JP4073452B2 - Thermoplastic elastomer composition - Google Patents

Description

  The present invention relates to a thermoplastic elastomer composition, and more specifically, a heat containing a thermoplastic elastomer having a characteristic (hereinafter sometimes referred to as “recyclability”) capable of repeatedly reproducing cross-linking and cross-linking by temperature change. The present invention relates to a plastic elastomer composition.

In recent years, reuse of used materials is desired from the standpoints of environmental protection and resource saving. Cross-linked rubber (vulcanized rubber) has a stable three-dimensional network structure in which a polymer substance and a cross-linking agent (vulcanizing agent) are covalently bonded, and exhibits very high strength. Reforming is difficult. On the other hand, a thermoplastic elastomer utilizes physical cross-linking and can be easily molded by heating and melting without requiring a complicated vulcanization / molding process including pre-molding.
A typical example of such a thermoplastic elastomer includes a resin component and a rubber component, and at room temperature, the microcrystalline resin component serves as a hard segment serving as a crosslinking point of a three-dimensional network structure, and the rubber component (soft segment) Thermoplastic elastomers that prevent plastic deformation of the resin and that are plastically deformed by softening or melting of the resin component by increasing the temperature are known. However, since such a thermoplastic elastomer contains a resin component, the rubber elasticity tends to be lowered. Therefore, a material that can impart thermoplasticity without containing a resin component is required.

  In response to such a problem, the present inventor has previously proposed that a hydrogen-bonding thermoplastic elastomer comprising an elastomeric polymer having a carbonyl group-containing group and a heterocyclic amine-containing group in the side chain is subjected to a temperature change utilizing hydrogen bonds. The hydrogen bondable thermoplastic elastomer comprising the elastomeric polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in the side chain. As a method for producing the thermoplastic elastomer, an elastomeric polymer having a cyclic acid anhydride group in the side chain and a heterocyclic amine-containing compound are synthesized, and the heterocyclic amine-containing compound is chemically synthesized with a cyclic acid anhydride group. Have proposed a method for producing a thermoplastic elastomer that is obtained by reacting at a temperature at which it can be mechanically bonded (see, for example, Patent Document 1). See).

  The thermoplastic elastomer having such characteristics has high industrial utility value and environmental protection value, and further has high cross-linking strength, and there is no change in physical properties even after repeated cross-linking and cross-linking. It is expected as a material with excellent recyclability.

JP 2000-169527 A

However, even if the thermoplastic elastomer described in Patent Document 1 is used as a composition by blending a filler or polypropylene, the excellent flexibility of the thermoplastic elastomer itself is reduced. In some cases, the fluidity at high temperatures may decrease.
Further, it was found that when uncrosslinked ethylene-propylene rubber (EPM) is blended for the purpose of improving the fluidity at high temperatures, the mechanical strength is lowered although the fluidity is improved.

  Then, this invention makes it a subject to provide the thermoplastic elastomer composition which is excellent in the fluidity | liquidity and mechanical strength at high temperature which hold | maintains the outstanding softness | flexibility.

Therefore, as a result of intensive studies to solve the above problems, the present inventor has obtained a thermoplastic elastomer composition containing a thermoplastic elastomer having a side chain containing a predetermined structure and a specific ethylene-propylene copolymer. The inventors have found that excellent flexibility is maintained and that fluidity and mechanical strength at high temperatures are excellent, and the present invention has been achieved.
That is, this invention provides the thermoplastic elastomer composition as described in following (I)-(XVII).

  (I) a thermoplastic elastomer (A) having a side chain containing at least one selected from the group consisting of an imino group, a nitrogen-containing heterocycle and a covalently linked crosslinking site, and a carbonyl-containing group, a polypropylene block and ethylene An ethylene-propylene copolymer (B) having a propylene block, and a thermoplastic elastomer composition.

  (II) The thermoplastic elastomer composition according to (I), wherein the ethylene propylene copolymer (B) has the polypropylene block in a proportion of 1 to 50 mol%.

  (III) The thermoplastic elastomer composition according to (I) or (II), wherein the polypropylene block has stereoregularity.

  (IV) The thermoplastic elastomer composition according to (III), wherein the polypropylene block is isotactic.

  (V) The content of the ethylene propylene copolymer (B) is 1 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). A thermoplastic elastomer composition.

  (VI) The thermoplastic elastomer composition according to any one of (I) to (V), wherein the side chain of the thermoplastic elastomer (A) contains a structure represented by the following formula (1).

  In the formula, A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is A hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups.

  (VII) The above-mentioned containing the structure represented by the following formula (2) or (3) in which the side chain containing the structure represented by the formula (1) is bonded to the main chain at the α-position or the β-position ( VI) The thermoplastic elastomer composition.

In the formula, A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; oxygen atom, amino group NR ′ (R ′ is . a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or Ri is also good organic group der contain these atoms or groups, D is a single bond; oxygen atom, an amino group NR '(R' Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or an organic group which may contain a sulfur atom.

  (VIII) The thermoplastic elastomer composition according to any one of the above (I) to (V), wherein the side chain of the thermoplastic elastomer (A) contains a structure represented by the following formula (4).

  In the formula, E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; An organic group that may contain atoms or groups.

  (IX) The above-mentioned containing the structure represented by the following formula (5) or (6) in which the side chain containing the structure represented by the formula (4) is bonded to the main chain at the α-position or the β-position ( VIII). The thermoplastic elastomer composition.

In the formula, E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; contain an atom or group Ri may optionally organic group der, D is a single bond; oxygen atom, an amino group NR '(. R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or may contain a sulfur atom Good organic group.

  The nitrogen-containing heterocycle is preferably a 5- or 6-membered ring.

  The nitrogen-containing heterocycle is preferably a triazole ring, thiadiazole ring, pyridine ring, thiazole ring, imidazole ring or hydantoin ring.

  (X) The above (I) to (IX), which can be cross-linked by at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether at the covalent cross-linking site. The thermoplastic elastomer composition according to any one of the above.

  (XI) The above (I) to (IX), wherein the covalently crosslinked site is crosslinked by at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. The thermoplastic elastomer composition according to any one of the above.

  It is preferred that the cross-linking at the covalent cross-linking site contains a tertiary amino group.

  (XII) The thermoplastic elastomer composition according to the above (XI), wherein the crosslinking at the covalent bond crosslinking site contains at least one structure represented by any one of the following formulas (7) to (9).

  In the formula, K, L, Q and R are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; It is an organic group which may contain an atom or a group, and T is a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom and which may be branched.

  (XIII) The above (XII) containing at least one structure represented by any one of the following formulas (10) to (12) in which the crosslinking at the covalent bond site is bonded to the main chain at the α-position or β-position The thermoplastic elastomer composition as described in 1).

  In the formula, K, L, Q and R are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; It is an organic group which may contain an atom or a group, and T is a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom and which may be branched.

  Any T in the above formulas (7) to (12) preferably contains a tertiary amino group.

  It is preferable that the crosslinking at the covalent bond crosslinking site is formed by a reaction between a cyclic acid anhydride group and a hydroxyl group or an amino group and / or an imino group.

  The side chain containing the structure represented by the above formula (4) preferably contains a structure represented by the following formula (13), the following formula (14) or (15), or the following formula (16). .

  In the formula, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group that may contain these atoms or groups. And G and J are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  Any one of the following formulas (17) or (18) and the following formulas (19) to (22) in which the side chain containing the structure represented by the formula (4) is bonded to the main chain at the α-position or the β-position. Or a structure represented by the following formula (23) or (24).

In the formula, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups D is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or an organic group which may contain a sulfur atom, and G and J are Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  (XIV) The thermoplastic elastomer composition according to any one of (I) to (XIII), further comprising a styrene-based thermoplastic elastomer.

  The styrene-based thermoplastic elastomer preferably has a styrene content of 10 to 60% by mass.

  (XV) The thermoplastic elastomer composition according to (XIV), wherein the content of the styrenic thermoplastic elastomer is 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).

  (XVI) The thermoplastic elastomer composition according to any one of (I) to (XV), further containing a filler.

  (XVII) The thermoplastic elastomer composition according to (XVI), in which the content of the filler is 1 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).

  As described below, the present invention is useful because it can provide a thermoplastic elastomer composition that retains excellent flexibility and is excellent in fluidity and mechanical strength at high temperatures.

The present invention is described in detail below.
The thermoplastic elastomer composition according to the first aspect of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) is made from the group consisting of an imino group, a nitrogen-containing heterocyclic ring and a covalently linked crosslinking site. Thermoplastic elastomer containing at least one selected, a thermoplastic elastomer (A) having a side chain containing a carbonyl-containing group, and an ethylene-propylene copolymer (B) having a polypropylene block and an ethylene-propylene block It is a composition.
The composition of the present invention preferably further contains a styrenic thermoplastic elastomer from the viewpoint of improving compression set.
Moreover, it is preferable that the composition of this invention contains a filler from a viewpoint of making reinforcement property and workability favorable.
Hereinafter, the thermoplastic elastomer (A) and the ethylene propylene copolymer (B) contained in the composition of the present invention, and the styrenic thermoplastic elastomer and filler which may be optionally contained will be described in detail.

<Thermoplastic elastomer (A)>
The thermoplastic elastomer (A) used in the composition of the present invention is at least selected from the group consisting of an elastomeric polymer of a natural polymer or a synthetic polymer, an imino group, a nitrogen-containing heterocyclic ring and a covalently linked crosslinking site. One has a side chain containing a carbonyl-containing group.
In the present invention, “side chain” refers to a side chain and a terminal of an elastomeric polymer. Further, “having a side chain containing at least one selected from the group consisting of an imino group, a nitrogen-containing heterocycle and a covalently linked cross-linking site and a carbonyl-containing group” means that the main chain of the elastomeric polymer is formed A chemically stable bond (for example, a covalent bond) to at least one selected from the group consisting of an imino group, a nitrogen-containing heterocyclic ring, and a covalently bonded crosslinking site, and a carbonyl-containing group. , Ionic bond, etc.).

The elastomeric polymer that is the main chain of the thermoplastic elastomer (A) is a generally known natural polymer or synthetic polymer, and has a glass transition point of room temperature (25 ° C.) or lower, that is, an elastomer. If there is no particular limitation.
Specific examples of such elastomeric polymers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), and acrylonitrile. -Diene rubbers such as butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM), and hydrogenated products thereof; ethylene-propylene rubber, ethylene-acrylic rubber (AEM) Olefin-based rubbers such as ethylene-butene rubber (EBM), chlorosulfonated polyethylene, acrylic rubber, fluororubber, polyethylene rubber, and polypropylene rubber; epichlorohydrin rubber; polysulfide rubber; silicone rubber; urethane rubber;

  Further, the elastomeric polymer may be an elastomeric polymer containing a resin component, and specific examples thereof may be a hydrogenated polystyrene elastomeric polymer (for example, SBS, SIS, SEBS, etc.), Examples include polyolefin-based elastomeric polymers, polyvinyl chloride-based elastomeric polymers, polyurethane-based elastomeric polymers, polyester-based elastomeric polymers, and polyamide-based elastomeric polymers.

Further, the elastomeric polymer may be liquid or solid, and the molecular weight thereof is not particularly limited, and is appropriately selected according to the use in which the composition of the present invention is used and the physical properties required for these. be able to.
When emphasizing the fluidity when the composition of the present invention is heated (decrosslinked), the elastomeric polymer is preferably in a liquid state. For example, in diene rubbers such as isoprene rubber and butadiene rubber, the weight average The molecular weight is preferably 1,000 to 100,000, and particularly preferably about 1,000 to 50,000.
On the other hand, when emphasizing the strength of the composition of the present invention, the elastomeric polymer is preferably in a solid state. For example, in diene rubbers such as isoprene rubber and butadiene rubber, the weight average molecular weight is 100,000 or more. It is preferable that it is about 500,000-1,500,000.
In the present invention, the weight average molecular weight is a weight average molecular weight (polystyrene conversion) measured by gel permeation chromatography (GPC). For the measurement, tetrahydrofuran (THF) is preferably used as a solvent.

In the present invention, two or more of the above elastomeric polymers can be mixed and used. In this case, the mixing ratio of the respective elastomeric polymers can be set to any ratio depending on the use of the composition of the present invention, the physical properties required for the composition of the present invention, and the like.
The glass transition point of the elastomeric polymer is preferably 25 ° C. or less as described above. When the elastomeric polymer has two or more glass transition points, or two or more elastomeric polymers are mixed. When used, at least one of the glass transition points is preferably 25 ° C. or lower. When the glass transition point of the elastomeric polymer is within this range, a molded article made of the composition of the present invention is preferable because it exhibits rubber-like elasticity at room temperature.
In the present invention, the glass transition point is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry). The temperature raising rate is preferably 10 ° C./min.

  Such elastomeric polymers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), Diene rubber such as butyl rubber (IIR); Olefin rubber such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM); A molded product made of the composition of the present invention obtained is preferable because it exhibits rubber-like elasticity at room temperature. Moreover, when an olefin rubber is used, deterioration of the composition is suppressed because there is no double bond.

In the present invention, the bound styrene amount of the styrene-butadiene rubber (SBR), the hydrogenation rate of the hydrogenated elastomeric polymer and the like are not particularly limited, and the use of the composition of the present invention and the composition of the present invention. It can be adjusted to an arbitrary ratio according to physical properties required for the material.
When ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM) is used as the main chain of the elastomeric polymer, its ethylene content Is preferably 10 to 90 mol%, more preferably 40 to 90 mol%. It is preferable for the ethylene content to be in this range because it is excellent in compression set resistance and mechanical strength when used as a composition.

  The thermoplastic elastomer (A) used in the composition of the present invention comprises at least one selected from the group consisting of an imino group, a nitrogen-containing heterocyclic ring and a covalently bonded crosslinking site, and a carbonyl-containing group. It is preferable that the side chain contains a nitrogen-containing heterocyclic ring or a covalently linked crosslinking site and a carbonyl-containing group, and is covalently bonded to the imino group and the nitrogen-containing heterocyclic ring. More preferably, it contains a crosslinking site and a carbonyl-containing group.

  In the present invention, when the side chain contains an imino group and a carbonyl-containing group, the side chain preferably contains a structure represented by the following formula (1).

  In the formula, A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is A hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups.

The substituent A is not particularly limited as long as it is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
Specific examples of such substituent A include, for example, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a dodecyl group, and a stearyl group; an isopropyl group Branched alkyl groups such as isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl group, 2-ethylhexyl group; benzyl group Aralkyl groups such as phenethyl group; aryl groups such as phenyl group, tolyl group (o-, m-, p-), dimethylphenyl group, mesityl group; and the like.
Among these, an alkyl group, in particular, a butyl group, an octyl group, a dodecyl group, an isopropyl group, and a 2-ethylhexyl group is preferable because the resulting composition of the present invention has good fluidity at high temperatures.

Substituent B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group that may contain these atoms or groups There is no particular limitation.
Specific examples of such substituent B include, for example, a single bond; an oxygen atom, a sulfur atom, or an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms); A C1-C20 alkylene group or aralkylene group which may contain a group; a C1-C20 alkylene ether group (an alkyleneoxy group such as —O—CH ₂ CH ₂₎ having these atoms or groups at its end. - group), an alkylene group (e.g., _{-NH-CH 2 CH} 2 - group) or an alkylene thioether group (alkylene thio group, for example, _{-S-CH 2 CH} 2 - group); having them end, carbon And an aralkylene ether group (aralkyleneoxy group), an aralkylene amino group, or an aralkylene thioether group;

Here, the alkyl group having 1 to 10 carbon atoms of the amino group NR ′ includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, including isomers. Group, decyl group and the like.
An oxygen atom, a sulfur atom and an amino group NR ′ of the substituent B; and; an alkylene ether group, an alkylene amino group, an alkylene thioether group, or an aralkylene having 1 to 20 carbon atoms terminated with these atoms or groups. Oxygen atom such as ether group, aralkyleneamino group, aralkylenethioether group, amino group NR 'and sulfur atom combine with adjacent carbonyl group to form conjugated ester group, amide group, imide group, thioester group, etc. It is preferable to do.
Among these, the substituent B is an oxygen atom, a sulfur atom or an amino group forming a conjugated system; an alkylene ether group having 1 to 20 carbon atoms, an alkyleneamino group or an alkylenethioether having these atoms or groups at the terminal Preferably an amino group (NH), an alkyleneamino group (—NH—CH ₂ — group, —NH—CH ₂ CH ₂ — group, —NH—CH ₂ CH ₂ CH ₂ — group), alkylene ether A group (—O—CH ₂ — group, —O—CH ₂ CH ₂ — group, —O—CH ₂ CH ₂ CH ₂ — group) is particularly preferred.

  The thermoplastic elastomer (A) used in the composition of the present invention has the following formula (2) or a side chain containing a structure represented by the above formula (1), which is bonded to the main chain at the α-position or β-position. It is preferable to have as a side chain containing the structure represented by (3).

In the formula, A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; oxygen atom, amino group NR ′ (R ′ is . a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or Ri is also good organic group der contain these atoms or groups, D is a single bond; oxygen atom, an amino group NR '(R' Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or an organic group which may contain a sulfur atom.

Wherein the substituents A is basically the same as the substituent A in the formula (1), the substituent B is Ri substituent B is basically similar to Der above following formula (1), substituent D Is basically the same as the corresponding one of the substituents B in the above formula (1).
However, the substituent D in the above formula (3) is a C 1-20 which may contain a single bond; an oxygen atom, an amino group NR ′ or a sulfur atom, among those exemplified as the substituent B in the above formula (1). It is preferably one that forms a conjugated system with an imide nitrogen of an alkylene group or an aralkylene group, and particularly preferably an alkylene group. That is, it is preferable to form an alkyleneamino group or an aralkyleneamino group having 1 to 20 carbon atoms which may contain an oxygen atom, an amino group NR ′ or a sulfur atom together with the imide nitrogen of the above formula (3). It is particularly preferred to form
Specific examples of the substituent D include, for example, a single bond; an alkylene ether group, an alkylene amino group, and an alkylene thioether having 1 to 20 carbon atoms having an oxygen atom, a sulfur atom, or an amino group as a terminal. Group, aralkylene ether group, aralkylene amino group, aralkylene thioether group and the like; methylene group, ethylene group, propylene group, butylene group, hexylene group, phenylene group, xylylene group and the like including isomers.

  In the present invention, a side chain containing an imino group and a carbonyl-containing group (specifically, a side chain containing a structure represented by the above formula (1) or the above formula (2) or (3)) is It is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the elastomeric polymer. If it is less than 0.1 mol%, the strength at the time of crosslinking may not be sufficient, and if it exceeds 50 mol%, the crosslinking density may increase and rubber elasticity may be lost. When the introduction ratio is within this range, the interaction between the side chains of the elastomeric polymer occurs between molecules or within the molecule, and these are formed in a well-balanced manner, so that the tensile strength during crosslinking of the resulting composition of the present invention is , High recyclability, and good compression set resistance. From the viewpoint that these properties are more excellent, it is more preferable that side chains are introduced at a ratio of 0.1 to 30 mol%, and side chains are introduced at a ratio of 0.5 to 20 mol%. Further preferred.

  In the present invention, when the side chain contains a nitrogen-containing heterocyclic ring and a carbonyl-containing group, the side chain preferably contains a structure represented by the following formula (4).

In the formula, E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; contain an atom or group Ri may optionally organic group der, D is a single bond; oxygen atom, an amino group NR '(. R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or may contain a sulfur atom Good organic group.

Here, the nitrogen-containing heterocyclic ring E specifically includes the nitrogen-containing heterocyclic rings exemplified below.
Further, the substituent B is Ri substituent B is basically similar to Der above following formula (1), substituent D is basically the same as the corresponding among the substituent B in the formula (1) is there.

The nitrogen-containing heterocycle can be used even if it contains a nitrogen atom in the heterocycle and has a heteroatom other than the nitrogen atom in the heterocycle, such as a sulfur atom, an oxygen atom, or a phosphorus atom. Here, the reason why the heterocyclic compound is used is that if it has a heterocyclic structure, hydrogen bonds that form a bridge are strengthened, and the tensile strength of the resulting composition of the present invention is improved.
The nitrogen-containing heterocycle may have a substituent, and specific examples of the substituent include alkyl groups such as a methyl group, an ethyl group, a (iso) propyl group, and a hexyl group; Alkoxy groups such as methoxy group, ethoxy group, (iso) propoxy group; groups consisting of halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; cyano group; amino group; aromatic hydrocarbon group; ester group; An ether group; an acyl group; a thioether group; and the like can be mentioned, and these can be used in combination. The substitution position of these substituents is not particularly limited, and the number of substituents is not limited.
Further, the nitrogen-containing heterocycle may or may not have aromaticity, but the tensile strength at the time of crosslinking of the composition of the present invention obtained if it has aromaticity. Is higher, and the mechanical strength is further improved.

The nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring.
Specific examples of such nitrogen-containing heterocycle include pyrrololine, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl, phthalimidine, β -Isoindigo, monoporphyrin, diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyroerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone Hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, in , Indoline, oxylindole, carbazole, phenothiazine, indolenine, isoindole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine , Pyrazine, phenazine, tetrazine, benzoxazole, benzoisoxazole, anthranyl, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthrazolin, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline, triazine, histidine , Triazolidine, melamine, adenine, guanine, thymine, cytosine And derivatives thereof. Among these, particularly the nitrogen-containing 5-membered ring is preferably exemplified by the following compound, a triazole derivative represented by the following formula (25) and an imidazole derivative represented by the following formula (26). These may have the above-described various substituents, or may be hydrogenated or eliminated.

  In the formula, the substituent X is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and is basically the same as the substituent A in the above formula (1). It is the same.

  Moreover, about a nitrogen-containing 6-membered ring, the following compound is illustrated preferably. These may have various substituents as described above, or may be hydrogenated or eliminated.

  Moreover, what condensed the said nitrogen-containing heterocyclic ring, a benzene ring, or nitrogen-containing heterocyclic rings can also be used, Specifically, the following condensed ring is illustrated suitably. These condensed rings may also have the above-described various substituents, and may have hydrogen atoms added or eliminated.

  Among such nitrogen-containing heterocycles, it is a triazole ring, thiadiazole ring, pyridine ring, thiazole ring, imidazole ring and hydantoin ring. It is preferable because of its excellent strength and hardness.

  The thermoplastic elastomer (A) used in the composition of the present invention has the following formula (5) or a side chain containing a structure represented by the above formula (4), which is bonded to the main chain at the α-position or β-position. It is more preferable to have as a side chain containing the structure represented by (6).

In the formula, E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; contain an atom or group Ri may optionally organic group der, D is a single bond; oxygen atom, an amino group NR '(. R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or may contain a sulfur atom Good organic group.

Here, the nitrogen-containing heterocyclic ring E specifically includes the nitrogen-containing heterocyclic rings exemplified above.
Further, the substituent B is Ri substituent B is basically similar to Der above following formula (1), substituent D is basically the same as the corresponding among the substituent B in the formula (1) is there.
However, the substituent D in the above formula (6) forms a conjugated system with a single bond; an imide nitrogen of an alkylene group having 1 to 20 carbon atoms or an aralkylene group which may contain an oxygen atom, an amino group NR ′ or a sulfur atom. It is preferable that it is a thing, and it is especially preferable that it is a single bond. That is, it is preferable to form an alkyleneamino group or an aralkyleneamino group having 1 to 20 carbon atoms which may contain an oxygen atom, an amino group NR ′ or a sulfur atom together with the imide nitrogen of the above formula (6). It is particularly preferable that the nitrogen-containing heterocyclic ring is directly bonded to the imide nitrogen of 6) (single bond).

  When the thermoplastic elastomer (A) used in the composition of the present invention has a side chain containing a triazole ring, an imidazole ring or a thiazole ring as the side chain containing the nitrogen-containing heterocycle, the above formula (4) ) As a side chain containing the structure represented by the following formula (13), the following formula (14) or (15), or the following formula (16). It is preferable that any one of the following formulas (17) or (18), the following formulas (19) to (22) bonded to the main chain at the α-position or the β-position, or the following formula (23) or (24) It is more preferable that it has as a side chain containing the structure made.

In the formula, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups D is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or an organic group which may contain a sulfur atom, and G and J are Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

Here, the substituents B and D are each independently the same as the substituents B and D in the above formulas (4) to (6).
Specific examples of the substituents G and J include, for example, a hydrogen atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, exemplified as the substituent A in the above formula (1), Linear alkyl groups such as dodecyl group and stearyl group; isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl Groups, branched alkyl groups such as 2-ethylhexyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group (o-, m-, p-), dimethylphenyl group and mesityl group Each may be the same or different.

  In the present invention, a side chain containing a nitrogen-containing heterocyclic ring and a carbonyl-containing group (specifically, a side chain containing a structure represented by the above formula (4) or the above formula (5) or (6)). ) Is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the elastomeric polymer. If it is less than 0.1 mol%, the strength at the time of crosslinking may not be sufficient, and if it exceeds 50 mol%, the crosslinking density increases, rubber elasticity may be lost, and recyclability may be impaired. When the introduction ratio is within this range, the interaction between the side chains of the elastomeric polymer occurs between molecules or within the molecule, and these are formed in a well-balanced manner, so that the tensile strength during crosslinking of the resulting composition of the present invention is , High recyclability, and good compression set resistance. From the viewpoint that these properties are more excellent, it is more preferable that side chains are introduced at a ratio of 0.1 to 30 mol%, and side chains are introduced at a ratio of 0.5 to 20 mol%. Further preferred.

Further, in the present invention, when having a side chain containing a nitrogen-containing heterocycle and a carbonyl-containing group together with a side chain containing an imino group and a carbonyl-containing group, these side chains are added together to give the elastomeric property. It is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the polymer, and the ratio of introduction into the side chain (nitrogen-containing heterocycle and carbonyl). The side chain containing the containing group / the side chain containing the imino group and the carbonyl containing group) is more preferably 1/99 to 99/1, and still more preferably 10/90 to 90/10.
When the introduction rate and the introduction ratio are within this range, the tensile strength at the time of crosslinking is high, the recyclability is excellent, and the mechanical strength such as tensile strength is maintained while maintaining the property of good compression set resistance. This is preferable because it can be further improved and coloring of the composition derived from the introduced nitrogen-containing heterocycle can be suppressed.

Next, the bonding position of the nitrogen-containing heterocyclic ring in the case where the thermoplastic elastomer (A) used in the composition of the present invention has a side chain containing a nitrogen-containing heterocyclic ring will be described. For convenience, the nitrogen-containing heterocycle is referred to as “nitrogen-containing n-membered ring compound (n ≧ 3)”.
The bonding positions described below ("positions 1 to n") are based on the IUPAC nomenclature. For example, in the case of a compound having three nitrogen atoms having an unshared electron pair, the bonding position is determined by the order based on the IUPAC nomenclature. Specifically, the bonding positions are indicated on the 5-membered, 6-membered and condensed nitrogen-containing heterocycles exemplified above.
In the thermoplastic elastomer (A), the bonding position of the nitrogen-containing n-membered ring compound bonded to the copolymer directly or through an organic group is not particularly limited, and may be any bonding position (position 1 to position n). . Preferably, it is the 1-position or 3-position to n-position.

When the nitrogen-containing n-membered ring compound contains one nitrogen atom (for example, a pyridine ring), the chelate is easily formed in the molecule, and the physical properties such as tensile strength when the composition is obtained are excellent. The (n-1) position is preferred.
By selecting the bonding position of the nitrogen-containing n-membered ring compound, the thermoplastic elastomer can easily form crosslinks due to hydrogen bonds, ionic bonds, coordination bonds, etc., between the molecules of the thermoplastic elastomer, making it easy to recycle. Excellent, excellent mechanical properties.

  In the present invention, when the side chain contains a covalent crosslinking site and a carbonyl-containing group, the covalent crosslinking site is selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. More preferably, it can be crosslinked by at least one selected bond. Further, the thermoplastic elastomer (A) used in the composition of the present invention may be one in which crosslinking is formed by such a bond.

The side chain containing a covalent bond crosslinking site and a carbonyl-containing group reacts with a “compound that forms a covalent bond” in addition to the carbonyl-containing group, so that amide, ester, lactone, urethane, ether, thiourethane and The side chain is not particularly limited as long as it is a side chain having a functional group capable of causing at least one bond selected from the group consisting of thioethers as a covalent crosslinking site.
In the present invention, examples of the “compound that forms a covalent bond” include, for example, two or more amino groups and / or imino groups in one molecule (in the case where both amino groups and imino groups are present, these groups are added together). Polyamine compound having 2 or more); polyol compound having 2 or more hydroxyl groups in one molecule; polyisocyanate compound having 2 or more isocyanate (NCO) groups in one molecule; thiol group (mercapto group) in one molecule And a polythiol compound having two or more.

  Examples of the polyamine compound include the following alicyclic amines, aliphatic polyamines, aromatic polyamines, nitrogen-containing heterocyclic amines, and the like.

  Specific examples of the alicyclic amine include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane, and di- (aminomethyl). ) Cyclohexane and the like.

  Specific examples of the aliphatic polyamine include, for example, methylenediamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, 1,3-diaminopentane, hexamethylenediamine, diaminoheptane, diaminododecane, diethylenetriamine, diethylaminopropylamine. N-aminoethylpiperazine, triethylenetetramine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-dimethyl-1,3-propanediamine, N , N′-diethyl-1,3-propanediamine, N, N′-diisopropyl-1,3-propanediamine, N, N′-dimethyl-1,6-hexanediamine, N, N′-diethyl-1, 6-Hexanediamine N, N ', N' '- trimethylbis (hexamethylene) triamine, and the like.

  Specific examples of the aromatic polyamine and nitrogen-containing heterocyclic amine include diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tris (dimethylaminomethyl) phenol, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, Examples include 3-amino-1,2,4-triazole.

  In the polyamine compound, one or more of its hydrogen atoms may be substituted with an alkyl group, an alkylene group, an aralkylene group, an oxy group, an acyl group, a halogen atom, etc., and the skeleton has an oxygen atom or a sulfur atom. And may contain a heteroatom such as.

  Moreover, the said polyamine compound may be used individually by 1 type, or may use 2 or more types together. The mixing ratio in the case of using two or more kinds in combination can be adjusted to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.

  Among the polyamine compounds exemplified above, hexamethylenediamine, N, N′-dimethyl-1,6-hexanediamine, diaminodiphenylsulfone, etc. are highly effective in improving compression set resistance, mechanical strength, particularly tensile strength. preferable.

  As long as the polyol compound is a compound having two or more hydroxyl groups, the molecular weight and skeleton thereof are not particularly limited, and examples thereof include the following polyether polyols, polyester polyols, other polyols, and mixed polyols thereof. It is done.

  Specific examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3- At least one selected from polyhydric alcohols such as butanediol, 1,4-butanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxyphenylmethane, pentaerythritol, ethylene oxide, propylene oxide, butylene Polyols obtained by adding at least one selected from oxide, styrene oxide and the like; polyoxytetramethylene oxide; and the like may be used, and these may be used alone or in combination of two or more.

  Specific examples of the polyester polyol include ethylene glycol, propylene glycol, butanediol pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, and other low molecular polyols. A condensation polymer of two or more with one or more of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid and other low molecular carboxylic acids and oligomeric acids; Ring-opening polymers such as propionlactone and valerolactone; and the like. These may be used alone or in combination of two or more.

  Specific examples of other polyols include, for example, polymer polyol, polycarbonate polyol; polybutadiene polyol; hydrogenated polybutadiene polyol; acrylic polyol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, Hexanediol, polyethylene glycol laurylamine (for example, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (for example, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine) Polyethylene glycol octylamine (for example, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octyl Amines (eg, N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine ( For example, low molecular polyols such as N, N-bis (2-methyl-2-hydroxyethyl) stearylamine) may be used, and these may be used alone or in combination of two or more.

Polyisocyanate compounds include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI). ), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5 -Aromatic polyisocyanates such as naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (N DI) of an aliphatic polyisocyanate, trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (hydrogenated MDI), H ₆ TDI (hydrogenated TDI) Diisocyanate compounds such as alicyclic polyisocyanates such as; Polyisocyanate compounds such as polymethylene polyphenylene polyisocyanates; Carbodiimide-modified polyisocyanates of these isocyanate compounds; Isocyanurate-modified polyisocyanates of these isocyanate compounds; Urethane prepolymers obtained by reacting with the polyol compounds exemplified in the above, and the like. These may be used alone or in combination of two or more.

  As long as the polythiol compound is a compound having two or more thiol groups, its molecular weight and skeleton are not particularly limited. Specific examples thereof include methanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, , 9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1,2-propanedithiol, 1,3-propadithiol, toluene-3,4-dithiol, 3,6-dichloro-1, 2-benzenedithiol, 1,5-naphthalenedithiol, 1,2-benzenedimethanethiol, 1 3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 4,4′-thiobisbenzenethiol, 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6- Dioxaoctane, 1,5-dimercapto-3-thiapentane, 1,3,5-triazine-2,4,6-trithiol (trimercapto-triazine), 2-di-n-butylamino-4,6-dimercapto -S-triazine, trimethylolpropane tris (β-thiopropionate), trimethylolpropane tris (thioglycolate), polythiol (thiocol or thiol-modified polymer (resin, rubber, etc.)) and the like. You may use individually by 1 type or may use 2 or more types together.

  As a functional group capable of generating at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers by reacting with such “compounds that form a covalent bond” Preferred examples include a cyclic acid anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, and a thiol group.

The side chain containing a covalent bond crosslinking site and a carbonyl-containing group is not particularly limited as long as it is a side chain having such a functional group and a carbonyl-containing group.
In the thermoplastic elastomer (A) used in the composition of the present invention, the crosslinking at the covalent cross-linking site, that is, the cross-linking by the covalent bond between the functional group and the above-mentioned “compound that generates a covalent bond” is 1 It is preferable to have at least one in the molecule, and in particular, when at least one bond selected from the group consisting of lactone, urethane, ether, thiourethane and thioether forms a crosslink, two or more are present. It is preferable to have 2-20, more preferably 2-10.
In the present invention, the crosslinking at the covalent crosslinking site contains a tertiary amino group (-N =). The compression set and mechanical strength of the resulting composition of the present invention ( This is preferable because the elongation at break and the strength at break are further improved. This is considered to be due to the tertiary amino group being further hydrogen-bonded (interacted) with the carbonyl-containing group and the nitrogen-containing heterocyclic ring to further improve the crosslinking density. Therefore, as the “compound that forms a covalent bond”, among those exemplified above, polyethylene glycol laurylamine (eg, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (eg, N , N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (eg, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octylamine (eg, N, N -Bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (for example, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine (for example, N, N- Scan is preferably (2-methyl-2-hydroxyethyl) stearylamine).

  In the present invention, it is preferable that the cross-linking at the covalent cross-linking site contains at least one structure represented by any of the following formulas (7) to (9). More preferably contains a tertiary amino group.

  In the formula, K, L, Q and R are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; It is an organic group which may contain an atom or a group, and T is a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom and which may be branched.

Here, each of the substituents K, L, Q, and R is independently the same as the substituent B in the above formula (1).
Specific examples of the substituent T include, for example, a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, a 1,6-hexylene group, Alkylene groups such as 1,7-heptylene group, 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 1,11-undecylene group, 1,12-dodecylene group; N, N-diethyl Dodecylamine-2,2'-diyl, N, N-dipropyldodecylamine-2,2'-diyl, N, N-diethyloctylamine-2,2'-diyl, N, N-dipropyloctylamine- 2,2'-diyl, N, N-diethylstearylamine-2,2'-diyl, N, N-dipropylstearylamine-2,2'-diyl; vinylene group; 1,4-cyclohexylene group Divalent such as Alicyclic hydrocarbon group; divalent aromatic hydrocarbon group such as 1,4-phenylene group, 1,2-phenylene group, 1,3-phenylene group, 1,3-phenylenebis (methylene) group; propane Trivalent carbonization such as -1,2,3-triyl, butane-1,3,4-triyl, trimethylamine-1,1 ′, 1 ″ -triyl, triethylamine-2,2 ′, 2 ″ -triyl A hydrogen group; a tetravalent hydrocarbon group represented by the following formulas (27) and (28); and a substituent formed by combining these;

  Furthermore, in the present invention, the crosslinking at the covalent crosslinking site is represented by any one of the following formulas (10) to (12) that are bonded to the main chain of the elastomeric polymer at the α-position or β-position. It is preferable that at least one structure is contained, and it is more preferable that T in the formula contains a tertiary amino group. Specific examples of the structure represented by any one of the following formulas (10) to (12) include compounds represented by the following formulas (29) to (40).

  Here, the substituents K, L, Q and R are each independently the same as the substituents K, L, Q and R in the above formulas (7) to (9), and the substituent T is This is basically the same as the substituent T in the formula (7).

（式中、ｌは、１以上の整数を表す。）

(In the formula, l represents an integer of 1 or more.)

（式中、ｌ、ｍおよびｎは、それぞれ独立に１以上の整数を表す。）

(In the formula, l, m and n each independently represents an integer of 1 or more.)

  In the present invention, the cross-linking at the covalent cross-linking site is preferably formed by a reaction between a cyclic acid anhydride group and a hydroxyl group or an amino group and / or an imino group.

  Further, the thermoplastic elastomer (A) used in the composition of the present invention preferably has a glass transition point of 25 ° C. or lower, and when the thermoplastic elastomer has two or more glass transition points, or two or more kinds. When the thermoplastic elastomer is used in combination, at least one of the glass transition points is preferably 25 ° C. or lower. When the glass transition point is 25 ° C. or lower, the molded article exhibits rubber-like elasticity at room temperature.

  The composition of the present invention contains one or more of such thermoplastic elastomers. The mixing ratio in the case of containing two or more kinds can be set to any ratio depending on the use in which the composition of the present invention is used, the physical properties required for the composition, and the like.

The manufacturing method of the thermoplastic elastomer (A) used for the composition of this invention is not specifically limited, A normal method can be selected.
Specifically, as a method for producing a thermoplastic elastomer (A) having a side chain containing an imino group and a carbonyl-containing group, an imino group is added to the elastomeric polymer containing a cyclic acid anhydride group in the side chain. A production method comprising a reaction step of reacting a compound that can be introduced (hereinafter referred to as “reaction step A”) is preferably exemplified, and a thermoplastic elastomer having a side chain containing a nitrogen-containing heterocyclic ring and a carbonyl-containing group As a method for producing (A), a reaction step of reacting a compound capable of introducing a nitrogen-containing heterocycle with an elastomeric polymer containing a cyclic acid anhydride group in the side chain (hereinafter referred to as “reaction step B”). A production method comprising In addition, as a method for producing the thermoplastic elastomer (A) having a side chain containing an imino group, a nitrogen-containing heterocyclic ring, and a carbonyl-containing group, there is a method comprising both the reaction step A and the reaction step B. Preferably exemplified. In this method, the reaction step B may be included as a step performed simultaneously with the reaction step A, or may be included as a pre-step or a post-step of the reaction step A. It is preferably provided as a post-process.
On the other hand, as a method for producing a thermoplastic elastomer (A) having a side chain containing a covalently crosslinked site and a carbonyl-containing group, specifically, the elastomeric polymer and a cyclic acid anhydride group described later are used. To a production method comprising a reaction step (hereinafter referred to as “reaction step C”) for reacting a compound that can be introduced, or an elastomeric polymer containing a cyclic acid anhydride group obtained by this production method in the side chain, Furthermore, the manufacturing method which comprises the reaction process (henceforth "reaction process D") which reacts the compound which produces | generates the covalent bond mentioned above; etc. are mentioned.
Hereinafter, the elastomeric polymer containing a cyclic acid anhydride group in the side chain, the compound capable of introducing an imino group, the compound capable of introducing a nitrogen-containing heterocyclic ring, and reaction steps A to D will be described in detail.

(Elastomeric polymer containing cyclic acid anhydride groups in the side chain)
An elastomeric polymer containing a cyclic acid anhydride group in the side chain is an elastomeric polymer in which the cyclic acid anhydride group has a chemically stable bond (covalent bond) to the atom forming the main chain. In other words, it is obtained by reacting the elastomeric polymer with a compound capable of introducing a cyclic acid anhydride group.
Specific examples of the compound capable of introducing a cyclic acid anhydride group include cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride.

In the present invention, the elastomeric polymer containing a cyclic acid anhydride group in the side chain is obtained by subjecting the cyclic polymer to a cyclic acid by the usual method, for example, the usual conditions such as stirring under heating. An anhydride may be produced by a graft polymerization method, or a commercially available product may be used.
Examples of commercially available products include maleic anhydride-modified isoprene rubbers such as LIR-403 (manufactured by Kuraray Co., Ltd.) and LIR-410A (Kuraray Co., Ltd.); modified isoprene rubbers such as LIR-410 (manufactured by Kuraray Co., Ltd.); Clinac 110 , 221 and 231 (manufactured by Policer), carboxy-modified nitrile rubber; CPIB (manufactured by Nisseki Chemical), carboxy-modified polybutene such as HRPIB (manufactured by Nisseki Chemical Co., Ltd.); , Maleic anhydride modified ethylene-propylene rubber such as Yucaron (Mitsubishi Chemical Co., Ltd.), Tuffmer M (for example, MA8510 (Mitsui Chemicals)), etc. Anhydrous maleic such as Tuffmer M (for example, MH7020 (Mitsui Chemicals)) Acid-modified ethylene-butene rubber; Adtex series (maleic anhydride-modified E A, maleic anhydride modified EMA (manufactured by Nippon Polyolefin Co., Ltd.), HPR series (maleic anhydride modified EEA, maleic anhydride modified EVA (manufactured by Mitsui & DuPont Polyolefin)), Bond Fast series (maleic anhydride modified EMA (Sumitomo) Chemical)), Dumiran series (Maleic anhydride modified EVOH (Takeda Pharmaceutical Co., Ltd.)), Bondine (Maleic anhydride modified EEA (Atofina)), Tuftec (Maleic anhydride modified SEBS, M1943 (Asahi Kasei) Manufactured)), Kraton (maleic anhydride modified SEBS, FG1901X (manufactured by Kraton Polymer)), tufprene (maleic anhydride modified SBS, 912 (Asahi Kasei)), Septon (maleic anhydride modified SEPS (manufactured by Kuraray)) Lexpearl (maleic anhydride modified EE ET-182G, 224M, 234M (manufactured by Nippon Polyolefin Co., Ltd.)), maleic anhydride-modified polyethylene such as Aurorene (maleic anhydride-modified EEA, 200S, 250S (manufactured by Nippon Paper Chemical Co., Ltd.)); Admer (for example, QB550, LF128 (manufactured by Mitsui Chemicals)) and the like;

(Compound capable of introducing imino group)
A compound capable of introducing an imino group is a compound having an imino group that does not constitute a part of a cyclic compound such as a heterocyclic ring and other active hydrogen groups (for example, a hydroxyl group, a thiol group, an amino group, etc.) in the molecule. Specific examples are not particularly limited, and specific examples thereof include N-methylaminoethanol, N-ethylaminoethanol, Nn-propylaminoethanol, Nn-butylaminoethanol, Nn-pentylaminoethanol, N -N-hexylaminoethanol, Nn-heptylaminoethanol, Nn-octylaminoethanol, Nn-nonylaminoethanol, Nn-decylaminoethanol, Nn-undecylaminoethanol, N- n-dodecylaminoethanol, N- (2-ethylhexyl) aminoethanol, N-methylaminopropa And alkylamino alcohols such as N-methylaminobutanol; aromatic aminoalcohols such as N-phenylaminoethanol, N-toluylaminoethanol, N-phenylaminopropanol and N-phenylaminobutanol; N-methylamino Alkylaminothiols such as ethanethiol, N-ethylaminoethanethiol, Nn-propylaminoethanethiol, Nn-butylaminoethanethiol, N-methylaminopropanethiol, N-methylaminobutanethiol; N- Aromatic aminothiols such as phenylaminoethanethiol, N-toluylaminoethanethiol, N-phenylaminopropanethiol, N-phenylaminobutanethiol; N-methylethylenediamine, N-ethylethylene Alkyl diamines such as amines, Nn-propylethylenediamine, N-methylpropanediamine, N-ethylpropanediamine, N-methylbutanediamine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine; N- And aromatic diamines such as phenylethylenediamine, N-phenylpropanediamine, N-phenylbutanediamine, and N, N′-diphenylethylenediamine;
Of these, Nn-butylaminoethanol, Nn-octylaminoethanol, and Nn-dodecylaminoethanol are preferable.

(Compound capable of introducing nitrogen-containing heterocycle)
The compound capable of introducing a nitrogen-containing heterocyclic ring may be the nitrogen-containing heterocyclic ring itself exemplified above, and a substituent that reacts with a cyclic acid anhydride group such as maleic anhydride (for example, a hydroxyl group, a thiol group, It may be a nitrogen-containing heterocyclic ring having an amino group or the like.

(Reaction step A)
In the reaction step A, a compound capable of introducing an imino group and an elastomeric polymer containing a cyclic acid anhydride group in the side chain are mixed, and the compound and the cyclic acid anhydride group can be chemically bonded. It is a step of reacting (for example, 60 to 250 ° C.) (opening a cyclic acid anhydride group). By this reaction, the structure represented by the above formula (2) or (3) is contained in the side chain of the thermoplastic elastomer obtained.
Moreover, what is necessary is just to make the compound which can introduce | transduce an imino group react with a part or whole quantity of the cyclic acid anhydride group contained in the side chain of the said elastomeric polymer. The part is preferably 1 mol% or more, more preferably 10 mol% or more, and particularly preferably 30 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. Within this range, high physical properties (for example, breaking properties) are sufficiently exhibited, and compression set resistance is further improved.

(Reaction step B)
In the reaction step B, a compound capable of introducing a nitrogen-containing heterocycle and an elastomeric polymer containing a cyclic acid anhydride group in the side chain are mixed, and the compound and the cyclic acid anhydride group are chemically bonded. This is a step of reacting (opening a cyclic acid anhydride group) at a temperature (for example, 60 to 250 ° C.). By this reaction, the structure represented by the above formula (5) or (6) is contained in the side chain of the thermoplastic elastomer obtained.
Moreover, what is necessary is just to make the compound which can introduce | transduce a nitrogen-containing heterocyclic ring react with a part or whole quantity of the cyclic acid anhydride group contained in the side chain of the said elastomeric polymer. The part is preferably 1 mol% or more, more preferably 50 mol% or more, particularly preferably 80 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. Within this range, the effect of introducing a nitrogen-containing heterocyclic ring is exhibited, and mechanical strength such as tensile strength at the time of crosslinking is further improved.

Further, when both the compound capable of introducing the imino group and the compound capable of introducing the nitrogen-containing heterocycle are used, both the reaction step A and the reaction step B are provided. In this case, the compound capable of introducing an imino group and the compound capable of introducing a nitrogen-containing heterocycle may be reacted with a part or all of the cyclic acid anhydride group contained in the side chain of the elastomeric polymer. . The reaction ratio of each compound with respect to the cyclic acid anhydride group is not particularly limited, but in total, it is preferably 1 mol% or more, more preferably 50 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. 80 mol% or more is particularly preferable. Within this range, tensile properties, compression set resistance, and tensile strength at the time of crosslinking are further improved while maintaining recyclability.
The ratio of the reaction ratio of each compound to the cyclic acid anhydride group (compound capable of introducing an imino group: compound capable of introducing a nitrogen-containing heterocyclic ring) is preferably 1:99 to 99: 1. It is more preferably 10:90 to 99: 1, and particularly preferably 20:80 to 90:10.

(Reaction step C)
The reaction step C is a step of producing an elastomeric polymer containing a cyclic acid anhydride group in a side chain by reacting an elastomeric polymer with a compound capable of introducing a cyclic acid anhydride group.

(Reaction process D)
In the reaction step D, an elastomeric polymer containing a cyclic acid anhydride group in the side chain and a compound that forms a covalent bond are mixed, and the temperature at which the cyclic acid anhydride group and the compound can chemically bond ( For example, the reaction is performed at 60 to 250 ° C. (cyclic acid anhydride group is opened). By this reaction, the structure represented by the above formulas (10) to (12) is contained in the side chain of the thermoplastic elastomer obtained.
Moreover, the compound which produces | generates a covalent bond should just make it react with the one part or all quantity of the cyclic acid anhydride group contained in the side chain of the said elastomeric polymer. The part is preferably 1 mol% or more, more preferably 10 mol% or more, and particularly preferably 30 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. Within this range, high physical properties (for example, breaking properties) are sufficiently exhibited, and compression set resistance is further improved.

Such a production method includes, for example, an elastomeric polymer containing a cyclic acid anhydride group in the side chain, a compound capable of introducing an imino group and / or a compound capable of introducing a nitrogen-containing heterocycle, of 60 to 250. It may be a method of mixing using a roll, a kneader, a pressure kneader, a Banbury mixer, a single screw extruder, a twin screw extruder, a universal stirrer and the like at a temperature of ° C.
Further, in such a production method, each group (structure) of the side chain of the thermoplastic elastomer, that is, an unreacted cyclic acid anhydride group, the above formulas (2), (3), (5), (6 ) And the like can be confirmed by commonly used analytical means such as NMR and IR spectra.

<Ethylene propylene copolymer (B)>
The ethylene-propylene copolymer (B) used in the composition of the present invention has a polypropylene block and an ethylene-propylene block, and more specifically, a block composed of a polypropylene component (polypropylene block) and a propylene / ethylene random copolymer. It is a block copolymer in which blocks composed of polymer components (ethylene propylene block) are linked.
By containing such an ethylene propylene copolymer (B), the thermoplastic elastomer composition obtained retains excellent flexibility, and is excellent in fluidity and mechanical strength at high temperatures. This is because of the presence of polypropylene blocks with high crystallinity and hardness, mechanical strength such as heat resistance, modulus, and breaking strength is improved, and flexibility and fluidity at high temperatures are achieved due to the presence of ethylene-propylene blocks that are random copolymers. Is considered to be good.

  In this invention, it is preferable that the said ethylene propylene copolymer (B) has the said polypropylene block in the ratio of 1-50 mol%, and has the said polypropylene block in the ratio of 10-25 mol%. More preferably. When the proportion of the polypropylene block is within this range, the mechanical strength of the composition of the present invention containing the ethylene-propylene copolymer (B) becomes better.

  In the present invention, the polypropylene block is preferably stereoregular from the viewpoint that the mechanical strength of the composition of the present invention containing the ethylene-propylene copolymer (B) becomes better. From the viewpoint of further improving the strength, it is preferably isotactic.

  Furthermore, in the present invention, in the ethylene propylene block, other than propylene and ethylene, other polybutene components may be contained in an amount of about 5% by weight or less as required.

  In this invention, it is preferable that content of the said ethylene propylene copolymer (B) is 1-200 mass parts with respect to 100 mass parts of said thermoplastic elastomers (A), and is 30-150 mass parts. Is more preferable. When the content of the ethylene-propylene copolymer (B) is within this range, the fluidity and mechanical properties at high temperatures are maintained while maintaining the flexibility of the composition of the present invention containing the ethylene-propylene copolymer (B). Strength becomes better.

Conventionally, the soft material which consists of polyolefin resin is manufactured by mixing the amorphous ethylene propylene rubber (EPR) etc. which were manufactured using the vanadium catalyst in polypropylene.
On the other hand, the ethylene-propylene copolymer (B) used in the present invention simultaneously polymerizes an elastomer component of polypropylene and a propylene / ethylene random copolymer in one polymerization tank using a titanium compound or an organoaluminum compound. It is preferable to manufacture by doing. Alternatively, it may be produced by transferring separately synthesized polypropylene to another synthesis tank, charging ethylene and propylene therein, and polymerizing in the presence of a catalyst or the like.

  Such an ethylene-propylene copolymer (B) is preferably a so-called reactor-type copolymer in which the ethylene content in the ethylene-propylene block is increased. As a soft type of prime TPO manufactured by Prime Polymer Co., Ltd. A commercially available product, specifically, a product marketed under the trade name of M142E is preferably used.

<Styrenic thermoplastic elastomer>
The styrenic thermoplastic elastomer which may be optionally contained in the composition of the present invention is a known styrenic thermoplastic elastomer obtained as a block copolymer from an aromatic vinyl compound and a conjugated diene.
In the present invention, the styrenic thermoplastic elastomer has a block polymerized portion by an aromatic vinyl corresponding to a crosslinking point at the terminal and has a weight average molecular weight of 100,000 or more from the viewpoint of improving compression set. It is preferable.
Specific examples of the aromatic vinyl compound include styrene, α-methyl styrene, 3-methyl styrene, 4-propyl styrene, and the like. You may use together.
Specific examples of the conjugated diene include butadiene, isoprene, and mixtures thereof.

  By containing such a styrenic thermoplastic elastomer, the thermoplastic elastomer composition obtained has a good compression set. This is because the styrenic thermoplastic elastomer is incompatible, has low fluidity and forms an independent phase, and since the styrenic thermoplastic elastomer has a high affinity with oil, the styrenic thermoplastic elastomer and This is presumably because the oil is taken into the crosslinked structure of the thermoplastic elastomer (A) in a state where the styrene thermoplastic elastomer has absorbed the oil.

In the present invention, the method for producing the styrenic thermoplastic elastomer is not particularly limited. For example, the polymer (block (A)) obtained by polymerizing the aromatic vinyl compound and the conjugated diene are polymerized. A method obtained by copolymerization (block copolymerization) with the obtained polymer (block (B)) is preferably exemplified.
Here, the number average molecular weight of the block (A) is preferably in the range of 3000 to 50000. When the molecular weight is within this range, the mechanical strength of the resulting styrenic thermoplastic elastomer is good, and the compression set resistance when obtaining the composition of the present invention using the styrenic thermoplastic elastomer is good.
Moreover, it is preferable that the number average molecular weights of the said block (B) are the range of 10,000-200000. When the molecular weight is within this range, the viscosity at the time of mixing and melting in obtaining the composition of the present invention using the resulting styrenic thermoplastic elastomer becomes good, and the viscosity at the time of mixing and melting of the resulting composition of the present invention is high. It becomes good.
Furthermore, the styrenic thermoplastic elastomer obtained as a block copolymer has one or more blocks (A) and one or more blocks (B), and the block form is A- (BA ) _N or (AB) _m . Among these, the form of A-B-A is preferable because the fluidity and mechanical properties are good, and the form of using AB and A-B-A together is also possible.

  In the present invention, the styrene thermoplastic elastomer preferably has a styrene content of 10 to 60% by mass, more preferably 30 to 50% by mass. When the styrene content is within this range, the viscosity at the time of mixing and melting when the composition of the present invention is obtained is improved, and the mechanical strength and compression set resistance of the resulting composition of the present invention are further improved.

Specific examples of such styrenic thermoplastic elastomers include, for example, hydrogenated styrene-isoprene block copolymer (SEPS: styrene ethylene propylene styrene block copolymer), styrene ethylene ethylene propylene styrene block copolymer. (Hereinafter referred to as “SEEPS”), styrene ethylene butylene styrene block copolymer (hereinafter referred to as “SEBS”), and the like.
In the present invention, as such a styrenic thermoplastic elastomer, commercially available products such as Septon 2006 (SEPS, manufactured by Kuraray Co., Ltd.), Septon 4055 (SEEPS, manufactured by Kuraray Co., Ltd.) can be used.

  In the composition of the present invention, the content of the styrenic thermoplastic elastomer is preferably 1 to 500 parts by mass, and 30 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). More preferably, it is more preferably 50 to 150 parts by mass. When the content of the styrenic thermoplastic elastomer is within this range, the mechanical strength and compression set resistance of the resulting composition of the present invention are further improved.

<Filler>
As the filler which may be optionally contained in the composition of the present invention, known fillers used in general resin compositions and rubber compositions can be used. Specific examples thereof include carbon black, silica , Iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, kaolin clay, calcined clay, filler containing amino groups (hereinafter, These are simply referred to as “amino group-introduced filler”), and these may be used alone or in admixture of two or more.
By containing such a filler, the thermoplastic elastomer composition obtained has good mechanical strength.

In the present invention, it is preferable that at least one selected from the group consisting of carbon black, silica and calcium carbonate is contained as a filler.
The type of carbon black is appropriately selected according to the application. Generally, carbon black is classified into hard carbon and soft carbon based on the particle diameter. Soft carbon has low reinforcement to rubber, and hard carbon has strong reinforcement to rubber.
The content of carbon black (when used alone) is 1 to 200 parts by weight, preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the thermoplastic elastomer (A). More preferably, it is 80 parts by mass.

Silica is not particularly limited, and specifically, for example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, diatomaceous earth, etc., the content (when silica alone is used) is It is 1-200 mass parts with respect to 100 mass parts of said thermoplastic elastomer (A), It is preferable that it is 10-100 mass parts, and it is more preferable that it is 20-80 mass parts. Of these, precipitated silica is preferred.
When silica is used as the filler, a silane coupling agent can be used in combination. Examples of the silane coupling agent include bis (triethoxysilylpropyl) tetrasulfide (Si69), bis (triethoxysilylpropyl) disulfide (Si75), γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and the like. Moreover, the aminosilane compound mentioned later can also be used.

Calcium carbonate is not particularly limited, and examples thereof include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate, and the like. Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used.
The content of calcium carbonate (when used alone as calcium carbonate) is 1 to 200 parts by weight, preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the thermoplastic elastomer (A). More preferably, it is 80 parts by mass. Of these, precipitated silica is preferred.

  The total content of carbon black, silica and calcium carbonate when using any two or more thereof is 1 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). It is preferable that it is 10-100 mass parts, and it is more preferable that it is 20-80 mass parts.

  Moreover, in this invention, it is preferable to contain the amino group introduction | transduction filler as a filler. Examples of the filler that serves as a base for the amino group-introduced filler (hereinafter sometimes referred to simply as “filler that serves as a base”) include fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, Silicas such as diatomaceous earth; carbon black, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, kaolin clay, calcined clay, etc. Silica, carbon black, and calcium carbonate are preferred, and silica is more preferred from the viewpoint of easy introduction of groups and easy adjustment of the introduction ratio (introduction ratio).

The amino group introduced into the filler serving as the substrate (hereinafter sometimes simply referred to as “amino group”) is not particularly limited, and specific examples thereof include an aliphatic amino group, an aromatic amino group, a complex Examples thereof include an amino group constituting a ring, and a plurality of mixed amino groups of these amino groups.
Here, in the present invention, an amino group having an amino group in an aliphatic amine compound is bonded to an aliphatic amino group, an aromatic group having an amino group bonded to an aromatic group, and an amino group having an amino group in a heterocyclic amine compound. It is called a heterocyclic amino group.
Among these, from the viewpoint of appropriately forming an interaction with the thermoplastic elastomer (A) and being effectively dispersible in the thermoplastic elastomer, a mixture containing a heterocyclic amino group and a heterocyclic amino group An amino group or an aliphatic amino group is preferable, and a heterocyclic amino group or an aliphatic amino group is preferable.

The series of the amino group is not particularly limited, and may be any of primary (—NH ₂ ), secondary (imino group,> NH), tertiary (> N—) or quaternary (> N ⁺ <). May be.
When the amino group is primary, the interaction with the thermoplastic elastomer (A) tends to be strong, and gelation may occur depending on the conditions for preparing the composition. On the other hand, when the amino group is tertiary, the interaction with the thermoplastic elastomer (A) tends to be weak, and the improvement effect such as compression set resistance when used as a composition may be small.
From such a viewpoint, the series of the amino group is preferably primary or secondary, and more preferably secondary.

  That is, the amino group is preferably a heterocyclic amino group, a mixed amino group containing a heterocyclic amino group, or a primary or secondary aliphatic amino group, and is preferably a heterocyclic amino group or a primary or secondary amino group. Particularly preferred is an aliphatic amino group.

  It is sufficient that at least one amino group is present on the surface of the filler serving as the substrate, but it is preferable to have a plurality of amino groups from the viewpoint of excellent effect of improving compression set resistance and the like when used as a composition.

In the case of having a plurality of amino groups, at least one of the plurality of amino groups is preferably a heterocyclic amino group, and further a primary or secondary amino group (an aliphatic amino group, an aromatic amino group, a complex amino group). It is more preferable to have a cyclic amino group.
Moreover, the kind and series of an amino group can arbitrarily adjust the said amino group according to the physical property requested | required of a composition.

The amino group-introduced filler is obtained by introducing the amino group into the filler serving as the substrate.
The method for introducing the amino group is not particularly limited, and specific examples thereof include surface treatment methods generally used for various fillers, reinforcing agents, etc. (for example, surface modification methods, surface coating methods, etc.). Can be mentioned. Preferred methods include a method of reacting a compound having a functional group capable of reacting with the filler serving as the substrate and an amino group with the filler (surface modification method), and a filler serving as the substrate with a polymer having an amino group. The method of coating the surface (surface coating method) or the method of reacting a compound having an amino group or the like in the synthesis process of the filler.

The amino group-introduced fillers may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.
The content of the amino group-introduced filler (when the amino group-introduced filler is used alone) is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). More preferably, it is more preferably 30 parts by mass or more.

  The content of fillers other than carbon black, silica, calcium carbonate and amino group-introduced filler is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). More preferably, it is part by mass.

  The composition of the present invention is a polymer other than the thermoplastic elastomer (A) and the ethylene propylene copolymer (B), and the amino group-introduced filler, as necessary, within a range not impairing the object of the present invention. Other amino group-containing compounds, compounds containing metal elements (hereinafter simply referred to as “metal salts”), maleic anhydride-modified polymers, plasticizers, anti-aging agents, antioxidants, pigments (dyes), thixotropic agents , UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, rust preventives, adhesion-imparting agents, antistatic agents, fillers, etc. it can.

As the additive and the like, commonly used ones can be used, and specific examples thereof are shown below, but are not limited to those exemplified.
As the polymer other than the thermoplastic elastomer (A) and the ethylene propylene copolymer (B), a polymer having a glass transition temperature of 25 ° C. or lower is preferable for the same reason as described above. Specifically, for example, natural rubber (NR), isoprene rubber (IR), polyethylene (PE), polypropylene (PP), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), Examples include acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), etc. A polymer having no unsaturated bond of IIR, EPM, EBM or a polymer having a low unsaturated bond (for example, EPDM) is preferred. A polymer having a site capable of hydrogen bonding is also preferable, and examples thereof include polyester, polylactone, polyamide and the like.
In the composition of the present invention, the polymer other than the thermoplastic elastomer (A) and the ethylene propylene copolymer (B) may contain one or more polymers, and the content of the polymer is The amount is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).

The amino group-containing compound other than the amino group-introduced filler will be described.
The amino group in the amino group-containing compound is basically the same as that described in the amino group-introduced filler, and is not particularly limited as long as the amino group content is 1 or more. It is preferable that the number is at least one because the thermoplastic elastomer (A) can form two or more crosslinks and is excellent in the effect of improving physical properties.

The series of the amino group in the amino group-containing compound is not particularly limited, and is the same as the amino group in the amino group-introduced filler, primary (—NH ₂ ), secondary (imino group,> NH), tertiary ( > N-) or quaternary (> N ⁺ <), which is optional depending on physical properties such as recyclability, compression set resistance, mechanical strength and hardness required for the composition of the present invention. Can be selected. When a secondary amino group is selected, mechanical strength tends to be excellent, and when a tertiary amino group is selected, recyclability tends to be excellent. In particular, it is preferable to have two secondary amino groups because the resulting composition of the present invention is excellent in recyclability and compression set resistance, and also in the balance of both physical properties.
In the case where the amino group-containing compound contains two or more amino groups, the number of primary amino groups in the amino group-containing compound is preferably 2 or less, and 1 or less. More preferably. When it has 3 or more primary amino groups, the (crosslinking) bond formed by the amino group and the functional group in the thermoplastic elastomer (A) (particularly, the carboxy group that is a carbonyl-containing group) becomes strong, It may impair excellent recyclability.

  That is, the series and number of amino groups and the structure of the amino group-containing compound are appropriately adjusted and selected in consideration of the bonding strength between the functional group in the thermoplastic elastomer (A) and the amino group in the amino group-containing compound. can do.

Specific examples of such an amino group-containing compound include N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-dimethyl-1,3- Propanediamine, N, N'-diethyl-1,3-propanediamine, N, N'-diisopropyl-1,3-propanediamine, N, N'-dimethyl-1,6-hexanediamine, N, N'- Secondary aliphatic diamines such as diethyl-1,6-hexanediamine and N, N ′, N ″ -trimethylbis (hexamethylene) triamine; Tertiary aliphatics such as tetramethyl-1,6-hexanediamine Diamines; polyamines containing aromatic primary amines such as aminotriazole and aminopyridine and heterocyclic amines; such as dodecylamine Tertiary heterocyclic diamines such as dipyridyl; alkyl monoamine etc., compression set, the improvement of mechanical strength is preferably exemplified by higher reasons.
Of these, secondary aliphatic diamines, polyamines containing aromatic primary amines and heterocyclic amines, or tertiary heterocyclic diamines are more preferred.

  In addition to these examples, a polymer compound having an amino group can be used as the amino group-containing compound.

The polymer compound having an amino group is not particularly limited, and specific examples thereof include polyamide, polyurethane, urea resin, melamine resin, polyvinylamine, polyallylamine, polyacrylamide, polymethacrylamide, polyaminostyrene, amino group-containing poly Examples thereof include polymers such as siloxane, and polymers obtained by modifying various polymers with a compound having an amino group.
The physical properties such as average molecular weight, molecular weight distribution, and viscosity of these polymers are not particularly limited, and may be any physical property depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like. be able to.

  The polymer compound having an amino group is preferably a polymer obtained by polymerizing (polyaddition or polycondensation) a condensable or polymerizable compound (monomer) having an amino group. A polysiloxane having an amino group which is a single condensate of a silyl compound having a group or a cocondensate of the silyl compound and a silyl compound having no amino group, is easily available, easy to produce, and has a molecular weight It is more preferable because it is easy to adjust the amino acid and the amino group introduction rate.

The silyl compound having a hydrolyzable substituent and an amino group is not particularly limited, and examples thereof include aminosilane compounds. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ An aminosilane compound having an aliphatic primary amino group such as aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane (manufactured by Nihon Unicar); N, N-bis [(3-trimethoxysilyl) propyl] amine, N, N-bis [(3-triethoxysilyl) propyl] amine, N, N-bis [(3-tripropoxysilyl) propyl] amine (Nippon Unicar Company), 3- (n-butylamino) propyltrimethoxysilane (Dyn Silane 1189 (manufactured by Degussa Huls)), N-ethyl-aminoisobutyltrimethoxysilane (Silquest A-Link 15 silane, manufactured by OSi Specialties) and other aminosilane compounds having an aliphatic secondary amino group; N-β (aminoethyl) ) Aliphatic primary such as γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane (Nihon Unicar) And aminosilane compounds having secondary amino groups; aminosilane compounds having aromatic secondary amino groups such as N-phenyl-γ-aminopropyltrimethoxysilane (Nihon Unicar); imidazole trimethoxysilane (Japan Energy) Ami And the like are; triazole and epoxysilane compound or isocyanate silane compounds and the presence or absence of a catalyst, the aminosilane compound having a heterocyclic amino group, such as triazole silane obtained by reacting at room temperature or above.
Among these, from the viewpoint of high effect of improving physical properties such as compression set resistance, the above-mentioned aminosilane compounds having an aliphatic primary amino group, aminosilane compounds having an aliphatic secondary amino group, and aliphatic primary and 2 An aminoalkylsilane compound of an aminosilane compound having a secondary amino group is preferable.

The silyl compound not having an amino group is not particularly limited as long as it is a compound different from the silyl compound having a hydrolyzable substituent and an amino group and does not contain an amino group. Examples include alkoxysilane compounds and halogenated silane compounds. Of these, alkoxysilane compounds are preferred from the viewpoints of availability, easy handling, and excellent physical properties of the resulting cocondensate.
Specific examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, and methyltriisopropoxysilane. , Phenyltrimethoxysilane, dimethyldimethoxysilane and the like.
Specific examples of the halogenated silane compound include tetrachlorosilane and vinyltrifluorosilane.
Of these, tetraethoxysilane and tetramethoxysilane are preferred from the viewpoint of low cost and safe handling.

  The silyl compound having a hydrolyzable substituent and an amino group and the silyl compound not having an amino group may be used alone or in combination of two or more.

  Such a polymer compound having an amino group may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.

Further, the content of the polymer compound having an amino group can be defined by the number of nitrogen atoms (equivalent) in the compound with respect to the side chain of the thermoplastic elastomer (A) as in the case of the amino group-containing compound. However, there may be an amino group that cannot effectively form an interaction with the thermoplastic elastomer depending on the structure and molecular weight of the polymer compound.
Therefore, the content of the polymer compound having an amino group is preferably 1 to 200 parts by mass, more preferably 5 parts by mass or more, with respect to 100 parts by mass of the thermoplastic elastomer (A). It is particularly preferably 10 parts by mass or more.

The metal salt is not particularly limited as long as it is a compound containing at least one metal element, and is composed of Li, Na, K, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Al. A compound containing one or more metal elements selected from the group is preferable.
Specific examples of the metal salt include saturated fatty acid salts having 1 to 20 carbon atoms such as formate, acetate and stearate containing one or more of these metal elements, and (meth) acrylates. And unsaturated fatty acid salts such as, metal alkoxides (reactants with alcohols having 1 to 12 carbon atoms), nitrates, carbonates, bicarbonates, chlorides, oxides, hydroxides, complexes with diketones, and the like. .
Here, the “complex with diketone” refers to a complex in which a 1,3-diketone (for example, acetylacetone) or the like is coordinated to a metal atom.

  Of these, from the viewpoint of further improving the compression set resistance of the composition of the present invention obtained, Ti, Al, and Zn are preferable as the metal element, and these acetates, stearates, and the like as the metal salts C1-C20 saturated fatty acid salts, metal alkoxides (reactants with C1-C12 alcohols), oxides, hydroxides, complexes with diketones are preferred, and C1-C20 such as stearates. Particularly preferred are saturated fatty acid salts, metal alkoxides (reactants with alcohols having 1 to 12 carbon atoms), and complexes with diketones.

  The said metal salt may be used individually by 1 type, or may use 2 or more types together. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.

  It is preferable that content of the said metal salt is 0.05-3.0 equivalent with respect to the carbonyl group contained in the said thermoplastic elastomer (A), and it is 0.1-2.0 equivalent. More preferred is 0.2 to 1.0 equivalent. When the content of the metal salt is within this range, the resulting composition of the present invention is preferably improved in physical properties such as compression set resistance, mechanical strength and hardness.

In addition, as the metal salt, any hydroxide, metal alkoxide, carboxylate, or the like that the metal can take can be used. For example, taking a hydroxide as an example, when the metal is iron, Fe (OH) ₂ and Fe (OH) ₃ may be used alone or in combination.
Further, as described above, the metal salt is one or more selected from the group consisting of Li, Na, K, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Al. Although it is preferable that it is a compound containing a metal element, you may contain metal elements other than these in the range which does not impair the effect of this invention. Although the content rate of metal elements other than these is not specifically limited, For example, it is preferable that it is 1-50 mol% with respect to all the metal elements in the said metal salt.

  The maleic anhydride modified polymer is a polymer obtained by modifying the elastomeric polymer with maleic anhydride, and the side chain of the maleic anhydride modified polymer is other than the maleic anhydride residue and the nitrogen-containing heterocyclic ring. However, it is preferable to have only a maleic anhydride residue.

The maleic anhydride residue is introduced (modified) into the side chain or terminal of the elastomeric polymer and is not introduced into the main chain of the elastomeric polymer. The maleic anhydride residue is a cyclic acid anhydride group, and the cyclic acid anhydride group (part) does not open.
Therefore, as the maleic anhydride-modified thermoplastic polymer, for example, as shown in the following formula (41), a cyclic acid is added to the side chain obtained by reacting an ethylenically unsaturated bond portion of maleic anhydride with an elastomeric polymer. Examples include thermoplastic elastomers having an anhydride group and no nitrogen-containing heterocycle, and specific examples thereof include those exemplified for the above-described elastomeric polymer containing a cyclic acid anhydride group in the side chain. .

（式中、Ｘはエチレン残基またはプロピレン残基であり、ｌ、ｍおよびｎはそれぞれ独立に０．１〜８０の数を表す。）

(In the formula, X represents an ethylene residue or a propylene residue, and l, m and n each independently represents a number of 0.1 to 80.)

  The amount of maleic anhydride modification is preferably 0.1 to 50 mol% with respect to 100 mol% of the main chain portion of the elastomeric polymer from the viewpoint of improving compression set resistance without impairing excellent recyclability. More preferably, it is 0.3-30 mol%, Most preferably, it is 0.5-10 mol%.

  The maleic anhydride-modified polymer may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.

The content of the maleic anhydride-modified polymer is preferably 1 to 100 parts by mass and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). When the content of the maleic anhydride-modified polymer is within this range, the flowability and mechanical strength at high temperatures of the resulting composition of the present invention are improved, which is preferable.
In addition, when producing the thermoplastic elastomer of the present invention, specifically, in the reaction step A or B, if an elastomeric polymer containing a cyclic acid anhydride group in the side chain remains as an unreacted product, Without removing the carbonyl-containing group-modified elastomer, the composition of the present invention can be contained as it is.

Specific examples of the plasticizer include oils such as paraffin oil, process oil, and aroma oil; liquid rubbers such as liquid polyisoprene (LIR), liquid polybutadiene (LBR), and liquid ethylene-propylene rubber (LEPM); Tetrahydrophthalic acid, azelaic acid, benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid and derivatives thereof; dioctyl phthalate (DOP), dibutyl Phthalate (DBP); polybutene; dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate; adipic acid B propylene glycol polyester, adipic acid butylene glycol polyester; and the like.
Of these, oil and polybutene are preferably used from the viewpoints of oil bleeding and fluidity at high temperatures.

  The said plasticizer may be used individually by 1 type, or may use 2 or more types together. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.

  The content of the plasticizer is preferably 1 to 500 parts by weight, more preferably 5 to 300 parts by weight, with respect to 100 parts by weight of the thermoplastic elastomer (A). More preferably. When the content of the plasticizer is within this range, the flexibility and high-temperature fluidity of the resulting composition of the present invention are further improved.

Specific examples of the anti-aging agent include hindered phenol compounds, aliphatic and aromatic hindered amine compounds, and the like.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Specific examples of the pigment include, for example, titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and other inorganic pigments, azo pigments, copper phthalocyanine pigments, and the like. Organic pigments and the like.

Specific examples of the thixotropic agent include benton, silicic anhydride, silicic acid derivatives, urea derivatives, and the like.
Specific examples of the ultraviolet absorber include 2-hydroxybenzophenone, benzotriazole, and salicylic acid ester.
Specific examples of the flame retardant include phosphorus-based materials such as TCP, halogen-based materials such as chlorinated paraffin and perchlorpentacyclodecane, antimony-based materials such as antimony oxide, and aluminum hydroxide.

Specific examples of the solvent include hydrocarbons such as hexane and toluene; halogenated hydrocarbons such as tetrachloromethane; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; ethyl acetate. And ester systems such as
Specific examples of the surfactant (leveling agent) include polybutyl acrylate, polydimethylsiloxane, a modified silicone compound, and a fluorine-based surfactant.
Specific examples of the dehydrating agent include vinyl silane and the like.

Specific examples of the rust inhibitor include zinc phosphate, tannic acid derivatives, phosphate esters, basic sulfonates, and various rust preventive pigments.
Specific examples of the adhesion imparting agent include known silane coupling agents, silane compounds having an alkoxysilyl group, titanium coupling agents, zirconium coupling agents, and the like. More specifically, trimethoxyvinylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like can be mentioned.
Generally as an antistatic agent, hydrophilic compounds, such as a quaternary ammonium salt or polyglycol and an ethylene oxide derivative, are mentioned.

  It is preferable that content of various additives other than the additive which mentions content above is 0.1-10 mass parts with respect to 100 mass parts of said thermoplastic elastomers (A), and 1-5 masses. More preferably, it is a part.

The thermoplastic elastomer (A) may be self-crosslinkable, but a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, a vulcanization retarder, etc. may be used in combination as long as the object of the present invention is not impaired. it can.
Examples of the vulcanizing agent include sulfur-based, organic peroxide-based, metal oxide-based, phenolic resin, quinone dioxime and other vulcanizing agents.
Specific examples of the sulfur vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, and the like.
Specific examples of the organic peroxide vulcanizing agent include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di- (T-Butylperoxy) hexane, 2,5-dimethylhexane-2,5-di (peroxylbenzoate) and the like.
Other examples include magnesium oxide, risurge (lead oxide), p-quinonedioxime, tetrachloro-p-benzoquinone, p-dibenzoylquinonedioxime, poly-p-dinitrosobenzene, and methylenedianiline.

Specific examples of the vulcanization aid include zinc oxide, magnesium oxide, and amines; fatty acids such as acetyl acid, propionic acid, butanoic acid, stearic acid, acrylic acid, and maleic acid; zinc acetylate, propionic acid. And fatty acid zinc such as zinc, zinc butanoate, zinc stearate, zinc acrylate, and maleate.
Specific examples of the vulcanization accelerator include thiurams such as tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (TETD); aldehydes / ammonias such as hexamethylenetetramine; guanidines such as diphenylguanidine; Thiazoles such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide (DM); sulfenes such as N-cyclohexyl-2-benzothiazylsulfenamide and Nt-butyl-2-benzothiazylsulfenamide Amide type; and the like. Furthermore, alkylphenol resins and their halides can also be used.
Specific examples of the vulcanization retarder include, for example, organic acids such as phthalic anhydride, benzoic acid, salicylic acid, acetylsalicylic acid; N-nitrosodiphenylamine, N-nitrosophenyl-β-naphthylamine, N-nitroso- Nitroso compounds such as polymers of trimethyl-dihydroquinoline; halides such as trichloromelanin; 2-mercaptobenzimidazole; N- (cyclohexylthio) phthalimide (Santguard PVI);
The content of these vulcanizing agents is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).

  Curing conditions when the composition of the present invention is permanently cross-linked (by a vulcanizing agent) can be appropriately selected according to various components to be blended, and are not particularly limited. For example, curing conditions for curing at a temperature of 130 to 200 ° C. for 5 to 60 minutes are preferable.

When the composition of the present invention is heated to about 80 to 200 ° C., the three-dimensional crosslinked bond (crosslinked structure) is dissociated and softened to impart fluidity. This is considered to be because the interaction between the side chains formed between the molecules or within the molecule is weakened.
When the composition of the present invention softened and imparted with fluidity is allowed to stand at about 80 ° C. or less, the dissociated three-dimensional cross-linked bond (cross-linked structure) is re-bonded and cured. By repeating this, the composition of the present invention exhibits recyclability.

  The production method of the composition of the present invention is not particularly limited. For example, the thermoplastic elastomer (A) and the ethylene propylene copolymer (B) and the styrenic thermoplastic elastomer that may be contained as necessary, Examples thereof include a method for producing the filler and various additives by mixing them using a roll, a kneader, a pressure kneader, a Banbury mixer, a single screw extruder, a twin screw extruder, a universal agitator, and the like.

  The composition of the present invention can be used for various rubber applications by utilizing rubber elasticity, for example. Moreover, since it can improve heat resistance and recyclability, it is preferable to use it as a hot melt adhesive or as an additive contained therein. The composition of the present invention can be suitably used around an automobile or the like.

  Specific examples of the above-mentioned automobile surroundings include, for example, tire treads, carcass, sidewalls, inner liners, under treads, belt portions, and the like; exterior radiator grilles, side moldings, garnishes (pillars, rears, cowls) Top), aero parts (air dam, spoiler), wheel cover, weather strip, cow belt grille, air outlet louver, air scoop, hood bulge, vent parts, anti-corrosion parts (over fender, side seal panel, molding ( Window, hood, door belt)), marks, etc .; interior window frame parts such as door, light, wiper weather strip, glass run, glass run channel; air duct hose, radiator hose, brake hose; crankshaft Lubricant, valve stem seal, head cover gasket, A / T oil cooler hose, mission oil seal, P / S hose, P / S oil seal and other lubricating oil parts; fuel hose, emission control hose, inlet filler hose, diaphragm Fuel system parts such as engine parts; Anti-vibration parts such as engine mounts and in-tank pump mounts; Boots such as CVJ boots and rack and pinion boots; Air conditioning parts such as A / C hoses and A / C seals; Belt parts such as timing belts and auxiliary belts; sealers such as windshield sealers, vinyl plastisol sealers, anaerobic sealers, body sealers, spot weld sealers; and the like.

  Further, when a rubber modifier, for example, a flow preventing agent, is included in a resin or rubber that causes a cold flow at room temperature, it is possible to prevent a flow during extrusion or a cold flow.

  Furthermore, the composition of the present invention comprising the thermoplastic elastomer (A), the ethylene propylene copolymer (B), carbon black and / or silica, etc. has improved tensile strength, tear strength, bending strength, and particularly a tire. , Hose, belt, sheet, anti-vibration rubber, roller, lining, rubberized cloth, sealing material, gloves, fender, medical rubber (syringe gasket, tube, catheter), gasket (for home appliances, construction), asphalt It is suitably used for applications such as modifiers, hot melt adhesives, boots, grips, toys, shoes, sandals, keypads, gears, PET bottle cap liners.

  The composition of the present invention is excellent in compression set resistance while maintaining the same level of recyclability and mechanical properties as compared with compositions containing conventional thermoplastic elastomers. Among them, it is suitably used for applications that require particularly recyclability and compression set resistance.

EXAMPLES Next, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited to these.
(Examples 1 and 2, Comparative Examples 1 and 2)
First, a maleic anhydride-modified ethylene-propylene copolymer (MP-0620, manufactured by Mitsui Chemicals, hereinafter abbreviated as “maleinized EPM”) 80.0 g and an antioxidant ( Irganox 1010, Nagase Sangyo Co., Ltd.) 0.8 g was added, and further, parts by mass (40 g) of polypropylene (S119, manufactured by Prime Polymer Co.) or ethylene propylene copolymer B1 (M142E, manufactured by Prime Polymer Co.) or ethylene shown in Table 1 below Propylene copolymer B2 (prototype) was added and kneaded for 5 minutes.
Next, 0.9 g of 4H-3-amino-1,2,4-triazole (ATA, manufactured by Otsuka Chemical Co., Ltd.) was added, and the mixture was further kneaded for 10 minutes to prepare a thermoplastic elastomer composition. It was confirmed by IR analysis that it contained a thermoplastic elastomer having a triazole ring introduced.

  The hardness, tensile properties, and viscosity of each obtained thermoplastic elastomer composition were measured by the following methods. The results are shown in Table 1 below.

<JIS-A hardness>
Each of the obtained thermoplastic elastomer compositions was hot press molded at 200 ° C. for 10 minutes, and then a flat plate sample having a thickness of 2 cm × length 15 cm × width 15 cm was produced. Three obtained flat plate samples are stacked, hot pressed at 200 ° C. for 20 minutes, and measured for JIS-A hardness after 5 seconds at room temperature using a spring type hardness tester (type A) according to JIS K6253. did.

<Tensile properties>
Each obtained thermoplastic elastomer composition was hot-pressed at 180 ° C. for 10 minutes to produce a sheet having a thickness of 2 mm.
Punched No. 3 dumbbell-shaped test piece from the sheet, subjected to a tensile test at a tensile rate of 500 mm / min in accordance with JIS K6251, 100% modulus _{(M 100) [MPa],} 300% modulus (M ₃₀₀₎ [MPa ], Breaking strength (T _B ) [MPa], and breaking elongation (E _B ) [%] were measured at room temperature (25 ° C.).
Since the thermoplastic elastomer composition obtained in Comparative Example 2 had a breaking elongation of 90%, 100% modulus and 300% modulus were indicated as “−” in Table 1 below.

<Viscosity>
Capillary viscosity at 230 ° C. and a shear rate of 243 (s ⁻¹ ) was measured according to JIS K7199: 1999, and fluidity at high temperature was evaluated. When the value of the capillary viscosity is 1000 Pa · s or less, the fluidity at high temperature is excellent.

  As apparent from Table 1 above, the thermoplastic elastomer compositions obtained in Examples 1 and 2 retain excellent flexibility as compared with Comparative Examples 1 and 2 that do not contain an ethylene propylene copolymer. It was also found that the fluidity at high temperature, and the tensile properties such as strength and elongation are excellent.

(Examples 3-6, Comparative Examples 3 and 4)
First, 80.0 g of maleated EPM and 0.8 g of anti-aging agent (Irganox 1010, Nagase Sangyo) were charged into a pressure kneader set at 200 ° C., and further, ethylene-propylene rubber (P0080K) in parts by mass shown in Table 2 below. , Mitsui Chemicals Co., Ltd.) or ethylene propylene copolymer B1 (M142E, Prime Polymer Co., Ltd.) was added and kneaded for 5 minutes. After kneading, polybutene (HV-100, manufactured by Shin Nippon Petrochemical Co., Ltd.) and styrene-based thermoplastic elastomer 1 (Septon 2006, styrene content 30% by mass, weight average molecular weight 150,000 or more, Kuraray Co., Ltd.) was added and kneaded for another 10 minutes.
Next, 4H-3-amino-1,2,4-triazole (ATA, manufactured by Otsuka Chemical Co., Ltd.) and Nn-octylaminoethanol (Nymene C-201, Nippon Oil & Fats Co., Ltd.) in parts by mass shown in Table 2 below. Or trifunctional alcohol (Uniox G450, manufactured by Nippon Oil & Fats Co., Ltd.), and carbon black (manufactured by Nippon Kayaku Co., Ltd.) and calcium carbonate (manufactured by Maruo Calcium Co., Ltd.). A thermoplastic elastomer composition was prepared by kneading. By performing IR analysis, it was confirmed that Comparative Example 3 and Example 3 contained a thermoplastic elastomer having a triazole ring and an imino group introduced. In Comparative Example 4 and Examples 4 to 6, It was confirmed that the thermoplastic elastomer containing the bond was contained.

  The tensile properties, compression set and viscosity of each obtained thermoplastic elastomer composition were measured by the following methods. The results are shown in Table 2 below.

<Tensile properties>
For each thermoplastic elastomer composition obtained in the same method as the measuring method described above, the 100% modulus _{(M 100) [MPa],} 300% modulus (M ₃₀₀₎ [MPa], tensile strength (T _B) [ MPa] and elongation at break (E _B ) [%] were measured at room temperature (25 ° C.) and 100 ° C.
The thermoplastic elastomer composition obtained in Example 6 had a breaking elongation at 25 ° C. of 170%, and therefore the 300% modulus was indicated as “−” in Table 2 below.

<Compression set (C-Set)>
Each of the obtained thermoplastic elastomer compositions was hot-pressed at 200 ° C. for 10 minutes to produce a sheet having a thickness of 2 mm, and then 7 sheets of the sheets were stacked and hot-pressed at 200 ° C. for 20 minutes to obtain a cylindrical sample ( Diameter 29 × thickness 12.5 mm).
This cylindrical sample was compressed 25% with a dedicated jig and allowed to stand at 70 ° C. for 22 hours, and then the compression set was measured according to JIS K6262.

<Viscosity>
About each obtained thermoplastic elastomer composition, capillary viscosity was measured by the method similar to the measuring method mentioned above.

  As is clear from Table 2 above, the thermoplastic elastomer compositions obtained in Examples 3 to 6 retain excellent flexibility as compared with Comparative Examples 3 and 4 that do not contain an ethylene propylene copolymer. It was also found that the fluidity at high temperature, and the tensile properties such as strength and elongation are excellent.

Claims (14)

Containing a thermoplastic elastomer (A) having a side chain containing an imino group and a carbonyl-containing group, and an ethylene-propylene copolymer (B) having a polypropylene block and an ethylene-propylene block,
A thermoplastic elastomer composition containing a structure represented by the following formula (2) or (3) in which the side chain of the thermoplastic elastomer (A) is bonded to the main chain at the α-position or β-position.

Wherein A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups, D is a single bond; an oxygen atom, an amino group NR ′ (R ′ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) Or an organic group which may contain a sulfur atom. A thermoplastic elastomer (A) having a side chain containing a nitrogen-containing heterocyclic ring and a carbonyl-containing group, and an ethylene-propylene copolymer (B) having a polypropylene block and an ethylene-propylene block,
A thermoplastic elastomer composition comprising a structure represented by the following formula (5) or (6) in which the side chain of the thermoplastic elastomer (A) is bonded to the main chain at the α-position or β-position.

Wherein E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; And D may contain a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom. Good organic group.) A thermoplastic elastomer (A) having a side chain containing a covalently-bonded crosslinking site and a carbonyl-containing group, and an ethylene-propylene copolymer (B) having a polypropylene block and an ethylene-propylene block,
A thermoplastic elastomer composition obtained by reacting the thermoplastic elastomer (A) with a compound that forms a covalent bond with an elastomeric polymer containing a cyclic acid anhydride group in the side chain.   The thermoplastic-elastomer composition in any one of Claims 1-3 in which the said ethylene propylene copolymer (B) has the said polypropylene block in the ratio of 1-50 mol%.   The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the polypropylene block has stereoregularity.   The thermoplastic elastomer composition according to claim 5, wherein the polypropylene block is isotactic.   The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the content of the ethylene propylene copolymer (B) is 1 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). . Wherein the covalent crosslinking site, amides, esters, and urethanes or thermoplastic elastomer composition according to any one of the at least one claim by crosslinking by the binding Ranaru selected from the group 3-7. The thermoplastic elastomer composition according to claim 8, wherein the crosslinking at the covalent crosslinking site contains at least one structure represented by any of the following formulas (7) to (9).

Wherein K, L, Q and R are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or these And T is an hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom, and may be branched.) The bridge | crosslinking in the said covalent bond crosslink site | part contains at least 1 structure represented by either of following formula (10)-(12) couple | bonded with a principal chain in (alpha) position or (beta) position. Thermoplastic elastomer composition.

Wherein K, L, Q and R are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or these And T is an hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom, and may be branched.)   Furthermore, the thermoplastic-elastomer composition in any one of Claims 1-10 containing a styrene-type thermoplastic elastomer.   The thermoplastic elastomer composition according to claim 11, wherein the content of the styrenic thermoplastic elastomer is 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).   Furthermore, the thermoplastic-elastomer composition in any one of Claims 1-12 containing a filler.   The thermoplastic elastomer composition according to claim 13, wherein a content of the filler is 1 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).