% by mass or more of structural units derived from α-methylstyrene from the viewpoint of flexibility and mechanical properties of the obtained thermoplastic polymer composition. It is preferable that it is composed only of structural units derived from α-methylstyrene. The polymer block A is an unsaturated monomer other than α-methylstyrene, such as butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3, unless the object and effect of the present invention are disturbed. -Pentadiene, 1,3-hexadiene, isobutylene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, methacrylic acid One or more structural units derived from methyl, methyl vinyl ether, N-vinyl carbazole, β-pinene, 8,9-p-mentene, dipentene, methylene norbornene, 2-methylenetetrahydrofuran, etc. are used in small amounts, preferably heavy. Existence in the range of 10% by mass or less as a proportion of the combined block A You may do it. The form in the case where the polymer block A contains other structural units other than α-methylstyrene may be random, block, or tapered.

  The number average molecular weight of the polymer block A of the block copolymer (I) is preferably in the range of 1000 to 50000, and more preferably in the range of 2000 to 40000. When the number average molecular weight of the polymer block A is less than 1000, the resulting thermoplastic polymer composition tends to have poor scratch resistance, wear resistance, and mechanical performance, and the number average molecular weight exceeds 50,000. Tends to decrease the molding processability, scratch resistance, and wear resistance of the thermoplastic polymer composition obtained. In addition, the number average molecular weight as used in this specification is the molecular weight of polystyrene conversion calculated | required by the gel permeation chromatography (GPC) measurement.

The content of the polymer block A in the block copolymer (I) is preferably in the range of 10 to 50% by mass. When the content of the polymer block A is less than 10% by mass, the resulting thermoplastic polymer composition tends to have poor scratch resistance, wear resistance, and mechanical performance, whereas it exceeds 50% by mass. The thermoplastic polymer composition obtained tends to be less flexible. The content of the polymer block A in the block copolymer (a), for example, can be determined by such ^{1 H-NMR} spectrum.

  Conjugated diene units constituting the polymer block B of the block copolymer (I) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Examples are derived from the structural unit. These conjugated dienes may be used alone or in combination of two or more. Among these, the polymer block B is preferably composed of a butadiene unit, an isoprene unit, or both a butadiene unit and an isoprene unit.

  The polymer block B is a small amount, preferably within the range of 10% by mass or less as a proportion of the polymer block B, as long as the gist of the present invention is not impaired, other anion polymerizable monomers other than the conjugated diene, for example, Styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, pt-butyl styrene, 2,4-dimethyl styrene, vinyl naphthalene, vinyl anthracene, methyl methacrylate, methyl vinyl ether, N-vinyl carbazole, A structural unit derived from β-pinene, 8,9-p-mentene, dipentene, methylene norbornene, 2-methylenetetrahydrofuran and the like may be contained. The form in the case where the polymer block B contains these structural units may be random, block, or tapered.

  The number average molecular weight of the polymer block B is preferably in the range of 10,000 to 500,000, and more preferably in the range of 20,000 to 400,000. When the number average molecular weight of the polymer block B is less than 10,000, the resulting thermoplastic polymer composition tends to have poor scratch resistance, wear resistance, and mechanical performance, and is obtained when the molecular weight exceeds 500,000. There exists a tendency for the moldability of a thermoplastic polymer composition to fall.

From the viewpoint of heat resistance and weather resistance, the polymer block B in the block copolymer (I) is hydrogenated (hydrogenated) at least 50 mol% of the carbon-carbon double bond based on the conjugated diene unit. More preferably, 70 mol% or more is hydrogenated, and more preferably 90 mol% or more is hydrogenated. In addition, said hydrogenation rate is based on the content of the carbon-carbon double bond based on the conjugated diene unit in the polymer block B, before and after hydrogenation, iodine value measurement, infrared spectrophotometer, ¹ H- It can be measured from NMR and obtained from the measured value.

  In the block copolymer (I), as long as the polymer block A and the polymer block B are bonded, the bonding mode is not limited, and linear, branched, radial, or two of them Any of the above combined forms may be used. Among them, it is preferable that the bond form of the polymer block A and the polymer block B is linear, as an example, when the polymer block A is represented by A and the polymer block B is represented by B, A triblock copolymer represented by A-B-A, a tetrablock copolymer represented by A-B-A-B, a pentablock copolymer represented by A-B-A-B-A, (A -B) nX type copolymer (X represents a coupling agent residue, and n represents an integer of 2 or more). These block copolymers may be used alone or in a mixture of two or more. Among these, a triblock copolymer (ABA) is preferably used from the viewpoint of ease of production of the block copolymer (I) and flexibility.

  The block copolymer (I) is a carboxyl group, a hydroxyl group, or an acid anhydride group (group represented by the formula: —CO—O—CO—) in the molecular chain or at the molecular end unless the purpose of the present invention is impaired. In addition, one or more functional groups such as amino group and epoxy group may be contained. Further, as the block copolymer (I), the block copolymer (I) having the functional group described above and the block copolymer (I) having no functional group may be mixed and used.

The block copolymer (I) can be produced by an anionic polymerization method, and examples thereof include the following production methods.
(1) α-methylstyrene after polymerization of a conjugated diene using a dianionic initiator such as 1,4-dilithio-1,1,4,4-tetraphenylbutane in a tetrahydrofuran solvent and then at −78 ° C. Are sequentially polymerized to obtain a triblock copolymer represented by A-B-A (see Macromolecules, Vol. 2, pages 453-458 (1969)),
(2) After α-methylstyrene is polymerized with an anionic polymerization initiator such as sec-butyllithium in a nonpolar solvent such as cyclohexane, conjugated diene is polymerized, and then coupling such as tetrachlorosilane and diphenyldichlorosilane is performed. (AB) Method of obtaining an nX type block copolymer by adding an agent (α, α′-dichloro-p-xylene, phenyl benzoate, etc.) and conducting a coupling reaction (Kaucuk) Gumi Kunststoffe (Kautsch. Gummi, Kunstst.), 37, 377-379 (1984); Polymer Bulletin, 12, 71-77 (1984)),
(3) In a nonpolar solvent, an organolithium compound is used as an initiator, and a concentration of 5 to 50% by mass at a temperature of −30 to 30 ° C. in the presence of a polar compound having a concentration of 0.1 to 10% by mass. A method of obtaining an ABA block copolymer by adding a coupling agent after polymerizing α-methylstyrene of the above, polymerizing a conjugated diene to the resulting living polymer,
(4) In a nonpolar solvent, an organolithium compound is used as an initiator, and a concentration of 5 to 50% by mass at a temperature of −30 to 30 ° C. in the presence of a polar compound having a concentration of 0.1 to 10% by mass. Α-methylstyrene is polymerized, the resulting living polymer is polymerized with a conjugated diene, and the resulting α-methylstyrene polymer block and conjugated diene polymer block are used as a living block polymer other than α-methylstyrene. A method for obtaining an ABC type block copolymer by polymerizing the anionic polymerizable monomer.
Among the production methods described above, the methods (3) and (4) include the mild polymerization conditions (temperature, solution viscosity, etc.) and the control of the microstructure (1,4-bond amount) of the conjugated diene part. Preferably, the method (3) is more preferably employed. Hereinafter, the method (3) will be described in more detail.

  Examples of the organic lithium compound used as the polymerization initiator in the method (3) include monolithium compounds such as n-butyllithium, sec-butyllithium and tert-butyllithium, and dilithium compounds such as tetraethylenedilithium. It is done. These compounds may be used alone or in combination of two or more.

  The solvent used in the polymerization of α-methylstyrene is a nonpolar solvent, such as aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, n-heptane, aromatic hydrocarbons such as benzene, toluene, xylene, etc. Is mentioned. These may be used alone or in combination of two or more.

  The polar compound used in the polymerization of α-methylstyrene is a compound that does not have a functional group (hydroxyl group, carbonyl group, etc.) that reacts with anionic species and has a hetero atom such as an oxygen atom or a nitrogen atom in the molecule. Examples thereof include diethyl ether, monoglyme, tetramethylethylenediamine, dimethoxyethane, and tetrahydrofuran. These compounds may be used alone or in combination of two or more.

  The concentration of the polar compound in the reaction system is such that α-methylstyrene is polymerized at a high conversion rate, and when the subsequent conjugated diene is polymerized, the amount of 1,4-bond in the conjugated diene polymer block is controlled. Therefore, it is preferably in the range of 0.1 to 10% by mass, and more preferably in the range of 0.5 to 3% by mass.

  The α-methylstyrene concentration in the reaction system is preferably in the range of 5 to 50% by mass from the viewpoint of the viscosity of the reaction solution in the latter stage of polymerization, by polymerizing α-methylstyrene at a high conversion rate. A range of ˜40% by mass is more preferable.

  The above conversion rate means the ratio of unpolymerized α-methylstyrene converted to a polymer by polymerization, and in the present invention, the degree is preferably 70% or more, and 85% or more. More preferably.

  The temperature conditions during the polymerization of α-methylstyrene are the ceiling temperature of α-methylstyrene (the temperature at which the polymerization reaction reaches an equilibrium state and does not proceed substantially), the polymerization rate of α-methylstyrene, the living property, etc. From this point, it is preferably within the range of -30 to 30 ° C, more preferably -20 to 10 ° C, and further preferably -15 to 0 ° C. By setting the polymerization temperature to 30 ° C. or less, α-methylstyrene can be polymerized at a high conversion rate, and the proportion of the living polymer to be deactivated is small, so that homopoly α- Mixing of methylstyrene is suppressed, and physical properties are not easily impaired. In addition, by setting the polymerization temperature to −30 ° C. or higher, the reaction solution can be stirred without increasing the viscosity in the latter stage of polymerization of α-methylstyrene, and the cost necessary to maintain the low temperature state does not increase. Economically favorable

  In the above method, as long as the characteristics of the α-methylstyrene polymer block (polymer block A) are not impaired, other structural units that the polymer block A may have during polymerization of α-methylstyrene. The unsaturated monomer exemplified above may be allowed to coexist and may be copolymerized with α-methylstyrene. These unsaturated monomers may be used alone or in combination of two or more.

  Living poly α-methylstyryl lithium is produced by polymerization of α-methylstyrene using the organolithium compound described above as an initiator. This is then polymerized with a conjugated diene. Examples of the conjugated diene include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. These compounds may be used alone or in combination of two or more. Among these, butadiene or isoprene is preferable, and these may be used in combination.

  The conjugated diene is subjected to polymerization by being added to the reaction system. The method for adding the conjugated diene to the reaction system is not particularly limited, and the conjugated diene may be added directly to the living poly α-methylstyryllithium solution or diluted with a solvent. As a method of diluting a conjugated diene in a solvent, the conjugated diene may be added and then diluted with a solvent, the conjugated diene and the solvent may be added simultaneously, or the conjugated diene may be added after diluting with a solvent. Good. Suitably, an amount of conjugated diene corresponding to 1 to 100 molar equivalents, preferably 5 to 50 molar equivalents, is added to the living poly α-methylstyryl lithium to add a conjugated diene block (hereinafter referred to as polymer block b1). The living active terminal is variably formed and diluted with a solvent, and then the remaining conjugated diene is added, and the polymerization is carried out at a temperature exceeding 30 ° C., preferably in the temperature range of 40 to 80 ° C. A method of carrying out the reaction to further form a conjugated diene block (hereinafter sometimes referred to as polymer block b2) is recommended. In changing the active terminal of the living poly α-methylstyryl lithium, instead of conjugated diene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, Vinyl aromatic compounds such as 1,1-diphenylethylene may be used.

  Examples of the solvent that can be used for dilution include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-heptane, and aromatic hydrocarbons such as benzene, toluene, and xylene. . These solvents may be used alone or in combination of two or more.

  For example, a polyfunctional coupling agent is added to a living polymer of a block copolymer comprising an α-methylstyrene polymer block and a conjugated diene polymer block obtained by copolymerizing a conjugated diene with living poly α-methylstyryl lithium. By reacting, a triblock or radial teleblock type block copolymer (I) can be produced. The block copolymer in this case is a mixture containing diblock, triblock, and radial teleblock block copolymers at an arbitrary ratio, which is obtained by adjusting the amount of the polyfunctional coupling agent used. May be. Examples of multifunctional coupling agents include phenyl benzoate, methyl benzoate, ethyl benzoate, ethyl acetate, methyl acetate, methyl pivalate, phenyl pivalate, ethyl pivalate, α, α′-dichloro-o-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-p-xylene, bis (chloromethyl) ether, dibromomethane, diiodomethane, dimethyl phthalate, dichlorodimethylsilane, dichlorodiphenylsilane, trichloromethylsilane, Examples include tetrachlorosilane and divinylbenzene. In addition, what is necessary is just to adjust suitably the usage-amount of a polyfunctional coupling agent according to the number average molecular weight of block copolymer (I), and there is no restriction | limiting in a strict meaning.

  A triblock or radial teleblock type block copolymer (I) obtained by reacting a living polymer of a block copolymer comprising an α-methylstyrene polymer block and a conjugated diene polymer block with a polyfunctional coupling agent (I ) Is hydrogenated (hydrogenated), if necessary, an active hydrogen compound such as alcohols, carboxylic acids, water, etc. is added to stop the coupling reaction, followed by a known method described later. The hydrogenated block copolymer (I) can be produced by hydrogenation in the presence of a hydrogenation catalyst in an active organic solvent.

  In addition, the hydrogenated block copolymer (I) is polymerized with a conjugated diene by polymerizing living poly α-methylstyryl lithium, and then added with an active hydrogen compound such as alcohols, carboxylic acids, and water. It can also be produced by stopping and hydrogenating in the presence of a hydrogenation catalyst in an inert organic solvent according to a known method described later.

  Unfunctionalized non-hydrogenated block copolymer consisting of α-methylstyrene polymer block and conjugated diene polymer block, or living polymer of block copolymer consisting of α-methylstyrene polymer block and conjugated diene polymer block An unhydrogenated triblock or radial teleblock type block copolymer (both included in the block copolymer (I) used in the present invention) obtained by reacting a reactive coupling agent is produced Without replacing the solvent used in the above, it can be directly subjected to hydrogenation.

  In the hydrogenation reaction, Raney nickel; a heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, Ni is supported on a carrier such as carbon, alumina, diatomaceous earth; transition metal compound (nickel octylate, nickel naphthenate, nickel acetyl) Acetate, cobalt octylate, cobalt naphthenate, cobalt acetylacetonate, etc.) and a Ziegler catalyst comprising a combination of an organoaluminum compound such as triethylaluminum and triisobutylaluminum or an organolithium compound; titanium, zirconium, hafnium, etc. Hydrogenation catalysts such as metallocene catalysts composed of combinations of transition metal bis (cyclopentadienyl) compounds and organometallic compounds composed of lithium, sodium, potassium, aluminum, zinc or magnesium The standing down, the reaction temperature 20 to 100 ° C., can be performed under conditions of hydrogen pressure 0.1 to 10 MPa. The unhydrogenated block copolymer (I) is hydrogenated until 50% or more, more preferably 70% or more, more preferably 90% or more of the carbon-carbon double bonds in the conjugated diene polymer block are saturated. It is desirable to improve the weather resistance of the block copolymer (I).

  As the block copolymer (I) used in the present invention, those obtained by the above method are preferably used. Particularly, in a nonpolar solvent, an organic lithium compound is used as an initiator, and a concentration of 0.1 to 10% by mass is used. In the presence of the polar compound, α-methylstyrene having a concentration of 5 to 50% by mass is polymerized at a temperature of −30 to 30 ° C., and then in the polymerization of the conjugated diene, the living poly α-methylstyryl lithium It is obtained by polymerizing 1 to 100 molar equivalents of conjugated diene to form polymer block b1, and then polymerizing by adding conjugated diene at a temperature exceeding 30 ° C. to form polymer block b2. It is desirable that the thermoplastic polymer composition has excellent characteristics in a wide temperature range. That is, in this case, the polymer block B is composed of the polymer block b1 and the polymer block b2.

  The structure of the block copolymer (I) is not limited to a linear or branched structure, but the block copolymer (I) includes a block copolymer having a structure represented by the formula: A-b1-b2. Is preferred. Such block copolymers include Ab1-b2-b2-b1-A type copolymer, Ab1-b2-b2-b1-A type copolymer and Ab1-b2 type copolymer. And a mixture (A-b1-b2) nX copolymer (X represents a coupling agent residue, n is an integer of 2 or more).

  The number average molecular weight of the polymer block b1 in the block copolymer (I) is preferably in the range of 1000 to 30000, more preferably in the range of 2000 to 25000, and the conjugated diene constituting the polymer block b1. The unit has a 1,4-bond content of preferably less than 30%. The number average molecular weight of the polymer block b2 is preferably in the range of 10,000 to 400,000, more preferably in the range of 20,000 to 400,000, and the 1,4-bond amount of the conjugated diene unit constituting the polymer block b2. Is preferably 30% or more, more preferably 35% to 95%, and still more preferably 40% to 80%.

The non-aromatic rubber softener (II) that may be contained in the thermoplastic polymer composition forming the polymer composition layer (b) in the laminate of the present invention includes paraffinic and naphthenic types. Petroleum softeners such as process oil; paraffin; vegetable oil softeners such as peanut oil and rosin; and synthetic softeners such as ethylene-α-olefin oligomer, polybutene, and low molecular weight polybutadiene. As the non-aromatic rubber softener (II), a softener having a kinematic viscosity at 40 ° C. of ²⁰ to 800 mm ² / s, particularly paraffin oil is preferable. These non-aromatic softeners (II) can be used singly or in combination of two or more. Examples of the non-aromatic rubber softener (II) that can be suitably used in the present invention include paraffinic process oils in the “Diana Process Oil” (trade name; Idemitsu Kosan Co., Ltd.) series.

  The content of the non-aromatic rubber softener (II) is 200 parts by mass or less, preferably 150 parts by mass or less, with respect to 100 parts by mass of the block copolymer (I). If the content of the non-aromatic rubber softener (II) exceeds 200 parts by mass with respect to 100 parts by mass of the block copolymer (I), the mechanical performance of the resulting thermoplastic polymer is reduced, and The non-aromatic rubber softener (II) tends to bleed out from the molded body.

  The thermoplastic resin (III) contained in the thermoplastic polymer composition forming the polymer composition layer (b) in the laminate of the present invention is an acrylic resin, a polystyrene resin, a polyphenylene ether resin, or a polycarbonate resin. It is at least one thermoplastic resin selected from the group consisting of a resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a polyester resin, and a polyamide resin.

  Examples of the acrylic resin include a homopolymer of methyl methacrylate, and a copolymer obtained by copolymerizing methyl methacrylate as a main component and another copolymerizable monomer. Examples of other copolymerizable monomers include acrylic acid or a metal salt thereof; methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate, t-butyl acrylate, acrylic acid 2 -Acrylic esters such as ethylhexyl; methacrylic acid or metal salts thereof; ethyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacrylic acid Methacrylic acid esters such as cyclohexyl; Vinyl acetate; Aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; Maleic anhydride; Maleimides such as N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide Compounds etc. It is below. When these are copolymerized with methyl methacrylate, one type may be used alone or two or more types may be used in combination.

  Examples of the polystyrene resin include polystyrene, poly α-methylstyrene, poly p-methylstyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, and maleic anhydride-styrene resin.

  The polyphenylene ether resin is a resin having an oxyphenylene group as a main structural unit, and each structural unit may have a substituent such as a halogen atom or an alkyl group. Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2-methyl-6-ethyl). -1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6) -Propyl-1,4-phenylene) ether and the like. In addition, those obtained by blending polystyrene or the like or those grafted with polystyrene can be used as the polyphenylene ether resin.

  Examples of the polycarbonate-based resin include aromatic polycarbonates, aliphatic polycarbonates, aromatic-aliphatic polycarbonates, and among them, aromatic polycarbonates are preferably used. Aromatic polycarbonate reacts with aromatic dihydroxy compound or a small amount of polyhydroxy compound with phosgene or carbonic acid diester by phosgene method (interfacial polymerization method), melting method (transesterification method), etc. Can be manufactured. The aromatic polycarbonate produced by the melting method may have a terminal hydroxyl group adjusted. As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4 , 4-dihydroxydiphenyl and the like. As an aromatic polycarbonate, it is derived from a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds. Polycarbonate copolymers are preferred.

  Examples of the polyvinyl chloride resin include a homopolymer of vinyl chloride and a copolymer obtained by copolymerizing other monomers having vinyl chloride as a main component and other copolymerizability. Examples of other copolymerizable monomers include ethylene, propylene, vinyl acetate, vinyl bromide, vinylidene chloride, acrylonitrile, maleimide and the like. When these are copolymerized with vinyl chloride, one type may be used alone or two or more types may be used in combination.

  Examples of the polyvinyl acetate resin include a homopolymer of vinyl acetate and a copolymer obtained by copolymerizing a monomer having vinyl acetate as a main component and other copolymerizable monomers. Examples of other copolymerizable monomers include ethylene, propylene, vinyl chloride, acrylonitrile, maleimide and the like. When these are copolymerized with vinyl chloride, one type may be used alone or two or more types may be used in combination.

  Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polylactic acid, and polycaprolactone.

  Polyamide resins include polyamide 6, polyamide 6,6, polyamide 6,10, polyamide 11, polyamide 12, polyamide 6,12, polyhexamethylenediamine terephthalamide, polyhexamethylenediamine isophthalamide, xylene group-containing polyamide, and the like. Can be mentioned.

  In the thermoplastic polymer composition forming the polymer composition layer (b) in the laminate of the present invention, the content of the thermoplastic resin (III) is 10 to 10 parts by mass with respect to 100 parts by mass of the block copolymer (I). It is in the range of 200 parts by mass, and preferably in the range of 10 to 150 parts by mass. When the content of the thermoplastic resin (III) component is less than 10 parts by mass with respect to 100 parts by mass of the block copolymer (I), the resulting thermoplastic polymer composition has scratch resistance, abrasion resistance, surface When the adhesiveness with the treatment layer is lowered and the amount exceeds 200 parts by mass, the scratch resistance, abrasion resistance, flexibility and the like of the resulting thermoplastic polymer composition are lowered.

  In the thermoplastic polymer composition forming the polymer composition layer (b) in the laminate of the present invention, the thermoplastic resin (III) component includes acrylic resin, polystyrene resin, polyphenylene ether resin, and polycarbonate resin. The thermoplastic polymer composition in which these resins are excellent in compatibility with the block copolymer (I) and exhibit good scratch resistance, wear resistance, and flexibility regardless of the kneading conditions. It is preferable in that it is easy to obtain.

  If the thermoplastic polymer composition which forms the polymer composition layer (b) in the laminate of the present invention is within a range not impairing the gist of the present invention, the above block copolymer (I ) Other thermoplastic elastomers, rubber reinforcing agents, and fillers may be further contained. Examples of the other thermoplastic elastomers include styrene-based thermoplastic elastomers having a block made of styrene as a hard segment, which is different from the block copolymer (I), and the content thereof is a thermoplastic polymer composition. It is preferable to make it into 10 mass% or less with respect to the whole quantity.

  Examples of the rubber reinforcing agent and filler include inorganic fillers such as carbon black, calcium carbonate, talc, silica, and diatomaceous earth; and organic fillers such as rubber powder and wood powder. These may be used alone or in combination of two or more. When a rubber reinforcing agent or a filler is contained, the content is preferably 30% by mass or less based on the total amount of the thermoplastic polymer composition.

  If the thermoplastic polymer composition forming the polymer composition layer (b) in the laminate of the present invention is within a range that does not impair the gist of the present invention, reinforcement such as α-methylstyrene resin is necessary. It may contain a resin, a flame retardant, a heat stabilizer, an antioxidant, a light stabilizer, an antistatic agent and the like.

  The thermoplastic polymer composition for forming the polymer composition layer (b) can be produced by a method used in the production of ordinary resin compositions or elastomer compositions. That is, using a kneading machine such as a single screw extruder, twin screw extruder, Banbury mixer, heating roll, various kneaders, etc., the block copolymer (I), the thermoplastic resin (III), and if necessary non- It can be produced by melt-kneading a mixture in which other components such as an aromatic rubber softener (II) are mixed. The melt kneading temperature is preferably in the range of 150 to 280 ° C.

  The present invention provides a laminate in which a thermoplastic polymer foam layer (c) is laminated in the order of surface layer (a) / polymer composition layer (b) / thermoplastic polymer foam layer (c). Is included. The thermoplastic polymer foam layer (c) [hereinafter sometimes referred to simply as “foam layer (c)”] is a flexible and / or elastic foam formed from a thermoplastic polymer. Any layer can be used. Among them, the foam layer (c) is preferably a layer made of a foam formed using at least one of an olefin resin and a thermoplastic elastomer, and is an olefin thermoplastic elastomer or polystyrene thermoplastic. The polymer composition layer (the polymer composition layer) is a layer made of a foam formed using at least one selected from the group consisting of an elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, and a polyurethane-based thermoplastic elastomer. More preferable from the viewpoints of good adhesiveness and flexibility with b). The foam constituting the foam layer (c) may be either a foam obtained by a chemical foaming method using a foaming agent or a foam obtained by a physical foaming method such as stirring bubbles. There may be. As the foam constituting the foam layer (c), a commercially available product may be purchased and used as it is, or may be manufactured for carrying out the present invention. The specific gravity of the foam constituting the foam layer (c) can be adjusted according to the use of the laminate of the present invention, but is generally about 0.02 to 0.80, particularly 0.09 to A value of about 0.60 is preferable from the viewpoint of the flexibility, lightness, mechanical properties, and the like of the obtained laminate.

  The thicknesses of the surface layer (a), the polymer composition layer (b) and the foam layer (c) in the laminate of the present invention are adjusted according to the type of material forming each layer, the use of the laminate, and the like. In general, the thickness of the surface layer (a) is 3 to 80 μm, particularly 5 to 40 μm, the thickness of the polymer composition layer (b) is 50 μm to 3 mm, especially 100 μm to 2.5 mm, foaming The thickness of the body layer (c) is preferably 150 μm to 5 mm, particularly 300 μm to 3 mm, from the viewpoints of the flexibility, lightness, mechanical properties, and handleability of the laminate. The total thickness of the laminate of the present invention can be adjusted according to the type of material forming each layer, the use of the laminate, etc., but in terms of flexibility, lightness, mechanical properties, handleability, etc. In general, the thickness is preferably 250 μm to 9 mm, and more preferably 500 μm to 5 mm.

  In the laminate of the present invention, the surface layer (a) and the polymer composition layer (b) may be bonded using an adhesive, but the surface layer (a) is formed on the polymer composition layer (b). ) Is preferably laminated and bonded directly by fusion without using an adhesive or a primer from the viewpoints of flexibility and light weight of the obtained laminate, simplification of the laminate production process, cost, and the like. Moreover, in the laminated body of this invention, although a polymer composition layer (b) and a foam layer (c) may be adhere | attached with the adhesive agent, a polymer composition layer (b) is used without using an adhesive agent. ) Is preferably directly laminated and adhered on the foam layer (c) by fusion from the viewpoints of flexibility and light weight of the obtained laminate, simplification of the laminate production process, and the like.

  The production method of the laminate of the present invention is not particularly limited, and the order of surface layer (a) / polymer composition layer (b) or surface layer (a) / polymer composition layer (b) / foam layer ( Any method can be adopted as long as it can produce a laminate in which two or three layers are bonded and integrated in the order of c). Among them, the polymer composition layer (b) is directly laminated and adhered to the foam layer (c) by fusion without using an adhesive, and the surface layer (a In order to obtain a three-layer laminate directly laminated without using an adhesive, for example, a polymer composition layer (b) is formed on a foam formed using a thermoplastic polymer. The thermoplastic polymer composition described above is melt coated (melt bonded) by an appropriate method (for example, melt extrusion method, calender method, casting method, casting method, insert molding method, two-color molding method, etc.). Then, a two-layer structure laminate comprising the polymer composition layer (b) / foam layer (c) is produced, and then a surface layer (b) is formed on the surface of the polymer composition layer (b) of the two-layer structure laminate. A method of coating a coating material consisting primarily of a polymer to form a) High production property, are preferably employed from the addition point is common.

The laminate of the present invention consisting of surface layer (a) / polymer composition layer (b) or surface layer (a) / polymer composition layer (b) / foam layer (c) It has excellent properties such as scratch resistance, abrasion resistance, flexibility, and workability, and is extremely useful for a wide range of applications as a skin material for manufacturing various products. In particular, the laminate of the present invention is at least one selected from a thermoplastic resin, metal, fabric, leather, glass and wood on the lower surface side of the polymer composition layer (b) or the lower surface side of the foam layer (c). Manufacture various laminated structures (laminate products) with the laminate of the present invention having excellent properties such as flexibility, scratch resistance and abrasion resistance by bonding and laminating to the seed material layer (d). can do.
Here, “the lower surface side of the polymer composition layer (b) or the lower surface side of the foam layer (c)” as used herein refers to a laminate composed of the surface layer (a) / polymer composition layer (b). Foaming on the side of the polymer composition layer (b) that is not bonded to the surface layer (a), or a laminate comprising the surface layer (a) / polymer composition layer (b) / foam layer (c) It refers to the side of the body layer (c) that is not bonded to the polymer composition layer (b).

  As the material laminated on the lower surface side of the polymer composition layer (b) or the foam layer (c) of the laminate of the present invention, it is preferable to use a thermoplastic resin, and as the thermoplastic resin, a polyphenylene ether resin is used. Polyamide resins such as polyamide 6, polyamide 6,6, polyamide 6,10, polyamide 11, polyamide 12, polyamide 6,12, polyhexamethylenediamine terephthalamide, polyhexamethylenediamine isophthalamide; polyethylene terephthalate, polybutylene terephthalate Polyester resins such as polyacrylic resins such as polymethyl acrylate and polymethyl methacrylate; Polyoxymethylene resins such as polyoxymethylene homopolymers and polyoxyethylene copolymers; Polystyrene, acrylonitrile-styrene Styrenic resins such as fat (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin); polycarbonate resin; polypropylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), ethylene-propylene copolymer Polymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer , Ethylene-1-α-olefin copolymers such as ethylene-1-nonene copolymer and ethylene-1-decene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester Copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid Polyester resins such as ester copolymers or resins modified with maleic anhydride, ethylene-propylene rubber (EPM), ethylene-propylene-nonconjugated diene rubber (EPDM); styrene-butadiene block copolymer, styrene- Styrenic thermoplastic elastomers such as isoprene block copolymers or hydrogenated products thereof; Olefin thermoplastic elastomers; Polyurethane thermoplastic elastomers; Polyamide thermoplastic elastomers; Polyester thermoplastic elastomers; Styrenic thermoplastic elastomers Examples thereof include a resin composition containing, for example, a styrene thermoplastic elastomer, an olefin resin, a resin composition containing a softening agent, and the like. Among these, the resin composition containing an olefin resin, an olefin thermoplastic elastomer, a styrene thermoplastic elastomer or a styrene thermoplastic elastomer is used for adhesion to the foam layer (c) and recyclability. From the point of view, it is preferable.

  In producing a laminated structure in which a thermoplastic resin layer is laminated as a material layer (d) on the lower surface side of the polymer composition layer (b) or foam layer (c) of the laminate of the present invention, a polymer The composition layer (b) or the foam layer (c) and the thermoplastic resin layer may be bonded and laminated with an adhesive, but the polymer composition layer (b) or the foam layer ( It is preferable to directly bond and laminate a thermoplastic resin layer on the lower surface side of c). As a method for producing such a laminate structure, for example, a method of directly coating a thermoplastic resin on the lower surface side of the polymer composition layer (b) or the foam layer (c) of the laminate by extrusion coating, calendar coating or the like. The laminate of the present invention is placed in a mold with the lower surface side of the polymer composition layer (b) or foam layer (c) facing inward (inserted), and filled with a thermoplastic resin. And a method for producing a molded body by injection or injection. When manufacturing the laminated structure which laminated the thermoplastic resin on the lower surface side of the foam layer (c), the kind of thermoplastic polymer which forms the foam layer (c), and the foam layer (c) If the kind of thermoplastic resin laminated | stacked on the lower surface side is made the same or approximate, adhesion of a foam layer (c) and a thermoplastic resin can be performed favorably, without using an adhesive agent. In addition, when the material laminated on the lower surface side of the polymer composition layer (b) or the foam layer (c) of the laminate is metal, fabric, leather, glass, wood, etc. Can be bonded and laminated. Moreover, the laminated body of this invention can also be used for uses, such as the interior material for vehicles, such as a motor vehicle, a sofa, and the skin material for various chairs, without laminating | stacking a material layer (d).

  The laminate of the present invention consisting of a surface layer (a) / polymer composition layer (b) or a surface layer (a) / polymer composition layer (b) / foam layer (c) It is excellent in various properties such as abrasion, scratch resistance, flexibility, and mechanical performance, and accordingly, the laminate is used as a skin material and its back side [polymer composition layer (b) or foam layer (c) The laminated body in which the layer (d) made of another material such as thermoplastic resin, metal, wood, and fabric is further laminated on the lower surface side of the resin also has various characteristics such as wear resistance, scratch resistance, flexibility, and mechanical performance. These laminates take advantage of the properties described above, and are used for film and sheet applications such as daily goods packaging, industrial packaging, flooring, furniture, building materials, wire coverings, hoses, etc. Paper feed rollers and rolls for paper, tubes, grommets such as belts and household appliances, copiers, etc. Office machine parts such as take-up rollers, industrial parts with various packings, building materials such as packing for sealing doors and window frames, automobiles such as instrument panels, center console boxes, door trims, pillars, assist grips, malls, seats Automotive parts such as interior / exterior parts, rack & pinion boots, suspension boots, constant velocity joint boots, grip materials for various products (eg, scissors, drivers, toothbrushes, ski stocks, pens, etc.), footwear (eg, gentlemen)・ Women's / school children's shoes, sports shoes, safety shoes, ski shoes, sandals, etc.), underwater glasses, sports equipment such as snorkels, leisure goods, stationery, and toys can be used effectively.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples. In the following examples and comparative examples, the hardness of the polymer composition layer (b) in the laminate, as well as the scratch resistance, abrasion resistance, and surface layer adhesion of the laminate were evaluated by the following methods. went.

(1) Hardness of the polymer composition layer (b) in the laminate:
In Examples 1 to 8 and Comparative Examples 1 to 5, a sheet-like test piece of length × width × thickness = 110 mm × 110 mm × 2 mm was cut out from the polymer composition layer before forming the surface layer (coating layer). Using the test piece, the type A hardness was measured in accordance with JIS K-6253, and used as an index of flexibility.

(2) Scratch resistance of the laminate:
In Examples 1 to 8 and Comparative Examples 1 to 5, a test piece having a size of length × width × thickness = 150 mm × 50 mm × 2 mm was cut out from the obtained laminate, and the surface layer (a) of the test piece was cut. Scratch at a speed of 1 cm / sec with a cross-cut test needle jig (ASTM D2197) applied with a load of 200 g, and measure the depth of the scratch with a surface roughness meter. The shallower the scratch, the better the scratch resistance. Was excellent.

(3) Wear resistance of the laminate:
In Examples 1 to 8 and Comparative Examples 1 to 5, a disk-shaped test piece having a diameter of 110 mm was punched out from the obtained laminate, and JIS K-6264 was used on the surface layer (a) side using the test piece. In accordance with the above, the amount of Taber wear was measured under the conditions of 1 kg load and 1000 revolutions using an H-22 wear wheel. The smaller the amount of wear, the better the wear resistance.

(4) Paintability of the surface layer of the laminate:
In Examples 1 to 8 and Comparative Examples 1 to 5, a test piece having a size of length × width × thickness = 150 mm × 50 mm × 2 mm was cut out from the obtained laminate, and the test piece was placed on the surface layer (a) side. Then, 10 × 10 grids were prepared at intervals of 2 mm with a stainless cutter, and cellophane tape (manufactured by Nichiban) was pressure-bonded with a 1 kg roller from above, and peeled off vigorously, and the number of grids remaining was counted. The paintability is expressed by the number of residual grids / 100, and the greater the residual amount, the better the paintability.

Moreover, each component used by the Example and the comparative example is as follows.
Block copolymer (I)
Reference Example 1 (Production of block copolymer (I) -1)
Α-methylstyrene 90.9 g, cyclohexane 138 g, methylcyclohexane 15.2 g and tetrahydrofuran 3.1 g were charged into a pressure-resistant vessel equipped with a stirrer purged with nitrogen. To this mixed solution, 9.4 ml of sec-butyllithium (1.3 M cyclohexane solution) was added and polymerized at −10 ° C. for 3 hours. When the number average molecular weight of poly α-methylstyrene (Block A) 3 hours after the start of polymerization was measured by GPC, it was 6600 in terms of polystyrene, and the polymerization conversion of α-methylstyrene was 89%. Next, 23 g of butadiene was added to the reaction mixture and stirred at −10 ° C. for 30 minutes to polymerize the block b1, and then 930 g of cyclohexane was added. At this time, the polymerization conversion of α-methylstyrene was 89%, and the number average molecular weight (GPC measurement, polystyrene conversion) of the polybutadiene block (b1) was 3700. 1,4 determined from ¹ H-NMR measurement -The binding amount was 19%.
Next, 141.3 g of butadiene was further added to the reaction solution, and a polymerization reaction was performed at 50 ° C. for 2 hours. The number average molecular weight (GPC measurement, polystyrene conversion) of the polybutadiene block (b2) of the block copolymer (structure: A-b1-b2) obtained by sampling at this time is 29800, and is determined from ¹ H-NMR measurement. The amount of 1,4-bond was 60%.

Subsequently, 12.2 ml of dichlorodimethylsilane (0.5 M toluene solution) was added to the polymerization reaction solution, and the mixture was stirred at 50 ° C. for 1 hour to obtain an α-methylstyrene-butadiene-α-methylstyrene triblock copolymer. Got. The coupling efficiency at this time was determined by the coupling body (α-methylstyrene-butadiene-α-methylstyrene triblock copolymer: A-b1-b2-X-b2-b1-A; When calculated from the area ratio of UV absorption in GPC of a residue (representing —Si (Me ₂ ) —) and an unreacted block copolymer (α-methylstyrene-butadiene block copolymer: A-b1-b2) 94%. As a result of ¹ H-NMR analysis, the α-methylstyrene-butadiene-α-methylstyrene triblock copolymer had an α-methylstyrene polymer block content of 33%, and the entire butadiene polymer block B ( That is, the amount of 1,4-bond in block b1 and block b2) was 56%.

In the polymerization reaction solution obtained above, a Ziegler-based hydrogenation catalyst formed from nickel octylate and triethylaluminum was added in a hydrogen atmosphere, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and 80 ° C. for 5 hours. Then, a hydrogenated product of α-methylstyrene-butadiene block copolymer (hereinafter, abbreviated as block copolymer (I) -1) was obtained. As a result of GPC measurement of the obtained block copolymer (I) -1, the main components were Mt (peak top of average molecular weight) = 81,000, Mn (number average molecular weight) = 78,700, Mw (weight average molecular weight) ) = 79,500, Mw / Mn = 1.01 α-methylstyrene-butadiene-α-methylstyrene triblock copolymer hydrogenated (coupled), UV (254 nm) absorption in GPC From the area ratio, it was found that 94% of the coupling body was contained. ^{Further, 1} H-NMR measurement hydrogenation ratio of butadiene block B composed of blocks b1 and the block b2 was 99%. These molecular properties are summarized in Table 1.

Reference Example 2 (Production of block copolymer (I) -2)
In Reference Example 1, the amount of sec-butyllithium (1.3 M cyclohexane solution) used was changed from 9.4 ml to 5.7 ml, and the amount of dichlorodimethylsilane (0.5 M toluene solution) used was changed from 12.2 ml to 7.4 ml. Instead, other operations were carried out in the same manner as in Reference Example 1 to obtain a block copolymer (hereinafter abbreviated as block copolymer (I) -2). The molecular properties are summarized in Table 1. The polymerization conversion rate of α-methylstyrene was 89%. Moreover, the number average molecular weight (GPC measurement, polystyrene conversion) of the obtained poly α-methylstyrene block (block A) is 10600, the number average molecular weight of the polybutadiene block b1 is 1500, and 1,4 determined from ¹ H-NMR measurement. -The bond amount was 17%, the number average molecular weight of the polybutadiene block b2 was 48000, and the 1,4-bond amount was 56%.

Reference Example 3 (Production of Styrenic Block Copolymer (i) -1)
In a pressure vessel equipped with a stirrer purged with nitrogen, 81 g of styrene, 1100 g of cyclohexane, and 3.1 g of tetrahydrofuran were charged. To this solution, 9.4 ml of sec-butyllithium (1.3 M, cyclohexane solution) was added and polymerized at 50 ° C. for 1 hour. Next, 164.3 g of butadiene was added to this reaction mixture, and polymerization was carried out at 50 ° C. for 1 hour. Thereafter, 12.2 ml of dichlorodimethylsilane (0.5 M, toluene solution) was further added to the reaction mixture, and the mixture was stirred at 50 ° C. for 1 hour to obtain a reaction mixture containing a polystyrene-polybutadiene-polystyrene triblock copolymer. Obtained. A hydrogenation catalyst composed of nickel octylate / triethylaluminum was added to this reaction mixture, and a hydrogenation reaction was carried out at 80 ° C. for 5 hours at a hydrogen pressure of 0.8 MPa, to obtain a polystyrene-polybutadiene-polystyrene triblock copolymer. A hydrogenated product (hereinafter abbreviated as block copolymer (i) -1) was obtained. The molecular properties are summarized in Table 1.

Non-aromatic rubber softener (II)
Paraffinic process oil (trade name, Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd., kinematic viscosity: 381.6 mm ² / s (40 ° C.))

Acrylic resin (III)
After putting 500 g of pure water into a 1000 ml three-necked flask equipped with a reflux condenser and sufficiently purging with nitrogen, a mixed solution of 425 g of methyl methacrylate, 55 g of methyl acrylate, 2.5 g of lauryl peroxide and 4 g of lauryl mercaptan was charged. Polymerization was carried out at 80 ° C. for 4 hours to obtain an acrylic resin (hereinafter referred to as “acrylic resin (III)”). In addition, the intrinsic viscosity of the obtained acrylic resin in chloroform at 20 ° C. was 0.301 dl / g.

Polycarbonate resin (III)
Polycarbonate (trade name, Panlite L-1225L, manufactured by Teijin Chemicals Ltd.)

Polystyrene resin (III)
Polystyrene (trade name, GPPS679, manufactured by PS Japan Ltd.)

Polyphenylene ether resin (III)
Polyphenylene ether (trade name, Nonyl PPO534, manufactured by Nippon GEP Co., Ltd.)

Olefin resin (IV)
Linear low density polyethylene (LLDPE) (trade name, Novatec LL UJ480, manufactured by Nippon Polychem)

Examples 1-8, Comparative Examples 1-4
(1) Block copolymer (I) -1 to 2 or block copolymer (i) -1 obtained in Reference Examples 1 to 3, non-aromatic rubber softener (II), acrylic Resin (III), polycarbonate-based resin (III), polystyrene-based resin (III), polyphenylene ether-based resin (III), and olefin-based resin (IV) are twin-screw extruders according to the formulation (parts by weight) shown in Tables 2 to 4 (Toshiba Machine Co., Ltd. “TEM-35B”), kneaded together at 230 ° C. and screw rotation of 200 rpm, extruded into a strand, and then cut the strand with a pelletizer, thereby polymer composition layer A pellet-shaped thermoplastic polymer composition was prepared.
(2) Thermoplastic prepared in the above (1) on one surface of a polyethylene foam sheet (manufactured by Sanwa Chemical Co., Ltd., trade name “San Peruka L-2500”, thickness 1.0 mm, specific gravity 0.4) Two layers having a polymer composition layer having a thickness of 1.0 mm on the foam layer (c) (foam sheet layer) by melt coating the polymer composition at 165 ° C. using two rolls A structural laminate was produced.
When the hardness of the polymer composition layer in this two-layer structure laminate was measured by the method described above, it was as shown in Tables 2 to 4 below.
(3) On the thermoplastic polymer composition layer of the laminate obtained in the above (2), a urethane surface treatment agent (“High Corp U AD402” manufactured by Special Colorant Industries Co., Ltd.) is thickened using a doctor blade. After coating to a thickness of 20 μm, it was dried with hot air at a temperature of 40 ° C. to produce a laminate comprising surface layer (a) (coating layer) / polymer composition layer / foam layer (c).
(4) When the scratch resistance and abrasion resistance evaluation of the laminate obtained in the above (3) was performed by the methods described above, the results were as shown in Tables 2 to 4 below.

Comparative Example 5
In the same manner as in the above (1) to (2), a laminate having a two-layer structure having a polymer composition layer but not having a surface layer (a) (coating layer) was produced. When the hardness, scratch resistance, and abrasion resistance of this laminate were evaluated by the methods described above, the results were as shown in Table 4 below.

  As is clear from the results in Tables 2 to 4 above, the laminates of Examples 1 to 8 are excellent in scratch resistance, wear resistance, adhesion to the surface layer, and excellent in flexibility. I understand. On the other hand, in the laminate of Comparative Example 1, the content of the acrylic resin in the polymer composition layer exceeds the range of the present invention, and the scratch resistance and wear resistance are inferior. In addition, the laminate of Comparative Example 2 does not contain the thermoplastic resin (III) in the polymer composition layer, and is inferior in scratch resistance, wear resistance, and adhesion to the surface layer. Moreover, since the laminated body of the comparative example 3 does not have an alpha-methylstyrene polymer block, it is inferior to scratch resistance and abrasion resistance. Since the laminate of Comparative Example 4 contains an olefin resin instead of the thermoplastic resin (III) in the polymer composition layer, it is inferior in scratch resistance, wear resistance, and adhesion to the surface layer. . Moreover, since the laminated body of the comparative example 5 does not include a surface layer, scratch resistance and abrasion resistance are not sufficient.

The laminate of the present invention contains a layer with excellent scratch resistance, wear resistance, flexibility and the like, and can be easily manufactured without requiring a complicated process such as applying a primer. The laminate of the present invention is used as a skin material, and the back side thereof [the lower surface side of the polymer composition layer (b) or the lower surface side of the foam layer (c)] is made of a material such as a thermoplastic resin, metal, wood, or cloth. By laminating the layers, it can be effectively used in a wide range of applications such as automobile parts, home appliance parts, building materials, furniture, toys, sports equipment, and daily necessities.

Claims (5)

A laminate that is laminated in the order of surface layer (a) / polymer composition layer (b);
The surface layer (a) is a layer mainly composed of a polymer; and
The polymer composition layer (b)
(I) At least one block selected from an α-methylstyrene block copolymer having a polymer block A mainly composed of α-methylstyrene units and a polymer block B mainly composed of conjugated diene units and a hydrogenated product thereof For 100 parts by mass of copolymer (I),
(II) 200 parts by mass or less of non-aromatic rubber softener (II),
(III) At least one heat selected from the group consisting of acrylic resins, polystyrene resins, polyphenylene ether resins, polycarbonate resins, polyvinyl chloride resins, polyvinyl acetate resins, polyester resins and polyamide resins. A laminate comprising a thermoplastic polymer composition containing 10 to 200 parts by mass of the plastic resin (III). The laminate according to claim 1, wherein the surface layer (a) is a coating layer made of a polyurethane-based or acrylic polymer. The polymer block A in the block copolymer (I) is a polymer block mainly composed of α-methylstyrene units and having a number average molecular weight of 1,000 to 50,000, and the polymer block B is composed of the following polymer blocks b1 and b2. And the block copolymer (I) has the formula:
A-b1-b2
(Wherein A is polymer block A,
b1 is a polymer block having a number average molecular weight of 1,000 to 30,000, mainly consisting of conjugated diene units, wherein the 1,4-bond amount of the conjugated diene units is less than 30%;
(b2 represents a polymer block having a number average molecular weight of 10,000 to 400,000, which is mainly composed of conjugated diene units, and the 1,4-bond amount of the conjugated diene units is 30% or more)
The laminated body of Claim 1 or 2 characterized by including the structure shown by these. Furthermore, the thermoplastic polymer foam layer (c) is laminated in the order of surface layer (a) / polymer composition layer (b) / thermoplastic polymer foam layer (c). It is a laminated body of any one of these, Comprising:
The thermoplastic polymer foam layer (c) comprises an olefin resin, an olefin thermoplastic elastomer, a polystyrene thermoplastic elastomer, a polyester thermoplastic elastomer, a polyamide thermoplastic elastomer, and a polyurethane thermoplastic elastomer. A laminate formed using at least one selected. Furthermore, the material layer (d) consisting of at least one selected from the group consisting of thermoplastic resin, metal, fabric, leather, glass and wood is a surface layer (a) / polymer composition layer (b) / material layer. Either of (d) or surface layer (a) / polymer composition layer (b) / thermoplastic polymer foam layer (c) / material layer (d) are laminated in this order. The laminate according to Item 1.