JP2008174759A - Thermoplastic elastomer composition and thermoplastic resin composition produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition having high flexibility and excellent thermal deformation resistance and moldability and especially excellent in the compatibility with a resin having a polar group, and to provide a thermoplastic resin composition using the same. <P>SOLUTION: The thermoplastic elastomer composition is obtained by melting and kneading a composition containing 5-300 pts.wt. of a rubber softener (b), 0.01-3 pts.wt. of an organic peroxide (c) and 1-80 pts.wt. of a liquid polybutadiene having a hydroxyl group (d) on the terminal with 100 pts.wt. of an elastomer (a) prepared by mixing a hydrogenated material (a-1) obtained by hydrogenating ≥90% of a conjugated diene block of a block copolymer composed of at least two polymer blocks A composed mainly of an aromatic vinyl compound and at least one polymer block B composed mainly of a conjugated diene compound and a hydrogenated material (a-2) having a hydrogenation ratio of <90% at an (a-1)/(a-2) ratio of 5-95/95-5 (wt.%). The thermoplastic resin composition using the elastomer composition is also disclosed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic elastomer composition and a thermoplastic resin composition (alloyed product) using the thermoplastic elastomer composition, and particularly, a resin having high flexibility, heat distortion resistance, molding processability, and polar group. The present invention relates to a thermoplastic elastomer composition excellent in compatibility with the thermoplastic resin composition and a thermoplastic resin composition using the same.

  In recent years, thermoplastic elastomers, which are soft materials with rubber elasticity and do not require a vulcanization process, can be molded and processed like thermoplastic resins, and can be recycled. Automotive elastomers, home appliance parts, wire coatings, medical use Widely used in the fields of parts, footwear, sundries, etc.

  Among thermoplastic elastomers, polystyrene-based thermoplastic elastomers such as styrene-butadiene block polymer (SBS) and styrene-isoprene block polymer (SIS), which are block copolymers of aromatic vinyl compound-conjugated diene compound, are flexible. The thermoplastic elastomer composition that is rich and has good rubber elasticity at normal temperature and has excellent processability is widely used as a substitute for vulcanized rubber.

  In addition, an elastomer composition obtained by hydrogenating an intramolecular double bond of a block copolymer of styrene and a conjugated diene in these elastomers is further improved as an elastomer having improved heat aging resistance (thermal stability) and weather resistance. Widely used.

  However, thermoplastic elastomer compositions using these hydrogenated block copolymers still have problems with rubber-like properties such as oil resistance, heat-press deformation rate (compression set) and rubber elasticity at high temperatures. In order to improve this point, a crosslinked product obtained by crosslinking a composition containing a hydrogenated derivative of the block copolymer has been proposed (see, for example, Patent Documents 1 to 5).

  In addition, the crosslinked composition of the hydrogenated block copolymer disclosed in the above publication has a problem that the compression set is still insufficient at a high temperature, particularly at 100 ° C., and the mechanical strength tends to decrease. The current level of performance has not reached the performance level required for vulcanized rubber applications. In extrusion molding, the shape retention is deteriorated due to low melt tension at high temperature, and there are many problems on the molding surface such as a longer molding cycle in injection molding.

  Furthermore, attempts have been made to blend these thermoplastic elastomers with a resin having a polar group such as a polyamide polymer, a polyester polymer, or a polyurethane polymer. For example, Patent Documents 6 to 7 include hydrogenated SBS blocks. A melt blend of a thermoplastic polymer selected from a copolymer, an olefin elastomer, a diene elastomer, a urethane elastomer, and a plasticized polyvinyl chloride and a polyester thermoplastic elastomer or a polyether block amide has been proposed.

  However, the composition has a drawback that the property balance between compression set and hardness is poor, and the bending fatigue property and wear resistance are poor due to insufficient compatibility.

  In order to solve this problem, Patent Document 8 discloses a modified polystyrene system containing an epoxy group, an acid anhydride group, or an oxazoline group in a composition containing a hydrogenated derivative of a block copolymer and a polyester resin. By adding a resin and / or a modified polyolefin resin, a composition improved in compatibility and excellent in flexibility, heat resistance and chemical resistance is disclosed. Patent Documents 9 to 10 disclose block copolymers. And a hydrogenated derivative containing a carboxylic acid group or a derivative group thereof, and a composition comprising a polyolefin resin and a thermoplastic polyester.

  Patent Documents 11 to 14 disclose a composition comprising a hydrogenated derivative of a block copolymer, a hydrogenated derivative containing a carboxylic acid group or a derivative group thereof, and further a thermoplastic polyurethane. A composition comprising a hydrogenated derivative of a block copolymer and an epoxy group, or a hydrogenated derivative containing the derivative group, and further a thermoplastic polyurethane is disclosed.

However, none of the compositions is yet sufficiently compatible with the thermoplastic elastomer, the tensile properties at high temperatures, particularly at 100 ° C. or more, deteriorate, and the property balance between compression set and hardness is poor. Had. Depending on the alloy ratio with the thermoplastic elastomer, surface layer peeling and flow marks may occur during injection molding, and moldability may deteriorate due to the occurrence of grease and rough skin during extrusion molding, and low molecular weight components may bleed. Also had the disadvantage of.
JP 59-6236 A JP-A 63-57662 Japanese Patent Publication No. 3-49927 Japanese Patent Publication No. 3-11291 Japanese Patent Publication No. 6-13628 JP-A-1-139241 Japanese Patent Laid-Open No. 3-100045 JP-A-5-214209 Japanese Patent Publication No. 5-75016 Japanese Patent Laid-Open No. 1-230660 JP-A-3-234745 JP-A-3-234755 Japanese Patent Laid-Open No. 5-171003 Japanese Patent Laid-Open No. 7-126474 Japanese Patent Laid-Open No. 2-97554

  In view of the above problems, an object of the present invention is a thermoplastic elastomer composition which is rich in flexibility, excellent in heat distortion resistance and molding processability, particularly excellent in compatibility with a resin having a polar group, and the same. The object is to provide a thermoplastic resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have identified two types of hydrogenated blocks having different hydrogenation ratios between the high hydrogenation rate hydrogenated block copolymer and the low hydrogenated block copolymer. A resin having a polar group by graft-polymerizing the monomer to the elastomer by heat-treatment by blending various monomers with the rubber softener, organic peroxide, liquid polybutadiene and, if necessary, the elastomer mixture in a proportion The present inventors have found that a thermoplastic elastomer composition excellent in compatibility with can be obtained, thereby completing the present invention.

  That is, the first invention of the present invention comprises (a) (a-1) at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least two polymer blocks B mainly composed of a conjugated diene compound. 5 to 95% by weight of a hydrogenated block copolymer obtained by hydrogenating 90% or more of a conjugated diene block of a single block copolymer, and (a-2) a polymer mainly composed of an aromatic vinyl compound. Hydrogenated block copolymer obtained by hydrogenating less than 90% of a conjugated diene block of a block copolymer comprising at least two of block A and at least one of polymer block B mainly composed of a conjugated diene compound (B) 5 to 300 parts by weight of a rubber softening agent, (c) 0.01 to 3 parts by weight of an organic peroxide, and (d) the powder, based on 100 parts by weight of an elastomer comprising 5 to 95% by weight A thermoplastic elastomer composition obtained a composition containing the liquid polybutadiene 1-80 parts by weight of a hydroxyl group are melt kneaded.

  Moreover, 2nd invention of this invention is the range whose number average molecular weight of polystyrene conversion of (a-1) hydrogenated block copolymer is 100,000-400,000, (a-2) hydrogenated block The thermoplastic elastomer composition according to the first invention, wherein the copolymer has a polystyrene-equivalent number average molecular weight in the range of 10,000 to 200,000.

  The third invention of the present invention is the thermoplastic elastomer composition according to the first or second invention, further comprising (e) 1 to 20 parts by weight of an unsaturated glycidyl compound or a derivative thereof. is there.

  The fourth aspect of the present invention is the thermoplastic elastomer according to any one of the first to third aspects, further comprising (f) 1 to 20 parts by weight of an unsaturated carboxylic acid or derivative thereof. It is a composition.

  The fifth aspect of the present invention is the thermoplastic elastomer according to any one of the first to fourth aspects, further comprising (g) 0.02 to 10 parts by weight of an ester-based crosslinking aid. It is a composition.

  The sixth invention of the present invention further comprises (h) 1 to 200 parts by weight of a peroxide-decomposable olefin resin, and the thermoplastic as described in any one of the first to fifth inventions It is an elastomer composition.

  The seventh aspect of the present invention is the thermoplastic elastomer composition according to any one of the first to sixth aspects, further comprising (i) 1 to 200 parts by weight of an olefin copolymer rubber. It is a thing.

  The eighth invention of the present invention is the thermoplastic elastomer composition according to any one of the first to seventh inventions, further comprising (j) 1 to 200 parts by weight of an inorganic filler. .

  The ninth invention of the present invention comprises 100 parts by weight of the thermoplastic elastomer composition according to any one of the first to eighth inventions and 10 to 1500 parts by weight of a resin having a polar group. It is a thermoplastic resin composition.

  According to a tenth aspect of the present invention, the resin having a polar group is an ionomer, acrylic rubber, ethylene-ethyl acrylate copolymer, ethylene-methacrylate copolymer, ethylene-vinyl acetate copolymer, saponified ethylene- Vinyl acetate copolymer, polyamide resin, polyamide thermoplastic elastomer, biodegradable polyester resin, polyester resin, polyester thermoplastic elastomer, urethane thermoplastic elastomer, nitrile-butadiene rubber and partially crosslinked nitrile-butadiene rubber The thermoplastic resin composition according to the ninth invention, which is at least one resin selected from the group consisting of:

  Since the thermoplastic elastomer composition of the present invention is excellent in heat distortion resistance, molding processability, bleed resistance, and compatibility with polar group-containing resins, it can be used as a modifier for polar group-containing resins. The thermoplastic resin composition of the thermoplastic elastomer composition and a resin having a polar group is rich in flexibility, excellent in heat distortion resistance, molding processability, bleed resistance, electric wire / electric part, industrial machine part, medical It can be used in fields such as equipment / food-related parts, automobile parts, and building materials.

  The components, production methods, and uses constituting the present invention will be described in detail below.

1. Component (1) of thermoplastic elastomer composition
Elastomer (a)
The elastomer (a) component used in the thermoplastic elastomer composition of the present invention is a mixture of the following (a-1) high hydrogenation rate hydrogenated block copolymer and (a-2) low hydrogenation rate hydrogenated block copolymer: It is an elastomer consisting of

(A-1) Hydrogenated block copolymer elastomer The high hydrogenation rate hydrogenated block copolymer (a-1) used in component (a) is at least two polymer blocks A mainly composed of an aromatic vinyl compound. And a hydrogenation rate hydrogen obtained by hydrogenating 90% or more of an aliphatic double bond part derived from a conjugated diene in a conjugated diene block of a block copolymer consisting of at least one polymer block B mainly composed of a conjugated diene compound It is a monster. For example, the hydrogenation rate of a conjugated diene block of an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as ABA, BABA, ABBABA, etc. A hydrogenated block copolymer obtained by hydrogenation of 90% or more can be exemplified.

  The polymer block A mainly composed of an aromatic vinyl compound is preferably composed of an aromatic vinyl compound alone, or a conjugated diene hydrogenated with 50% by weight or more, preferably 70% by weight or more of the aromatic vinyl compound. It is a copolymer block with a compound.

  The polymer block B mainly composed of a hydrogenated conjugated diene compound is preferably composed of only a hydrogenated conjugated diene compound or 50% by weight or more, preferably 70%, of a hydrogenated conjugated diene compound. It is a copolymer block of at least% by weight and an aromatic vinyl compound.

  The block copolymer contains 5 to 60% by weight, preferably 20 to 50% by weight of an aromatic vinyl compound.

  As the aromatic vinyl compound constituting the block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. preferable. In addition, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred.

  Further, in the polymer block A mainly composed of these aromatic vinyl compounds and the polymer block B mainly composed of conjugated diene compounds, the distribution of units derived from the conjugated diene compound or aromatic vinyl compound in the molecular chain is random, It may be tapered (in which the monomer component increases or decreases along the molecular chain), partially in a block form, or any combination thereof. When there are two or more polymer blocks A mainly composed of aromatic vinyl compounds or polymer blocks B mainly composed of conjugated diene compounds, each polymer block has a different structure even if each has the same structure. There may be.

  These block copolymers can be obtained by block polymerization in an inert medium using a lithium catalyst or a Ziegler type catalyst by a known method, for example, the method described in JP-B-40-23798. The hydrogenated block copolymer can be obtained by hydrogenating the above block copolymer by a known method. Hydrogenation mainly hydrogenates an aliphatic double bond derived from a conjugated diene of a conjugated diene block, and its hydrogenation rate needs to be 90% or more. When the hydrogenation rate is less than 90%, flexibility and transparency tend to deteriorate.

  The polymer structure B in the hydrogenated component (a-1) and mainly composed of a conjugated diene compound has an arbitrary microstructure. For example, in a polybutadiene block, the 1,2-microstructure is Preferably it is 20 to 50 weight%, Most preferably, it is 25 to 45 weight%. In the polyisoprene block, it is preferable that 70 to 100% by weight of isoprene has a 1,4-microstructure.

  The number average molecular weight (Mn) in terms of polystyrene of the hydrogenated block copolymer (a-1) is 30,000 to 500,000, preferably 100,000 to 400,000, more preferably 150,000 to 350,000. 000, more preferably in the range of 200,000-350,000, and the molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)) is preferably 5 or less, more preferably Is 2 or less. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof. When the number average molecular weight (Mn) is less than the lower limit, the heat resistance, scratch resistance and oil resistance are lowered. On the other hand, when the upper limit is exceeded, fluidity is deteriorated, and appearance defects such as short shots and flow marks occur in the molded product in injection molding. In extrusion molding, the occurrence of rough skin, eye grease, etc. becomes prominent. In addition, the molecular weight in this invention is the value calculated | required on the basis of the polystyrene whose molecular weight is known by GPC. Therefore, the value is a relative value, not an absolute value, and may vary by about ± 30% depending on GPC conditions such as a reference sample, apparatus, and data processing method.

  Specific examples of the hydrogenated block copolymer of component (a-1) include styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), and styrene-ethylene. -An ethylene-propylene-styrene copolymer (SEEPS) etc. can be mentioned.

(A-2) Low hydrogenation rate hydrogenated block copolymer elastomer The low hydrogenation rate hydrogenated block copolymer (a-2) component used in (a) is a polymer block mainly composed of an aromatic vinyl compound. Less than 90% of the aliphatic double bond portion derived from the conjugated diene of the conjugated diene block of the block copolymer comprising at least two of A and at least one of the polymer blocks B mainly composed of the conjugated diene compound Low hydrogenation rate hydride. For example, the hydrogen content of the conjugated diene block of the block copolymer of aromatic vinyl compound-conjugated diene compound having a structure such as ABA, BABA, ABBABA, etc. A hydrogenated block copolymer obtained by hydrogenation of less than 90% can be mentioned. Here, the polymer block A is preferably 40% by weight or less.

  The polymer block A mainly composed of an aromatic vinyl compound may be a polymer composed only of an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and less than 50% by weight of a conjugated diene compound. The polymer block B mainly composed of a conjugated diene compound may be a polymer composed solely of a conjugated diene compound or a copolymer of a conjugated diene compound and less than 50% by weight of an aromatic vinyl compound.

  As the aromatic vinyl compound constituting the component (a-2), for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc., among which styrene Is preferred. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene, and these The combination of is preferable.

  The microstructure in the polymer block B mainly composed of a conjugated diene compound can be selected arbitrarily. In the butadiene block, the 1,2-microstructure has a lower limit of 1% or more, preferably 5% or more, more preferably 10% or more, and an upper limit of 95% or less, preferably 80% or less, more preferably 75% or less. is there.

  The hydrogenation rate of the aliphatic double bond based on the conjugated diene of the conjugated diene block in the hydrogenated copolymer of component (a-2) is less than 90%, preferably less than 80%, more preferably 75. %, Particularly preferably less than 60%. The lower limit is preferably 3% or more, more preferably 5% or more, still more preferably 7% or more, and particularly preferably 9% or more. Further, the 1,2-vinyl bond after hydrogenation is preferably 0.5 to 12%, more preferably less than 10%, still more preferably 5% or less, and still more preferably 3% or less. When the hydrogenation rate exceeds 90%, the crosslinking efficiency tends to decrease and the heat resistance and oil resistance tend to decrease.

  The number average molecular weight in terms of polystyrene of the hydrogenated block copolymer (a-2) having the above structure is 10,000 to 500,000, preferably 10,000 to 200,000, more preferably 10,000 to. It is in the range of 150,000. The molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, and more preferably 2 or less. The molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.

  When the number average molecular weight (Mn) is less than the lower limit, the mechanical properties, heat resistance, scratch resistance, and oil resistance of the molded product are lowered. On the other hand, when the upper limit is exceeded, fluidity is deteriorated, and appearance defects such as short shots and flow marks occur in the molded product in injection molding. In extrusion molding, the occurrence of rough skin, eye grease, etc. becomes prominent. In addition, the molecular weight in this invention is the value calculated | required on the basis of the polystyrene whose molecular weight is known by GPC. Therefore, the value is a relative value, not an absolute value, and may vary by about ± 30% depending on GPC conditions such as a reference sample, apparatus, and data processing method.

  Specific examples of the hydrogenated block polymer component (a-2) having a hydrogenation rate of less than 90% include partially hydrogenated styrene-butadiene-styrene copolymer having 1,2-bonds selectively hydrogenated in the butadiene block. Examples include coalescence (SBBS). Moreover, a partially hydrogenated styrene-isoprene-styrene copolymer, a partially hydrogenated styrene-isoprene / butadiene-styrene copolymer, and the like can be given. In the present invention, the hydrogenated product of the aromatic vinyl compound-conjugated diene compound block copolymer may be used alone or in combination of two or more.

  The blending ratio of (a-1) and (a-2) in the elastomer component (a) is such that the component (a) is 5 to 95% by weight, preferably 50 to 85% by weight, and the component (a-2) Is 95 to 5% by weight, preferably 50 to 15% by weight. When the component (a-1) is less than 5% by weight (the component (a-2) exceeds 95% by weight), the heat resistance and mechanical properties of the resulting thermoplastic elastomer composition are deteriorated. In addition, the alloyed product has a decrease in heat resistance, flexibility, mechanical properties, and moldability. On the other hand, when the component (a-1) exceeds 95% by weight (the component (a-2) is less than 5% by weight), the heat resistance of the resulting thermoplastic elastomer composition is lowered. Moreover, fluidity | liquidity is insufficient and the moldability of the thermoplastic elastomer composition obtained will deteriorate. The alloyed product shows deterioration of mechanical properties and moldability due to a decrease in compatibility.

(2) Rubber softener (b)
The rubber softener (b) component used in the thermoplastic elastomer composition of the present invention may be a non-aromatic rubber softener component or an aromatic rubber softener component, and an ester plasticizer is also used. In particular, non-aromatic mineral oils and ester plasticizers are preferred. Non-aromatic mineral oil softeners include paraffin softeners in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total number of carbon atoms.

  Among the ester plasticizers, cyclic plasticizers include, for example, phthalic anhydride ester and trimellitic ester, N-cyclohexyl-p-toluenesulfonamide, dibenzyl sebacate, diethylene glycol dibenzoate, di-t -Octylphenyl ether, dipropanediol dibenzoate, N-ethyl-p-toluenesulfonamide, isopropylidene diphenoxypropanol, alkylated naphthalene, polyethylene glycol dibenzoate, o, p-toluenesulfonamide, trimethylpentanediol dibenzoate and And trimethylpentanediol, monoisobutyrate, monobenzoate and the like. In these, a phthalic anhydride ester and trimellitic acid ester are preferable.

  Representative examples of the phthalic anhydride ester include, for example, butyl octyl phthalate, butyl 2-ethylhexyl phthalate, butyl n-octyl phthalate, dibutyl phthalate, diethyl phthalate, diisodecyl phthalate, dimethyl phthalate, dioctyl phthalate, di (2 -Ethylhexyl) phthalate, diisooctyl phthalate, diisononyl phthalate (DINP), di-tridecyl phthalate, n-hexyl n-decyl phthalate, n-octyl n-decyl phthalate, alkyl benzyl phthalate, bis (4-methyl) -1,2-pentyl) phthalate, butyl benzyl phthalate, butyl cyclohexyl phthalate, di (2-butoxyethyl) phthalate, cyclohexyl isodecyl phthalate, disi Rohexyl phthalate, diethyl isophthalate, di-n-heptyl phthalate, dihexyl phthalate, di (2-methoxyethyl) phthalate, dimethyl isophthalate, dinonyl phthalate, dioctyl phthalate, dicapryl phthalate, di (2-ethylhexyl) isophthalate, Mixed dioctyl phthalate, diphenyl phthalate, 2- (ethylhexyl) isobutyl phthalate, butyl phthalyl butyl glycolate, ethyl (and methyl) phthalyl ethyl glycolate, polypropylene glycol bis (amyl) phthalate, hexyl isodecyl phthalate, isodecyl -Tridecyl phthalate, isooctyl, isodecyl phthalate, etc. are mentioned.

  Representative examples of trimellitic acid esters include, for example, triisooctyl trimellitate, tri-n-octyl / n-decyl trimellitate, trioctyl trimellitate, tri (2-ethylhexyl) trimellitate (TOTM) , Tri-n-hexyl / n-decyl trimellitate, tri-n-hexyl trimellitate, triisodecyl trimellitate, triisononyl trimellitate and the like.

  Acyclic plasticizers include phosphate ester, adipic acid ester, azelaic acid ester, citric acid ester, acetyl citrate ester, myristic acid ester, ricinoleic acid ester, acetyl ricinoleic acid ester, sebacic acid ester, stearic acid ester , Epoxidized esters, further 1,4-butanediol dicaprylate, butoxyethyl pelargonate di [(butoxyethoxy) ethoxy] methane, dibutyl tartrate, diethylene glycol dipelargonate, diisooctyl diglycolate, isodecyl Nonanoate, tetraethylene glycol di (2-ethyl-butyrate), triethylene glycol di (2-ethyl-hexanoate), triethylene glycol dipelargonate and branched 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, ester of aliphatic dihydric alcohol, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), Examples include acrylic polymers.

  Representative examples of phosphate esters include, for example, cresyl diphenyl phosphate, tricresyl phosphate, dibutyl phenyl phosphate, diphenyl octyl phosphate, methyl diphenyl phosphate, tributyl phosphate, triphenyl phosphate, tri (2-butoxyethyl) phosphate , Tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate and trioctyl phosphate.

  Representative examples of adipic acid esters include di [2- (2-butoxyethoxy) ethyl] adipate, di (2-ethylhexyl) adipate, diisononyl adipate (DINA), diisodecyl adipate, dioctyl adipate (diisooctyl) Adipate), n-hexyl n-decyl adipate, n-octyl n-decyl adipate and di-n-heptyl adipate.

  Representative examples of sebacic acid esters include, for example, dibutyl sebacate, di (2-ethylhexyl) sebacate, dibutoxyethyl sebacate, diisooctyl sebacate and diisopropyl sebacate.

  Representative examples of azelaic acid esters include, for example, di (2-ethylhexyl) azelaate, dicyclohexylazelaate, diisobutylazelaate and diisooctylazelaate.

  As the acrylic polymer plasticizer, a reaction product obtained by reacting a mixture of (i) a radical polymerizable monomer and (ii) a modifying compound in the presence or absence of a polymerization initiator. A polymer composed of a product is exemplified. This polymer is preferably (ii) a polymer in which the bonding mode of the modifying compound to the polymer is an ester bond, (i) using (meth) acrylic acid as a radical polymerizable monomer, and (ii) ) A polymer using an aliphatic or alicyclic alcohol as the modifying compound may be used.

  In the acrylic polymer plasticizer, as the radical polymerizable monomer (i), (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth) acrylates such as acrylate; hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; maleic anhydride, maleic acid, mono- and dialkyl esters of maleic acid; styrene, Aromatic vinyl monomers such as α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; (meth) acrylonitrile, (meth) acrylamide, and chloride Vinyl, chloride Vinylidene, allyl chloride and allyl alcohol and the like.

  The modifying compound (ii) includes cycloalkanols such as cyclohexyl alcohol; alkanols such as isopropyl alcohol; halogen-containing alcohols such as fluoroalkyl alcohol; alkylene diols such as ethylene glycol and butanediol; cyclohexanediol and cyclohexyldi Cycloalkylene diols such as methanol; hydroxyl group-containing modifiers such as polyethers having hydroxyl groups at the ends, polymers such as polyester, cyclohexyl carboxylic acid, cyclohexyl dicarboxylic acid, adipic acid, sebacic acid, fluoroalkyldicarboxylic acid, maleic anhydride and Carboxyl group-containing compounds such as fumaric acid; ethyl acetate, butyl acetate, cellosolve acetate, methylpropylene glycol acetate, carbitol acetate Ester group-containing modifiers such as bets and ethyl carbitol acetate, cyclohexene, include alkenes such as cyclopentene and isobutene.

  Examples of acrylic polymers in the combination of (i) and (ii) include (i) (meth) acrylic acid, maleic anhydride, maleic acid or maleic acid monoalkyl ester, and the like of (ii) A polymer in which the modifying compound is introduced into the polymer is obtained by esterification using a compound having a hydroxyl group. Further, by using an ester group-containing monomer such as (i) methyl (meth) acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate and a compound having a hydroxyl group of (ii), a transesterification reaction is performed. A functional polymer is obtained. Furthermore, the formation of an ester bond by the reaction of the hydroxyl group-containing monomer of (i) 2-hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate with the carboxyl group or ester group-containing compound of (ii) A polymer into which a functional group has been introduced is obtained. Furthermore, by using a carboxyl group-containing monomer such as (meth) acrylic acid (i) and an alkene (ii), the carboxyl group is added to an ethylenically unsaturated bond to form an ester bond, which is modified. A polymer into which the compound for quality is introduced is obtained.

  In the acrylic polymer plasticizer that can be used in the present invention, butyl acrylate, ethyl acrylate, hexyl acrylate, mesooxyethyl acrylate, and glycidyl acrylate are preferable as the above (i), and ethyl acrylate is the main component. Is optimal.

  The weight average molecular weight (Mw) of the acrylic polymer plasticizer is preferably 500 to 10,000, more preferably 1000 to 6000, still more preferably 1000 to 3000, and the viscosity is preferably 100 to 9000 mPa · s. More preferably, it is 1000 to 6000 mPa · s, more preferably 3000 to 5000 mPa · s, and the SP value obtained from Acetone-Water Tolerance is preferably 10.5 to 16.5, more preferably 13 to 16, Preferably it is 14-16.

  Among these plasticizers that are ester compounds, DINP, DINA, and TOTM are particularly preferable.

  The compounding quantity of a component (b) is 5-300 weight part with respect to 100 weight part of component (a), Preferably it is 20-150 weight part. If the blending amount is less than 5 parts by weight, the flexibility of the resulting thermoplastic elastomer composition is lowered. Moreover, the softness | flexibility of the alloyed material which is a thermoplastic resin composition of the thermoplastic elastomer composition and resin which has a polar group falls, and a moldability deteriorates. When it exceeds 300 parts by weight, the softening agent tends to bleed out from the resulting thermoplastic elastomer composition, and peeling, deformation and flow marks are likely to occur in the molded product. Furthermore, the gas generated during processing becomes significant. Also, the alloyed product is likely to be bleed.

(3) Organic peroxide (c)
The organic peroxide component (c) used in the present invention functions to generate radicals and cause the radicals to react in a chain manner to crosslink the component (a) and / or the component (i) blended as necessary. do. At the same time, the components (e) to (g) to be blended as necessary are graft-polymerized to the component (a) and / or the component (i), thereby improving the compatibility with the polar group-containing resin. Furthermore, the component (h) to be blended is decomposed or cross-linked as necessary to control the fluidity of the composition at the time of melt-kneading to improve the dispersion of the rubber component.

  Examples of the component (c) include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2. , 5-Di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3, 3,5- Trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert- Butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroylpa Oxide, tert- butyl cumyl peroxide, and the like. Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di, from the viewpoint of odor, colorability, and scorch safety. -(Tert-Butylperoxy) hexyne-3 is particularly preferred.

  The compounding quantity of a component (c) is 0.01-3 weight part with respect to 100 weight part of component (a), Preferably it is 0.05-1.5 weight part. When the blending amount is less than 0.01 parts by weight, crosslinking cannot be sufficiently achieved, and the heat resistance and oil resistance of the resulting thermoplastic elastomer composition are deteriorated. Moreover, the moldability of the alloyed product of the obtained thermoplastic elastomer composition and the resin having a polar group is deteriorated. On the other hand, even if it exceeds 3 parts by weight, the mechanical properties and moldability of the obtained thermoplastic elastomer are deteriorated, and the moldability of the alloyed product of the obtained thermoplastic elastomer composition and the resin having a polar group is deteriorated.

(4) Terminal hydroxyl group-containing liquid polybutadiene (d)
The terminal hydroxyl group-containing liquid polybutadiene component (d) used in the thermoplastic elastomer composition of the present invention is mainly composed of the component (a) and the component (i) which is blended as necessary when the elastomer composition is melt-processed. Graft polymerization is carried out in the presence of a peroxide to exhibit the effect of suppressing bleed-out of low molecular weight substances in the elastomer composition and at the same time improve the compatibility with the polar group-containing resin. Component (d) is a liquid polymer which is transparent at room temperature, and has a main chain microstructure of vinyl 1,2-bond type, trans 1,4-bond type, and cis 1,4-bond type. Here, the vinyl 1,2-bond is preferably 30% by weight or less, and if the vinyl 1,2-bond exceeds 30% by weight, the low temperature characteristics of the resulting thermoplastic elastomer composition are lowered, which is preferable. Absent.

  Here, the terminal hydroxyl group content (JIS K 1557) is preferably 0.05 to 3.0 mol / kg, more preferably 0.1 to 1.5 mol / kg.

  The number average molecular weight of the liquid polybutadiene is preferably 1,000 to 5,000, more preferably 2,000 to 4,000. When the number average molecular weight is less than 1,000, the heat-resistant deformation property of the resulting thermoplastic elastomer composition is lowered, and when it exceeds 5,000, the compatibility of the obtained thermoplastic elastomer composition is lowered. As a commercial item, Idemitsu Petrochemical Co., Ltd. R-45HT (trademark) is mentioned, for example.

  The amount of component (d) is preferably 1 to 80 parts by weight, particularly preferably 3 to 50 parts by weight, per 100 parts by weight of component (a). If the blending amount exceeds 80 parts by weight, the softening agent tends to bleed out from the resulting thermoplastic elastomer composition, and peeling, deformation and flow marks are likely to occur in the molded product. In addition, softening agent bleed out easily occurs in the alloyed product, and peeling, deformation and flow mark are easily generated in the molded product. When the amount is less than 1 part by weight, the thermoplastic elastomer composition is not improved in flexibility and moldability. In an alloyed product, peeling, deformation, and flow marks are likely to occur in a molded product due to a decrease in compatibility.

(5) Unsaturated glycidyl compound or derivative thereof (e)
If necessary, the thermoplastic elastomer composition of the present invention may contain an unsaturated glycidyl compound or a derivative component (e) thereof. Component (e) is used as a modifier, and preferably a glycidyl compound having an unsaturated group and a glycidyl group copolymerizable with an olefin in the molecule is used, particularly preferably glycidyl methacrylate (GMA). Is used. By the modifier, components such as a hydrogenated block copolymer soft component in the elastomer component (a), a copolymer rubber component, and a peroxide-crosslinked olefin resin blended as necessary are modified, Compatibility with a resin having a polar group is improved.

  When blended, the amount of component (e) is preferably 1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, per 100 parts by weight of component (a). When the amount exceeds 20 parts by weight, not only the heat distortion resistance and mechanical properties of the resulting thermoplastic elastomer composition are deteriorated, but also the effect of improving the compatibility with the resin having a polar group is not recognized.

(6) Unsaturated carboxylic acid or derivative thereof (f)
In the thermoplastic elastomer composition of the present invention, an unsaturated carboxylic acid or a derivative component (f) thereof can be blended as necessary. Component (f) is used as a modifier, and preferably includes acrylic acid, methacrylic acid, maleic acid, dicarboxylic acid or derivatives thereof such as acids, halides, amides, imides, anhydrides, ester derivatives and the like. Can be mentioned. Particularly preferably, maleic anhydride (MAH) is used. By the modifier, the peroxide-decomposable olefin-based resin of component (a) and component (h) blended as necessary, preferably polypropylene or the component (i) blended as necessary, is modified to polar group Improves compatibility with a resin having

  When blended, the amount of component (f) is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of component (a). When the blending amount exceeds 20 parts by weight, severe yellowing occurs in the thermoplastic elastomer composition, and not only the heat distortion resistance and mechanical properties deteriorate, but also when the polar group-containing resin is blended, The effect of improving the compatibility is not recognized.

(7) Ester-based crosslinking aid (g)
In the thermoplastic elastomer composition of the present invention, an ester-based crosslinking aid component (g) can be used as necessary. Component (g) can be blended in the crosslinking treatment with the above-mentioned (c) organic peroxide of the thermoplastic elastomer composition of the present invention, whereby a uniform and efficient crosslinking reaction can be performed. . In addition, by blending in a large amount, softeners for non-aromatic rubber, particularly low molecular weight paraffinic oil, etc. can be appropriately cross-linked, and bleeding out from the thermoplastic elastomer composition and alloyed product can be suppressed. .

  Specific examples of the component (g) include, for example, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol having 9 to 14 repetitions of ethylene glycol. Polyfunctional methacrylate compounds such as dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, 2-methyl-1,8-octanediol dimethacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol diacrylate, 1,6 -Hexanediol diacrylate, trimellirol propane tetraacrylate, sometimes pentaerythritol polyacrylate, neopentyling Call diacrylate, polyfunctional acrylate compounds such as propylene glycol diacrylate, can be mentioned polyfunctional vinyl compounds such as vinyl butyrate or vinyl stearate. These may be used alone or in combination of two or more. Of these crosslinking aids, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, and dipentaerythritol polyacrylate are particularly preferable.

  When blended, the amount of component (g) is preferably 0.02 to 10 parts by weight, more preferably 0.1 to 3 parts by weight, per 100 parts by weight of component (a). If it exceeds 10 parts by weight, the degree of cross-linking decreases due to self-polymerization and the effect cannot be obtained.

(8) Peroxide-decomposable olefin resin (h)
In the thermoplastic elastomer composition of the present invention, a peroxide-decomposable olefin resin component (h) can be blended as necessary. Ingredient (h) improves the rubber dispersion of the resulting thermoplastic elastomer composition, improves the appearance of the molded product, and has an effect of adjusting the hardness and shrinkage rate. The component is an olefin polymer or copolymer that is thermally decomposed by heat treatment in the presence of peroxide to reduce the molecular weight and increase fluidity at the time of melting, such as isotactic polypropylene and propylene. And other α-olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.

  The melting point by DSC measurement of the homo part of the olefin copolymer is preferably in the range of Tm of 150 to 167 ° C. and ΔHm of 25 to 83 mJ / mg. The crystallinity can be estimated from Tm and ΔHm of DSC measurement. When Tm and ΔHm are outside the above ranges, the oil resistance of the resulting thermoplastic elastomer composition and the rubber elasticity at 100 ° C. or higher are not improved.

  The melt flow rate (MFR, ASTM D-1238, L condition, 230 ° C.) of component (h) is preferably 0.1 to 200 g / 10 minutes, more preferably 0.5 to 100 g / 10 minutes. . If the MFR is less than 0.1 g / 10 minutes, the moldability of the resulting thermoplastic elastomer composition deteriorates, and if it exceeds 200 g / 10 minutes, the rubber elasticity of the obtained thermoplastic elastomer composition deteriorates.

  When blended, the amount of component (h) is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, per 100 parts by weight of component (a). If it exceeds 200 parts by weight, the moldability of the resulting thermoplastic elastomer composition will deteriorate, peeling, deformation and flow marks will tend to occur in the molded product, and the thermoplastic elastomer composition will become too hard and lose its flexibility. I can't get a rubber-like product.

(9) Olefin copolymer rubber (i)
If necessary, the thermoplastic elastomer composition of the present invention may contain an olefin copolymer rubber component (i). Component (i) includes an elastomer obtained by copolymerizing an α-olefin such as ethylene, propylene, 1-butene, 1-pentene, or an olefin copolymer rubber obtained by copolymerizing these with a non-conjugated diene. It is done.

  Examples of non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, and 5-ethylidene-2-norbornene.

  Specific examples of such olefin copolymer rubber include ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, ethylene-1-butene copolymer rubber, and ethylene-1. -Butene-nonconjugated diene copolymer rubber, ethylene-propylene-1-butene copolymer rubber, and the like.

  When blended, the amount of component (i) is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of component (a). When it exceeds 200 parts by weight, the mechanical strength of the resulting thermoplastic elastomer composition is significantly reduced.

(10) Inorganic filler (j)
An inorganic filler component (j) can be blended with the thermoplastic elastomer composition of the present invention as necessary. In addition to the effect of improving some physical properties such as compression set of a molded article obtained from the thermoplastic elastomer composition, the component (j) has an economic advantage due to the increase in the amount. As the component (j), wollastonite, chlorite, calcium carbonate, talc, silica, diatomaceous earth, barium sulfate, magnesium carbonate, magnesium hydroxide, mica, clay, titanium oxide, carbon black, glass fiber, hollow glass balloon, Examples thereof include carbon fiber, calcium titanate fiber, natural silicic acid, and synthetic silicic acid (white carbon). Of these, calcium carbonate, wollastonite, chlorite and talc are particularly preferred.

  When blended, the amount of component (j) is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, per 100 parts by weight of component (a). When the amount exceeds 200 parts by weight, the mechanical strength of the resulting thermoplastic elastomer composition is remarkably lowered, the hardness is increased, the flexibility is lost, and a rubber-like product cannot be obtained.

(11) Amorphous polyolefin component (l)
In the elastomer composition of the present invention, an amorphous polyolefin component (l) can be blended as necessary. The amorphous polyolefin component (l) used in the present invention is an amorphous copolymer mainly composed of propylene having a melt viscosity at 190 ° C. of 250 to 50,000 mPa · s, preferably 10,000 to 25,000 mPa · s. A relatively low molecular weight polymer made of a polymer and having a crystallinity measured by X-ray diffraction of 50% or less, preferably 20% or less. The glass transition temperature of the amorphous polyolefin is preferably −33 to −23 ° C., and the softening point is preferably 120 to 135 ° C.

  Specific examples of the amorphous polyolefin include amorphous homopolymer atactic polypropylene and other olefins mainly composed of propylene (for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl- 1-pentene, 1-octene, 1-decene and the like) and the like. Of these amorphous polyolefins, atactic polypropylene, propylene / ethylene amorphous copolymer, and propylene / 1-butene amorphous copolymer are preferable. The amorphous polyolefin may be a random copolymer or a block copolymer. In the case of a block copolymer, the bonding mode of propylene units needs to be an atactic structure. Further, when the amorphous copolymer is a copolymer of propylene and ethylene, the content of the propylene unit is preferably 50 mol% or more, particularly preferably 60 to 100 mol%. For example, Eastman Chemical Co., Ltd. E-1200 is mentioned as an amorphous polyolefin.

  When blended, the amount of component (l) is preferably 1 to 150 parts by weight, more preferably 3 to 80 parts by weight, per 100 parts by weight of component (a). If the blending amount exceeds 150 parts by weight, the softening agent tends to bleed out from the resulting elastomer composition, and peeling, deformation and flow marks are likely to occur in the molded product. Moreover, the oil resistance and heat resistance of the alloy of the elastomer composition obtained and resin which has a polar group fall.

(12) Other components In addition to the above components, the thermoplastic elastomer composition of the present invention may further include various blocking inhibitors, sealability improvers, thermal stabilizers, antioxidants, It is also possible to contain a light stabilizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a colorant and the like. Here, examples of the antioxidant include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4 , 4-dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like, phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and the like. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred. The antioxidant is preferably 0 to 3.0 parts by weight, particularly preferably 0.1 to 1.0 parts by weight based on 100 parts by weight of the total of the components (a) to (i).

  In addition to the above components, the thermoplastic elastomer composition of the present invention may further include an ester group, a carboxyl group, a carbonyl group, an acid anhydride group, an amino group, a hydroxyl group, a glycidyl group, and an oxazolyl group, if necessary. It is also possible to contain a compound having one or more polar groups selected from the group consisting of: For example, saponified ethylene-vinyl acetate copolymer (saponified EVA), maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, ethylene-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate (HEMA) and the like can be mentioned. When the saponified ethylene-vinyl acetate copolymer (saponified EVA) and 2-hydroxyethyl methacrylate (HEMA) are contained, the blending amount is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the component (a). More preferably, it is 0.1-50 weight part.

2. Production of Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention is prepared by adding the above components (a) to (d), or components (e) to (l) as necessary, and simultaneously adding each component or It can be produced by adding and kneading in any order.

  The method of melt kneading is not particularly limited, and generally known methods can be used. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders can be used. For example, the above operation can be continuously performed by using a suitable L / D twin screw extruder, Banbury mixer, pressure kneader, or the like. Here, the temperature of melt kneading is preferably 160 to 220 ° C.

3. Thermoplastic resin composition The thermoplastic resin composition of the present invention is a composition containing the thermoplastic elastomer composition obtained above and a resin having a polar group. The thermoplastic elastomer composition of the present invention has good compatibility with a resin having a polar group, and the flexibility, extrusion moldability, injection moldability, etc. of the resin having a polar group are reduced in heat resistance and oil resistance. And can be improved without bleed of low molecular weight.

  The resin having a polar group that can be used in the present invention is not particularly limited as long as it is a thermoplastic resin, elastomer, or rubber having a polar group. For example, polyester resins (PET, PBT, PEN, PCT, PETG, etc.), polyamide resins (PA), polycarbonates (PC), resins mainly composed of a copolymer of ethylene and a vinyl group-containing monomer, nitrile-butadiene rubber (NBR), partially crosslinked nitrile- Examples thereof include butadiene rubber, polyurethane-based thermoplastic elastomer (TPU), polyester-based thermoplastic elastomer (COPE), polyamide-based thermoplastic elastomer (COAE), biodegradable polyester-based resin, and acrylic rubber. These resins and rubbers may be used alone or in combination of two or more.

  Among these, in particular, polyurethane-based thermoplastic elastomer (TPU), polyester-based resin (PET, PBT, PEN, PCT, PETG, etc.), polyester-based thermoplastic elastomer (COPE), polyamide-based resin (PA), polyamide-based Thermoplastic elastomers (COAE), ionomers, resins based on copolymers of ethylene and vinyl group-containing monomers, nitrile-butadiene rubber (NBR), crosslinked nitrile-butadiene rubber (crosslinked NBR), biodegradable Polyester resins and acrylic rubber are preferred.

  The polyurethane-based thermoplastic elastomer (TPU) having a polar group used in the present invention is generally prepared from a polyol, a diisocyanate, and a chain extender. Examples of the polyol include polyester polyol, polyester ether polyol, polycarbonate polyol, and polyether polyol.

  Here, examples of the polyester polyol include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, or their acid esters or acid anhydrides, ethylene glycol, 1,3-propylene glycol, 1 , 2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1 , 3-octanediol, 1,9-nonanediol, etc. Details, polyester polyols obtained by dehydration condensation reaction of a mixture thereof; polylactone diols obtained by ring-opening polymerization of lactones monomer such as ε- caprolactone.

  Examples of the polycarbonate polyol include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6. -One or more polyhydric alcohols such as hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol and diethylene carbonate, Polycarbonate polyols obtained by reacting with dimethyl carbonate, diethyl carbonate and the like can be mentioned.

  Further, examples of the polyester ether polyol include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, or their acid esters or anhydrides and glycols such as diethylene glycol or propylene oxide adducts, etc. Or the compound obtained by dehydration condensation reaction with these mixtures is mentioned.

  Furthermore, examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide, and tetrahydrofuran, and copolyethers thereof.

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

  Next, as the isocyanate, for example, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diene Isocyanate (XDI), hydrogenated XDI, triisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, 1,8-diisocyanate methyloctane, lysine ester triisocyanate, 1,3,6-hexa Examples include methylene triisocyanate and bicycloheptane triisocyanate. Of these, 4,4′-diphenylmethane diisocyanate (MDI) is preferably used.

  Further, as the chain extender, a low molecular weight polyol is used. For example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol And aliphatic polyols such as glycerin, and aromatic glycols such as 1,4-dimethylolbenzene, bisphenol A, bisphenol A ethylene oxide or propylene oxide adducts.

  Examples of the polyester-based resin having a polar group used in the present invention include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), 1,4-cyclohexanedimethanol (CHDM), modified PET ( PETG), polycyclohexylene dimethylene terephthalate (PCT), a copolymer of PET and PCT, a copolymer of PCT and polycyclohexylene dimethylene isophthalate, and the like.

  As the polyester-based thermoplastic elastomer (COPE) of the resin having a polar group used in the present invention, a polyester or polyester having a low glass transition temperature (Tg) as a soft segment and a polyester or polyester as a soft segment is used. Block copolymers are preferred. For example, an aromatic crystalline polyester such as polybutylene terephthalate as a hard segment, a polyester / polyether type using a polyether as a soft segment, an aromatic crystalline polyester as a hard segment, an aliphatic as a soft segment Examples include polyester / polyester molds using polyester.

  Here, examples of the polyester / polyether type include those synthesized by transesterification and polycondensation reactions using dimethyl terephthalate, 1,4-butanediol, polytetramethylene glycol, and the like as starting materials. Examples of the polyester / polyester type include those synthesized by transesterification and ring-opening reactions using dimethyl terephthalate, 1,4-butanediol, and ε-caprolactone as starting materials.

  Examples of the polyamide-based resin (PA) having a polar group used in the present invention include nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon 11, nylon 12, and nylon. -6, 12 or nylon MXD6 (aliphatic polyamide having an aromatic ring in the main chain).

  The polyamide-based thermoplastic elastomer (COAE) of a resin having a polar group used in the present invention is a thermoplastic elastomer having a polyamide-constrained phase and a polyether / polyester structure as a soft segment. The basic structure is in the form of a polyester block polyamide elastomer or a polyether ester block polyamide elastomer. For example, a polyamide-based thermoplastic elastomer using a PA12 component as a polyamide constrained phase is obtained by adding water as a lactam ring-opening catalyst to lauryl lactam, dicarboxylic acid, and polyether diol, Rick nylon 12 oligomer is obtained and then obtained by a condensation reaction with polyether diol.

  Here, a polyamide-based thermoplastic elastomer having various characteristics can be obtained depending on the type of diol used. For example, polyamides such as nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon 11, nylon 12, or nylon-6,12 are hard segments, and soft segments are polyetheresters. And a block elastomer.

  Examples of the ionomer resin having a polar group used in the present invention include a copolymer of ethylene and a monomer represented by the general formula (I).

In the general formula (I), R ¹ represents hydrogen or a methyl group, and M represents a metal such as Na or Zn or hydrogen.

  Here, examples of the monomer represented by the general formula (I) include methacrylic acid metal salts, acrylic acid metal salts, methacrylic acid, and acrylic acid, and among them, methacrylic acid metal salts are preferable.

  An ionomer resin is an ionic copolymer having an ionic crosslink having a high rebound resilience, and specifically, a copolymer with an unsaturated organic acid such as ethylene and acrylic acid or methacrylic acid. What formed the salt completely or partially neutralized like Formula (I) is good. The cation is usually an alkali metal, zinc or the like, and particularly when sodium and zinc are used in combination, a high rebound resilience can be obtained.

  In the copolymer with ethylene, the monomer preferably occupies 3 to 20% by weight, particularly 4 to 15% by weight. An ethylene-methacrylic acid metal salt copolymer having a methacrylic acid metal salt content of 3 to 20% by weight, particularly 4 to 15% by weight, is preferred. If the above monomer is less than 3% by weight, there is a problem that it is not sufficiently dispersed in the resulting composition. If it exceeds 20% by weight, the required rebound resilience cannot be obtained. The copolymer preferably has a melt flow rate of 0.5 to 15 g / 10 min (measured at a temperature of 190 ° C. and a load of 21.18 N according to JIS K 6760). Here, if necessary, an ethylene-vinyl acetate copolymer and an ethylene-α-olefin copolymer can be blended, and a mixture of three or more resins can also be used.

  As a resin mainly composed of a copolymer of ethylene and a vinyl group-containing monomer of a resin having a polar group used in the present invention, a copolymer of ethylene and a monomer represented by the following general formula (II) is used. A polymer can be mentioned.

  In general formula (II), R2 represents a hydrogen atom or a methyl group, and R3 is represented by the following general formula (III).

In general formula (III), R ⁴ represents a hydrogen atom or an alkyl group. As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

  Specific examples of the monomer represented by the general formula (II) include, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, isopropenyl butyrate, methyl (meth) acrylate, and ethyl (meth). Examples include acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. These can be used alone or in combination of two or more. Particularly preferred monomers are selected from the group consisting of vinyl acetate and ethyl (meth) acrylate.

  In the copolymer of ethylene and the monomer represented by the general formula (II), the ratio of the ethylene and the monomer represented by the general formula (II) is not particularly limited, but preferably 97 to 70 wt. %, Monomer 3 to 30% by weight. The copolymer of ethylene and the monomer represented by the general formula (II) can further contain a monomer such as a modified olefin monomer, and the monomer such as a modified olefin monomer in that case The content of is not more than 50% by weight of the copolymer.

  Specific examples of the copolymer of ethylene and the monomer represented by the general formula (II) include, for example, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene- Examples thereof include a methacrylic acid copolymer and a saponified ethylene-vinyl acetate copolymer (saponified EVA).

  Here, the saponified ethylene-vinyl acetate copolymer (saponified EVA) is a compound obtained by saponifying EVA, having an ethylene content of 40 to 95% by weight, preferably 60 to 90% by weight, and vinyl acetate. The saponification degree of the component is 80% or more, preferably 90% or more. When the ethylene content is less than 40% by weight, the heat resistance is poor, and when it exceeds 95% by weight, the flexibility is poor. Further, when the saponification degree of the vinyl acetate component is less than 60%, the heat resistance is lowered.

  The saponified EVA preferably has a melt flow rate (MFR) of 0.1 to 30 g / 10 minutes measured at 190 ° C. under a load of 21.18 N in accordance with JIS K6924-2. When the MFR is less than 0.1 g / 10 minutes, the fluidity of the composition is poor, and when it exceeds 30 g / 10 minutes, the mechanical strength and heat resistance are poor.

The resin-containing nitrile-butadiene rubber (NBR) having a polar group used in the present invention is a copolymer rubber of an unsaturated nitrile and a conjugated diene, wherein the unsaturated nitrile and the conjugated diene are in a weight ratio (unsaturated nitrile). / Conjugated diene), copolymerized at a ratio of 10/90 to 60/40, preferably 20/80 to 50/50. If it is less than 10/90, the oil resistance is poor, and if it exceeds 60/40, the rubber elasticity is poor. The NBR preferably has a Mooney viscosity (ML _{1 + 4} ; 100 ° C.) of 20 to 120, more preferably 40 to 100. If it is less than 20, rubber elasticity is poor, and if it exceeds 120, processability is inferior.

  Here, specific examples of the unsaturated nitrile include α, β-unsaturated nitriles, and examples include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. The α, β-unsaturated nitrile can be used alone or in combination of two or more. Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, chloroprene and the like, among which 1,3-butadiene and isoprene are preferable. . Conjugated dienes can be used singly or in combination of two or more.

  Examples of the unsaturated nitrile-conjugated diene copolymer include acrylonitrile-butadiene copolymer rubber (NBR), acrylonitrile-butadiene-isoprene copolymer rubber (NBIR), acrylonitrile-isoprene copolymer rubber (NIR), acrylonitrile- Examples thereof include butadiene-butoxy acrylate copolymer rubber, acrylonitrile-butadiene-acrylic acid copolymer rubber, and acrylonitrile-butadiene-methacrylic acid copolymer rubber. Of these, NBR is preferably used.

  The partially crosslinked NBR of the resin having a polar group used in the present invention is an NBR partially crosslinked type, and has a gel fraction of 60 to 95%, preferably 70 to 90%. If the gel fraction is less than 60%, the permanent elongation is bad, and if it exceeds 95%, the workability suddenly deteriorates. The NBR gel fraction referred to here means an extraction residue which is immersed in xylene at 120 ° C. for 20 hours and separated by an 80 mesh filter. The acrylonitrile content in the partially crosslinked NBR used here is preferably 30 to 45% by weight, more preferably 32 to 35% by weight. If it is out of this range, the oil resistance deteriorates.

Examples of the biodegradable polyester-based resin having a polar group used in the present invention include biodegradable aliphatic polyesters, and industrially, starting from aliphatic dicarboxylic acid and excess diol, Synthesized by dehydration polycondensation reaction and dediol reaction, further introduced with aromatic compound, ring opening polymerization of lactide, condensation polymerization of lactic acid, high molecular weight polycaprolactone, synthesized from carbon monoxide and formalin Examples include polyglycolic acid. Among the biodegradable aliphatic polyesters, an aliphatic-aromatic random copolyester is a copolymer polyester resin of diol, fatty acid and aromatic acid, and the repeating unit is [-{(O—R ¹ —O ^{_{) a - (CO-R 2}} -CO) b} - {(O-R 3 -O) c - (CO-Ar-CO) d} -] is a polyester resin comprising, further branching agent as an optional component ( BA) [— {(O—R ¹ —O) _a — (CO—R ² —CO) _b } — {(O—R ³ —O) _c — (CO—Ar—CO) _d } — containing _x ] (BA) A structure such as _x may be used.

Here, in the structural unit, the fatty acid residue: —CO—R ² —CO— is a residue of a fatty acid having 3 to 40 carbon atoms, preferably 3 to 12, and examples of the fatty acid include malonic acid. Succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, Selected from the group consisting of 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,5-norbornanedicarboxylic acid, 4- (hydroxymethyl) cyclohexanecarboxylic acid, hydroxypivalic acid, 6-hydroxyhexane Hydroxy acids such as acids, glycolic acid, lactic acid, and their ester-forming derivatives are also used. It can be used as the fatty acid component for preparing et copolyester.

  The aromatic acid residue: -CO-Ar-CO- is an aromatic acid residue having 8 to 40 carbon atoms, preferably 8 to 14 carbon atoms. -Selected from the group consisting of terephthalic acid, 1,3-terephthalic acid, 2,6-naphthoic acid, 1,5-naphthoic acid, their ester-forming derivatives and combinations thereof.

Furthermore, the diol residues: —O—R ¹ —O— and —O—R ³ —O— are residues of a diol having 2 to 20 carbon atoms, and examples of the diol include ethylene glycol, diethylene glycol, Propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3- It is selected from the group consisting of cyclobutanediol, triethylene glycol, tetraethylene glycol and combinations thereof. The diol components may be the same or different.

Furthermore, a branching agent as an optional component: (BA) _x (where x represents the weight% of the branching agent, preferably 0.01 to 10% by weight, more preferably 0.1 to 1.0% by weight). ) Has a weight average molecular weight of preferably about 50 to 5000, more preferably 92 to 3000, a polyol having 3 to 6 hydroxy groups, a polycarboxylic acid having 3 or 4 carboxyl groups, or Examples thereof include hydroxy acids having 3 to 6 hydroxyl groups and carboxyl groups in total. For example, examples of low molecular weight polyols include glycerol, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakis (hydroxy Methyl) cyclohexane, tris (2-hydroxyethyl) isocyanurate and dipentaerythritol. Examples of high molecular weight polyols (Mw: 400-3000) include triols derived by condensing C2-C3 alkylene oxides such as ethylene oxide and propylene oxide with a polyol initiator. Examples of polycarboxylic acids include hemimellitic acid, trimellitic acid, trimesic acid, pyromellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2- Examples include ethanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, and 1,2,3,4, -cyclopentanetetracarboxylic acid, although acids may be used in this way, but preferably When a lower alkyl ester or a cyclic anhydride can be formed, it is used in the form of the cyclic anhydride. Hydroxy acids include malic acid, citric acid, tartaric acid, 3-hydroxyglutaric acid, mucinic acid (or mucoic acid), trihydroxyglutaric acid and 4- (β-hydroxyethyl) phthalic acid, such as Hydroxy acids contain a combination of three or more hydroxyl groups and carboxyl groups. Among these, particularly preferred branching agents include trimellitic acid, trimesic acid, pentaerythritol, trimethylolpropane, and 1,2,4-butanetriol.

  Examples of the biodegradable aliphatic polyester suitably used in the present invention include polybutylene succinate (binary condensate of succinic acid and 1,4-butanediol), polybutylene succinate adipate (succinic acid and adipic acid) , And a ternary condensate of 1,4-butanediol), polybutylene succinate terephthalate (a ternary condensate of succinic acid and terephthalic acid, and 1,4-butanediol).

  In addition, in the biodegradable aliphatic polyester used in the present invention, reactive groups such as isocyanate groups and urethane groups are introduced into the structure for the purpose of functional modification within the range not impairing the biodegradable function. It is also possible to do. Furthermore, various copolymers such as a copolyester obtained by copolymerizing polylactic acid can also be used.

  As the biodegradable aliphatic polyester used in the present invention, those commercially available as biodegradable resins can be used. For example, as a trade name, Bionore (manufactured by Showa Polymer Co., Ltd.), Ester Bio (manufactured by Eastman Chemicals), Biopol (manufactured by Monsanto Japan), Biomax (manufactured by DuPont), Ecoflex (manufactured by BASF), etc. can be mentioned. The resin according to the characteristics can be arbitrarily selected.

  As the acrylic rubber of the rubber having a polar group used in the present invention, a rubber obtained by copolymerizing a small amount of monomers having various functional groups with an alkyl acrylate such as ethyl acrylate and butyl acrylate as a monomer component As a monomer that is an elastic body and is copolymerized, methyl vinyl ketone, acrylic acid, acrylonitrile, β-chloroethyl vinyl ether, butadiene, or the like can be used as appropriate. Specifically, Nipol AR (trade name, manufactured by Nippon Zeon Co., Ltd.), JSR AR (trade name, manufactured by JSR Corp.) or the like can be used. In particular, it is preferable to use methyl acrylate as the monomer component. In that case, a binary copolymer with ethylene and an unsaturated hydrocarbon having a carboxyl group such as acrylic acid in the side chain. A ternary copolymer to which is added as a third component can be particularly preferably used. Specifically, in the case of a binary copolymer, Baymac D or Baymac DLS, and in the case of a ternary copolymer, Baymac G, Baymac HG, Baymac LS, Baymac GLS (trade names, both of which are Mitsui and DuPont) Polychemical Co., Ltd.) can be used.

  The compounding quantity of the resin which has the above polar groups is 10-1500 weight part with respect to 100 weight part of thermoplastic elastomer compositions, Preferably it is 20-1200 weight part. When the blending amount is less than 10 parts by weight, the effect of addition is not recognized, and when it exceeds 1500 parts by weight, the flexibility of the resulting thermoplastic resin composition is lowered. By blending the thermoplastic elastomer composition, oil resistance, abrasion resistance, high temperature properties such as tensile properties at high temperatures, etc. of the resulting thermoplastic resin composition can be dramatically improved.

4). Manufacturing method of thermoplastic resin composition The manufacturing method of the thermoplastic resin composition of this invention can be manufactured by the method similar to the manufacturing method of said thermoplastic elastomer composition. That is, it can be manufactured by adding and kneading a thermoplastic elastomer composition and a resin having polarity and, if necessary, optional components such as an antioxidant used in the thermoplastic elastomer composition described above.

  The method of melt kneading is not particularly limited, and generally known methods can be used. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders can be used. For example, the above operation can be continuously performed by using a suitable L / D twin screw extruder, Banbury mixer, pressure kneader, or the like. Here, the melt kneading temperature varies depending on the resin used, but is preferably 160 to 250 ° C.

  The alloyed product which is the thermoplastic resin composition of the present invention is rich in flexibility, excellent in heat distortion resistance and molding processability, and particularly excellent in oil resistance, wear resistance, and mechanical properties at high temperatures. In particular, it can be used for electric wires / electric parts, industrial machine parts, medical equipment parts, food-related parts, automobile parts, building materials and the like.

  Specifically, examples of the electric wires / electric parts include connectors, switch covers, plugs, gaskets, grommets, cable jacket curl cords, electric wire insulation coatings, etc., and examples of industrial machine parts include pressure hoses, diaphragms, etc. , Gaskets, packing, casters, grommets, roller coupling grips, hoses, etc., and medical equipment / food-related parts include, for example, syringe tips, drug stoppers, grommets, blood collection caps, cap seals, etc. Examples of automobile parts include CVJ boots, rack and opinion boots, shock absorber dust boots, vacuum connectors, air ducts, tubes, run channels, grommets, handle covers, and air bag outer covers stearins. , It includes mudguards, etc., as a building material, for example, window frame seals, expansion joints, sponge seals, handrail cover, stair slip and the like. Other applications include, for example, grip materials such as pen grips, bicycle grips, toothbrush grips, toy parts, mats, goggles, dust / gas masks, and shoe soles.

  The present invention will be specifically described by the following examples and comparative examples, but the present invention is not limited to these examples. In addition, the measuring method and sample of the physical property used by this invention are shown below.

1. Test method (1) Specific gravity: In accordance with JIS K 7112, the test piece was measured using a gel or solid sample.
(2) Hardness: Measured in accordance with JIS K 6253 with durometer hardness, type A (indicated in the table as “A” after the number), and type D (in the table, indicated as “D” after the number). . A 6.3 mm thick press sheet was used as the test piece.
(3) Tensile strength: In accordance with JIS K 6251, the test piece was a 1 mm thick press sheet punched into a No. 3 dumbbell-type test piece. The tensile speed was 500 mm / min. (Measured at room temperature and 100 ° C)
(4) 100% elongation stress: In accordance with JIS K 6251, a 1 mm thick press sheet was punched into a No. 3 dumbbell type test piece and used. The tensile speed was 500 mm / min.
(5) Elongation at break: In accordance with JIS K 6251, the test piece was a 1 mm thick press sheet punched into a No. 3 dumbbell type test piece. The tensile speed was 500 mm / min.
(6) Volume change rate: In accordance with JIS K 6258, a 1 mm thick press sheet was punched into a No. 3 dumbbell-shaped test piece. Using IRM # 903 oil, the weight change at 120 ° C. for 72 hours was measured.
(7) Injection moldability: Using an injection molding machine with a clamping pressure of 120 tons, a molding temperature of 220 ° C., a mold temperature of 40 ° C., an injection speed of 55 mm / second, an injection pressure of 600 kg / cm ² , and a holding pressure of 400 kg / cm ^2. A sheet of 13.5 × 13.5 × 2 mm was formed with an injection time of 6 seconds and a cooling time of 45 seconds. The presence or absence of delamination, surface layer peeling, deformation, and the presence of a flow mark that significantly deteriorated the appearance was judged by visual observation, and evaluated according to the following criteria.
◯: Good x: Bad (8) Extrudability: A sheet of 50 mm × 1 mm was extruded, the drawdown property, surface appearance and shape were observed, and evaluated according to the following criteria.
○: Good x: Bad (9) Bleed resistance: Extruded sheet that is bent and fixed with a clip is allowed to stand at room temperature and 110 ° C. for 168 hours and visually observed for low molecular weight bleed and blooming. Evaluation based on the criteria.
○: Good x: Bad (10) Hydrogenation rate of the conjugated diene block part: A sample is collected in an NMR sample tube (5 mmφ), deuterated chloroform is added, and then sufficiently dissolved, and a nuclear magnetic resonance apparatus (NMR) Using a JSX GSX-400 model, ¹ H-NMR measurement was performed at normal temperature, 400 MHz, and 3029 times of integration, to obtain a hydrogenation rate.

2. Samples used in Examples and Comparative Examples (1) High hydrogenation rate hydrogenated block copolymer component (a-1): Septon 4077 (SEPS; manufactured by Kuraray Co., Ltd.), styrene content: 30% by weight, number average molecular weight: 260,000, weight average molecular weight: 320,000, molecular weight distribution: 1.23, hydrogenation rate: 90% or more (2) low hydrogenation rate hydrogenated block copolymer component (a-2): Tuftec P series JT90C (SBBS; manufactured by Asahi Kasei Corporation), styrene content: 30% by weight, number average molecular weight: 99,000, weight average molecular weight; 110,000, molecular weight distribution; 1.11, hydrogenation rate of butadiene block: 75.1 %, (Hydrogenation rate of 1,2-butadiene 92.7%, hydrogenation rate of 1,4-butadiene 61.0%)
(3) Rubber softener component (b): PW90 (trademark; manufactured by Idemitsu Petrochemical Co., Ltd.), number average molecular weight 980
(4) Organic peroxide component (c): Perhexa 25B (2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane; manufactured by NOF Corporation)
(5) Terminal hydroxyl group-containing liquid polybutadiene component (d): R-45HT (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group (0.83 mol / kg) as a functional group and copolymerizable unsaturated double bond (1,4 Bond: 80%), number average molecular weight 2800
(6) Unsaturated glycidyl compound component (e): glycidyl methacrylate (GMA) (manufactured by NOF Corporation)
(7) Unsaturated carboxylic acid component (f): maleic anhydride (MAH) (manufactured by NOF Corporation)
(8) Ester-based crosslinking assistant component (g): TMPT (Trimethylol Propane Trimethacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.) Molecular weight: 338,
(9) Peroxide-decomposable olefin resin component (h): PP-BC8 (polypropylene (PP); manufactured by Nippon Polychem Co., Ltd.), crystallinity: Tm 166 ° C., ΔHm; 82 mJ / mg, MFR: 1.8 g / 10 minutes (10) ethylene-butene copolymer rubber component (i): Esprene N0441 (EBR; manufactured by Sumitomo Chemical Co., Ltd.)
(11) Calcium carbonate component (j): NS400 (manufactured by Sankyo Seiko Co., Ltd.)
(12) Hindered phenol / phosphite / lactone composite antioxidant component (k): HP2215 (manufactured by Ciba Specialty Chemicals)

(13) Resin having a polar group (i) Urethane thermoplastic elastomer (TPU): Pandex T-8180 (manufactured by DIC Bayer Polymer Co., Ltd.)
(Ii) Polyester thermoplastic elastomer (COPE): Hytrel 4056 (manufactured by Toray DuPont)
(Iii) Polyamide-based thermoplastic elastomer (COAE): Pebax 5533SN01 (manufactured by Toray Industries, Inc.)
(Iv) Ionomer: High Milan 1554 (Mitsui / Dupont Polychemical Co., Ltd.)
(V) Polyamide (PA6): Grillon R47HWNZ (Mus Japan)
(Vi) Polyester (PET): SA-1346P (manufactured by Unitika Ltd.)
(Vii) EVA: EVAFLEX EV-40LX (Mitsui / DuPont Polychemical Co., Ltd.)
(Viii) EEA: NUC-6170 (manufactured by Nippon Unicar Co., Ltd.)
(Ix) Saponified EVA: Mersen H6051 (manufactured by Tosoh Corporation)
(X) NBR: PNC-38 (manufactured by JSR Corporation)

Examples 1-2 and Comparative Examples 1-8
Using each component in the amount shown in Table 1, the mixture was put into a twin screw extruder having an L / D of 47, and melt kneaded at a kneading temperature of 180 ° C. and a screw rotation speed of 350 rpm to be pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Table 1.

  As is clear from Table 1, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are all thermoplastic elastomer compositions regardless of the presence or absence of optional components (e) to (k). Good properties were shown.

  On the other hand, in Comparative Examples 1 and 2, the blending amounts of the component (a-1) and the component (a-2) are out of the scope of the present invention. When there are too many components (a-1) ((a-2) is too few), heat resistance and a moldability will deteriorate and mechanical characteristics will fall. When there are too many components (a-2) (too few (a-1)), heat resistance and mechanical characteristics will fall. In Comparative Examples 3 and 4, the amount of component (b) is out of the scope of the present invention. If the amount of the component (b) is too small, the resulting thermoplastic elastomer composition will be too hard, and if the amount of the component (b) is too large, the mechanical properties will decrease, and the softening agent will be removed from the resulting thermoplastic elastomer composition. It is easy to bleed out, and peeling, deformation, and flow marks are likely to occur in the molded product. Furthermore, the gas generated during processing becomes significant. In Comparative Examples 5 and 6, the amount of component (c) is out of the scope of the present invention. When the amount of component (c) is too small, crosslinking cannot be sufficiently achieved, the heat resistance and oil resistance of the resulting thermoplastic elastomer composition are lowered, stickiness becomes remarkable, and the amount of generated gas increases. . Even if the component (c) is too much, the mechanical properties are lowered, the mechanical properties and moldability of the resulting thermoplastic elastomer composition are lowered, and the pellet shape and moldability are deteriorated. In Comparative Examples 7 and 8, the amount of component (d) is out of the scope of the present invention. When there is too little component (d), the softness | flexibility of the thermoplastic elastomer composition obtained will fall, and a pellet shape and a moldability will deteriorate. When there is too much component (d), a softening agent tends to bleed out from the thermoplastic elastomer composition obtained, and it will become easy to produce peeling, a deformation | transformation, and a flow mark in a molded article. Furthermore, the gas generated during processing becomes significant. When SBS (hydrogenation rate 0% VECTOR2518 manufactured by DEXCO POLYMERS) was used instead of the component (a-2), the resulting thermoplastic elastomer was slightly hardened and the moldability was also lowered.

Examples 3-4, Comparative Example 9
The thermoplastic elastomer composition obtained in Examples 1 and 2 and a urethane-based thermoplastic elastomer (TPU) were blended at a ratio of 30:70 (% by weight), and charged into a twin screw extruder having an L / D of 47. Then, the mixture was melt-kneaded at a kneading temperature of 200 ° C. and a screw rotation speed of 350 rpm to form pellets. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Table 2. Moreover, as Comparative Example 9, evaluation was performed in the case of TPU alone. The results are shown in Table 2.

  As is clear from Table 2, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with TPU and are more flexible and mechanical properties than the case of TPU alone shown in Comparative Example 9. A TPU thermoplastic resin composition having an excellent balance of oil resistance, moldability, and bleed resistance can be obtained.

Comparative Examples 10-17
Physical properties and injection molding of pellets obtained in the same manner as in Examples 3 to 4 from a composition obtained by blending the thermoplastic elastomer composition obtained in Comparative Examples 1 to 8 and TPU at a ratio of 30:70 (% by weight) Property, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 2. The thermoplastic elastomer compositions outside the scope of the present invention in Comparative Examples 1 to 8 were inferior in compatibility with TPU and deteriorated in moldability or bleed resistance.

Examples 5-6, Comparative Example 18
The thermoplastic elastomer composition obtained in Examples 1 and 2 and a polyester-based thermoplastic elastomer (COPE) were blended in a ratio of 30:70 (% by weight) and charged into a twin screw extruder having an L / D of 47. Then, the mixture was melt-kneaded at a kneading temperature of 220 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Table 3. Further, as Comparative Example 18, evaluation was performed in the case of COPE alone. The results are shown in Table 3.

  As is clear from Table 3, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with COPE, and are more flexible, mechanical properties, compared to the case of COPE alone shown in Comparative Example 18. A COPE thermoplastic resin composition having an excellent balance of oil resistance, moldability, and bleed resistance can be obtained.

Comparative Examples 19 to 26
Physical properties and injection molding of pellets obtained in the same manner as in Examples 5 to 6 from compositions obtained by blending the thermoplastic elastomer compositions obtained in Comparative Examples 1 to 8 and COPE at a ratio of 30:70 (% by weight) Property, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 3. The thermoplastic elastomer compositions outside the scope of the present invention in Comparative Examples 1 to 8 were inferior in compatibility with COPE and deteriorated in moldability or bleed resistance.

Examples 7-8, Comparative Example 27
The thermoplastic elastomer composition obtained in Examples 1 and 2 and the polyamide-based thermoplastic elastomer (COAE) were blended at a ratio of 30:70 (% by weight) and charged into a twin screw extruder having an L / D of 47. Then, the mixture was melt-kneaded at a kneading temperature of 220 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Table 4. Further, as Comparative Example 27, evaluation was performed in the case of COAE alone. The results are shown in Table 4.

  As is clear from Table 4, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with COAE, compared with the case of COAE alone shown in Comparative Example 27, mechanical properties, oil resistance, A COAE-based thermoplastic resin composition excellent in moldability and bleed resistance can be obtained.

Comparative Examples 28-35
Physical properties and injection molding of pellets obtained in the same manner as in Examples 7 to 8 from compositions obtained by blending the thermoplastic elastomer compositions obtained in Comparative Examples 1 to 8 and COAE at a ratio of 30:70 (% by weight) Property, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 4. The thermoplastic elastomer compositions outside the scope of the present invention in Comparative Examples 1 to 8 were inferior in compatibility with COAE and deteriorated in moldability or bleed resistance.

Examples 9 to 10, Comparative Example 36
The thermoplastic elastomer compositions obtained in Examples 1 and 2 and the ionomer were blended at a ratio of 30:70 (% by weight) and charged into a twin screw extruder having an L / D of 47, and a kneading temperature of 190 ° C. Then, the mixture was melt-kneaded at a screw rotation speed of 350 rpm and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Table 5. Further, as Comparative Example 36, an evaluation was made in the case of an ionomer alone. The results are shown in Table 5.

  As is clear from Table 5, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with ionomers, compared with the case of the ionomer alone shown in Comparative Example 36, mechanical properties, oil resistance, An ionomer thermoplastic resin composition having excellent moldability and bleed resistance can be obtained.

Comparative Examples 37-44
Physical properties and injection molding of pellets obtained in the same manner as in Examples 9 to 10 from a composition obtained by blending the thermoplastic elastomer composition obtained in Comparative Examples 1 to 8 and an ionomer in a ratio of 30:70 (% by weight). Property, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 5. The thermoplastic elastomer compositions outside the scope of the present invention in Comparative Examples 1 to 8 were inferior in compatibility with the ionomer and deteriorated in moldability or bleed resistance.

Examples 11-12, Comparative Example 45
The thermoplastic elastomer composition obtained in Examples 1 and 2 and nylon 6 (PA6) were blended at a ratio of 30:70 (% by weight) and charged into a twin screw extruder having an L / D of 47, The mixture was melt-kneaded at a kneading temperature of 240 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Table 6. Further, as Comparative Example 45, evaluation was performed in the case of PA6 alone. The results are shown in Table 6.

  As is clear from Table 6, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with PA6, compared with the case of PA6 alone shown in Comparative Example 45, mechanical properties, oil resistance, A PA6 thermoplastic resin composition having excellent moldability and bleed resistance can be obtained.

Comparative Examples 46-53
Physical properties and injection molding of pellets obtained in the same manner as in Examples 11 to 12 from compositions obtained by blending the thermoplastic elastomer compositions obtained in Comparative Examples 1 to 8 and PA6 in a ratio of 30:70 (% by weight) Property, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 6. The thermoplastic elastomer compositions outside the scope of the present invention in Comparative Examples 1 to 8 were inferior in compatibility with PA6 and deteriorated in moldability or bleed resistance.

Examples 13-14, Comparative Example 54
The thermoplastic elastomer composition obtained in Examples 1 and 2 and polyethylene terephthalate (PET) were blended at a ratio of 30:70 (% by weight), and charged into a twin screw extruder having an L / D of 47. The mixture was melt-kneaded at a kneading temperature of 240 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. Table 7 shows the evaluation results. Further, as Comparative Example 54, evaluation was performed in the case of PET alone. The results are shown in Table 7.

  As is clear from Table 7, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with PET, compared with the case of PET alone shown in Comparative Example 54, mechanical properties, oil resistance, A PET thermoplastic resin composition excellent in moldability and bleed resistance can be obtained.

Comparative Examples 55-62
Injection using pellets obtained in the same manner as in Examples 13 to 14 from a composition obtained by blending the thermoplastic elastomer composition obtained in Comparative Examples 1 to 8 and PET in a ratio of 30:70 (% by weight). The moldability, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 7. The thermoplastic elastomer compositions outside the scope of the present invention of Comparative Examples 1 to 8 were inferior in compatibility with PET and deteriorated in moldability or bleed resistance.

Examples 15-16, Comparative Example 63
The thermoplastic elastomer composition obtained in Examples 1 and 2 and an ethylene-vinyl acetate copolymer (EVA) were blended at a ratio of 30:70 (% by weight), and a twin screw extruder having an L / D of 47. The mixture was melt-kneaded at a kneading temperature of 190 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Table 8. Further, as Comparative Example 63, evaluation was performed in the case of EVA alone. The results are shown in Table 8.

  As is clear from Table 8, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with EVA, compared with the case of EVA alone shown in Comparative Example 63, mechanical properties, oil resistance, An EVA thermoplastic resin composition excellent in moldability and bleed resistance can be obtained.

Comparative Examples 64-71
Physical properties and injection of pellets obtained in the same manner as in Examples 15 to 16 from a composition obtained by blending the thermoplastic elastomer composition obtained in Comparative Examples 1 to 8 and EVA in a ratio of 30:70 (% by weight). The moldability, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 8. The thermoplastic elastomer compositions outside the scope of the present invention in Comparative Examples 1 to 8 were inferior in compatibility with EVA and deteriorated in moldability or bleed resistance.

Examples 17-18, Comparative Example 72
The thermoplastic elastomer composition obtained in Examples 1 and 2 and an ethylene-ethyl acrylate copolymer (EEA) were blended at a ratio of 30:70 (% by weight), and a twin screw extruder having an L / D of 47. The mixture was melt-kneaded at a kneading temperature of 190 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. Table 9 shows the evaluation results. Further, as Comparative Example 72, evaluation in the case of EEA alone was performed. The results are shown in Table 9.

  As is clear from Table 9, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with EEA, compared to the case of EEA alone shown in Comparative Example 72, mechanical properties, oil resistance, An EEA thermoplastic resin composition excellent in moldability and bleed resistance can be obtained.

Comparative Examples 73-80
Physical properties and injection of pellets obtained in the same manner as in Examples 17 to 18 from compositions obtained by blending the thermoplastic elastomer compositions obtained in Comparative Examples 1 to 8 and EEA in a ratio of 30:70 (% by weight) The moldability, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 9. The thermoplastic elastomer compositions outside the scope of the present invention in Comparative Examples 1 to 8 were inferior in compatibility with EEA and deteriorated in moldability or bleed resistance.

Examples 19-20, Comparative Example 81
The thermoplastic elastomer composition obtained in Examples 1 and 2 and a saponified ethylene-vinyl acetate copolymer (saponified EVA) were blended at a ratio of 30:70 (% by weight), and a biaxial L / D of 47. The mixture was put into an extruder, melt kneaded at a kneading temperature of 200 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. Table 10 shows the evaluation results. Further, as Comparative Example 81, evaluation was performed in the case of saponified EVA alone. The results are shown in Table 10.

  As is clear from Table 10, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with saponified EVA, and have mechanical properties and oil resistance as compared with the case of saponified EVA alone shown in Comparative Example 81. A saponified EVA thermoplastic resin composition having excellent properties, moldability and bleed resistance can be obtained.

Comparative Examples 82-89
Using the pellets obtained in the same manner as in Examples 19 to 20 from a composition obtained by blending the thermoplastic elastomer composition obtained in Comparative Examples 1 to 8 and saponified EVA in a ratio of 30:70 (% by weight). The injection moldability, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 10. The thermoplastic elastomer compositions outside the scope of the present invention in Comparative Examples 1 to 8 were inferior in compatibility with saponified EVA and deteriorated in moldability or bleed resistance.

Examples 21-22, Comparative Example 90
The thermoplastic elastomer composition obtained in Examples 1 and 2 and nitrile rubber (NBR) were blended at a ratio of 30:70 (% by weight), and charged into a twin screw extruder having an L / D of 47. The mixture was melt-kneaded at a kneading temperature of 190 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Table 11. Further, as Comparative Example 90, evaluation was performed in the case of NBR alone. The results are shown in Table 11.

  As is clear from Table 11, the thermoplastic elastomer compositions of the present invention of Examples 1 and 2 are excellent in compatibility with NBR, compared to the case of NBR alone shown in Comparative Example 90, mechanical properties, oil resistance, An NBR thermoplastic resin composition excellent in moldability and bleed resistance can be obtained.

Comparative Examples 91-98
Physical properties and injection of pellets obtained in the same manner as in Examples 21 to 22 from a composition obtained by blending the thermoplastic elastomer composition obtained in Comparative Examples 1 to 8 and NBR at a ratio of 30:70 (% by weight). The moldability, extrusion moldability, and bleed resistance were evaluated. The results are shown in Table 11. The thermoplastic elastomer compositions outside the scope of the present invention in Comparative Examples 1 to 8 were inferior in compatibility with NBR and deteriorated in moldability or bleed resistance.

  When SBS (hydrogenation rate 0% VECTOR2518 manufactured by DEXCO POLYMERS) was used instead of component (a-2), the alloyed product of the thermoplastic elastomer and the resin resin having a polar group also became slightly hard, and the moldability also decreased. did.

Claims (10)

  (A) (a-1) Conjugation of a block copolymer comprising at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound At least two of 5 to 95% by weight of a hydrogenated block copolymer obtained by hydrogenation of 90% or more of a diene block, (a-2) a polymer block A mainly composed of an aromatic vinyl compound, and a conjugated diene compound 100% by weight of an elastomer comprising 5 to 95% by weight of a hydrogenated block copolymer obtained by hydrogenating less than 90% of the conjugated diene block of a block copolymer comprising at least one of the polymer blocks B mainly comprising (B) 5 to 300 parts by weight of a rubber softener, (c) 0.01 to 3 parts by weight of an organic peroxide, and (d) a liquid polybutadiene having a hydroxyl group at the terminal Thermoplastic elastomer composition obtained compositions containing emissions 1 to 80 parts by weight were melted and kneaded.   (A-1) The polystyrene-equivalent number average molecular weight of the hydrogenated block copolymer is in the range of 100,000 to 400,000, and (a-2) the polystyrene-equivalent number average molecular weight of the hydrogenated block copolymer is The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer composition is in the range of 10,000 to 200,000.   (E) The thermoplastic elastomer composition according to claim 1 or 2, further comprising 1 to 20 parts by weight of an unsaturated glycidyl compound or a derivative thereof.   (F) The thermoplastic elastomer composition according to any one of claims 1 to 3, further comprising 1 to 20 parts by weight of an unsaturated carboxylic acid or a derivative thereof.   (G) The thermoplastic elastomer composition according to any one of claims 1 to 4, further comprising 0.02 to 10 parts by weight of an ester-based crosslinking aid.   (H) The thermoplastic elastomer composition according to any one of claims 1 to 5, further comprising 1 to 200 parts by weight of a peroxide-decomposable olefin resin. (I) The thermoplastic elastomer composition according to any one of claims 1 to 6, further comprising 1 to 200 parts by weight of an olefin copolymer rubber.   (J) The thermoplastic elastomer composition according to any one of claims 1 to 7, further comprising 1 to 200 parts by weight of an inorganic filler.   A thermoplastic resin composition comprising 100 parts by weight of the thermoplastic elastomer composition according to any one of claims 1 to 8 and 10 to 1500 parts by weight of a resin having a polar group.   Resin having polar group is ionomer, acrylic rubber, ethylene-ethyl acrylate copolymer, ethylene-methacrylate copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, polyamide resin, polyamide At least one resin selected from the group consisting of thermoplastic thermoplastic elastomers, biodegradable polyester resins, polyester resins, polyester thermoplastic elastomers, urethane thermoplastic elastomers, nitrile-butadiene rubbers and partially crosslinked nitrile-butadiene rubbers The thermoplastic resin composition according to claim 9, wherein the composition is a thermoplastic resin composition.