JP2005239935A - Thermoplastic elastomer composition, molded product comprised of the same, two-layered molded product comprising molded product and polyurethane foam laminated thereon, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which exhibits an excellent non-self-adhesive property and gives a molded product excellent in adhesion properties to a polyurethane foam without using a chlorine-containing primer. <P>SOLUTION: The thermoplastic elastomer composition comprises the components (I)-(IV) below, where the contents of the component (III) and (IV) are 0.1-50 pts. wt. and 1.0-100 pts. wt., respectively, based on 100 pts. wt. of the total of the components (I) and (II): (I) a polyolefin resin; (II) a polyolefin rubber and/or a styrene thermoplastic elastomer; (III) a composite thermoplastic elastomer obtained by bonding the styrene thermoplastic elastomer to the urethane thermoplastic elastomer; and (IV) at least one copolymer selected from among ethylene-unsaturated carboxylic acid copolymers, ethylene-unsaturated carboxylate copolymers, ethylene-vinyl acetate copolymers and saponified products of ethylene-vinyl acetate copolymers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic elastomer composition, a molded body comprising the composition, a two-layer molded body in which a polyurethane foam is laminated on the molded body, and a method for producing the same. More specifically, the present invention is a thermoplastic elastomer composition that provides a molded article having excellent non-tackiness and excellent adhesion to polyurethane foam without using a chlorine atom-containing primer, and the composition. The present invention relates to a molded body, a two-layer molded body in which a polyurethane foam is laminated on the molded body, and a method for producing the same.

  Skin materials such as automobile interior parts are required to have a complex uneven pattern such as skins and stitches on the surface, and to have a complicated design as seen in the visor part of an instrument panel, etc. . From the viewpoint of environmental problems (suppression of harmful gas generation during combustion treatment), etc., the skin material is an excellent thermoplastic as a substitute for a molded article made of a polyvinyl chloride resin composition having a chlorine atom unit. Vacuum molded bodies, powder molded bodies, injection molded bodies, compression molded bodies and the like made of an elastomer composition are used.

  Examples of the thermoplastic elastomer composition used in such a molded article include a thermoplastic elastomer composition comprising, for example, an olefin resin and an ethylene-α-olefin copolymer rubber, a nonpolar resin such as polypropylene, and a specific material. A composition comprising a hydrogenated diene copolymer is known (see, for example, Patent Document 1 and Patent Document 2).

JP-A-5-5050 Japanese Unexamined Patent Publication No. 3-72512

  However, when a two-layer molded article excellent in tactile sensation is produced by lining the polyurethane foam to these molded articles by the injection foaming method, the adhesiveness at the interface between these molded articles and the polyurethane foam is insufficient. May peel off easily and was not sufficiently satisfactory for practical use.

  In addition, by applying an organic solvent solution (primer) of a compound containing a chlorine atom unit, such as chlorinated polyolefin or chloroprene rubber, to the adhesive surface of these molded products, the polyurethane foam is lined to form these molded products. The adhesion at the interface between the body and the polyurethane foam can be increased. However, the thermoplastic elastomer composition used for such a molded body is an alternative to a molded body of vinyl chloride resin, but a compound containing a chlorine atom is used to produce a two-layer molded body. Inevitably, there was still concern over the above problems, so it was not fully satisfactory. Furthermore, the step of applying the primer and the subsequent drying step are not satisfactory in that they are complicated.

  Under such circumstances, the problem to be solved by the present invention is thermoplasticity which gives a molded article having excellent non-adhesiveness and excellent adhesion to polyurethane foam without using a primer containing a chlorine atom unit. An object of the present invention is to provide an elastomer composition, a molded body comprising the composition, a two-layer molded body in which a polyurethane foam is laminated on the molded body, and a method for producing the same.

That is, the first of the present invention contains the following components (I) to (IV), and the content of component (III) relative to 100 parts by weight of the total amount of component (I) and component (II) is 0. It relates to a thermoplastic elastomer composition having 1 to 50 parts by weight and a component (IV) content of 1.0 to 100 parts by weight.
(I): Polyolefin-based resin (II): Polyolefin-based rubber and / or styrene-based thermoplastic elastomer (III): Composite thermoplastic elastomer obtained by bonding a styrene-based thermoplastic elastomer and a urethane-based thermoplastic elastomer (IV ): At least one copolymer selected from ethylene-unsaturated carboxylic acid copolymer, ethylene-unsaturated carboxylic acid ester copolymer, ethylene-vinyl ester copolymer and saponified ethylene-vinyl ester copolymer Combined The second aspect of the present invention relates to a molded article made of the thermoplastic elastomer composition.
A third aspect of the present invention relates to a two-layer molded body in which a polyurethane foam is laminated on the molded body.

  According to the present invention, a thermoplastic elastomer composition that gives a molded article excellent in non-tackiness and excellent in adhesion to a polyurethane foam even without using a primer containing a chlorine atom unit, a molded article comprising the composition, A two-layer molded article obtained by laminating a polyurethane foam on the molded article and a method for producing the same can be provided.

  Component (I) used in the thermoplastic elastomer composition of the present invention: polyolefin resin means one or more olefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene and 1-hexene. It is a polymer containing 50% by weight or more of repeating units derived from JIS K-6253 (1997), and the A hardness exceeds 98.

  The polyolefin resin may contain a repeating unit derived from a monomer other than olefin. Examples of the monomer other than olefin include 1,3-butadiene and 2-methyl-1,3-butadiene. (Isoprene), 1,3-pentadiene, conjugated dienes having 4 to 8 carbon atoms such as 2,3-dimethyl-1,3-butadiene; dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, Non-conjugated dienes having 5 to 15 carbon atoms such as 1,5-dicyclooctadiene and 7-methyl-1,6-octadiene; vinyl ester compounds such as vinyl acetate; methyl acrylate, ethyl acrylate, butyl acrylate , Unsaturated carboxylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated compounds such as acrylic acid and methacrylic acid Carboxylic acid and the like.

  Examples of polyolefin resins include ethylene homopolymer, propylene homopolymer, 1-butene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, Ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene Examples include -1-hexene copolymer and ethylene-propylene-1-octene copolymer. These polyolefin resins are used alone or in combination of two or more.

  Among the polyolefin-based resins, a polypropylene-based resin in which the content of repeating units derived from propylene is 80% by weight or more is preferably used from the viewpoint of the heat resistance (shape retention) of the obtained molded body. The content of the repeating unit derived from propylene in the polypropylene resin is more preferably 90% by weight or more, and still more preferably 95% by weight or more.

  The polyolefin resin melt flow rate (MFR) is preferably from 0.1 to 500 g / 10 min, more preferably from the viewpoint of further improving the meltability during molding of the thermoplastic elastomer composition. It is 5 to 400 g / 10 minutes, more preferably 1 to 300 g / 10 minutes. The MFR is measured under conditions of a temperature of 230 ° C. and a load of 21.18 N according to JIS K-7210 (1976).

  Component (II) used in the thermoplastic elastomer composition of the present invention: The polyolefin rubber and / or styrene thermoplastic elastomer is at least one selected from polyolefin rubber and styrene thermoplastic elastomer. .

  The polyolefin rubber is derived from one or more olefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, 2-methylpropylene, 3-methyl-1-butene and 1-hexene. And a polymer having an A hardness of 98 or less according to JIS K-6253 (1997). The polyolefin rubber may contain a repeating unit derived from a monomer other than olefin. Examples of the monomer other than olefin include 1,3-butadiene and 2-methyl-1,3-butadiene. (Isoprene), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and other conjugated dienes having 4 to 8 carbon atoms; dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene , 1,5-dicyclooctadiene, 7-methyl-1,6-octadiene, 5-vinyl-2-norbornene and other non-conjugated dienes having 5 to 15 carbon atoms.

  Examples of the polyolefin rubber include propylene homopolymer, 1-butene homopolymer, 2-methylpropene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-3-methyl- 1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer A copolymer, an ethylene-propylene-5-ethylidene-2-norbornene copolymer, an ethylene-propylene-1-butene copolymer, an ethylene-propylene-1-hexene copolymer, and an ethylene-propylene-1-octene copolymer. These polyolefin rubbers are used alone or in combination of two or more. These can be produced by known methods.

  Among polyolefin-based rubbers, an ethylene-α-olefin copolymer is preferably used from the viewpoint of further improving the cold shock resistance of the obtained molded product. Here, as the α-olefin, propylene, 1-butene, 1-hexene and 1-octene are preferable from the viewpoint of availability.

  Among the polyolefin-based rubbers, an ethylene-α-olefin copolymer having an A hardness of JIS K-6253 (1997) of 80 or less is preferable from the viewpoint of further improving the flexibility and cold shock resistance of the obtained molded product ( Condition (1)).

  The melt flow rate (MFR) of the polyolefin rubber is preferably 0.5 to 50 g / 10 from the viewpoint of further improving the meltability at the time of molding of the thermoplastic elastomer composition and the cold shock resistance of the resulting molded article. Minute, more preferably 1 to 30 g / 10 minutes. In addition, MFR is measured on condition of temperature 190 degreeC and load 21.18N according to JISK-7210 (1976).

  The styrenic thermoplastic elastomer is a vinyl aromatic compound-conjugated diene copolymer or a hydrogenated product thereof (vinyl aromatic compound-conjugated diene copolymer hydrogenated product).

  As the vinyl aromatic compound, for example, a vinyl aromatic compound having 8 to 12 carbon atoms is used, and the 1- or 2-position of the vinyl group may be substituted with an alkyl group such as a methyl group. Specifically, styrene, p-methylstyrene, α-methylstyrene and the like can be mentioned, and these are used alone or in combination of two or more. Among these, styrene is preferable from the viewpoint of availability.

  As the conjugated diene, for example, a conjugated diene having 4 to 8 carbon atoms is used, and butadiene, 2-methyl-1,3-butadiene (isoprene), pentadiene, 2-3-dimethyl-1,3-butadiene and the like are used. These may be used alone or in combination of two or more. Among these, butadiene and / or 2-methyl-1,3-butadiene (isoprene) are preferable from the viewpoint of further increasing the mechanical strength of the obtained molded body and from the viewpoint of availability.

  Examples of the vinyl aromatic compound-conjugated diene copolymer include a styrene-butadiene copolymer and a styrene-isoprene copolymer, which are used alone or in combination of two or more. Further, these can be produced by the methods described in, for example, JP-A-3-72512, JP-A-5-271325, JP-A-5-271327, JP-A-6-287365, etc. Are used singly or in combination of two or more.

  The vinyl aromatic compound-conjugated diene copolymer may be composed of one block or may be composed of two or more blocks having different structures. Examples of the structure composed of one block include a copolymer having a structure in which vinyl aromatic compounds and conjugated dienes are randomly arranged, for example, a styrene-butadiene random copolymer and a styrene-isoprene random copolymer. . As what is comprised from two or more blocks from which a structure differs, it is comprised from the copolymer comprised from a styrene homopolymer block-butadiene homopolymer, a styrene homopolymer block-isoprene homopolymer block, for example Copolymer, styrene homopolymer block-butadiene homopolymer block-copolymer composed of styrene homopolymer block, styrene homopolymer block-isoprene homopolymer block-styrene homopolymer block Copolymer, copolymer composed of styrene homopolymer block-butadiene-isoprene copolymer block-styrene homopolymer block, styrene homopolymer block-styrene-butadiene copolymer block-styrene homopolymer block Copolymer composed of In such a copolymer, the styrene-butadiene copolymer block may be a block having a structure in which styrene and butadiene are randomly copolymerized, and the styrene unit content gradually decreases or increases. -It may be a block having a par-like structure.

  The hydrogenated vinyl aromatic compound-conjugated diene copolymer is a polymer obtained by hydrogenating the aforementioned vinyl aromatic compound-conjugated diene copolymer. As the hydrogenated vinyl aromatic compound-conjugated diene copolymer, a hydrogenated copolymer having the structure described above consisting of one block, or a hydrogenated copolymer consisting of two or more blocks having different structures is used. These are used, and these may be used alone or in combination of two or more.

  The melt flow rate (MFR) measured at 230 ° C. under a load of 21.18 N in accordance with JIS K-7210 (1976) of a styrenic thermoplastic elastomer is a viewpoint of further improving the meltability at the time of molding a thermoplastic elastomer composition. Therefore, it is preferably 1 to 200 g / 10 minutes, more preferably 2 to 100 g / 10 minutes, and further preferably 3 to 80 g / 10 minutes.

Among the styrenic thermoplastic elastomers, hydrogenated vinyl aromatic compound-conjugated diene copolymer satisfying the following condition (2) from the viewpoint of further improving the heat resistance (shape retention) and light resistance of the obtained molded product. It is preferable that it is a thing.
Condition (2): Hydrogenated vinyl aromatic compound-conjugated diene copolymer containing structural units of the following (A) and (B) (A): Vinyl aromatic compound homopolymer block (B ): At least one block selected from the following (B1) and (B2) (B1): copolymer block of vinyl aromatic compound and conjugated diene (B2): conjugated diene homopolymer block

  The hydrogenated vinyl aromatic compound-conjugated diene copolymer satisfying the above condition (2) is represented by the general formula [(A)-(B)] n, [(A)-(B)] n- (A ), [(B)-(A)] n- (B) (where n is an integer of 1 or more, and when (A) and (B) are plural, the plural (A) and (B) are Each may be the same or different.], For example, [(A)-(B1)] n- (A), [(A)-(B2)] n- (A ).

  Among the hydrogenated vinyl aromatic compound-conjugated diene copolymer hydrogenated products satisfying the above condition (2), the resulting molded product has heat resistance (shape retention), light resistance, mechanical strength and cold impact resistance. From the viewpoint of further enhancement and availability, those represented by (A)-(B1)-(A), (A)-(B2)-(A) are more preferably used. For example, styrene homopolymer block-butadiene-styrene copolymer block (random copolymer block or taper-like block in which styrene gradually increases) -hydrogenated copolymer comprising a styrene homopolymer block, styrene Homopolymer block-butadiene homopolymer block-hydrogenated copolymer consisting of styrene homopolymer block, styrene homopolymer block-isoprene-styrene copolymer block (random copolymer block or styrene gradually increasing Taper block) -hydrogenated copolymer composed of styrene homopolymer block, styrene homopolymer block-isoprene homopolymer block-copolymer composed of styrene homopolymer block Among these, (A)-(B2 The vinyl aromatic compound-conjugated diene copolymer hydrogenated product represented by-(A) is particularly preferred, and is a copolymer composed of a styrene homopolymer block, a butadiene homopolymer block, and a styrene homopolymer block. Hydrogenated products are particularly preferred.

  Among the styrene-based thermoplastic elastomers, from the viewpoint of further improving the heat resistance (shape retention) and flexibility of the obtained molded product, it is a hydrogenated vinyl aromatic compound-conjugated diene copolymer, and its all vinyl The aromatic compound monomer unit content (T: wt%) is preferably 10 to 18 wt% when the vinyl aromatic compound-conjugated diene copolymer hydrogenated product is 100 wt%. What is ˜17% by weight is more preferably used (condition (3)).

The total vinyl aromatic compound monomer unit content can be determined by ¹ H-NMR measurement using a solution of hydrogenated vinyl aromatic compound-conjugated diene copolymer such as carbon tetrachloride.

  Further, among styrene-based thermoplastic elastomers, vinyl aromatic compound-conjugated diene copolymer water is used from the viewpoint of further improving the appearance (bending whitening resistance), scratch resistance, abrasion resistance and flexibility of the obtained molded product. Content of hydrogenated conjugated diene monomer unit which is an additive and the number of carbon atoms in the side chain is 2 or more when the content of hydrogenated conjugated diene monomer unit is 100% by weight (U: weight) %) Exceeds 60% by weight, more preferably 65 to 85% by weight (condition (4)). However, the content of hydrogenated conjugated diene monomer units in the hydrogenated vinyl aromatic compound-conjugated diene copolymer is 100% by weight. When the molded body is inferior in bending whitening resistance, when the molded body is shaped into a specific shape before the polyurethane foam is bonded, a portion that has been subjected to deformation such as bending may be whitened.

  In addition, by hydrogenating the vinyl aromatic compound-conjugated diene copolymer, the unsaturated bond in the repeating unit derived from the conjugated diene of the polymer is saturated, but the saturated unit is converted to water. The added conjugated diene monomer unit.

  The content can be determined by the Morero method using infrared analysis.

Further, among the hydrogenated vinyl aromatic compound-conjugated diene copolymer hydrogenated products, from the viewpoint of further improving the heat resistance of the resulting molded product (gloss of the molded product surface and prevention of bridging), (A) vinyl aromatic Content of vinyl aromatic compound monomer unit in compound polymer block (S:% by weight However, content of vinyl aromatic compound monomer unit in hydrogenated vinyl aromatic compound-conjugated diene copolymer) It is preferable that the relationship between (T) in condition (3) and (U) in condition (4) satisfies the following formula (A) (condition (5)).
U ≦ 0.375 × S + 1.25 × T + 40 (A)

Among these, when a vinyl aromatic compound-conjugated diene copolymer hydrogenated material satisfying the above conditions (2) to (5) is used, the heat resistance (shape retention, gloss of the molded body surface, A molded article having excellent resistance to light), light resistance, mechanical strength, cold shock resistance, flexibility, scratch resistance, abrasion resistance, and appearance (bending whitening resistance).
Examples of the hydrogenated vinyl aromatic compound-conjugated diene copolymer include commercially available products such as Dynalon 8600P manufactured by JSR Corporation.

  The hydrogenated vinyl aromatic compound-conjugated diene copolymer is disclosed in, for example, JP-A-3-72512, JP-A-5-271325, JP-A-5-271327, JP-A-6-287365, and the like. It can be produced by the method described.

  The mixing ratio of the component (I) and the component (II) is preferably 95: 5 to 5:95 (weight ratio), more preferably 90:10 to 10:90 (weight ratio), and particularly preferably. Is 80:20 to 20:80 (weight ratio) (provided that the total amount of component (I) and component (II) is 100 parts by weight).

  When the content of component (I) is too small, the resulting molded article may be inferior in heat resistance (shape retention, gloss of the molded article surface and prevention of bleeding). Moreover, when there is too much content of component (I), the softness | flexibility of the molded object obtained may be inferior.

  Flexibility, cold shock resistance, heat resistance (shape retention, gloss of molded body surface and prevention of bridging), mechanical strength, light resistance, scratch resistance, wear resistance and appearance (resistance) From the standpoint of enhancing (bending whitening), a polyolefin-based resin, an ethylene-α-olefin copolymer that satisfies the above condition (1), and a vinyl aromatic-conjugated diene that satisfies all of the above requirements (2) to (5) Copolymer hydrogenates are preferably used in combination.

  In this case, the content of the polyolefin-based rubber is preferably 20 to 200 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the component (I), from the viewpoint of further improving the flexibility and cold shock resistance of the obtained molded body. Is 25 to 150 parts by weight.

  The content of the hydrogenated vinyl aromatic-conjugated diene copolymer is determined by the heat resistance (shape retention, gloss of the molded body surface and prevention of bridging), light resistance, and mechanical strength of the resulting molded body. From the viewpoint of enhancing flexibility, scratch resistance, abrasion resistance and appearance (bending whitening resistance), the amount is preferably 20 to 300 parts by weight, more preferably 25 to 150 parts per 100 parts by weight of component (I). Parts by weight.

  When the thermoplastic elastomer composition contains a polyolefin rubber, the mechanical strength of the resulting molded article can be further improved by further containing a hydrogenated conjugated diene polymer. Examples of the hydrogenated conjugated diene polymer include a raw material conjugated diene polymer that is one or more polymers having 4 to 8 carbon atoms such as butadiene, isoprene, pentadiene, and 2-3dimethylbutadiene. Examples of the hydrogenated product include a hydrogenated product of polybutadiene, a hydrogenated product of polyisoprene, and the like. By hydrogenating the raw material conjugated diene polymer, the unsaturated bond in the repeating unit derived from the conjugated diene is saturated, but when the saturated unit is a hydrogenated conjugated diene monomer unit, As the hydrogenated conjugated diene polymer, the content of the hydrogenated conjugated diene monomer unit having 2 or more carbon atoms in the side chain is more than 50% by weight from the viewpoint of further improving the flexibility of the obtained molded product. It is preferable. However, the content of the hydrogenated conjugated diene monomer unit in the hydrogenated conjugated diene polymer is 100% by weight. The hydrogenated conjugated diene polymer may be composed of two or more blocks having different ratios. Examples of such a hydrogenated conjugated diene polymer include polymers described in JP-A-3-74409, and commercially available products such as “Dynalon CEBC6200” manufactured by JSR Corporation.

  When the thermoplastic elastomer composition of the present invention contains the above hydrogenated conjugated diene polymer, the content of the component (I) and the polyolefin rubber is from the viewpoint of mechanical strength and flexibility of the resulting molded article. Preferably it is 1-20 weight part with respect to 100 weight part of total amounts, More preferably, it is 2-10 weight part.

  Component (III) used in the thermoplastic elastomer composition of the present invention: A composite thermoplastic elastomer obtained by bonding a styrene thermoplastic elastomer and a urethane thermoplastic elastomer is a block made of a styrene thermoplastic elastomer. And a block copolymer having a structure in which a block made of a urethane-based thermoplastic elastomer is chemically bonded. The composite thermoplastic elastomer may be a block composed of a plurality of styrenic thermoplastic elastomers and a block composed of a plurality of urethane thermoplastic elastomers. A composite thermoplastic elastomer obtained by bonding a block made of one urethane-based thermoplastic elastomer is preferable from the viewpoint of availability.

  The composite thermoplastic elastomer includes, for example, a urethane thermoplastic elastomer produced in advance, and a styrene thermoplastic elastomer (terminated with a terminal modified with a hydroxyl group, carboxyl group, acid anhydride group, amino group, epoxy, or the like by a modifier. The modified thermoplastic elastomer can be obtained by kneading and reacting with a modified styrenic thermoplastic elastomer) under a melting condition, and then recovering and purifying the composite thermoplastic elastomer after extraction (for example, JP-A No. 2003-119343). See).

  The urethane-based thermoplastic elastomer used for the production of the composite thermoplastic elastomer is not particularly limited, but is generally produced by reacting a polymer diol, an organic diisocyanate and a chain extender.

  Examples of the polymer diol include polyester diol, polyether diol, polyester ether diol, polycarbonate diol, polyester polycarbonate diol and the like, and these are used alone or in combination of two or more.

  As the polyester diol, a polyester diol obtained by reaction of at least one dicarboxylic acid component selected from aliphatic dicarboxylic acids, aromatic dicarboxylic acids and ester-forming derivatives thereof with a low molecular diol, and ring-opening polymerization of a lactone The polyester diol obtained etc. can be mentioned, These are used 1 type or in combination of 2 or more types.

  Examples of the polyester diol include aliphatic dicarboxylic acids having 6 to 12 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and orthophthalic acid. And one or more of these ester-forming derivatives, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol , 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, etc., preferably obtained by polycondensation reaction with one or more aliphatic diols having 2 to 10 carbon atoms. Polyester diol, polycaprolactone diol, polyvalerolactone diol, etc. It can be mentioned.

  Examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Examples of the polycarbonate diol include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 2-methyl-1,8-octane. Examples thereof include polycarbonate diols obtained by reacting one or more aliphatic diols such as diols with carbonates or phosgene such as diphenyl carbonate and dialkyl carbonate.

  Although the kind of organic diisocyanate is not specifically limited, 1 type (s) or 2 or more types of aromatic diisocyanate with a molecular weight of 500 or less, alicyclic diisocyanate, and aliphatic diisocyanate are used preferably.

  Examples of organic diisocyanates include 4,4′-diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate (4,4′-dicyclohexylmethane diisocyanate), and isophorone diisocyanate. And hexamethylene diisocyanate. Among these organic diisocyanates, 4,4′-diphenylmethane diisocyanate is preferably used.

  A known chain extender can be used, but the type is not particularly limited, but one or more of aliphatic diol, alicyclic diol and aromatic diol are preferably used. It is done.

As chain extenders, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,9 -Nonanediol, cyclohexanediol, diols such as 1,4-bis (β-hydroxyethoxy) benzene can be mentioned.
Among these, an aliphatic diol having 2 to 6 carbon atoms is preferably used, and 1,4-butanediol is more preferably used.

  The structure of the terminal-modified styrenic thermoplastic elastomer is not particularly limited, but those containing structural units similar to those of the styrenic thermoplastic elastomer described in the component (II) are preferably used. In particular, a molding in which a terminal-modified styrenic thermoplastic elastomer in which the terminal of the vinyl aromatic compound-conjugated diene copolymer hydrogenated product satisfying the above conditions (2) to (5) is modified with a hydroxyl group or a carboxyl group is obtained. It is particularly preferably used from the viewpoint of the tensile properties and availability of the body.

  The vinyl aromatic compound-conjugated diene copolymer hydrogenated product satisfying the above conditions (2) to (5) modified with a hydroxyl group is, for example, ethylene at the completion of polymerization of the vinyl aromatic compound-conjugated diene copolymer. It can manufacture by adding alkylene oxides, such as an oxide and a propylene oxide, as a terminator, and hydrogenating what was obtained.

  Moreover, the vinyl aromatic compound-conjugated diene copolymer hydrogenated material satisfying the above conditions (2) to (5) modified with a carboxyl group is, for example, completion of polymerization of the vinyl aromatic compound-conjugated diene copolymer. Sometimes it can be produced by adding an alcohol such as methanol or ethanol and carbon dioxide as a terminator and hydrogenating the resulting product.

  A styrene-based heat modified at both ends, which is produced by producing the vinyl aromatic compound-conjugated diene copolymer using a polymerization initiator having two polymerization initiation points and then performing the above modification. Plastic elastomers can also be used.

  In addition, the composite thermoplastic elastomer is terminated at the beginning of the reaction or during the reaction when the urethane-based thermoplastic elastomer part is produced by reacting the polymer diol, the organic isocyanate and the chain extender in an extruder, for example. It can also be obtained by blending the modified styrenic elastomer to form a reaction product containing the composite thermoplastic elastomer, and recovering and purifying the composite thermoplastic elastomer after extraction.

  Examples of the composite thermoplastic elastomer include commercially available products such as TU polymer HM45395 and S5865 manufactured by Kuraray Co., Ltd.

  The content of component (III) with respect to 100 parts by weight of the total amount of component (I) and component (II) is 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, and 3 to 30 parts by weight. It is more preferable that Here, when there is too little this content, it may be inferior to the adhesiveness of the molded object which consists of a thermoplastic elastomer composition, and a polyurethane foam. Moreover, when there is too much this content, the non-adhesiveness of the molded object obtained may be inferior.

  Component (IV) used in the thermoplastic elastomer composition of the present invention includes ethylene-unsaturated carboxylic acid copolymer, ethylene-unsaturated carboxylic acid ester copolymer, ethylene-vinyl ester copolymer and ethylene- It is at least one polymer selected from saponified products of vinyl ester copolymers. These can be produced by known methods.

  The ethylene-unsaturated carboxylic acid copolymer is a copolymer of ethylene and an unsaturated carboxylic acid, and examples of the unsaturated carboxylic acid include acrylic acid and methacrylic acid. Examples of the ethylene-unsaturated carboxylic acid copolymer include an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer.

  The ethylene-unsaturated carboxylic acid ester copolymer is a copolymer of ethylene and an unsaturated carboxylic acid ester, and examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid. Examples include methyl acid, ethyl methacrylate, butyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. Examples of the ethylene-unsaturated carboxylic acid ester copolymer include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, Ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-methyl methacrylate copolymer, etc. Can be mentioned. These copolymers may be copolymers with unsaturated carboxylic acids such as acrylic acid and methacrylic acid.

  The ethylene-vinyl ester copolymer is a copolymer of ethylene and vinyl ester, and examples of the vinyl ester include vinyl acetate and vinyl propionate. Examples of the ethylene-vinyl ester copolymer include an ethylene-vinyl acetate copolymer and an ethylene-vinyl propionate copolymer. These copolymers may be a copolymer with an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, or a copolymer with an unsaturated carboxylic acid ester such as methyl acrylate or methyl methacrylate. (For example, an ethylene-glycidyl methacrylate-vinyl acetate copolymer may be mentioned).

  The saponified ethylene-vinyl ester copolymer can be obtained by saponifying the above-mentioned ethylene-vinyl ester copolymer, and the obtained saponified product is composed of ethylene units, vinyl ester units and vinyl alcohol units. Is done. Here, the degree of saponification is appropriately selected. In addition, it can be set as the copolymer comprised from an ethylene unit and a vinyl alcohol unit by completely saponifying the vinyl ester unit of an ethylene-vinyl ester copolymer.

  These components (IV) are olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 2-methylpropylene, 3-methyl-1-butene and 1-hexene; 1,3-butadiene, 2- Conjugated dienes having 4 to 8 carbon atoms such as methyl-1,3-butadiene (isoprene), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene; dicyclopentadiene, 5-ethylidene-2- Non-conjugated dienes having 5 to 15 carbon atoms such as norbornene, 1,4-hexadiene, 1,5-dicyclooctadiene, 7-methyl-1,6-octadiene and 5-vinyl-2-norbornene are copolymerized. May be.

  Among these components (IV), a copolymer having an ethylene unit of 5 to 95% by weight, preferably 10 to 90% by weight, particularly preferably 15 to 40% by weight, is obtained by bonding the resulting molded product to the polyurethane foam. (However, the total amount of the ethylene unit, unsaturated carboxylic acid unit, unsaturated carboxylic acid ester copolymer, vinyl ester unit and other monomer units in the copolymer is 100). (Weight%)

  The melt flow rate (MFR) of the copolymer is preferably 0.5 to 250 g / 10 minutes, more preferably 1 from the viewpoint of further improving the meltability at the time of molding the thermoplastic elastomer composition. ~ 200 g / 10 min. In addition, MFR is measured on condition of temperature 190 degreeC and load 21.18N according to JISK-7210 (1976).

  The content of component (IV) with respect to 100 parts by weight of the total amount of component (I) and component (II) is 1.0 to 100 parts by weight, preferably 5 to 80 parts by weight, and 10 to 60 parts by weight. It is more preferable that Here, when there is too little this content, it may be inferior to the adhesiveness of the molded object which consists of a thermoplastic elastomer composition, and a polyurethane foam. Moreover, when there is too much this content, the non-adhesiveness of the molded object obtained may be inferior.

  The thermoplastic elastomer composition of the present invention may contain other thermoplastic elastomer components such as a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, and a polyamide-based thermoplastic elastomer.

  In addition, the thermoplastic elastomer composition of the present invention includes, for example, a softening agent such as process oil; and a heat-resistant stabilizer such as phenol, sulfite, phenylalkane, phosphite, amine, and amide; Antistatic agent; Antistatic agent; Pigment; Silicone compound; Metal soap; Wax such as paraffinic, microcrystalline, hydrogenated terpene resin; Antifungal agent; Antibacterial agent; Filler; Alkali metal or alkaline earth metal Or oxides such as alkali metals or alkaline earth metals; inorganic salts; and various additives such as foaming agents.

  When the thermoplastic elastomer composition of the present invention contains a pigment, the molded product can be colored in a desired color. Examples of pigments include organic pigments such as azo, phthalocyanine, selenium, and dyeing lakes; oxides such as titanium oxide, chromic molybdate, selenium sulfide compounds, ferrocyan compounds, and carbon black. Inorganic pigments are used. In addition, although a pigment can also be used independently, the mixture with the master batch and pigment dispersant (vehicle) which disperse | distributed the pigment to various thermoplastic resins or thermoplastic elastomers at high concentration can also be used. . Examples of the pigment dispersant include fatty acid such as powdered palmitic acid, stearic acid, oleic acid and linoleic acid, or alkaline earth metal of fatty acid, and metal salt such as lithium and aluminum.

  When the thermoplastic elastomer composition of the present invention contains a silicone compound having a siloxane bond in the molecule, it is possible to further improve the wear resistance of the resulting molded article. The silicone compound may be modified with acrylic, epoxy, carboxylic acid, amine, urethane or the like.

  When the silicone compound is contained, the content of the component (I) and the component (II) is from the viewpoint of enhancing the wear resistance of the resulting molded article and the meltability during molding of the thermoplastic elastomer composition. It is 0.1-10 weight part normally with respect to 100 weight part of total amounts, Preferably it is 0.3-7 weight part, More preferably, it is 0.5-5 weight part.

  The thermoplastic elastomer composition of the present invention is produced by melt-kneading the above-mentioned components (I) to (IV) and other polymer components and / or additives blended as necessary. Can do.

  Alternatively, all or several kinds of the above components may be selected and kneaded or dynamically crosslinked, and then the components not selected may be melt-kneaded. Here, for melt kneading, known kneading equipment such as a single screw extruder, a twin screw extruder, a kneader, and a roll can be used. In addition, other polymer components and additives can be blended by using at least one of components (I) to (IV) in which these are blended in advance. It can also be blended. The temperature at the time of melt-kneading is not a problem as long as it is equal to or higher than the melting point of component (I), but is usually 120 to 320 ° C, preferably 140 to 300 ° C.

  The dynamic crosslinking can be performed by kneading the components subjected to the dynamic crosslinking and the crosslinking agent under heating. As the crosslinking agent, organic peroxides such as 2,5-dimethyl-2,5-di (tert-butylperoxyno) hexane and dicumyl peroxide are usually used. The crosslinking agent is usually 1 part by weight or less, preferably 0.1 to 0.8 parts by weight, more preferably 0.2 to 0.6 parts by weight per 100 parts by weight of the total components to be subjected to dynamic crosslinking. Used in the range of

  When an organic peroxide is used as a crosslinking agent, a molded article having excellent heat resistance and tensile properties can be obtained by dynamic crosslinking using a crosslinking aid such as a bismaleimide compound. The amount of the crosslinking aid used is usually 1.5 parts by weight or less, preferably 0.2-1 part by weight, more preferably 0.4-0, per 100 parts by weight of the total components to be subjected to dynamic crosslinking. .8 parts by weight. The crosslinking aid is preferably blended before the addition of the crosslinking agent, and is usually added when the components to be crosslinked are pre-kneaded. Dynamic crosslinking can be performed by kneading in a temperature range of, for example, 150 to 250 ° C. under heating using a single screw extruder or a twin screw extruder. It is also possible to perform crosslinking by a method such as sulfur crosslinking.

  The melt flow rate (MFR) of the thermoplastic elastomer composition of the present invention is preferably 0.01 to 500 g / 10 min or more, more preferably 0.1 to 300 g / 10 min or less. If the MFR is too small, the meltability during molding may be inferior. Moreover, when this MFR is too large, the heat resistance of the obtained molded object may be inferior. Here, MFR is measured under conditions of a temperature of 230 ° C. and a load of 21.18 N according to JIS K-7210 (1976).

  It is also possible to increase the meltability during molding of the thermoplastic elastomer composition by increasing the MFR of the thermoplastic elastomer composition obtained by blending the above organic peroxide during melt kneading. It is.

  Examples of the organic peroxide include diacyl peroxide, peroxy ester, diallyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2.5-dimethyl-2.5- Di (t-butylperoxy) -hexane-3,1,3-bis (t-butylperoxy-isopropyl) benzene, 1,1-di-butylperoxy-3,3,5-trimethylcyclohexane, etc. Those having a one-minute half-life of 150 to 250 ° C. are preferably used.

  The amount of the organic peroxide added is preferably 0.01 to 5.0 parts by weight and 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the total amount of components melted and kneaded at that time. It is more preferable. If the amount added is too small, the effect of improving the meltability may not be sufficiently obtained. Moreover, when there is too much this addition amount, the decomposition | disassembly of the component melt-kneaded will become excess and the intensity | strength of the molded object obtained may fall.

  By applying a molding method such as a vacuum molding method, a powder molding method, an injection molding method, a compression molding method, and an extrusion molding method to the thermoplastic elastomer composition of the present invention, a molded body having a desired shape is produced. Can do.

  The molding temperature in these moldings is not a problem as long as the temperature is equal to or higher than the melting point of component (I), but is usually in the range of 160 to 320 ° C, preferably 180 to 300 ° C.

  Among the molding methods described above, the powder molding method is preferably used from the viewpoint of producing a two-layer molded body or a multilayer molded body having a complicated shape.

When the thermoplastic elastomer composition of the present invention is applied to a powder molding method, the complex dynamic viscosity η * (1) at 250 ° C. is 1 × 10 5 from the viewpoint of further enhancing the appearance of the obtained powder molded body. The range of ² to 8 × 10 ⁴ poise is preferable, 3 × 10 ^{2 to} 5 × 10 ⁴ poise, more preferably 3 × 10 ² to 1 × 10 ⁴ poise. Here, the complex dynamic viscosity η * (1) is the following calculation formula using the storage elastic modulus G ′ (1) and loss elastic modulus G ″ (1) at a temperature of 250 ° C. and a vibration frequency of 1 radian / second. It is a value calculated by (b).
η * (1) = {[G ′ (1)] ² + [G ″ (1)] ² } ^1/2 (b)

  The powder made of the thermoplastic elastomer composition of the present invention used for powder molding is a method of mechanically pulverizing pellets made of the thermoplastic elastomer composition of the present invention, a strand cut method, a die face cut method. Or it can manufacture by methods, such as a solvent processing method (for example, refer Unexamined-Japanese-Patent No. 2003-113278).

  Further, the powder can further improve its powder fluidity by coating fine powder on its surface. As the fine powder, a fine powder having a primary particle size of 10 μm or less is used. Fine powders include inorganic oxides such as alumina, silica, alumina silica, and calcium carbonate (the surface may be coated with dimethyl silicone oil or the like, or may be surface-treated with a trimethylsilyl group or the like. Good), vinyl chloride resin for paste, fatty acid metal salt, calcium carbonate, powder pigment (however, when the pigment is contained in the thermoplastic elastomer composition, it is preferably the same color as the pigment, azo-based, Examples include organic pigments such as phthalocyanine, selenium, and dye lake, oxides such as titanium oxide, inorganic pigments such as molybdate chromate, selenium sulfide compounds, ferrocyan compounds, and carbon black. .) Etc. The primary particle size of the fine powder is required to be 10 μm or less, preferably 5 μm or less, and more preferably 5 nm to 5 μm. Here, the primary particle size is a fine powder photograph taken with a transmission electron microscope (TEM), arbitrarily selecting about 1000 particles, measuring the diameter of the particles, and determining the diameter of these particles. The value divided by the number of particles.

  These fine powders may be used alone or in combination of two or more. For example, an inorganic oxide alone can be used, or a powder pigment and an inorganic oxide can be used in combination. Further, as the fine powder, two or more kinds of fine powders having different primary particle sizes may be used in combination. For example, a fine powder having a primary particle size of 300 nm or less and a fine powder having a particle size of 300 nm to 10 μm are used. When used in combination, it is possible to obtain a powder having further excellent packing properties and anti-aggregation properties as compared with the case where each is used alone.

  The addition amount of the fine powder is usually 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight with respect to 100 parts by weight of the powder. If the amount added is too small, the effect of improving the powder fluidity may be lowered. If the amount added is too large, heat fusion between the powders is lowered. May be inferior in appearance.

  The method of blending the fine powder with the powder is not particularly limited as long as the fine powder is uniformly deposited on the powder made of the thermoplastic elastomer composition. For example, a blending method using a blender such as a jacketed blender, a high-speed rotating mixer, a nauta mixer, or a polisher may be used. The blending is usually performed at room temperature.

  The average particle size of the powder is usually 50 to 500 μm, preferably 150 to 400 μm. If the average particle size is too small, the workability of the powder may be inferior. If the average particle size is too large, the powder is inferior in meltability, so that pinholes and the like are generated in the resulting powder molded product, which may be inferior in appearance. In addition, the average particle diameter of the powder is sieved according to JIS R-6002 (1978) using a standard sieve defined in JIS Z-8801 (1976). Plotting the weight fraction of the powder molding powder that passed through each standard sieve, and based on the cumulative weight fraction line obtained from each plot, the cumulative weight fraction line and the cumulative weight fraction line of 50% by weight It is calculated from the intersection of

  The powder made of the thermoplastic elastomer composition of the present invention can be applied to various powder molding methods such as powder slush molding, fluid dipping, electrostatic coating, powder spraying, and powder rotation molding. However, it is particularly suitable for the powder slush molding method.

For example, in the powder slush molding method, it is manufactured by a method comprising the following first to fifth steps.
1st process: The process of supplying a powder on the molding surface of the metal mold | die heated more than the melting temperature of a powder Usually, metal mold | die temperature is 160-320 degreeC, The heating method of a metal mold | die is gas heating. A furnace method, a heat medium oil circulation method, a dipping method in heat medium oil or heat fluidized sand, a high frequency induction heating method, or the like is used.

Second step: A step of heating the powder on the molding surface of the first step for a predetermined time, and fusing the powders whose surfaces are melted to each other. Third step: Melting after a predetermined time has passed in the second step. Step of recovering powder that has not arrived Fourth step: Step of further heating the mold on which the molten powder is placed, if necessary Fifth step: After the fourth step, the die is cooled. And removing the molded body formed thereon from the mold

  In order to further improve the demoldability, a fluorine-based or silicone-based mold release agent is formed on the molding surface of the mold before heating the mold to a temperature higher than the melting temperature of the powder in the first step. You may coat this. Examples of the fluorine-based spray include Daikin GA-6010 (diluted organic solvent) and ME-413 (water-diluted product) manufactured by Daikin, and silicone-based sprays are manufactured by Shin-Etsu Silicon Co., Ltd. KF96SP (diluted product with organic solvent), Furilys 800 (diluted product with water) manufactured by Neos, and the like.

  The two-layer molded article of the present invention can be produced by laminating a polyurethane foam on one surface side of a molded article made of a thermoplastic elastomer composition by an injection foaming method.

  Further, the molded body made of the thermoplastic elastomer composition of the present invention may be a foam, and the foam is produced by a known method. In addition, the molded body made of the thermoplastic elastomer composition of the present invention may be a molded body composed of a plurality of layers, but at least the surface to be laminated with the polyurethane foam by the method described later is the thermoplastic elastomer composition of the present invention. It is necessary to be a molded body made of a product.

  The injection foaming method includes polyhydric alcohols such as polyether polyol, methylene bis (4,1-phenylene) diisocyanate (may be abbreviated as MDI), and polymethylene polyphenyl polyisocyanate (abbreviated as polymeric MDI). A mixed liquid by stirring an isocyanate such as toluene diisocyanate, hexamethylene diisocyanate and the like and an amine-based and tin-based catalyst with a rotary mixer; It is a method of laminating polyurethane foam by pouring on a surface to be laminated, foaming and curing. In mixing, a foam stabilizer such as silicone, an auxiliary foaming agent such as chlorofluorocarbon, water or the like can be blended. Mixing conditions (shape of stirring blade and rotation conditions (temperature, rotation speed, etc.)) and heating temperature at the time of lamination are appropriately selected.

  In addition, after injecting the above-mentioned mixed solution at the time of stacking, the injection surface side of the mixed solution is clamped by using a molded mold (pressurization can be performed as necessary) to achieve homogeneity. Can be produced.

  Moreover, after manufacturing said 2 layer molded object, the adhesiveness between a molded object and a polyurethane foam can also be improved by heating this 2 layer molded object at the temperature below melting | fusing point of a component (I). it can. In this case, the heating temperature and the heating time are appropriately selected.

  In addition, the molded body made of the thermoplastic elastomer composition of the present invention can be suitably used, for example, as a skin material for automobile interior parts such as instrument panels, door trims, console boxes, pillars, etc. A multilayer molded article obtained by laminating a thermoplastic resin core on the polyurethane foam side of the molded article or the two-layer molded article can be suitably used for these automobile interior materials.

  Examples of the synthetic resin constituting the thermoplastic resin core include polyolefin resins such as polypropylene and polyethylene, ABS (acrylonitrile-butadiene-styrene copolymer), and the like. A metal can also be used instead of the thermoplastic resin core.

  The multilayer molded body can be manufactured by laminating a thermoplastic resin core previously molded by an injection molding method or the like to the foam side of the two-layer molded body using an adhesive or the like. Alternatively, it can be produced by mounting a molded body on one mold, placing a thermoplastic resin core on the other mold, and forming a polyurethane foam between them by the above-mentioned injection foaming method. In this case, a thermoplastic resin core having an injection port opened may be used, and the above-described mixed liquid may be injected from the injection port.

  In addition, in order to improve adhesiveness with a polyurethane foam, the adhesive surface of this thermoplastic resin core body may be previously processed by methods, such as a flame process, a corona discharge process, a plasma discharge process.

Hereinafter, the present invention will be described in detail with reference to examples.
First, various evaluation methods and raw materials in the present invention will be described.
[1] Evaluation method (1) Melt flow rate (MFR)
According to JIS K-7210 (1976), the load was 21.18N and the temperature was 230 ° C.
(2) Content of hydrogenated conjugated diene monomer unit having 2 or more carbon atoms in the side chain (U: wt%)
It was determined by the Morero method using infrared analysis.
(3) Content of vinyl aromatic compound monomer unit in hydrogenated vinyl aromatic compound-conjugated diene copolymer (T: wt%)
It calculated | required from the < ¹ > H-NMR measuring method (frequency 90MHz) using the carbon tetrachloride solution of the vinyl aromatic compound-conjugated diene copolymer hydrogenated material.

(4) Hydrogenation rate of hydrogenated vinyl aromatic compound-conjugated diene copolymer hydrogenated carbon tetrachloride solution of vinyl aromatic compound-conjugated diene copolymer, vinyl aromatic compound-conjugated diene copolymer hydrogenated It calculated | required from the < ¹ > H-NMR measuring method (frequency 90MHz) using the carbon tetrachloride solution.
(5) Non-adhesiveness of molded article made of thermoplastic elastomer composition The non-adhesiveness of the two-layer molded article obtained by the following method on the molded article side made of the thermoplastic elastomer composition was evaluated based on the following criteria.
○: No tackiness was observed when touched with a finger.
X: Tackiness was recognized when touched with a finger.

(6) Adhesiveness between a molded article made of a thermoplastic elastomer composition and a polyurethane foam
A two-layer molded article was produced by the following method, and the interface between the molded article and the polyurethane foam was peeled off at a rate of 100 mm / min. The adhesion was evaluated based on the following criteria.
○: The polyurethane foam was adhered to the surface of the molded body laminated with the polyurethane foam (the ratio of the adhered surface was 80% or more).
(Triangle | delta): The polyurethane foam had adhered partially to the surface laminated | stacked with the polyurethane foam of the molded object (The ratio of the surface to which it adhered was 30% or more and less than 80%).
X: The polyurethane foam hardly adhered to the surface of the molded body laminated with the polyurethane foam (the ratio of the adhered surface was less than 30%).

[2] Raw material (1) Thermoplastic elastomer (i) Polyolefin resin: Propylene-ethylene random copolymer resin (PPD200 manufactured by Sumitomo Chemical Co., Ltd., ethylene unit content 5 wt%, MFR = 220 g / 10 min)
(Ii) ethylene-α-olefin copolymer: ethylene-butene copolymer (manufactured by Sumitomo Chemical Co., Ltd. CX5501, MFR = 30 g / 10 min (however, measured at a load of 21.18 N and a temperature of 190 ° C.), A Hardness 71)
(Iii) Hydrogenated vinyl aromatic compound-conjugated diene copolymer: hydrogenated styrene-butadiene-styrene block copolymer (total styrene unit content 15% by weight, vinyl in vinyl aromatic compound polymer block 100% by weight of aromatic compound unit, 80% by weight of hydrogenated conjugated diene unit having 2 or more carbon atoms in the side chain, 98% hydrogenation rate of double bond of conjugated diene unit, MFR = 30 g / 10 minutes)
(2) Composite thermoplastic elastomer obtained by bonding a styrene thermoplastic elastomer and a urethane thermoplastic elastomer: Kuraray Co., Ltd., TU polymer HM45395, MFR = 1.0 g / 10 min (however, load 21.18N , Measured at a temperature of 230 ° C)
(3) At least one copolymer selected from ethylene-unsaturated carboxylic acid copolymers, ethylene-unsaturated carboxylic acid ester copolymers, ethylene-vinyl ester copolymers, and saponified ethylene-vinyl ester copolymers. Polymer
(iv): ethylene-vinyl ester copolymer: ethylene-vinyl acetate copolymer (Dainippon Ink Co., Ltd., Ebaslene 830, vinyl acetate unit content 80% by weight, MFR = 9 g / 10 min (however, load 21.18N, measured at 190 ° C)))
(V): Ethylene-unsaturated carboxylic acid ester copolymer: ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Acrylift WK402, methyl methacrylate unit content 25% by weight, MFR = 20 g / 10 Minute (however, measured at a load of 21.18N and a temperature of 190 ° C))
(4) Additive Hydrogenated Terpene Resin: Clearon P135, manufactured by Yasuhara Chemical Co., Ltd.
Antioxidant: IRGANOX1076 manufactured by Ciba Specialty Chemicals Co., Ltd.
Pigment: Gray pigment (manufactured by Sumika Color Co., Ltd. Gray PPM8Y1853)
(5) Fine powder Melamine resin: Nippon Shokubai Co., Ltd. Eposter S, primary particle size 0.2 μm
Alumina silica: JC30, made by Mizusawa Chemical Co., Ltd., primary particle size 3 μm

Example 1
[Manufacture of powder for powder molding]
100 parts by weight of propylene-ethylene copolymer resin, 96 parts by weight of ethylene-butene copolymer, 156 parts by weight of hydrogenated styrene-butadiene-styrene block copolymer, 16 parts by weight of hydrogenated terpene resin, styrene-based thermoplastic Biaxially mixed 18 parts by weight of a composite thermoplastic elastomer obtained by bonding an elastomer and a urethane-based thermoplastic elastomer, 56 parts by weight of an ethylene-vinyl ester copolymer, 2.2 parts by weight of an antioxidant and 11 parts by weight of a pigment Using a kneader (manufactured by Nippon Steel Works Co., Ltd., TEX-44HCT), a thermoplastic elastomer was prepared by kneading at a cylinder temperature of 150 ° C., and this was cut into pellets by a cutting machine. The melt flow rate (MFR) of the thermoplastic elastomer was 50 g / 10 minutes.
The pellet was cooled to −120 ° C. with liquid nitrogen, pulverized while keeping the cooled state, and the pulverized product was sieved with a Tyler standard sieve (aperture 600 μm × 600 μm) to obtain a powder. The average particle size of the powder was 220 μm.
Subsequently, 1.0 part by weight of melamine resin powder and 1.0 part by weight of alumina silica were blended using a Henschel mixer (manufactured by Kawada Manufacturing Co., Ltd., 5 liter super mixer) to obtain a powder.

[Production of powder compact by powder slush molding method]
The above powder was supplied onto the molding surface of a mold with a weave pattern (15 cm square) heated to 290 ° C., and then allowed to stand for 15 seconds. Then, the excess powder was wiped off and placed in an oven at 280 ° C. for 1 minute. Stored. Thereafter, a powder-molded mold made of a thermoplastic elastomer composition melted into a sheet was cooled with water, and the sheet was removed from the mold to obtain a powder compact.

[Manufacture of two-layer molded product (lamination of powder molded product and polyurethane foam)]
100 parts by weight of polyether polyol (MHR-2197 manufactured by Mitsui Takeda Chemical Co., Ltd.) and 66.9 parts by weight of isocyanate (LDP-009 manufactured by Mitsui Takeda Chemical Co., Ltd.) , Homomixer model M type). Subsequently, it was put on one surface of the obtained powder molded body and kept at 30 ° C. for 15 minutes after clamping, thereby obtaining a two-layer molded body in which the powder molded body and the polyurethane foam were laminated. The obtained two-layer molded body was heated in an oven at an atmospheric temperature of 120 ° C. for 15 hours and then cooled at room temperature for 1 hour. The evaluation results are shown in Table 1. The powder molded body had a thickness of 1 mm, the polyurethane foam had a thickness of 9 mm, and the polyurethane foam had a specific gravity of 0.18. The evaluation results are shown in Table 1.

Example 2
The same procedure as in Example 1 was carried out except that 36 parts by weight of a composite thermoplastic elastomer obtained by bonding a styrene thermoplastic elastomer and a urethane thermoplastic elastomer and 112 parts by weight of an ethylene-vinyl ester copolymer were used. The evaluation results are shown in Table 1.

Example 3
The same procedure as in Example 2 was conducted except that an ethylene-unsaturated carboxylic acid ester copolymer was used instead of the ethylene-vinyl ester copolymer. The evaluation results are shown in Table 1.

Comparative Example 1
The same procedure as in Example 1 was performed except that a composite thermoplastic elastomer obtained by bonding a styrene thermoplastic elastomer and a urethane thermoplastic elastomer and an ethylene-vinyl ester copolymer were not used. The evaluation results are shown in Table 1.

Comparative Example 2
The same operation as in Example 1 was performed except that a composite thermoplastic elastomer obtained by bonding a styrene thermoplastic elastomer and a urethane thermoplastic elastomer was not used. The evaluation results are shown in Table 1.

Claims (11)

It contains the following components (I) to (IV), the content of component (III) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of components (I) and (II), A thermoplastic elastomer composition having a content of (IV) of 1.0 to 100 parts by weight.
(I): Polyolefin-based resin (II): Polyolefin-based rubber and / or styrene-based thermoplastic elastomer (III): Composite thermoplastic elastomer obtained by bonding a styrene-based thermoplastic elastomer and a urethane-based thermoplastic elastomer (IV ): At least one polymer selected from ethylene-unsaturated carboxylic acid copolymer, ethylene-unsaturated carboxylic acid ester copolymer, ethylene-vinyl ester copolymer and saponified ethylene-vinyl ester copolymer The thermoplastic elastomer composition according to claim 1, wherein the polyolefin rubber of component (II) is an ethylene-α-olefin copolymer satisfying the following condition (1).
(1): An ethylene-α-olefin copolymer having an A hardness of 80 or less measured according to JIS K-6253 (1997) The thermoplastic elastomer composition according to claim 1, wherein the styrene thermoplastic elastomer of component (II) is a hydrogenated diene copolymer satisfying all of the following conditions (2) to (5).
(2): Hydrogenated raw material diene copolymer containing structural units of (A) and (B) below (A): Vinyl aromatic compound polymer block (B): (B1) below And at least one block selected from (B2) (B1): a copolymer block of a vinyl aromatic compound and a conjugated diene (B2): a conjugated diene polymer block (3): in a hydrogenated diene copolymer The vinyl aromatic compound unit content (T: wt%) is 10 to 18 wt%. (4): The hydrogenated conjugated diene unit content in the hydrogenated diene copolymer is 100 wt%. The content (U: wt%) of hydrogenated conjugated diene units having 2 or more carbon atoms in the side chain exceeds 60 wt%.
(5): (A) Content of vinyl aromatic compound unit in vinyl aromatic compound polymer block (S: wt% where the content of vinyl aromatic compound unit in hydrogenated diene copolymer is 100 The relationship between (T) in condition (3) and (U) in condition (4) satisfies the following formula (A):
U ≦ 0.375 × S + 1.25 × T + 40 (A) A powder comprising the thermoplastic elastomer composition according to claim 1. A molded article comprising the thermoplastic elastomer composition according to claim 1. The molded article according to claim 5, wherein the molded article is a powder molded article obtained by powder molding the powder according to claim 4. A two-layer molded article obtained by laminating a polyurethane foam on one surface side of the molded article according to claim 5. A two-layer laminate is produced by laminating polyurethane foam on one surface side of the molded article according to claim 5 by an injection foaming method, and the two-layer laminate is produced at a temperature lower than the melting point of component (I). The manufacturing method of the two-layer molded object of Claim 7 including the process heated by. A two-layer laminate is produced by laminating a polyurethane foam on one surface side of the molded body according to claim 5 by an injection foaming method, and the two-layer laminate is produced at a temperature below the melting point of component (I). The method for bonding a molded body and a polyurethane foam according to claim 5, comprising a heating step. A multilayer molded article obtained by laminating a thermoplastic resin core on the polyurethane foam side of the two-layer molded article according to claim 7. The multilayer molded body according to claim 10, wherein the multilayer molded body is an automobile interior material.