JP2003286384A - Thermoplastic elastomer composition and thermoplastic resin composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition rich in flexibility, having excellent thermal deformation resistance and molding processability and especially excellent in the compatibility with a resin having a polar group, and a thermoplastic resin composition using the same. <P>SOLUTION: The thermoplastic elastomer composition is obtained by melting 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 at its terminal to knead the same with 100 pts.wt. of an elastomer (a) prepared by mixing 90% or more of hydrogenated matter (a-1) of the conjugated block of a block copolymer comprising at least two polymer blocks A based on an aromatic vinyl compound and at least one polymer block B based on a conjugated diene compound and >90% of the hydrogenated matter (a-2) in a ratio (a-1)/(a-2) of 5-95/95-5 (wt.%). The thermoplastic resin composition using the same is also disclosed. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition and a thermoplastic resin composition (alloyed product) using the thermoplastic elastomer composition. And a thermoplastic elastomer composition excellent in compatibility with a resin having a polar group, and a thermoplastic resin composition using the same.

[0002]

2. Description of the Related Art In recent years, a thermoplastic elastomer, which is a soft material having rubber elasticity and which does not require a vulcanization step and has the same moldability and recyclability as a thermoplastic resin, has been used in automobile parts, home electric appliance parts, It is widely used in the fields of wire coating, medical parts, footwear, and sundries.

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 It is highly flexible, has good rubber elasticity at room temperature, and the thermoplastic elastomer composition obtained from them has excellent processability and is widely used as a substitute for vulcanized rubber.

Further, the elastomer composition obtained by hydrogenating the intramolecular double bond of the block copolymer of styrene and the conjugated diene in these elastomers is an elastomer having improved heat aging resistance (heat stability) and weather resistance. Is widely used as a

However, thermoplastic elastomer compositions using these hydrogenated block copolymers still have rubber-like properties such as oil resistance, heat-pressurization deformation rate (compression set) and rubber elasticity at high temperatures. There is a problem, and in order to improve this point, a cross-linked product obtained by cross-linking the composition containing the hydrogenated derivative of the block copolymer has been proposed (for example, JP-A-59-6236, JP-A-63-57662, JP-B-3-49927, JP-B-3-11291 and JP-B-6-136.
No. 28).

Further, the crosslinked composition of the hydrogenated block copolymer disclosed in the above publication has a problem that the compression set is still insufficient at high temperature, especially at 100 ° C., and the mechanical strength is apt to decrease. However, at present, it has not reached the performance level conventionally required for vulcanized rubber applications. Further, in extrusion molding, the melt tension at a high temperature is low, so that the shape retention is deteriorated, and in injection molding, the molding cycle becomes long, and there are many problems on the molding surface.

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, JP-A-1-139241 and JP-A-1-139241 have been used. −
In each publication of 100045, a thermoplastic polymer selected from hydrogenated SBS block copolymer, olefin elastomer, diene elastomer, urethane elastomer, plasticized polyvinyl chloride and polyester thermoplastic elastomer or polyether block amide are disclosed. Melt blends have been proposed.

[0008] However, the composition has a drawback that the property balance between compression set and hardness is poor, and the compatibility is insufficient, so that the bending fatigue property and abrasion resistance are poor. .

To solve this problem, Japanese Unexamined Patent Publication No.
No. 214209 discloses a composition containing a hydrogenated derivative of a block copolymer and a polyester resin, a modified polystyrene resin and / or a modified polyolefin resin containing an epoxy group, an acid anhydride group, or an oxazoline group. By adding it, a composition having improved compatibility, excellent flexibility, heat resistance and chemical resistance is disclosed.
JP-A-75016 and JP-A-1-230660 disclose hydrogenated derivatives of block copolymers and hydrogenated derivatives containing a carboxylic acid group or its derivative group,
Further, a composition comprising a polyolefin resin and a thermoplastic polyester is disclosed.

Further, JP-A-3-234745 and 3-
234755, 5-171003, and 7-1.
JP-A No. 2-97554 discloses a composition comprising a hydrogenated derivative of a block copolymer, a hydrogenated derivative containing a carboxylic acid group or its derivative group, and a thermoplastic polyurethane. Has
A composition comprising a hydrogenated derivative of a block copolymer, an epoxy group, or a hydrogenated derivative containing the derivative group, and a thermoplastic polyurethane is disclosed.

However, none of the compositions has a sufficient compatibility with the thermoplastic elastomer, and at high temperature, especially 1
The tensile properties at 00 ° C. or higher deteriorate, and the property balance between compression set and hardness is poor. Also, depending on the alloy ratio with the thermoplastic elastomer, surface layer peeling and flow marks occur in injection molding, and eye mold and rough skin occur in extrusion molding, resulting in poor moldability and further bleeding of low molecular weight components. It also had a drawback.

[0012]

SUMMARY OF THE INVENTION In view of the above problems, the object of the present invention is to provide excellent heat resistance, which is excellent in flexibility, heat distortion resistance and molding processability, and particularly excellent in compatibility with a resin having a polar group. A plastic elastomer composition and a thermoplastic resin composition using the same are provided.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the hydrogenation rates of a hydrogenated block copolymer with a high hydrogenation rate and a hydrogenated block copolymer with a low hydrogenation rate are By adding a softening agent for rubber, an organic peroxide, liquid polybutadiene, and, if necessary, various monomers to an elastomer mixture of two different kinds of hydrogenated blocks at a specific ratio, and heat-treating the elastomer to obtain monomers, etc. Graft polymerization, it was found that a thermoplastic elastomer composition having excellent compatibility with a resin having a polar group can be obtained,
The present invention has been completed.

That is, the first aspect of the present invention is (a)
(A-1) A conjugated diene block of a block copolymer composed of at least two polymer blocks A mainly containing an aromatic vinyl compound and at least one polymer block B mainly containing a conjugated diene compound. 5 to 95% by weight of a hydrogenated block copolymer obtained by hydrogenation of 90% or more, and (a-2) at least two polymer blocks A containing an aromatic vinyl compound as a main component, and a conjugated diene compound as a main component. Of at least one polymer block B to be added to 100 parts by weight of an elastomer comprising 5 to 95% by weight of a hydrogenated block copolymer obtained by hydrogenating less than 90% of a conjugated diene block of a block copolymer. (B) 5 to 300 parts by weight of a softening agent for rubber, (c) an organic peroxide of 0.
It is a thermoplastic elastomer composition obtained by melt-kneading a composition containing 0 to 1 to 3 parts by weight and (d) 1 to 80 parts by weight of liquid polybutadiene having a hydroxyl group at the terminal.

The second invention of the present invention is (a-1)
The polystyrene reduced number average molecular weight of the hydrogenated block copolymer is in the range of 100,000 to 400,000,
(A-2) The thermoplastic elastomer composition according to the first invention, wherein the hydrogenated block copolymer has a polystyrene reduced number average molecular weight in the range of 10,000 to 200,000.

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

The fourth invention of the present invention is described in any one of the first to third inventions, which further comprises (f) 1 to 20 parts by weight of an unsaturated carboxylic acid or its derivative. It is a thermoplastic elastomer composition.

Further, the fifth invention of the present invention is described in any one of the first to fourth inventions, characterized in that the composition further comprises (g) 0.02 to 10 parts by weight of an ester-based crosslinking aid. It is a thermoplastic elastomer composition.

The sixth aspect of the present invention is the (h) part.
The thermoplastic elastomer composition according to any one of the first to fifth inventions, which further comprises 1 to 200 parts by weight of an oxide-decomposable olefin resin.

Further, the seventh invention of the present invention is characterized in that it further comprises (i) 1 to 200 parts by weight of an olefinic copolymer rubber. It is a plastic elastomer composition.

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

The ninth invention of the present invention is the thermoplastic elastomer composition 1 according to any one of the first to eighth inventions.
It is a thermoplastic resin composition containing 00 parts by weight and 10 to 1500 parts by weight of a resin having a polar group.

In a tenth aspect of the present invention, the resin having a polar group is an ionomer, an acrylic rubber, an ethylene-ethyl acrylate copolymer, an ethylene-methacrylate copolymer, an 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 -The thermoplastic resin composition according to the ninth invention, which is at least one resin selected from the group consisting of butadiene rubber.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The components constituting the present invention, the production method, and the use are described in detail below.

1. Component (1) Elastomer (a) of Thermoplastic Elastomer Composition The elastomer (a) component used in the thermoplastic elastomer composition of the present invention includes the following (a-1) high hydrogenation rate hydrogenated block copolymer and (a) -2) Low hydrogenation rate An elastomer composed of a mixture of hydrogenated block copolymers.

(A-1) Hydrogenated Block Copolymer Elastomer The high hydrogenation rate hydrogenated block copolymer (a-1) component used in the component (a) is a polymer block A containing an aromatic vinyl compound as a main component. At least 2 and at least 1 of the polymer block B mainly composed of the conjugated diene compound
In the conjugated diene block of the block copolymer consisting of
It is a hydride with a high hydrogenation rate that has been hydrogenated by at least%. For example, A
-B-A, B-A-B-A, A-B-B-A-B-A and the like aromatic vinyl compound-conjugated diene compound block copolymer conjugated diene block hydrogenation rate of 90% or more A hydrogenated block copolymer obtained by hydrogenation can be mentioned.

The polymer block A containing an aromatic vinyl compound as a main component preferably consists of an aromatic vinyl compound alone or is hydrogenated with 50% by weight or more, preferably 70% by weight or more of an aromatic vinyl compound. It is a copolymer block with a conjugated diene compound.

The polymer block B mainly composed of the hydrogenated conjugated diene compound is preferably composed of only the hydrogenated conjugated diene compound, or 50% by weight or more of the hydrogenated conjugated diene compound is preferable. Is 7
It is a copolymer block of 0% by weight or more and an aromatic vinyl compound.

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

As the aromatic vinyl compound constituting the block copolymer, for example, one kind or two or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like. But styrene is preferred. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3
-Dimethyl-1,3-butadiene or the like is selected from one kind or two or more kinds, and among them, butadiene, isoprene and a combination thereof are preferable.

In the polymer block A mainly composed of the aromatic vinyl compound and the polymer block B mainly composed of the conjugated diene compound, the distribution of the units derived from the conjugated diene compound or the aromatic vinyl compound in the molecular chain. May be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer blocks A mainly containing an aromatic vinyl compound or polymer blocks B mainly containing a conjugated diene compound, each polymer block may have the same structure or different structures. It 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 block copolymer by a known method. The hydrogenation mainly hydrogenates the aliphatic double bond derived from the conjugated diene of the conjugated diene block, and the hydrogenation rate thereof needs to be 90% or more. When the hydrogenation rate is less than 90%, flexibility and transparency tend to deteriorate.

In the hydrogenated product of the component (a-1), in the polymer block B containing a conjugated diene compound as a main component, its microstructure is optional. For example, in the polybutadiene block, 1,2- The microstructure is preferably 20 to 50% by weight, particularly preferably 25 to 45% by weight. In the polyisoprene block, preferably 70 to 100% by weight of isoprene has a 1,4-microstructure.

The polystyrene-reduced number average molecular weight (Mn) of the hydrogenated block copolymer (a-1) is 30,000-.
500,000, preferably 100,000 to 400,
000, more preferably 150,000 to 350,000
0, more preferably in the range of 200,000 to 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 value, heat resistance, scratch resistance, and oil resistance decrease. On the other hand, if the upper limit is exceeded,
The flowability will deteriorate, and in injection molding, appearance defects such as short shots and flow marks will occur in the molded product. Also,
In extrusion molding, the occurrence of rough skin and eye grease becomes remarkable.
The molecular weight in the present invention is a value determined by GPC based on polystyrene having a known molecular weight.
Therefore, the value is a relative value, not an absolute value, and may vary by about ± 30% depending on each condition of the GPC such as the reference sample, the apparatus and the data processing method.

Specific examples of the hydrogenated block copolymer of the component (a-1) include styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), Styrene-ethylene / ethylene / propylene-styrene copolymer (SE
EPS) etc. can be mentioned.

(A-2) Low hydrogenation rate hydrogenated block copolymer The low hydrogenation rate hydrogenated block copolymer component (a-2) used in the elastomer (a) is mainly composed of an aromatic vinyl compound. An aliphatic double bond portion derived from a conjugated diene of a conjugated diene block of a block copolymer comprising at least two polymer blocks A and at least one polymer block B mainly composed of a conjugated diene compound is used. It is a hydrogenated product having a low hydrogenation rate of less than%. For example, A-B-A,
Obtained by hydrogenating a conjugated diene block of an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as B-A-B-A or A-B-A-B-A with a hydrogen content of less than 90%. Hydrogenated block copolymers may be mentioned.
Here, the polymer block A is preferably 40% by weight or less.

The polymer block A containing an aromatic vinyl compound as a main component may be a polymer consisting of an aromatic vinyl compound alone or a copolymer of an aromatic vinyl compound and less than 50% by weight of a conjugated diene compound. Good. Further, the polymer block B containing a conjugated diene compound as a main component may be a polymer consisting only of the conjugated diene compound or a copolymer of the conjugated diene compound and an aromatic vinyl compound of less than 50% by weight.

As the aromatic vinyl compound constituting the component (a-2), for example, one kind or two or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like. Among them, styrene is preferable. Further, as the conjugated diene compound, for example,
Butadiene, isoprene, 1,3-pentadiene, 2,
One kind or two or more kinds are selected from 3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable.

The microstructure in the polymer block B mainly composed of the conjugated diene compound can be arbitrarily selected. 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.

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 80.
%, More preferably less than 75%, particularly preferably 6
It is less than 0%. The lower limit is preferably 3% or more, more preferably 5% or more, further preferably 7% or more, particularly preferably 9% or more. The hydrogenation 1,2-vinyl bond content is preferably 0.5 to 12%, more preferably 10%.
%, More preferably 5% or less, still more preferably 3% or less. If the hydrogenation rate exceeds 90%, the crosslinking efficiency tends to decrease, and the heat resistance and oil resistance tend to decrease.

The polystyrene-equivalent number average molecular weight of the hydrogenated block copolymer (a-2) having the above structure is 1
50,000 to 500,000, preferably 10,000
~ 200,000, more preferably 10,000-15
It is in the range of 10,000. Molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / 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.

If the number average molecular weight (Mn) is less than the above lower limit, the mechanical properties, heat resistance, scratch resistance, and oil resistance of the molded product deteriorate. On the other hand, when the content exceeds the upper limit, the fluidity is deteriorated, and in injection molding, appearance defects such as short shots and flow marks occur in the molded product. Further, in extrusion molding, the occurrence of rough skin, eye grease, etc. becomes remarkable. The molecular weight in the present invention is a value determined by GPC based on polystyrene having a known molecular weight. Therefore, the value is a relative value, not an absolute value, and may vary by about ± 30% depending on each condition of the GPC such as the reference sample, the apparatus and the data processing method.

A specific example of the hydrogenated block polymer component (a-2) having a hydrogenation rate of less than 90% is a partially hydrogenated styrene-butadiene-polymer in which the 1,2-bond of the butadiene block is selectively hydrogenated. Examples thereof include styrene copolymer (SBBS). Further, a partially hydrogenated styrene-isoprene-styrene copolymer, a partially hydrogenated styrene-isoprene-butadiene-styrene copolymer and the like can also be mentioned.
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. −
2) is 95 to 5% by weight, preferably 50 to 15% by weight. Less than 5% by weight of component (a-1) (component (a-2)
Exceeds 95% by weight. When it is), heat resistance and mechanical properties of the obtained thermoplastic elastomer composition are deteriorated. Further, alloyed products show a reduction in heat resistance, flexibility, mechanical properties, and moldability. On the other hand, when the content of the component (a-1) exceeds 95% by weight (the content of the component (a-2) is less than 5% by weight), the heat resistance of the obtained thermoplastic elastomer composition decreases. In addition, the fluidity is insufficient, and the moldability of the obtained thermoplastic elastomer composition deteriorates. Alloyed materials show deterioration in mechanical properties and moldability due to reduced compatibility.

(2) Softening agent for rubber (b) The softening agent for rubber (b) used in the thermoplastic elastomer composition of the present invention may be a softening agent component for non-aromatic rubber or a softening agent for aromatic rubber. Ingredients may be used, and ester plasticizers can also be used, but especially non-aromatic mineral oils,
Ester plasticizers are preferred. Examples of the non-aromatic mineral oil softener include paraffinic softeners having a paraffin chain carbon number of 50% or more of the total carbon number.

Among the ester plasticizers, examples of the cyclic plasticizer include phthalic anhydride ester and trimellitic acid ester, N-cyclohexyl-p-toluenesulfonamide, dibenzyl sebacate, diethylene glycol dibenzoate, and the like. Di-t-octyl phenyl ether, dipropanediol dibenzoate, N-
Ethyl-p-toluenesulfonamide, isopropylidene diphenoxypropanol, alkylated naphthalene,
Examples thereof include polyethylene glycol dibenzoate, o, p-toluenesulfonamide, trimethylpentanediol dibenzoate and trimethylpentanediol monoisobutyrate monobenzoate. Among these, phthalic anhydride ester and trimellitic acid ester are preferable.

Representative examples of the phthalic anhydride ester include, for example, butyloctylphthalate and 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, dicyclohexyl phthalate, diethyl isophthalate, di-n-heptyl phthalate, Dihexyl phthalate, di (2-methoxyethyl) phthalate, dimethylisophthalate, dinonylphthalate, dioctylphthalate, dicaprylphthalate, di (2-ethylhexyl) isophthalate, mixed dioctylphthalate, diphenylphthalate, 2- (ethylhexyl) isobutylphthalate, Butyl phthalyl butyl glycolate, ethyl (and methyl) phthalyl ethyl glycolate, polypropylene glycol bis (amyl) phthale DOO, hexyl isodecyl phthalate, isodecyl-tridecyl phthalate include isooctyl-isodecyl phthalate.

Typical examples of trimellitic acid ester 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 and triisononyl trimellitate.

As the acyclic plasticizer, phosphoric acid ester, adipic acid ester, azelaic acid ester, citric acid ester, acetyl citric acid ester, myristic acid ester, ricinoleic acid ester, acetylricinoleic acid ester, sebacic acid ester, Stearic acid ester, epoxidized ester, and 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 2,2,4-trimethyl-1,3 which is an ester compound of a branched aliphatic dihydric alcohol.
-Pentanediol monoisobutyrate, 2,2,4-
Trimethyl-1,3-pentanediol diisobutyrate (TXIB), an acrylic polymer, etc. may be mentioned.

Representative examples of the phosphoric acid ester include, for example, cresyl diphenyl phosphate, tricresyl phosphate, dibutyl phenyl phosphate, diphenyl octyl phosphate, methyl diphenyl phosphate, tributyl phosphate, triphenyl phosphate, tri (2-butoxy). Mention may be made of ethyl) phosphate, tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate and trioctylphosphate.

Typical examples of the adipic acid ester 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-
Examples include n-heptyl adipate.

Representative examples of the sebacate ester include 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,
Included are dicyclohexyl azelaate, diisobutyl azelaate and diisooctyl azelaate.

Examples of the acrylic polymer plasticizer include (i)
Examples of the polymer include a reaction product obtained by reacting a mixture of a radically polymerizable monomer and a (ii) modifying compound in the presence or absence of a polymerization initiator. This polymer is preferably a polymer in which the binding mode of the modifying compound to the polymer is (ii) an ester bond, (i) using (meth) acrylic acid as a radically polymerizable monomer, and (ii) ) It may be a polymer using an aliphatic or alicyclic alcohol as the modifying compound.

In the acrylic polymer plasticizer, the radical polymerizable monomer (i) is (meth) acrylic acid;
Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. Hydroxyl group-containing (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, chloride Examples thereof include vinyl, vinylidene chloride, allyl chloride and allyl alcohol.

As the modifying compound (ii), cycloalkanol such as cyclohexyl alcohol; alkanol such as isopropyl alcohol; halogen group-containing alcohol such as fluoroalkyl alcohol; alkylene diol such as ethylene glycol and butane diol;
Cycloalkylene diols such as cyclohexane diol and cyclohexyl dimethanol; modifiers containing hydroxyl groups such as polyethers having terminal hydroxyl groups, polymers such as polyesters, cyclohexyl carboxylic acid, cyclohexyl dicarboxylic acid, adipic acid, sebacic acid, fluoroalkyl dicarboxylic acid , Carboxyl group-containing compounds such as maleic anhydride and fumaric acid; ethyl acetate, butyl acetate,
Examples thereof include ester group-containing modifiers such as cellosolve acetate, methyl propylene glycol acetate, carbitol acetate and ethyl carbitol acetate, and alkenes such as cyclohexene, cyclopentene and isobutene.

Examples of the acrylic polymer in the combination of (i) and (ii) above include (i) (meth) acrylic acid, maleic anhydride, maleic acid or a monoalkyl ester of maleic acid, and the like. A polymer having a modifying compound introduced into the polymer is obtained by an esterification reaction using the compound having a hydroxyl group of ii). Further, by using an ester group-containing monomer such as methyl (meth) acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate of (i) and a compound having a hydroxyl group of (ii), a transesterification reaction can be achieved. , A functional polymer is obtained. Furthermore, in (i) 2-
Polymer having a functional group introduced by the formation of an ester bond by the reaction of the hydroxyl group-containing monomer of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate with the carboxyl group- or ester group-containing compound of (ii) Is obtained. Furthermore, by using a carboxyl group-containing monomer (i) such as (meth) acrylic acid and an alkene (ii), the carboxyl group is subjected to an addition reaction with an ethylenically unsaturated bond to form an ester bond. A polymer having the quality compound introduced therein is obtained.

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

The weight average molecular weight (Mw) of the acrylic polymer plasticizer is preferably 500 to 10,000,
The viscosity is more preferably 1000 to 6000, further preferably 1000 to 3000, and the viscosity is 100 to 9000.
mPa · s is preferable, and more preferably 1000 to 60
00 mPa · s, and more preferably 3000 to 5000
mPa · s and Acetone-Water To
SP value calculated from the tolerance is 10.5 to 16.
5 is preferable, 13 to 16 is more preferable, and 14 to 16 is still more preferable.

Among these ester-based plasticizers, DINP, DINA and TOTM are particularly preferable.

The blending amount of the component (b) is 100 parts of the component (a).
The amount is 5 to 300 parts by weight, preferably 20 to 150 parts by weight, relative to the parts by weight. If the blending amount is less than 5 parts by weight, the flexibility of the thermoplastic elastomer composition obtained will decrease. In addition, the flexibility of the alloyed product, which is a thermoplastic resin composition of the obtained thermoplastic elastomer composition and a resin having a polar group, decreases, and moldability deteriorates. If it exceeds 300 parts by weight, the softening agent is likely to bleed out from the resulting thermoplastic elastomer composition, and peeling or deformation and flow marks are likely to occur in the molded product. Furthermore, the gas generated during processing becomes remarkable. Further, alloyed products also tend to cause bleeding.

(3) Organic Peroxide (c) The organic peroxide component (c) used in the present invention generates radicals and causes the radicals to react in a chain reaction to obtain the component (a) and / or the necessary component. According to the above, it functions to crosslink the component (i) to be blended. At the same time, the components (e) to (g), which are blended as necessary, are graft-polymerized with the component (a) and / or the component (i) to improve the compatibility with the polar group-containing resin. Further, if necessary, the component (h) to be blended is decomposed or cross-linked to control the fluidity of the composition at the time of melt-kneading, and to disperse the rubber component well.

As the component (c), for example, dicumyl peroxide, di-tert-butyl peroxide, 2,
5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t
ert-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, ter
t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, ter
Examples thereof include t-butyl cumyl peroxide. Of these, 2,5-dimethyl-2,5-di- (ter) is preferable from the viewpoint of odor, coloring, and scorch safety.
t-butylperoxy) hexane, 2,5-dimethyl-
2,5-di- (tert-butylperoxy) hexyne-3 is particularly preferred.

The blending amount of the component (c) is 100 parts of the component (a).
0.01 to 3 parts by weight, preferably 0.
05-1.5 parts by weight. If the blending amount is less than 0.01 part by weight, crosslinking cannot be sufficiently achieved, and the thermoplastic elastomer composition obtained has poor heat resistance and oil resistance. Further, the moldability of the alloyed product of the obtained thermoplastic elastomer composition and the resin having a polar group becomes poor. On the other hand, if the amount exceeds 3 parts by weight, the mechanical properties and moldability of the obtained thermoplastic elastomer deteriorate, and the moldability of the alloyed product of the obtained thermoplastic elastomer composition and a resin having a polar group deteriorates.

(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 the component (a) when the elastomer composition is melt-processed. And a component (i), which is blended as necessary, is graft-polymerized in the presence of an organic peroxide to exert an effect of suppressing the bleed-out of low molecular weight substances in the elastomer composition, and at the same time a phase with a resin containing a polar group. Improves solubility. In the component (d), the fine structure of the main chain is vinyl 1,2-bond type, trans 1,4
It is a liquid polymer that is transparent at room temperature and consists of a bond type and a cis-1,4-bond type. Here, the vinyl 1,2-bond content is preferably 30% by weight or less.
If the 2-bond content exceeds 30% by weight, the low temperature properties of the resulting thermoplastic elastomer composition deteriorate, which is not preferable.

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. Number average molecular weight is 1,
When it is less than 000, the heat distortion resistance of the obtained thermoplastic elastomer composition is lowered, and when it exceeds 5,000, the compatibility of the obtained thermoplastic elastomer composition is lowered. Examples of commercially available products include R- manufactured by Idemitsu Petrochemical Co., Ltd.
45HT (registered trademark).

The blending amount of the component (d) is 100 parts of the component (a).
The amount is preferably 1 to 80 parts by weight, and particularly preferably 3 to 50 parts by weight, based on parts by weight. If the blending amount exceeds 80 parts by weight, the softening agent is likely to bleed out from the obtained thermoplastic elastomer composition, and peeling or deformation and flow marks are likely to occur in the molded product. Also in the alloyed product, bleeding out of the softening agent is likely to occur, and peeling or deformation and flow marks are likely to occur in the molded product. Compounding amount is 1
If the amount is less than parts by weight, the flexibility and moldability of the thermoplastic elastomer composition are not improved. In the alloyed product, peeling or deformation and flow marks are likely to occur in the molded product due to the decrease in compatibility.

(5) Unsaturated glycidyl compound or its derivative (e) In the thermoplastic elastomer composition of the present invention, if necessary, the unsaturated glycidyl compound or its derivative component (e)
Can be blended. The component (e) is used as a modifier, preferably a glycidyl compound having an unsaturated group capable of copolymerizing with an olefin and a glycidyl group in the molecule is used, and particularly preferably glycidyl methacrylate (GMA). Is used. With the modifier, the soft component of the hydrogenated block copolymer in the elastomer component (a), the copolymer rubber component, and further the components such as peroxide cross-linking olefin resin to be blended as necessary are modified, Compatibility with a resin having a polar group is improved.

The blending amount of the component (e) is as follows.
The amount is preferably 1 to 20 parts by weight, and particularly preferably 1 to 10 parts by weight, relative to 100 parts by weight of the component (a). If the blending amount exceeds 20 parts by weight, not only the heat distortion resistance and mechanical properties of the resulting thermoplastic elastomer composition deteriorate,
The effect of improving the compatibility with the resin having a polar group cannot be recognized.

(6) Unsaturated carboxylic acid or its derivative (f) In the thermoplastic elastomer composition of the present invention, if necessary, unsaturated carboxylic acid or its derivative component (f)
Can be blended. The component (f) is used as a modifier and is preferably acrylic acid, methacrylic acid, maleic acid, dicarboxylic acid or a derivative thereof, such as an acid, a halide, an amide, an imide, an anhydride or an ester derivative. Can be mentioned. Particularly preferably, maleic anhydride (MAH) is used. The modifying agent modifies the component (a) and the peroxide-decomposable olefinic resin of the component (h) which is optionally blended, preferably polypropylene or the like or the component (i) which is optionally blended, and a polar group. To improve the compatibility with the resin having.

The blending amount of the component (f) is as follows.
The amount is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the component (a). When the blending amount exceeds 20 parts by weight, not only the thermoplastic elastomer composition undergoes severe yellowing, but also the heat distortion resistance and mechanical properties are deteriorated, and when a polar group-containing resin is blended,
The effect of improving the compatibility of the components cannot be recognized.

(7) Ester-based cross-linking aid (g) In the thermoplastic elastomer composition of the present invention, an ester-based cross-linking aid component (g) can be used if necessary. The component (g) can be added during the crosslinking treatment of the thermoplastic elastomer composition of the present invention with the above-mentioned (c) organic peroxide, whereby a uniform and efficient crosslinking reaction can be carried out. . Further, by blending in a large amount, it is possible to moderately crosslink a non-aromatic softening agent for rubber, in particular, a low molecular weight paraffinic oil or the like, and suppress bleed-out from a thermoplastic elastomer composition and an alloyed product. .

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

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

(8) Peroxide-decomposing type olefin resin (h) The thermoplastic elastomer composition of the present invention may contain a peroxide-decomposing olefin resin component (h), if necessary. The component (h) improves the rubber dispersion of the resulting thermoplastic elastomer composition, improves the appearance of the molded product, and has the effect of adjusting the hardness and the shrinkage ratio. The component is an olefin-based polymer or copolymer that is thermally decomposed by heat treatment in the presence of peroxide to reduce the molecular weight and increase the fluidity at the time of melting. For example, isotactic polypropylene or propylene. And other α-olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-
Examples thereof include copolymers with penten, 1-octene and the like.

D of the homo portion of the above olefin-based copolymer
The melting point measured by SC is preferably Tm of 150 to 1
67 ° C., ΔHm is in the range of 25 to 83 mJ / mg. The crystallinity can be estimated from Tm and ΔHm measured by DSC. When Tm and ΔHm are out of the above ranges, the obtained thermoplastic elastomer composition has oil resistance and 100 ° C.
The rubber elasticity in the above is not improved.

Further, the melt flow rate of component (h) (MFR, ASTM D-1238, L condition, 230
C) 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 obtained thermoplastic elastomer composition will deteriorate, and if it exceeds 200 g / 10 minutes, the rubber elasticity of the obtained thermoplastic elastomer composition will deteriorate.

The blending amount of the component (h) is as follows.
The amount is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the component (a). Two
If it exceeds 100 parts by weight, the moldability of the resulting thermoplastic elastomer composition is deteriorated, peeling, deformation and flow marks are likely to occur in the molded product, and the hardness of the thermoplastic elastomer composition becomes too high and the flexibility is lost. A product with a rubbery feel cannot be obtained.

(9) Olefin Copolymer Rubber (i) The thermoplastic elastomer composition of the present invention may contain an olefin copolymer rubber component (i), if necessary. Component (i) is ethylene, propylene, 1
Examples include elastomers obtained by copolymerizing α-olefins such as butene and 1-pentene, and olefin copolymer rubbers obtained by copolymerizing these with a non-conjugated diene.

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

Specific examples of such olefinic copolymer rubbers include ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, ethylene-1-butene copolymer rubber, Ethylene-1
Examples include butene-non-conjugated diene copolymer rubber and ethylene-propylene-1-butene copolymer rubber.

The blending amount of the component (i) is as follows.
The amount is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the component (a). Two
When it exceeds 100 parts by weight, the mechanical strength of the obtained thermoplastic elastomer composition is significantly reduced.

(10) Inorganic Filler (j) The thermoplastic elastomer composition of the present invention may optionally contain an inorganic filler component (j). The component (j) has an effect of improving some physical properties such as compression set of a molded article obtained from the thermoplastic elastomer composition, and also has an economic advantage by increasing the amount. Component (j)
As, 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, carbon fiber, titanium Examples thereof include calcium acid fiber, natural silicic acid, and synthetic silicic acid (white carbon).
Of these, calcium carbonate, wollastonite, chlorite and talc are particularly preferred.

The blending amount of the component (j) is as follows.
The amount is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the component (a). Two
If it exceeds 100 parts by weight, the mechanical strength of the obtained thermoplastic elastomer composition is remarkably lowered, and the hardness is increased to lose the flexibility, so that a product having a rubber-like feel cannot be obtained.

(11) Amorphous polyolefin component (l) In the elastomer composition of the present invention, the amorphous polyolefin component (l) can be blended, if necessary. The amorphous polyolefin component (l) used in the present invention has a melt viscosity at 190 ° C. of 250 to 50,
000 mPa · s, preferably 10,000 to 25.0
It is composed of an amorphous copolymer mainly composed of 00 mPa · s of propylene and has a crystallinity of 50 as measured by X-ray diffraction.
% Or less, preferably 20% or less, a relatively low molecular weight polymer. The glass transition temperature of the amorphous polyolefin is preferably -33 to -23 ° C, and the softening point is 12
0-135 degreeC is preferable.

Specific examples of the amorphous polyolefin include:
Amorphous homopolymer atactic polypropylene, other olefins mainly composed of propylene (for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1- Examples thereof include amorphous copolymers with decene 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, but in the case of the block copolymer, the bonding mode of the propylene unit needs to be an atactic structure. Moreover, when the amorphous copolymer is a copolymer of propylene and ethylene, the content of the propylene unit is preferably 50 mol% or more, and particularly preferably 60 to 100 mol%. For example, as the amorphous polyolefin, E-1200 manufactured by Eastman Chemical Company may be mentioned.

The blending amount of the component (l) is as follows.
The amount is preferably 1 to 150 parts by weight, more preferably 3 to 80 parts by weight, relative to 100 parts by weight of the component (a). If the blending amount exceeds 150 parts by weight, the softening agent is likely to bleed out from the resulting elastomer composition, and peeling or deformation and flow marks are likely to occur in the molded product. Further, the oil resistance and heat resistance of the alloy of the obtained elastomer composition and the resin having a polar group are lowered.

(12) Other Components In addition to the above components, the thermoplastic elastomer composition of the present invention may further contain various antiblocking agents, sealability improvers, heat stabilizers, and oxidants, if necessary. It is also possible to contain an inhibitor, a light stabilizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a coloring agent and the like. Here, as the antioxidant,
For example, 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol,
2,4-dimethyl-6-tert-butylphenol,
Examples thereof include phenolic antioxidants such as 4,4-dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, phosphite antioxidants, and thioether antioxidants. Of these, phenol-based antioxidants and phosphite-based antioxidants are particularly preferable. The antioxidant is the above component (a).
To (i) are preferably 0 to 3.0 parts by weight, and particularly preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight.

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

2. Production of Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention comprises the above components (a) to (d) or, if necessary, components (e) to (l).
And the like, and each component is added at the same time or in an arbitrary order, and the mixture is melt-kneaded.

The melt-kneading method is not particularly limited, and a generally known method 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, a moderate L / D twin-screw extruder,
The above operation can be continuously performed by using a Banbury mixer, a pressure kneader or the like. Here, the temperature of the 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 is reduced in heat resistance and oil resistance is reduced. And low molecular weight bleeds can be improved.

The polar group-containing resin usable in the present invention is not particularly limited as long as it is a polar group-containing thermoplastic resin, elastomer or rubber.
Polyester resin (PET, PBT, PEN, PC
T, PETG, etc.), a polyamide resin (PA), a polycarbonate (PC), a resin containing a copolymer of ethylene and a vinyl group-containing monomer as a main component, a nitrile-butadiene rubber (NBR), a partially crosslinked nitrile- Butadiene rubber,
Examples thereof include 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, thermoplastic polyurethane elastomer (TPU), polyester resin (PET, PBT, PEN, PCT, PETG, etc.), polyester thermoplastic elastomer (COPE), polyamide resin (PA) , A thermoplastic polyamide-based elastomer (COAE), an ionomer, a resin containing a copolymer of ethylene and a vinyl group-containing monomer as a main component, a nitrile-butadiene rubber (NBR), a cross-linked nitrile-butadiene rubber (cross-linked NBR), Biodegradable polyester resin,
Acrylic rubber is preferred.

As the polyurethane-based thermoplastic elastomer (TPU) of a resin having a polar group used in the present invention,
Generally prepared from polyols, diisocyanates, and chain extenders. Polyols include polyester polyols, polyester ether polyols, polycarbonate polyols and polyether polyols.

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 naphthalene. Alicyclic dicarboxylic acids such as dicarboxylic acids, such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, or their acid esters or acid anhydrides, and 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., or a polyester polyol obtained by a dehydration condensation reaction with a mixture thereof; ε Examples thereof include polylactone diol obtained by ring-opening polymerization of a lactone monomer such as caprolactone.

As the polycarbonate polyol, 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- Examples thereof include polycarbonate polyols obtained by reacting one or more polyhydric alcohols such as nonanediol and diethylene glycol with diethylene carbonate, dimethyl carbonate, diethyl carbonate and the like.

Further, as the polyester ether polyol, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalene can be used. Alicyclic dicarboxylic acid such as dicarboxylic acid, for example, hexahydrophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, or the like, or an acid ester or acid anhydride thereof, and diethylene glycol, or propylene oxide adduct, etc. Examples thereof include glycols and the like, or compounds obtained by a dehydration condensation reaction with a mixture thereof.

Further, as the polyether polyol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran,
And these copolyethers.

Among the above-mentioned various polyols, the polyether polyol is preferable 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 diisocyanate (XDI),
Hydrogenated XDI, triisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, 1,8-diisocyanate methyloctane, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate,
Examples thereof include bicycloheptane triisocyanate.
Among them, 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
An aliphatic polyol such as nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol and glycerin, and an aromatic glycol such as 1,4-dimethylolbenzene, bisphenol A, ethylene oxide or propylene oxide adduct of bisphenol A Can be mentioned.

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

As the polyester thermoplastic elastomer (COPE) of a resin having a polar group used in the present invention, polyester is used as a hard segment in the molecule,
A multi-block copolymer using a polyether or polyester having a low glass transition temperature (Tg) as the soft segment is preferable. For example, aromatic crystalline polyester such as polybutylene terephthalate is used as the hard segment, polyester / polyether type using polyether as the soft segment, aromatic crystalline polyester is used as the hard segment, and aliphatic type is used as the soft segment. Examples include polyester / polyester type using polyester.

Here, as the polyester / polyether type, for example, those synthesized by transesterification reaction and polycondensation reaction using dimethyl terephthalate, 1,4-butanediol, polytetramethylene glycol and the like as starting materials are available. Can be mentioned. Examples of the polyester / polyester type include those synthesized by transesterification reaction and ring-opening reaction using dimethyl terephthalate, 1,4-butanediol, ε-caprolactone and the like as starting materials.

Examples of the polyamide resin (PA) which is a resin 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, Nylon-
6, 12 or nylon MXD6 (aliphatic polyamide having an aromatic ring in the main chain) and the like.

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 or 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 prepared by adding lauryl lactam, dicarboxylic acid, and polyether diol with water as a lactam ring-opening catalyst, and reacting with carboxyl carboxylic acid by heating under pressure. Rick nylon 12 oligomer is obtained, which is then obtained by a condensation reaction with a polyether diol.

Here, a polyamide-based thermoplastic elastomer having various properties can be obtained depending on the type of diol used and the like. For example, polyamide such as nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon 11, nylon 12, or nylon-6,12 is the hard segment and the soft segment is the polyether ester. A block elastomer composed of

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

[0111]

[Chemical 1]

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.

Examples of the monomer represented by the general formula (I) include methacrylic acid metal salts, acrylic acid metal salts, methacrylic acid, acrylic acid, and the like, of which methacrylic acid metal salts are preferable.

The ionomer resin is an ionic copolymer having an ionic crosslinking bond having a high impact resilience,
Specifically, it is preferably a copolymer of ethylene and an unsaturated organic acid such as acrylic acid or methacrylic acid, which is completely or partially neutralized as in the general formula (I) to form a salt. The cation is usually an alkali metal, zinc, etc.,
In particular, a mixture of sodium and zinc is preferable because a high impact resilience is obtained.

In the copolymer with ethylene, it is preferable that the above-mentioned monomer accounts for 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 preferable. If the amount of the above-mentioned monomer is less than 3% by weight, there is a problem that it is not sufficiently dispersed in the obtained composition, and if it exceeds 20% by weight, the required impact resilience cannot be obtained. Further, the copolymer preferably has a melt flow rate of 0.5 to 15 g / 10 minutes (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 kinds of resins can also be used.

The resin containing a polar group-containing resin as a main component of the copolymer of ethylene and a vinyl group-containing monomer used in the present invention includes ethylene and a monomer represented by the following general formula (II). And a copolymer thereof.

[0117]

[Chemical 2]

In the general formula (II), R ² represents a hydrogen atom or a methyl group, and R ³ is represented by the following general formula (III).

[0119]

[Chemical 3]

In 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 vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, isopropenyl butyrate, methyl (meth) acrylate and ethyl. (Meta)
Examples thereof include acrylate, propyl (meth) acrylate, butyl (meth) acrylate and the like. 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 ethylene and the monomer represented by the general formula (II) is not particularly limited, but ethylene 97 is preferable. ˜70 wt%, monomer 3˜30 wt%. Further, the copolymer of ethylene and the monomer represented by the general formula (II) can further contain a monomer such as a modified olefin monomer. In that case, a monomer such as a modified olefin monomer Content of the copolymer is 5
It is 0% by weight or less.

Specific examples of the copolymer of ethylene and the monomer represented by the general formula (II) include ethylene-
Vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer, saponified ethylene-vinyl acetate copolymer (saponified E
VA) etc. can be mentioned.

The saponified ethylene-vinyl acetate copolymer (saponified EVA) is a compound obtained by saponifying EVA and has an ethylene content of 40 to 95% by weight, preferably 6%.
It is 0 to 90% by weight, and the saponification degree of the vinyl acetate 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 95
When it exceeds the weight%, the flexibility is poor. Further, when the saponification degree of the vinyl acetate component is less than 60%, the heat resistance decreases.

The saponified EVA is JIS K6924-2.
The melt flow rate (MFR) measured at a load of 21.18 N at 190 ° C. is 0.1 to 30 g /
It is preferably 10 minutes. If the MFR is less than 0.1 g / 10 minutes, the fluidity of the composition will be poor, and if it exceeds 30 g / 10 minutes, the mechanical strength and heat resistance will be poor.

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

Specific examples of the unsaturated nitrile include α, β-unsaturated nitrile, acrylonitrile and methacrylonitrile, and acrylonitrile is preferable. 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 and chloroprene, and among them, 1,3-butadiene and isoprene are preferable. . The conjugated dienes can be used alone or in combination of two or more.

As the unsaturated nitrile-conjugated diene copolymer, acrylonitrile-butadiene copolymer rubber (NBR), acrylonitrile-butadiene-isoprene copolymer rubber (NBIR), acrylonitrile-isoprene copolymer rubber (NIR) , Acrylonitrile-butadiene-butoxy acrylate copolymer rubber, acrylonitrile-butadiene-acrylic acid copolymer rubber, acrylonitrile-butadiene-methacrylic acid copolymer rubber and the like. 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%.
Is. If the gel fraction is less than 60%, the permanent elongation is poor and
If it exceeds 5%, the workability suddenly deteriorates. NB here
The gel fraction of R means an extraction residue separated by 80 mesh filter after being immersed in xylene at 120 ° C. for 20 hours. 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 deviates from this range, the oil resistance becomes poor.

Raw Material of Resin Having Polar Group Used in the Present Invention
Examples of degradable polyester resins include biodegradable aliphatic poly
Examples thereof include esters, and industrially, aliphatic diesters are used.
Using carboxylic acid and excess diol as starting materials, dehydration weight
Also synthesized by condensation reaction and dediol reaction
Of lactide, which is further introduced with an aromatic compound.
Ring polymerization, polycondensation of lactic acid, high molecular weight polycaprolac
Ton, polyglycol synthesized from carbon monoxide and formalin
Cholic acid etc. are mentioned. Biodegradable aliphatic polyester
Among the aliphatic-aromatic random copolyesters
Of polyester, fatty acid, aromatic acid copolymerized polyester resin
Therefore, the repeating unit is [-{(OR¹-O)_a−
(CO-R^Two-CO)_b}-{(OR^Three-O)_c−
(CO-Ar-CO)_d}-] Made of polyester resin
Fat, and a branching agent (BA) as an optional component_xincluding
[-{(O-R¹-O)_a-(CO-R ^Two-CO)_b}
-{(OR^Three-O)_c-(CO-Ar-CO)_d}
-] (BA)_xIt may be a structure such as.

Here, in the above 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 carbon atoms. , 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, 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,
Selected from the group consisting of 5-norbornanedicarboxylic acid,
4- (hydroxymethyl) cyclohexanecarboxylic acid,
Hydroxy acids such as hydroxypivalic acid, 6-hydroxyhexanoic acid, glycolic acid, lactic acid, and their ester-forming derivatives can also be used as the fatty acid component to make these copolyesters.

Aromatic acid residue: --CO--Ar--CO
-Is a residue of an aromatic acid having 8 to 40 carbon atoms, preferably 8 to 14 carbon atoms, and examples of the aromatic acid include 1,4
-Terephthalic acid, 1,3-terephthalic acid, 2,6-naphthoic acid, 1,5-naphthoic acid, their ester-forming derivatives and combinations thereof.

Further, the diol residue: --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-cyclobutanediol, triethylene glycol,
It is selected from the group consisting of tetraethylene glycol and combinations thereof. The diol components may be the same or different.

Furthermore, a branching agent which is an optional component: (B
A) _x (where x represents the weight% of the branching agent, and is 0.01 to
10% by weight is preferable, and more preferably 0.1 to 1.0.
% By weight. ) Is a polyol having a weight average molecular weight of preferably about 50 to 5000, more preferably 92 to 3000 and having 3 to 6 hydroxy groups,
Examples thereof include polycarboxylic acids having 3 or 4 carboxyl groups or hydroxy acids having a total of 3 to 6 hydroxyl groups and carboxyl groups. 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 are mentioned. 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. As the polycarboxylic acid, hemimellitic acid, trimellitic acid, trimesic acid, pyromellitic acid,
Benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid,
Examples include 1,1,2-ethanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid, although acids may be used in this manner. Are preferably used in the form of their lower alkyl esters or their cyclic anhydrides, if they can be formed. Hydroxy acids include malic acid, citric acid, tartaric acid, 3-hydroxyglutaric acid, mutic acid (or mucus acid), trihydroxyglutaric acid and 4- (β-hydroxyethyl) phthalic acid. Hydroxy acids contain three or more combinations of hydroxyl and carboxyl groups. Among these, particularly preferable branching agents include trimellitic acid, trimesic acid, pentaerythritol, trimethylolpropane and 1,2,4-butanetriol.

The biodegradable aliphatic polyester preferably used in the present invention includes polybutylene succinate (binary condensation product 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 (succinic acid and terephthalic acid, and 1,4-butane).
And a ternary condensate of butanediol).

Further, the biodegradable aliphatic polyester used in the present invention has a reactive group such as an isocyanate group or a urethane group for the purpose of modifying the functionality within a range not impairing the biodegradable function. It is also possible to introduce it inside.
Further, various copolymers such as a copolyester obtained by copolymerizing polylactic acid can be used.

As the biodegradable aliphatic polyester used in the present invention, commercially available biodegradable resins can be used. For example, as product names, Bionore (manufactured by Showa High Polymer Co., Ltd.), Easter
Bio (manufactured by Eastoman Chemicals),
Biopol (manufactured by Japan Monsanto), Biomax (D
uPont), Ecoflex (BASF), and the like, but a resin can be arbitrarily selected according to the application and characteristics.

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

The amount of the resin having a polar group as described above is 10 to 1500 parts by weight, preferably 20 to 1200 parts by weight based on 100 parts by weight of the thermoplastic elastomer composition.
Parts by weight. If the compounding amount is less than 10 parts by weight, the effect of addition is not recognized, and if it exceeds 1500 parts by weight, the flexibility of the thermoplastic resin composition obtained is reduced. By blending the thermoplastic elastomer composition, oil resistance, abrasion resistance, high temperature physical properties such as tensile properties at high temperature of the resulting thermoplastic resin composition can be dramatically improved.

4. Production Method of Thermoplastic Resin Composition The production method of the thermoplastic resin composition of the present invention can be produced by the same method as the production method of the thermoplastic elastomer composition. That is, it can be produced by melt-kneading the thermoplastic elastomer composition, a resin having polarity, and further, if necessary, an optional component such as an antioxidant used in the above-mentioned thermoplastic elastomer composition.

The melt-kneading method is not particularly limited, and a generally known method 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, a moderate L / D twin-screw extruder,
The above operation can be continuously performed by using a Banbury mixer, a pressure kneader or the like. Here, the temperature of melt-kneading 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 excellent in flexibility, heat deformation resistance and molding processability, and particularly excellent in oil resistance, abrasion resistance and mechanical properties at high temperature. Therefore, it can be used particularly 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 / electrical parts include connectors, switch covers, plugs, gaskets, grommets, cable jacket curl cords, electric wire insulation coatings, and the like. Examples include hoses, diaphragms, gaskets, packings, casters, grommets, roller coupling grips, hoses, and medical device / food related parts such as syringe tips, drug stoppers, grommets, blood collection tube caps, cap seals, etc. Examples of automobile parts include CVJ boots, rack and opinion boots, shock absorber dust boots, vacuum connectors, air ducts, tubes,
Examples include run channels, grommets, handle covers, airbag outer cover steering, mudguards, and the like, and examples of building materials include window frame seals, expansion joints, sponge seals, handrail coatings, stair-slip stoppers, and the like. As other uses, for example, grip materials such as pen grips, bicycle grips, toothbrush grips, toy parts, mats,
Examples include goggles, dust / gas masks, and shoe soles.

[0144]

EXAMPLES The present invention will be specifically described with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The measuring methods of physical properties and samples used in the present invention are shown below.

1. Test method (1) Specific gravity: According to JIS K 7112, a test piece was measured using a gel or solid sample. (2) Hardness: According to JIS K 6253, the hardness was measured with durometer hardness, type A (expressed as “A” after the number in the table) and type D (expressed as “D” after the number in the table). . A 6.3 mm thick press sheet was used as the test piece. (3) Tensile strength: In accordance with JIS K 6251, a 1 mm thick press sheet was used as a test piece by punching out a No. 3 dumbbell type test piece. The pulling speed was 500 mm / min. (Measurement at room temperature and 100 ° C.) (4) 100% elongation stress: According to JIS K 6251, a 1 mm thick press sheet was punched out into a No. 3 dumbbell type test piece for use. Pulling speed is 500mm /
Minutes (5) Elongation at break: According to JIS K 6251, a 1 mm thick press sheet was used as a test piece by punching out a No. 3 dumbbell type test piece. The pulling speed was 500 mm / min. (6) Volume change rate: According to JIS K 6258, a 1 mm thick press sheet was punched out from a No. 3 dumbbell type test piece to be used. 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 mold clamping pressure of 120 tons, molding temperature 220 ° C., mold temperature 40 ° C., injection speed 5
5 mm / sec, injection pressure 600 kg / cm ² , holding pressure 4
1 at 00 kg / cm ² , injection time 6 seconds, cooling time 45 seconds
A 3.5 x 13.5 x 2 mm sheet was molded. The presence or absence of flow marks that delaminate, peel off the surface layer, deform, and significantly deteriorate the appearance was visually evaluated, and evaluated according to the following criteria. ◯: Good ×: Poor (8) Extrudability: A 50 mm × 1 mm sheet was extruded, and the drawdown property, surface appearance and shape were observed and evaluated according to the following criteria. ○: Good ×: Poor (9) Bleed resistance: The extruded sheet that was bent and fixed with a clip was left standing at room temperature and 110 ° C. for 168 hours, and visually observed for the presence of bleeding and blooming of low molecular weight substances. It evaluated by the standard of. ◯: Good ×: Poor (10) Hydrogenation rate of conjugated diene block portion: A sample was taken in an NMR sample tube (5 mmφ), and after deuterated chloroform was added, the sample was sufficiently dissolved and a nuclear magnetic resonance apparatus (N
MR) GSX-400 manufactured by JEOL Ltd., room temperature, 400
¹ H-NMR measurement was performed at 3029 times in MHz, and the hydrogenation rate was obtained.

2. Sample (1) used in Examples and Comparative Examples 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: 260,0
00, 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, butadiene block hydrogenation rate: 75.1%, (1,2-butadiene hydrogenation rate 9
2.7%, hydrogenation rate of 1,4-butadiene 61.0
%) (3) Softener component for rubber (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.), containing a hydroxyl group (0.83 mol / kg) and a copolymerization-reactive unsaturated double bond (1,4 bond: 80%) as a functional group, and a number average molecular weight of 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 aid component (g): TMPT (Tr
Imetyl Propane Trimeth
Acrylate; manufactured by Shin Nakamura Chemical Co., Ltd.) Molecular weight: 3
38, (9) Peroxide-decomposable olefin resin component (h): PP-BC8 (polypropylene (PP); manufactured by Nippon Polychem Co., Ltd.), crystallinity; Tm 166 ° C., ΔH.
m; 82 mJ / mg, MFR; 1.8 g / 10 min (10) Ethylene-butene copolymer rubber component (i): Esprene N0441 (EBR; Sumitomo Chemical Co., Ltd.) (11) Calcium carbonate component (j) : NS400 (manufactured by Sankyo Seiko Co., Ltd.) (12) Hindered phenol / phosphite / lactone compound antioxidant component (k): HP2215 (manufactured by Ciba Specialty Chemicals)

(13) Resin having polar group (i) Urethane type thermoplastic elastomer (TPU): Pandex T-8180 (manufactured by DIC Bayer Polymer Ltd.) (ii) Polyester type thermoplastic elastomer (COP)
E): Hytrel 4056 (manufactured by Toray DuPont Co., Ltd.) (iii) Polyamide thermoplastic elastomer (COA)
E): Pebax 5533SN01 (manufactured by Toray Industries, Inc.) (iv) Ionomer: Himilan 1554 (manufactured by Mitsui DuPont Polychemicals Co., Ltd.) (v) Polyamide (PA6): Grilon R47HWNZ
(Manufactured by Ems Japan) (vi) Polyester (PET): SA-1346P
(Unitika Co., Ltd.) (vii) EVA: Evaflex EV-40LX (Mitsui DuPont Polychemical Co., Ltd.) (viii) EEA: NUC-6170 (Nippon Unicar Co., Ltd.) (ix) Saponification EVA: Mersen H6051 ( (Tosoh Corporation) (x) NBR: PNC-38 (JSR Corporation)

Examples 1 and 2 and Comparative Examples 1 to 8 Using the components in the amounts shown in Table 1, the components were introduced into a twin-screw extruder having an L / D of 47, a kneading temperature of 180 ° C. and a screw rotation speed of 3
The mixture was melt-kneaded at 50 rpm and pelletized. next,
The obtained pellets were injection-molded to prepare test pieces, which were then subjected to respective tests. The evaluation results are shown in Table 1.

[0149]

[Table 1]

As is clear from Table 1, the thermoplastic elastomer compositions of Examples 1 and 2 of the present invention are not limited to the presence or absence of optional components (e) to (k). The composition also showed good properties.

On the other hand, in Comparative Examples 1 and 2, the component (a-1)
The compounding amounts of the component (a-2) and the component (a-2) are out of the range of the present invention. When the amount of the component (a-1) is too large (the amount of (a-2) is too small), heat resistance and moldability are deteriorated and mechanical properties are deteriorated. If the amount of component (a-2) is too large (the amount of (a-1) is too small), the heat resistance and mechanical properties will deteriorate. Comparative Examples 3 and 4
Indicates that the compounding amount of the component (b) is out of the range of the present invention. If the amount of component (b) is too small, the hardness of the resulting thermoplastic elastomer composition will be too hard, and if the amount of component (b) is too large, the mechanical properties will decrease and the resulting thermoplastic elastomer composition will contain a softening agent. Easy to bleed out,
Peeling, deformation, and flow marks easily occur on the molded product.
Furthermore, the gas generated during processing becomes remarkable. In Comparative Examples 5 and 6, the compounding amount of the component (c) was out of the range of the present invention. If the amount of the component (c) is too small, the crosslinking cannot be sufficiently achieved, the heat resistance and oil resistance of the obtained thermoplastic elastomer composition are deteriorated, and the stickiness becomes remarkable and the generated gas amount increases. . If the amount of the component (c) is too large, the mechanical properties are deteriorated, the mechanical properties and moldability of the obtained thermoplastic elastomer composition are deteriorated, and the pellet shape and moldability are deteriorated. In Comparative Examples 7 and 8, component (d)
The compounding amount of is outside the range of the present invention. If the amount of component (d) is too small, the flexibility of the thermoplastic elastomer composition obtained will decrease, and the pellet shape and moldability will deteriorate. If the amount of the component (d) is too large, the softening agent is likely to bleed out from the resulting thermoplastic elastomer composition, and peeling or deformation and flow marks are likely to occur in the molded product. Furthermore, the gas generated during processing becomes remarkable. Instead of the component (a-2), SBS (hydrogenation rate 0% VECTO
R2518 DEXCO POLYMERS) was used, the thermoplastic elastomer obtained was slightly hardened and the moldability was also lowered.

Examples 3 to 4 and Comparative Example 9 The thermoplastic elastomer compositions obtained in Examples 1 and 2 and the urethane thermoplastic elastomer (TPU) were mixed at 30: 7.
The mixture was blended at a ratio of 0 (% by weight), charged into a twin-screw extruder having an L / D of 47, melt-kneaded at a kneading temperature of 200 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, injection molding the obtained pellets to create a test piece,
I went to each test. The evaluation results are shown in Table 2. In addition, as Comparative Example 9, evaluation was performed in the case of TPU alone. The results are shown in Table 2.

[0153]

[Table 2]

As is clear from Table 2, the thermoplastic elastomer compositions of Examples 1 and 2 of the present invention are excellent in compatibility with TPU, and compared with the case of TPU alone shown in Comparative Example 9,
It is possible to obtain a TPU thermoplastic resin composition having an excellent balance of flexibility and mechanical properties, oil resistance, moldability, and bleed resistance.

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

Examples 5-6, Comparative Example 18 The thermoplastic elastomer compositions obtained in Examples 1-2 were blended with the polyester thermoplastic elastomer (COPE) at a ratio of 30:70 (wt%), L / D is 4
The mixture was charged into a twin-screw extruder No. 7 and melt-kneaded at a kneading temperature of 220 ° C. and a screw rotation speed of 350 rpm to form pellets. Next, the obtained pellets were injection-molded to prepare test pieces, which were subjected to respective tests. The evaluation results are shown in Table 3.
In addition, as Comparative Example 18, evaluation was performed when COPE was used alone. The results are shown in Table 3.

[0157]

[Table 3]

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

Comparative Examples 19 to 26 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). The obtained pellets were evaluated for physical properties, injection moldability, extrusion moldability, and bleed resistance. The results are shown in Table 3. The thermoplastic elastomer compositions of Comparative Examples 1 to 8 outside the scope of the present invention were poor in compatibility with COPE and deteriorated in moldability or bleeding resistance.

Examples 7 to 8 and Comparative Example 27 3 parts of the thermoplastic elastomer composition obtained in Examples 1 and 2 and a polyamide thermoplastic elastomer (COAE) were used.
Blended at a ratio of 0:70 (wt%), L / D is 47
It was charged into a twin-screw extruder, and melt-kneaded at a kneading temperature of 220 ° C. and a screw rotation speed of 350 rpm to form pellets. Next, the obtained pellets were injection-molded to prepare test pieces, which were subjected to respective tests. The evaluation results are shown in Table 4. In addition, as Comparative Example 27, evaluation was performed when COAE was used alone. The results are shown in Table 4.

[0161]

[Table 4]

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

Comparative Examples 28 to 35 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). The obtained pellets were evaluated for physical properties, injection moldability, extrusion moldability, and bleed resistance. The results are shown in Table 4. The thermoplastic elastomer compositions of Comparative Examples 1 to 8 outside the scope of the present invention were poor in compatibility with COAE and deteriorated in moldability or bleeding resistance.

Examples 9 to 10 and Comparative Example 36 The thermoplastic elastomer compositions obtained in Examples 1 to 2 and the ionomer were blended at a ratio of 30:70 (% by weight), and L / D was 47. The mixture was put into a shaft extruder, melt-kneaded at a kneading temperature of 190 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, the obtained pellets were injection-molded to prepare test pieces, which were subjected to respective tests. The evaluation results are shown in Table 5. In addition, as Comparative Example 36, evaluation was carried out when the ionomer was used alone. The results are shown in Table 5.

[0165]

[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 the ionomer, and have mechanical properties higher than those of the ionomer alone shown in Comparative Example 36. It is possible to obtain an ionomer-based thermoplastic resin composition having excellent oil resistance, moldability, and bleed resistance.

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

Examples 11 to 12 and Comparative Example 45 The thermoplastic elastomer compositions obtained in Examples 1 and 2 and nylon 6 (PA6) were blended at a ratio of 30:70 (% by weight) to give L / D. Is charged into a 47-screw extruder,
Melt kneading was performed at a kneading temperature of 240 ° C. and a screw rotation speed of 350 rpm to form pellets. Next, the obtained pellets were injection-molded to prepare test pieces, which were subjected to respective tests. The evaluation results are shown in Table 6. In addition, as Comparative Example 45,
The evaluation was performed in the case of PA6 alone. The results are shown in Table 6.

[0169]

[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, and have mechanical properties higher than those of PA6 alone shown in Comparative Example 45. A PA6 thermoplastic resin composition having excellent oil resistance, moldability, and bleed resistance can be obtained.

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

Examples 13 to 14 and Comparative Example 54 The thermoplastic elastomer compositions obtained in Examples 1 to 2 and polyethylene terephthalate (PET) were mixed at 30:70.
The mixture was blended at a ratio of (% by weight), charged into a twin-screw extruder having an L / D of 47, melt-kneaded at a kneading temperature of 240 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, injection molding the obtained pellets to create a test piece,
I went to each test. The evaluation results are shown in Table 7. In addition, as Comparative Example 54, evaluation was performed using PET alone. The results are shown in Table 7.

[0173]

[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, and have mechanical properties higher than those of PET alone shown in Comparative Example 54. A PET-based thermoplastic resin composition having excellent oil resistance, moldability, and bleed resistance can be obtained.

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

Examples 15 to 16 and Comparative Example 63 The thermoplastic elastomer compositions obtained in Examples 1 to 2 and the ethylene-vinyl acetate copolymer (EVA) were mixed at 30: 7.
The mixture was blended at a ratio of 0 (% by weight), charged into a twin-screw extruder having an L / D of 47, melt-kneaded at a kneading temperature of 190 ° C. and a screw rotation speed of 350 rpm, and pelletized. Next, injection molding the obtained pellets to create a test piece,
I went to each test. The evaluation results are shown in Table 8. In addition, as Comparative Example 63, evaluation was performed when EVA was used alone. The results are shown in Table 8.

[0177]

[Table 8]

As is clear from Table 8, the thermoplastic elastomer compositions of Examples 1 and 2 of the present invention are excellent in compatibility with EVA, and have mechanical properties, as compared with the case of EVA alone shown in Comparative Example 63, It is possible to obtain an EVA-based thermoplastic resin composition having excellent oil resistance, moldability, and bleed resistance.

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

Examples 17 to 18, Comparative Example 72 The thermoplastic elastomer compositions obtained in Examples 1 to 2 and the ethylene-ethyl acrylate copolymer (EEA) were blended at a ratio of 30:70 (% by weight). And L / D is 4
The mixture was charged into a twin-screw extruder No. 7 and melt-kneaded at a kneading temperature of 190 ° C. and a screw rotation speed of 350 rpm to pelletize. Next, the obtained pellets were injection-molded to prepare test pieces, which were subjected to respective tests. The evaluation results are shown in Table 9.
In addition, as Comparative Example 72, evaluation was performed when EEA was used alone. The results are shown in Table 9.

[0181]

[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, and have mechanical properties higher than those of EEA alone shown in Comparative Example 72. An EEA-based thermoplastic resin composition having excellent oil resistance, moldability, and bleed resistance can be obtained.

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

Examples 19 to 20, Comparative Example 81 The thermoplastic elastomer compositions obtained in Examples 1 to 2 and the saponified ethylene-vinyl acetate copolymer (saponified EVA) were mixed at a ratio of 30:70 (% by weight). Blended with, L / D is 4
The mixture was put into a twin-screw extruder No. 7 and melt-kneaded at a kneading temperature of 200 ° C. and a screw rotation speed of 350 rpm to form pellets. Next, the obtained pellets were injection-molded to prepare test pieces, which were subjected to respective tests. The evaluation results are shown in Table 10. Further, as Comparative Example 81, evaluation was carried out in the case of using saponified EVA alone. The results are shown in Table 10.

[0185]

[Table 10]

As is clear from Table 10, Examples 1-2
The thermoplastic elastomer composition of the present invention comprises a saponified EVA
It is possible to obtain a saponified EVA-based thermoplastic resin composition which is excellent in compatibility with and is excellent in mechanical properties, oil resistance, moldability, and bleeding resistance as compared with the case of saponified EVA alone shown in Comparative Example 81.

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

Examples 21 to 22 and Comparative Example 90 The thermoplastic elastomer compositions obtained in Examples 1 and 2 and nitrile rubber (NBR) were blended at a ratio of 30:70 (% by weight) to give L / D. No. 47 in a twin-screw extruder, kneading temperature 190 ° C., screw rotation speed 350 rpm
The mixture was melt-kneaded with and pelletized. Next, the obtained pellets were injection-molded to prepare test pieces, which were subjected to respective tests. The evaluation results are shown in Table 11. In addition, as Comparative Example 90, evaluation was performed in the case of NBR alone. The results are shown in Table 1.
Shown in 1.

[0189]

[Table 11]

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

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

Instead of the component (a-2), SBS (hydrogenation rate 0% VECTOR 2518 DEXCO POLYM
(Manufactured by ERS) was used, the alloy of the thermoplastic elastomer and the resin resin having a polar group was slightly hardened, and the moldability was also lowered.

[0193]

The thermoplastic elastomer composition of the present invention is excellent in heat distortion resistance, moldability, bleeding resistance and compatibility with a polar group-containing resin, and therefore should be used as a modifier for a polar group-containing resin. You can A thermoplastic resin composition of the thermoplastic elastomer composition and a resin having a polar group has excellent flexibility, excellent heat distortion resistance, molding processability, and bleeding resistance, and can be used for electric wires / electric parts, industrial machine parts, medical devices. It can be used in the fields of equipment / food related parts, automobile parts, building materials, etc.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/1515 C08K 5/1515 C08L 9/00 C08L 9/00 23/00 23/00 91/00 91 / 00 101/02 101/02 F-Term (reference) 4J002 AC07U AE05Y BB03Z BB06U BB07U BB12Z BB14Z BB15U BB15Z BB18U BB23U BE03U BG04U BP01W BP01X CF00U CK02U CK02U QL02 001Q0E 006 EK047 EH046 EH046 EH1460EK047 EH1460EK047

Claims (10)

[Claims] 1. A block comprising: (a) (a-1) at least two polymer blocks A mainly containing an aromatic vinyl compound and at least one polymer block B mainly containing a conjugated diene compound. At least two hydrogenated block copolymers obtained by hydrogenating 90% or more of the conjugated diene block of the copolymer, and at least two polymer blocks A containing (a-2) an aromatic vinyl compound as a main component. And a hydrogenated block copolymer obtained by hydrogenating less than 90% of a conjugated diene block of a block copolymer consisting of at least one polymer block B containing a conjugated diene compound as a main component, and 5 to 95% by weight. (B) 5 to 300 parts by weight of a softening agent for rubber, relative to 100 parts by weight of an elastomer composed of
(C) A thermoplastic elastomer composition obtained by melt-kneading a composition containing 0.01 to 3 parts by weight of an organic peroxide, and (d) 1 to 80 parts by weight of liquid polybutadiene having a hydroxyl group at a terminal. 2. The polystyrene-reduced number average molecular weight of the hydrogenated block copolymer (a-1) is 100,000 to 40.
And the polystyrene-reduced number average molecular weight of the hydrogenated block copolymer (a-2) is 10,000.
The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer composition is in the range of ˜200,000. 3. The thermoplastic elastomer composition according to claim 1 or 2, further comprising (e) 1 to 20 parts by weight of an unsaturated glycidyl compound or a derivative thereof. 4. The thermoplastic elastomer composition according to claim 1, further comprising (f) 1 to 20 parts by weight of an unsaturated carboxylic acid or a derivative thereof. 5. (g) 0.02 to 1 ester crosslinking aid
0 to 4 parts by weight are further contained.
The thermoplastic elastomer composition according to any one of 1. 6. The thermoplastic elastomer composition according to claim 1, further comprising (h) 1 to 200 parts by weight of a peroxide-decomposable olefin resin. 7. (i) Olefin-based copolymer rubber 1-2
1 to 100 parts by weight is further contained.
7. The thermoplastic elastomer composition according to any one of 6 above. 8. The method according to claim 1, further comprising (j) 1 to 200 parts by weight of an inorganic filler.
The thermoplastic elastomer composition according to the item. 9. 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. object. 10. The resin having a polar group is an ionomer, an acrylic rubber, an ethylene-ethyl acrylate copolymer, an ethylene-methacrylate copolymer, an ethylene-vinyl acetate copolymer, a saponified ethylene-vinyl acetate copolymer, Selected from the group consisting of polyamide resin, polyamide thermoplastic elastomer, biodegradable polyester resin, polyester resin, polyester thermoplastic elastomer, urethane thermoplastic elastomer, nitrile-butadiene rubber and partially cross-linked nitrile-butadiene rubber. The thermoplastic resin composition according to claim 9, which is at least one kind of resin.