JP2006232965A - Thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition with an excellent recycling property, mechanical strength, especially excellent in compression set resistance characteristics. <P>SOLUTION: The thermoplastic elastomer composition comprises: thermoplastic elastomer having a side chain with an imino group and/or a nitrogen containing heterocyclic ring and a carbonyl group; a styrene based thermoplastic elastomer with ≥100,000 of weight average molecular weight; and a plasticizer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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 when the thermoplastic elastomer described in Patent Document 1 is used as a composition containing a filler or the like, mechanical strength, particularly compression set resistance when released after being compressed for a predetermined time. There was a case that was not enough.

  Accordingly, an object of the present invention is to provide a thermoplastic elastomer composition that retains excellent recyclability and is excellent in mechanical strength, particularly compression set resistance.

  Therefore, as a result of intensive studies to solve the above problems, the present inventor has made a thermoplastic elastomer having a side chain containing a predetermined structure, a specific styrenic thermoplastic elastomer, and a plasticizer. It has been found that the elastomer composition has excellent recyclability and is excellent in physical properties such as mechanical strength and compression set resistance, and has achieved the present invention. That is, this invention provides the thermoplastic elastomer composition as described in the following (I)-(XXI).

  (I) containing a thermoplastic elastomer having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group, a styrene thermoplastic elastomer having a weight average molecular weight of 100,000 or more, and a plasticizer. Thermoplastic elastomer composition.

  (II) The thermoplastic elastomer composition according to (I), wherein the side chain contains an imino group and a carbonyl-containing group.

  (III) The thermoplastic elastomer composition according to (I), wherein the side chain contains an imino group, a nitrogen-containing heterocyclic ring, and a carbonyl-containing group.

  (IV) The thermoplastic elastomer composition according to any one of (I) to (III), wherein the side chain 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.

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

  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, and B and D are each independently 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 an organic group which may contain these atoms or groups.

  (VI) The thermoplastic elastomer composition according to (I) or (III), wherein the side chain 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.

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

  In the formula, E is a nitrogen-containing heterocyclic ring, B and D 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 sulfur. Atom; or an organic group that may contain these atoms or groups.

  (VIII) The thermoplastic elastomer composition according to the above (I), (III), (VI) or (VII), wherein the nitrogen-containing heterocycle is a 5- or 6-membered ring.

  (IX) The thermoplastic elastomer composition according to (VIII), wherein the nitrogen-containing heterocycle is a triazole ring, a thiadiazole ring, a pyridine ring, a thiazole ring, an imidazole ring or a hydantoin ring.

  (X) The side chain containing the structure represented by the above formula (4) contains the structure represented by the following formula (7), the following formula (8) or (9), or the following formula (10). The thermoplastic elastomer composition as described in (VI) above.

  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.

  (XI) The following formula (11) or (12), wherein the side chain containing the structure represented by the above formula (4) is bonded to the main chain at the α-position or β-position, or the following formulas (13) to (16) Or the thermoplastic elastomer composition according to the above (X), which contains a structure represented by the following formula (17) or (18):

  In the formula, B and D 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 atoms or groups. 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.

  (XII) The thermoplastic elastomer has another side chain containing a covalent bond cross-linking site, and the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether at the covalent cross-link site The thermoplastic elastomer composition according to any one of the above (I) to (XI), which can be crosslinked by at least one bond selected from the above.

  (XIII) The thermoplastic elastomer has another side chain containing a covalent crosslinking site, and the crosslinking at the covalent crosslinking site is from amide, ester, lactone, urethane, ether, thiourethane and thioether. The thermoplastic elastomer composition according to any one of the above (I) to (XI), which is formed by at least one bond selected from the group consisting of:

  (XIV) The thermoplastic elastomer composition as described in (XIII) above, wherein the crosslinking at the covalent crosslinking site contains a tertiary amino group.

  (XV) The thermoplastic elastomer according to (XIII) or (XIV) above, wherein the crosslinking at the covalent crosslinking site contains at least one structure represented by any of the following formulas (19) to (21): Composition.

  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.

  (XVI) The above (XV) containing at least one structure represented by any one of the following formulas (22) to (24) in which the crosslinking at the covalent crosslinking 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.

  (XVII) The thermoplastic elastomer composition according to the above (XV) or (XVI), wherein any T in the above formulas (19) to (24) contains a tertiary amino group.

  (XVIII) The crosslinking according to any one of (XIII) to (XVII) above, wherein the crosslinking at the covalent 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. Thermoplastic elastomer composition.

  (XIX) The thermoplastic elastomer composition according to any one of (I) to (XVIII), wherein the styrene-based thermoplastic elastomer has a styrene content of 10 to 60% by mass.

  (XX) The thermoplastic elastomer composition according to any one of (I) to (XIX), 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. object.

  (XXI) The thermoplastic elastomer composition according to any one of (I) to (XX), wherein the content of the plasticizer is 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.

  As will be described below, the present invention is useful because it can provide a thermoplastic elastomer composition that maintains excellent recyclability and is excellent in mechanical strength, particularly compression set resistance.

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”) contains an imino group and / or a nitrogen-containing heterocycle and a carbonyl-containing group. Thermoplastic containing side chain thermoplastic elastomer (hereinafter also referred to as “thermoplastic elastomer having a predetermined functional group”), a styrene thermoplastic elastomer having a weight average molecular weight of 100,000 or more, and a plasticizer. It is an elastomer composition.
Below, the thermoplastic elastomer which has a predetermined functional group used for the composition of this invention, a styrene-type thermoplastic elastomer, and a plasticizer are explained in full detail.

<Thermoplastic elastomer having a predetermined functional group>
The thermoplastic elastomer having a predetermined functional group used in the composition of the present invention contains an imino group and / or a nitrogen-containing heterocyclic group and a carbonyl-containing group in an elastomeric polymer of a natural polymer or a synthetic polymer. Has side chains.
In the present invention, “side chain” refers to a side chain and a terminal of an elastomeric polymer. Further, “having a side chain containing an imino group and / or a nitrogen-containing heterocyclic group and a carbonyl-containing group” means that an atom (usually a carbon atom) forming the main chain of the elastomeric polymer has an imino group and It means that the nitrogen-containing heterocyclic group and the carbonyl-containing group have a chemically stable bond (for example, covalent bond, ionic bond, etc.).

The elastomeric polymer that is the main chain of the thermoplastic elastomer having the predetermined functional group is a generally known natural polymer or synthetic polymer having a glass transition point of room temperature (25 ° C.) or lower, That is, it is not particularly limited as long as it is an elastomer.
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 (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), olefinic rubbers such as chlorosulfonated polyethylene, acrylic rubber, fluororubber, polyethylene rubber, polypropylene rubber; epichlorohydrin rubber; polysulfide rubber; silicone rubber; urethane rubber; Be mentioned

  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 product 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 having a predetermined functional group used in the composition of the present invention has a side chain containing an imino group and / or a nitrogen-containing heterocyclic group and a carbonyl-containing group in the elastomeric polymer. The side chain preferably contains an imino group and a carbonyl-containing group, and more preferably contains an imino group, a nitrogen-containing heterocyclic ring, 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 processability of the resulting composition of the present invention is improved.

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 having a predetermined functional group used in the composition of the present invention has the following formula (bonding a side chain containing the structure represented by the above formula (1) to the main chain at the α-position or the β-position ( It is preferable to have as a side chain containing the structure represented by 2) or (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, and B and D are each independently 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 an organic group which may contain these atoms or groups.

Here, the substituent A is basically the same as the substituent A in the above formula (1), and the substituents B and D are each independently the same as the substituent 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 rate 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. , High recyclability, and good compression set resistance. It is more preferable that the side chain is introduced at a ratio of 0.1 to 30 mol%, and that the side chain is introduced at a ratio of 0.5 to 20 mol% in terms of these characteristics being more excellent. 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 and D 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 sulfur. Atom; or an organic group that may contain these atoms or groups.

Here, the nitrogen-containing heterocyclic ring E specifically includes the nitrogen-containing heterocyclic rings exemplified below.
The substituents B and D are each independently the same as the substituent B in the above formula (1).

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, being a triazole ring, a thiadiazole ring, a pyridine ring, a thiazole ring, an imidazole ring, and a hydantoin ring, the recyclability, compression set resistance, mechanical properties of the obtained composition of the present invention are obtained. It is preferable because of its excellent strength and hardness.

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

  In the formula, E is a nitrogen-containing heterocyclic ring, B and D 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 sulfur. Atom; or an organic group that may contain these atoms or groups.

Here, the nitrogen-containing heterocyclic ring E specifically includes the nitrogen-containing heterocyclic rings exemplified above.
The substituents B and D are each independently the same as the substituent B in the above formula (1).
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 having a predetermined functional group 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 side chain containing the structure represented by the formula (4) is used as a side chain containing the structure represented by the following formula (7), the following formula (8) or (9), or the following formula (10). The following formula (11) or (12), which is bonded to the main chain at the α-position or β-position, any of the following formulas (13) to (16), or the following formula (17) or (18 It is more preferable that it has as a side chain containing the structure represented by this.

  In the formula, B and D 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 atoms or groups. 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.

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 rate 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. , High recyclability, and good compression set resistance. It is more preferable that the side chain is introduced at a ratio of 0.1 to 30 mol%, and that the side chain is introduced at a ratio of 0.5 to 20 mol% in terms of these characteristics being more excellent. 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 heterocycle when the thermoplastic elastomer having a predetermined functional group used in the composition of the present invention has a side chain containing a nitrogen-containing heterocycle 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 having the predetermined functional group, the bonding position of the nitrogen-containing n-membered ring compound bonded to the copolymer directly or via an organic group is not particularly limited, and 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.

  The thermoplastic elastomer having a predetermined functional group used in the composition of the present invention may have other side chain containing a covalent crosslinkable site, and an amide or ester is present at the covalent crosslinkable site. More preferably, it can be crosslinked by at least one bond selected from the group consisting of lactone, urethane, ether, thiourethane and thioether. Further, the thermoplastic elastomer having a predetermined functional group used in the composition of the present invention may be one in which a crosslink is formed by such a bond.

The other side chain containing the covalent cross-linking site is at least selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether by reacting with “compound that forms a covalent bond”. There is no particular limitation as long as it is a side chain having a functional group capable of causing one bond as a covalent bond cross-linking 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 other side chain containing a covalent bond cross-linking site is not particularly limited as long as it is a side chain having such a functional group.
In the thermoplastic elastomer having a predetermined functional group used in the composition of the present invention, the crosslinking at the covalent bond site, that is, the covalent bond between the functional group and the above-mentioned “compound capable of forming a covalent bond”. It is preferable to have at least one crosslink in one molecule. In particular, when the crosslink is formed by at least one bond selected from the group consisting of lactone, urethane, ether, thiourethane and thioether, 2 It is preferable to have two or more, more preferably 2 to 20, more preferably 2 to 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 (19) to (21). 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 (22) to (24) which 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 (22) to (24) 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 (19) to (21), and the substituent T is This is basically the same as the substituent T in the formula (19).

（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.

  In addition, the thermoplastic elastomer having a predetermined functional group 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 a glass transition point of 2 or more, or When two or more kinds of thermoplastic elastomers are 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 method for producing the thermoplastic elastomer having a predetermined functional group used in the composition of the present invention is not particularly limited, and a normal method can be selected. Specifically, a cyclic acid anhydride group is used as a side chain. A reaction step (hereinafter simply referred to as “reaction step A”) for reacting a compound capable of introducing an imino group with the elastomeric polymer contained and / or nitrogen-containing elastomeric polymer containing a cyclic acid anhydride group in the side chain A production method comprising a reaction step (hereinafter simply referred to as “reaction step B”) in which a compound capable of introducing a heterocyclic ring is reacted is preferable.
When both the reaction step A and the reaction step B are provided, the reaction step B may be provided as a step performed simultaneously with the reaction step A, even if it is provided before or after the reaction step A. However, it is preferably provided as a subsequent step of the reaction step A.
Hereinafter, an elastomeric polymer containing a cyclic acid anhydride group in the side chain, a compound capable of introducing an imino group, a compound capable of introducing a nitrogen-containing heterocyclic ring, and reaction steps A and B 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 rubber such as LIR-403 (manufactured by Kuraray Co., Ltd.) and LIR-410A (Kuraray Co., Ltd.); modified isoprene rubber 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.

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.

<Styrenic thermoplastic elastomer>
The styrenic thermoplastic elastomer used 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, and an aromatic corresponding to a crosslinking point at the terminal. If it has a block polymerization part by vinyl and a weight average molecular weight is 100,000 or more, it will not specifically limit.
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.

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 weight, preferably 30 to 200 parts per 100 parts by weight of the thermoplastic elastomer having the predetermined functional group. It is more preferable that it is a mass part, and it is still more preferable that it is 50-150 mass parts. 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.

<Plasticizer>
As the plasticizer used in the composition of the present invention, known plasticizers used in general resin compositions and rubber compositions can be used. Specific examples thereof include paraffin oil, process oil, aroma oil, and the like. Oils; liquid rubbers such as liquid polyisoprene (LIR), liquid polybutadiene (LBR), 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, acetylricinoleate methyl; tricresyl phosphate, trioctyl phosphate, adipic acid propylene glycol polyester, adipic acid butylene glycol polyester; and the like. These may be used alone or in combination of two or more.
Of these, oil and polybutene are preferably used from the viewpoint of oil bleeding and workability.

  In the composition of this invention, it is preferable that content of the said plasticizer is 1-500 mass% with respect to 100 mass parts of thermoplastic elastomers which have the said predetermined functional group, and is 5-300 mass parts. More preferably, it is more preferably 10 to 200 parts by mass. When the content of the plasticizer is within this range, the flexibility and workability of the resulting composition of the present invention are further improved.

  The composition of the present invention contains the styrenic thermoplastic elastomer and the plasticizer together with the thermoplastic elastomer having the predetermined functional group, so that the mechanical strength, particularly the resistance to resistance is maintained while maintaining excellent recyclability. Compression set can be improved. 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 having a predetermined functional group while the styrene-based thermoplastic elastomer has absorbed the oil. In addition, in the present invention, compression set resistance is improved for the same reason even when a polyolefin resin such as polypropylene (PP) or ethylene-propylene-diene rubber (EPDM) is used. Since a thermoplastic elastomer having a predetermined functional group is used, the degree of improvement in compression set resistance is improved and mechanical strength is also improved as compared with the case where these resins are used. In particular, as a thermoplastic elastomer having a predetermined functional group, a side chain containing an imino group and a carbonyl-containing group (specifically, represented by the above formula (1) or the above formula (2) or (3)). It is preferable to use a thermoplastic elastomer having a side chain containing a structure because the tensile strength at the time of crosslinking is increased and the compression set is further improved, and the imino group, the nitrogen-containing heterocyclic ring, and the carbonyl-containing group The reason why the mechanical strength such as tensile strength is further improved while maintaining the property that the tensile strength at the time of crosslinking is increased and the compression set resistance is further improved is to use a thermoplastic elastomer having a side chain containing Is more preferable.

  The composition of the present invention introduces a polymer other than the thermoplastic elastomer having the predetermined functional group, a reinforcing agent (filler), and an amino group, as necessary, as long as the object of the present invention is not impaired. A filler (hereinafter simply referred to as “amino group-introduced filler”), an amino group-containing compound other than the amino group-introduced filler, a compound containing a metal element (hereinafter simply referred to as “metal salt”), and anhydrous maleic acid. Acid-modified polymer, anti-aging agent, antioxidant, pigment (dye), thixotropic agent, ultraviolet absorber, flame retardant, solvent, surfactant (including leveling agent), dispersant, dehydrating agent, rust inhibitor , Various additives such as an adhesion-imparting agent, an antistatic agent and a filler can be contained.

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 having the predetermined functional group, a polymer having a glass transition temperature of 25 ° C. or lower is preferable 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 having the predetermined functional group may contain one kind or two or more kinds, and the content of the polymer is the same as the predetermined functional group. It is preferable that it is 0.1-100 mass parts with respect to 100 mass parts of thermoplastic elastomers to have, and it is more preferable that it is 1-50 mass parts.

The reinforcing agent preferably contains carbon black and / or silica. The type of the carbon black is appropriately selected according to the use. 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, based on 00 parts by weight of the thermoplastic elastomer having the predetermined functional group. It is more preferable that it is 20-80 mass parts.

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 thermoplastic elastomers which have the said predetermined functional group, 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 reinforcing agent, 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.

  When carbon black and silica are used in combination, the content (total amount of carbon black and silica) is 1 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer having the predetermined functional group. It is preferable that it is a mass part, and it is more preferable that it is 20-80 mass parts.

  Specific examples of reinforcing agents other than carbon black and silica include, for example, iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, and kaolin. Examples include clay and fired clay. The content of these reinforcing agents is preferably 10 to 100 parts by mass and more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer having the predetermined functional group.

  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 preferable, and silica is more preferable 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 aliphatic amino groups, aromatic amino groups, and complex groups. 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 having the predetermined functional group and being effectively dispersible in the thermoplastic elastomer, a heterocyclic amino group, a heterocyclic amino group It is preferably a mixed amino group or an aliphatic amino group containing a heterocyclic amino group or an aliphatic amino group.

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.
If the amino group is primary, the interaction with the thermoplastic elastomer having the predetermined functional group 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 having the predetermined functional group tends to be weak, and the improvement effect such as compression set resistance when used as a composition is small. There is.
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 is preferably 1 to 200 parts by mass, more preferably 10 parts by mass or more, with respect to 100 parts by mass of the thermoplastic elastomer having the predetermined functional group. It is particularly preferably 30 parts by mass or more.

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 it can form two or more cross-linked bonds with the thermoplastic elastomer having the predetermined functional group, 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 three or more primary amino groups are present, the (crosslinking) bond formed by the functional groups in the thermoplastic elastomer having the amino group and the predetermined functional group (particularly, a carboxy group that is a carbonyl-containing group) is strong. And may impair excellent recyclability.

  In other words, the amino group series, number, and structure of the amino group-containing compound are appropriately determined in consideration of the bonding strength between the functional group in the thermoplastic elastomer having the predetermined functional group and the amino group in the amino group-containing compound. Can be adjusted and selected.

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.

The content of the polymer compound having an amino group is defined by the number of nitrogen atoms (equivalent) in the compound with respect to the side chain of the thermoplastic elastomer having the predetermined functional group, like 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 and preferably 5 parts by mass or more with respect to 100 parts by mass of the thermoplastic elastomer having the predetermined functional group. More preferably, it is 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.

  The content of the metal salt is preferably 0.05 to 3.0 equivalents, preferably 0.1 to 2.0 equivalents with respect to the carbonyl group contained in the thermoplastic elastomer having the predetermined functional group. More preferably, it is particularly preferably 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 a maleic anhydride residue and a 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 having the predetermined functional group. . When the content of the maleic anhydride-modified polymer is within this range, the processability and mechanical strength 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 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.

  The content of various additives other than the additives whose contents are noted above is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer having the predetermined functional group. More preferably, it is -5 mass parts.

Some thermoplastic elastomers having the above-mentioned predetermined functional groups can self-crosslink, but vulcanizing agents, vulcanization aids, vulcanization accelerators, vulcanization retarders, etc. are used in combination as long as the object of the present invention is not impaired. You can also
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 organic acids such as phthalic anhydride, benzoic acid, salicylic acid, and 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 and the like 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 having the predetermined functional group. preferable.

  The curing conditions when the composition of the present invention is permanently crosslinked (with 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 method for producing the composition of the present invention is not particularly limited. For example, the thermoplastic elastomer having the predetermined functional group, the styrenic thermoplastic elastomer, the plasticizer, and various additives that may be contained as necessary. And the like 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, undertreads, 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 having the above-mentioned predetermined functional group and carbon black and / or silica has improved tensile strength, tear strength, bending strength, and in particular, tires, hoses, belts, sheets, Anti-vibration rubber, roller, lining, rubberized cloth, sealing material, gloves, fender, medical rubber (syringe gasket, tube, catheter), gasket (for home appliances, construction), asphalt modifier, hot melt bonding It is suitably used for applications such as agents, 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 1-4, Comparative Examples 1-3)
First, 300.0 g of maleic anhydride-modified ethylene-propylene copolymer (MP-0620, manufactured by Mitsui Chemicals, hereinafter abbreviated as “maleinized EPM1”) is charged into a kneader set at 200 ° C. for 3 minutes. After kneading, 2.5 g of 4H-3-amino-1,2,4-triazole (ATA, manufactured by Otsuka Chemical Co., Ltd.) was added and kneaded for 10 minutes to prepare thermoplastic elastomer 1. By performing IR analysis, it was confirmed that the thermoplastic elastomer was introduced with a triazole ring.
Next, to 100 parts by mass of the obtained thermoplastic elastomer 1, paraffin oil (Diana Process Oil PW90, weight average molecular weight 540, manufactured by Idemitsu Kosan Co., Ltd.) as a plasticizer is added in parts by mass as shown in Table 1 below. SEPS (Septon 2006, styrene content 30% by mass, weight average molecular weight 150,000 or more, manufactured by Kuraray Co., Ltd.), SEEPS (Septon 4055, styrene content 30% by mass, weight average molecular weight 150,000 or more, manufactured by Kuraray Co., Ltd.) ), SEPS (Septon 2063, styrene content 13 mass%, weight average molecular weight less than 100,000, manufactured by Kuraray Co., Ltd.) and SEPS (Septon 2002, styrene content 30 mass%, weight average molecular weight less than 100,000, manufactured by Kuraray Co., Ltd.) Add one part by mass as shown in Table 1 below for 10 minutes until uniform By mixing, to prepare each thermoplastic elastomer composition. In Comparative Example 1, no styrenic thermoplastic elastomer was added.

(Examples 5-7, Comparative Examples 4-6)
First, after putting 300.0 g of maleated EPM1 into a kneader set at 200 ° C. and masticating for 3 minutes, 1.0 g of Nn-octylaminoethanol (Nymene C-201, manufactured by NOF Corporation) was added. The mixture was kneaded for 5 minutes, and 2.0 g of 4H-3-amino-1,2,4-triazole (ATA, manufactured by Otsuka Chemical Co., Ltd.) was added to knead for 5 minutes to prepare thermoplastic elastomer 2. . By performing IR analysis, it was confirmed that the thermoplastic elastomer was introduced with a triazole ring and an imino group.
Next, to 100 parts by mass of the obtained thermoplastic elastomer 2, paraffin oil (Diana Process Oil PW90, weight average molecular weight 540, manufactured by Idemitsu Kosan Co., Ltd.) as a plasticizer is added in parts by mass as shown in Table 1 below. SEPS (Septon 2006, styrene content 30% by mass, weight average molecular weight 150,000 or more, manufactured by Kuraray Co., Ltd.), SEEPS (Septon 4055, styrene content 30% by mass, weight average molecular weight 150,000 or more, manufactured by Kuraray Co., Ltd.) ), SEPS (Septon 2063, styrene content 13% by mass, weight average molecular weight less than 100,000, manufactured by Kuraray) and SEPS (Septon 2002, styrene content 30% by mass, weight average molecular weight less than 100,000, manufactured by Kuraray) Add one part by mass as shown in Table 1 below for 10 minutes until uniform By mixing, to prepare each thermoplastic elastomer composition. In Comparative Example 4, no styrenic thermoplastic elastomer was added.

(Comparative Examples 7-9)
Paraffin oil (Diana Process Oil PW90, weight average molecular weight 540, manufactured by Idemitsu Kosan Co., Ltd.) as a plasticizer is added to 100 parts by mass of EPDM, and SEPS (Septon 2006, containing styrene) is added as a styrene-based thermoplastic elastomer. 30 mass%, weight average molecular weight 150,000 or more, manufactured by Kuraray Co., Ltd.) or SEEPS (Septon 4055, styrene content 30 mass%, weight average molecular weight 150,000 or more, manufactured by Kuraray Co., Ltd.) Then, each thermoplastic elastomer composition was prepared by kneading for 10 minutes until uniform. In Comparative Example 7, no styrenic thermoplastic elastomer was added.

  Each thermoplastic elastomer composition obtained was evaluated for appearance, hardness, compression set resistance, tensile properties and recyclability. 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 were stacked, hot-pressed at 200 ° C. for 20 minutes, and JIS-A hardness was measured at room temperature according to JIS K6253.

<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. Seven 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.

<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.
A No. 3 dumbbell-shaped test piece was punched out from this sheet, and a tensile test at a tensile speed of 500 mm / min was conducted according to JIS K6251. 50% modulus (M ₅₀ ) [MPa], 100% modulus (M ₁₀₀ ) [MPa ], 200% modulus (M ₂₀₀ ) [MPa], 300% modulus (M ₃₀₀ ) [MPa], 400% modulus (M ₄₀₀ ) [MPa], breaking strength (T _B ) [MPa], and elongation at break ( E _B ) [%] was measured at room temperature.

<Recyclability>
Each obtained thermoplastic elastomer composition was hot-pressed at 200 ° C. for 10 minutes to produce a sheet having a thickness of 2 mm. This sheet was finely cut and press-molded again, and evaluated by the number of times that a seamless integrated sheet could be produced.
As a result, any thermoplastic elastomer composition could be produced 10 times or more and evaluated as “◯”.

As is apparent from Table 1 above, the thermoplastic elastomer compositions obtained in Examples 1 to 7 were superior to Comparative Examples 1 to 6 that did not contain a specific amount of a specific styrenic thermoplastic elastomer. It was found that tensile properties and compression set resistance were excellent while maintaining recyclability. In particular, it was found that the compression set resistance of the thermoplastic elastomer compositions obtained in Examples 4 to 7 was reduced to around 50%, which was very excellent.
In addition, the thermoplastic elastomer compositions obtained in Examples 1 to 7 are comparative examples 7 to 9 that do not contain a thermoplastic elastomer having a predetermined functional group, in particular, a predetermined amount of a specific styrenic thermoplastic elastomer. It can be seen that the degree of improvement in compression set resistance is very large even in comparison with Comparative Examples 8 and 9 which are contained.

Claims (21)

  Thermoplastic elastomer containing a thermoplastic elastomer having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group, a styrene thermoplastic elastomer having a weight average molecular weight of 100,000 or more, and a plasticizer Composition.   The thermoplastic elastomer composition according to claim 1, wherein the side chain contains an imino group and a carbonyl-containing group.   The thermoplastic elastomer composition according to claim 1, wherein the side chain contains an imino group, a nitrogen-containing heterocyclic ring, and a carbonyl-containing group. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the side chain contains a structure represented by the following formula (1).

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. The side chain containing the structure represented by the formula (1) contains a structure represented by the following formula (2) or (3) bonded to the main chain at the α-position or the β-position. A thermoplastic elastomer composition.

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, and B and D 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 an organic group which may contain these atoms or groups. The thermoplastic elastomer composition according to claim 1 or 3, wherein the side chain contains a structure represented by the following formula (4).

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; An organic group that may contain any atom or group of The side chain containing the structure represented by said Formula (4) contains the structure represented by following formula (5) or (6) couple | bonded with a principal chain in (alpha) position or (beta) position. A thermoplastic elastomer composition.

(Wherein E is a nitrogen-containing heterocyclic ring, B and D 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 an organic group that may contain these atoms or groups.)   The thermoplastic elastomer composition according to claim 1, 3, 6, or 7, wherein the nitrogen-containing heterocycle is a 5- or 6-membered ring.   The thermoplastic elastomer composition according to claim 8, wherein the nitrogen-containing heterocycle is a triazole ring, a thiadiazole ring, a pyridine ring, a thiazole ring, an imidazole ring or a hydantoin ring. The side chain containing the structure represented by said Formula (4) contains the structure represented by following formula (7), following formula (8) or (9), or following formula (10). The thermoplastic elastomer composition described in 1.

Wherein 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 which may contain these atoms or groups. 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 of the following formulas (11) or (12) and the following formulas (13) to (16) 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 the thermoplastic elastomer composition of Claim 10 containing the structure represented by following formula (17) or (18).

Wherein B and D 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 atoms or groups 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.)   The thermoplastic elastomer has another side chain containing a covalent crosslinkable site, and the covalent crosslinkable site is selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. The thermoplastic elastomer composition according to any one of claims 1 to 11, which can be crosslinked by at least one bond.   The thermoplastic elastomer has another side chain containing a covalent crosslinking site, and the crosslinking at the covalent crosslinking site is selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. The thermoplastic elastomer composition according to any one of claims 1 to 11, which is formed by at least one selected bond.   The thermoplastic elastomer composition according to claim 13, wherein the crosslinking at the covalent crosslinking site contains a tertiary amino group. The thermoplastic elastomer composition according to claim 13 or 14, wherein the crosslinking at the covalent crosslinking site contains at least one structure represented by any of the following formulas (19) to (21).

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 (22)-(24) 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.)   The thermoplastic elastomer composition according to claim 15 or 16, wherein any T in the formulas (19) to (24) contains a tertiary amino group.   The thermoplastic elastomer composition according to any one of claims 13 to 17, wherein the crosslinking at the covalent 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 thermoplastic elastomer composition according to any one of claims 1 to 18, wherein the styrene-based thermoplastic elastomer has a styrene content of 10 to 60% by mass.   The thermoplastic elastomer composition according to any one of claims 1 to 19, wherein a content of the styrenic thermoplastic elastomer is 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.   The thermoplastic elastomer composition according to any one of claims 1 to 20, wherein a content of the plasticizer is 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.