TW201815980A - Thermoplastic elastomer composition and method of producing the same - Google Patents

Abstract

A thermoplastic elastomer composition containing an elastomeric polymer having a side chain containing a "hydrogen-bonding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring" and a glass transition point of 25 ° C or lower (A), and a group of elastomeric polymers (B) selected from the group consisting of hydrogen-bondable cross-linking sites and covalently-bondable cross-linking sites at side chains and a glass transition point of 25 ° C or lower At least one kind of elastomer component, and the group consisting of expanded graphite, nano carbon tube, fullerene, graphene, silicate natural nano fiber, silsesquioxane and layered titanic acid compound At least one is selected, and its content is an additive component of 20 parts by mass or less based on 100 parts by mass of the aforementioned elastomer component.

Description

   Thermoplastic elastomer composition and manufacturing method thereof   

The present invention relates to a thermoplastic elastomer composition and a method for producing the same.

Thermoplastic elastomers are extremely useful industrially because they can be melted at the processing temperature during molding and can be molded by a known resin molding method. Such a thermoplastic elastomer, for example, Japanese Patent Application Laid-Open No. 2006-131663 (Patent Document 1) discloses a hydrogen-bonding crosslinkable site having a side chain containing a carbonyl group-containing group and a nitrogen-containing heterocyclic ring, and other A thermoplastic elastomer formed from an elastomeric polymer having a glass transition point of 25 ° C or lower at a side chain containing a covalently-bondable crosslinking site. However, the thermoplastic elastomers described in these Patent Documents 1 are not very sufficient in terms of tensile strength based on 100% modulus and breaking strength, or abrasion resistance.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] JP 2006-131663

The present invention has been made in view of the problems of the foregoing conventional technologies, and aims to provide a tensile strength that can further improve the modulus and breaking strength by 100%, and can have a sufficient degree of wear resistance. The purpose is to provide a thermoplastic elastomer composition.

The present inventors have repeatedly conducted in-depth research to achieve the foregoing object, and found that a glass transition is carried out by containing: "a hydrogen-bonding crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring" having a side chain An elastomeric polymer (A) having a point of 25 ° C or lower, and an elastomeric polymer having a side chain containing a hydrogen-bondable crosslinked site and a covalently-bonded crosslinked site, and having a glass transition point of 25 ° C or lower (B) At least one kind of elastomer component selected by the group, and expanded graphite, nano carbon tube, fullerene, graphene, silicate natural nano fiber, silsesquioxane and At least one selected from the group consisting of layered titanic acid compounds, and its content is 20 parts by mass or less of the additive component based on 100 parts by mass of the aforementioned elastomer component. The obtained thermoplastic elastomer composition is more effective While increasing the tensile strength based on 100% modulus and breaking strength, the composition also has a sufficiently high abrasion resistance, and thus completed the present invention.

That is, the thermoplastic elastomer composition of the present invention contains elasticity having a side chain containing a "hydrogen-bonding crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring" and a glass transition point of 25 ° C or lower. Group of elastomeric polymers (A) and elastomeric polymers (B) having side chains containing hydrogen-bondable cross-linking sites and covalently-bondable cross-linking sites, and having a glass transition point of 25 ° C or lower At least one selected elastomer component is made of expanded graphite, carbon nanotubes, fullerene, graphene, silicate natural nanofibers, silsesquioxane, and layered titanate compounds At least one selected from the group, and its content is an added component of 20 parts by mass or less based on 100 parts by mass of the aforementioned elastomer component.

In the above thermoplastic elastomer composition of the present invention, the aforementioned elastomer component is preferably at least one kind of reactant selected from the group consisting of the following reactants (I) to (VI):

[Reactant (I)] Maleic anhydride-denatured elastomeric polymer, triazole which may have at least one of a hydroxyl group, a thiol group, and an amine group, and may have a hydroxyl group, a thiol group, and an amine group Pyridine with at least one kind of substituent, thiadiazole which may have at least one kind of substituent among hydroxyl group, thiol group and amine group, imidazole which may have at least one kind of substituent among hydroxy group, thiol group and amine group 3, isocyanurate which may have at least one kind of substituent of hydroxy, thiol and amine groups, three of which may have at least one kind of substituents of hydroxy, thiol and amine groups Hydantoin which may have at least one kind of substituents of a hydroxyl group, a thiol group and an amine group, and a hydrocarbon compound having at least one kind of substituents selected from a hydroxyl group, a thiol group and an amine group Reactants of at least one of the compounds of the present invention, trihydroxyethyl isotricyanate, thiamine, and polyether polyols

[Reactant (II)] A reactant of a hydroxyl-containing elastomeric polymer with a compound having at least one substituent selected from carboxyl, alkoxysilyl, and isocyanate groups

[Reactant (III)] A reactant of a carboxyl group-containing elastomeric polymer with a compound having at least one substituent selected from a hydroxyl group, a thiol group, and an amine group.

[Reactant (IV)] An elastomeric polymer containing an amine group, and a compound having at least one kind of substituent selected from carboxyl, epoxy, alkoxysilyl, and isocyanate groups Reactant

[Reactant (V)] Reactant of an alkoxysilyl-containing elastomeric polymer and a compound having at least one substituent selected from a hydroxyl group, a carboxyl group, and an amine group

[Reactant (VI)] A reactant of an epoxy-containing elastomeric polymer with a compound having at least one substituent selected from a thiol group and an amine group.

In the thermoplastic elastomer composition of the present invention, the elastomer component contained as the polymer main chain is composed of a diene rubber, a hydride of a diene rubber, an olefin rubber, and a hydrogenated polybenzene. Ethylene-based elastomeric polymers, polyolefin-based elastomeric polymers, polyvinyl chloride-based elastomeric polymers, polyurethane-based elastomeric polymers, polyester-based elastomeric polymers, and Preferably, at least one selected from the polyamide-based elastomeric polymers is formed.

According to the present invention, it is possible to provide a thermoplastic elastomer composition which can further improve the tensile strength based on 100% modulus and breaking strength, and can have a sufficiently high abrasion resistance.

     [Form of Implementing Invention]     

Hereinafter, the present invention will be described in detail according to appropriate embodiments.

The thermoplastic elastomer composition of the present invention is an elastomer containing: a side chain containing "a hydrogen-bondable cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring" and a glass transition point of 25 ° C or lower Polymer (A), and a group of elastomeric polymers (B) with side chains containing hydrogen-bondable cross-linking sites and covalently-bondable cross-linking sites, and having a glass transition point of 25 ° C or lower At least one selected elastomer component is made of expanded graphite, carbon nanotubes, fullerene, graphene, silicate natural nanofibers, silsesquioxane, and layered titanic acid compounds. At least one selected from the group, and its content is formed by an additive component of 20 parts by mass or less based on 100 parts by mass of the aforementioned elastomer component.

     (Elastomer composition)     

These elastomer components are at least one selected from the group consisting of the aforementioned elastomeric polymers (A) to (B). In these elastomeric polymers (A) to (B), "side chain" means the side chains and ends of the elastomeric polymer. In addition, a "side chain containing" a hydrogen-bonding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring "(hereinafter, also referred to as" side chain (a) "depending on the situation)" means On the atoms (usually carbon atoms) that form the main chain of the elastomeric polymer (the aforementioned elastomer component contained as the polymer main chain), in a manner of hydrogen-bonding cross-linking sites, the The group and / or the nitrogen-containing heterocyclic ring (more preferably, a carbonyl-containing group and a nitrogen-containing heterocyclic ring) form a chemically stable bond (covalent bond). In addition, "the side chain contains a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site" means a side chain having a hydrogen-bondable cross-linking site (hereinafter, also referred to as a "side chain depending on the situation," (a ') "), two side chains such as a side chain (hereinafter, depending on the case, also referred to as" side chain (b) ") having a covalent bonding cross-linking site, and The side chain includes both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site, as well as a side chain containing both a hydrogen-bondable cross-linking site and a covalent-bond cross-linking site ( One side chain contains both a hydrogen-bonding cross-linking site and a covalently-bonding cross-linking site. Hereinafter, these side chains are also referred to as "side chain (c)" depending on the situation, The concept of the case where both the hydrogen-bondable cross-linking site and the covalently-bondable cross-linking site are contained in the side chain of the polymer.

The main chains of the elastomeric polymers (A) to (B) (the aforementioned elastomer component contained as the polymer main chain: the polymer forming the main chain portion) are only required to be generally known natural high A molecule or a synthetic polymer whose glass transition point is below room temperature (25 ° C.) may be formed (that is, formed by a so-called elastomer), and there is no particular limitation. Therefore, the elastomeric polymers (A) to (B) may be, for example, elastomeric polymers containing glass transition points of natural polymers or synthetic polymers at room temperature (25 ° C) or lower as a main chain. In addition, those containing a side chain (a) having "a hydrogen-bondable cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring"; glass transition points containing natural polymers or synthetic polymers are at room temperature Elastomer polymer (25 ° C) or lower is used as the main chain, and the side chain is a side chain (a ') having a hydrogen-bonding cross-linking site and a side chain (b) having a covalent-bonding cross-linking site ; An elastomeric polymer containing glass transition point of natural polymers or synthetic polymers at room temperature (25 ° C) or lower as a main chain, and containing hydrogen-bondable crosslinked sites and covalently-bonded crosslinked sites Both sidechains (c); etc.

The main chains of the elastomeric polymers (A) to (B) (the aforementioned elastomer component contained as the polymer main chain: the polymer forming the main chain part), for example, natural rubber (NR), Isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloropine Diene rubbers such as chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM), and their hydrides; ethylene-propylene rubber (EPM), ethylene-acrylic acid Rubber (AEM), ethylene-butene rubber (EBM), chlorosulfonated polyethylene, acrylic-based rubber, fluororubber, polyethylene rubber, polypropylene rubber and other olefin-based rubbers; epichlorohydrin rubber; polyvulcanized rubber; Silicone rubber; urethane rubber; etc.

The main chain of the elastomeric polymers (A) to (B) (the aforementioned elastomer component contained as the polymer main chain: the polymer forming the main chain portion) may be a resin containing a resin component. Formed by elastomeric polymers, for example, hydrogenated polystyrene elastomeric polymers (for example, SBS, SIS, SEBS, etc.), polyolefin-based elastomeric polymers, polyvinyl chloride-based elastomers Polymers, polyurethane-based elastomeric polymers, polyester-based elastomeric polymers, polyamide-based elastomeric polymers, and the like.

The main chains of these elastomeric polymers (A) to (B) (the aforementioned elastomer components contained as the polymer main chain) are composed of diene rubber, dihydride rubber hydride, and olefin rubber , Hydrogenable polystyrene-based elastomeric polymer, polyolefin-based elastomeric polymer, polyvinyl chloride-based elastomeric polymer, polyurethane-based elastomeric polymer, polyester-based elasticity It is preferred that at least one selected from the group consisting of a body polymer and a polyamide-based elastomeric polymer. In addition, the main chains of the aforementioned elastomeric polymers (A) to (B) (the aforementioned elastomer component contained as the polymer main chain) do not have a double bond that is liable to age. Rubber hydrides and olefin-based rubbers are preferred, and from the viewpoint of low cost and high reactivity (compounds such as maleic anhydride have a large number of double bonds capable of undergoing diene reactions), diene-based rubbers are preferred.

In addition, the elastomeric polymers (A) to (B) may be liquid or solid, and the molecular weight is not particularly limited. The elastomeric polymers (A) to (B) can be used in accordance with the use or requirements of the thermoplastic elastomer composition of the present invention. Physical properties, etc., to make appropriate choices.

If the fluidity of the thermoplastic elastomer composition of the present invention during heating (de-crosslinking, etc.) is valued, the above-mentioned elastomeric polymers (A) to (B) are preferably liquid, for example, the main chain part is In the case of diene rubbers such as isoprene rubber and butadiene rubber, when the elastomeric polymers (A) to (B) are formed into a liquid component, the weight average molecular weight of the main chain portion is 1,000 to 100,000 is preferred, and about 1,000 to 50,000 is particularly preferred.

When the strength of the thermoplastic elastomer composition of the present invention is valued, the elastomeric polymers (A) to (B) are preferably solid. For example, the main chain part is isoprene rubber, butadiene In the case of a diene rubber such as olefin rubber, when the elastomeric polymers (A) to (B) are formed into a solid component, the weight average molecular weight of the main chain portion is preferably 100,000 or more, and 500,000 to 1,500,000. Left and right are particularly good.

These weight average molecular weights are weight average molecular weights (in terms of polystyrene) measured by gel permeation chromatography (GPC). In the measurement, it is preferable to use tetrahydrofuran (THF) as a solvent user.

In the thermoplastic elastomer composition of the present invention, the aforementioned elastomeric polymers (A) to (B) may be used in combination of two or more kinds. In this case, the mixing ratio of the respective elastomeric polymers to each other can be adjusted to an arbitrary ratio in accordance with the application, physical properties, and the like of the thermoplastic elastomer composition of the present invention.

The glass transition point of the elastomeric polymers (A) to (B) is 25 ° C or lower as described above. When the glass transition point of the elastomeric polymer is within this range, the thermoplastic elastomer composition of the present invention can exhibit rubber-like elasticity at room temperature. The “glass transition point” in the present invention is a glass transition point measured using a differential scanning calorimetry (DSC-Differential Scanning Calorimetry). During the measurement, the temperature rise rate is preferably 10 ° C / min.

The main chains of the elastomeric polymers (A) to (B) (the aforementioned elastomer components contained as the polymer main chain) transfer the glass of the elastomeric polymers (A) to (B). When the point is 25 ° C or lower, the molded article formed from the obtained thermoplastic elastomer composition is used at room temperature (25 ° C) for the purpose of showing rubber-like elasticity. Natural rubber (NR), isoprene rubber (IR) , Butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR) and other diene Based rubber; olefin based rubber such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), etc .; preferably. In addition, when the olefin-based rubber is used as the main chain of the elastomeric polymers (A) to (B), the tensile strength of the obtained thermoplastic elastomer composition can be improved, and there is no double bond, so it can be charged. Parts suppress the tendency of the composition to deteriorate.

There is no such thing as the amount of styrene that can be bonded to the aforementioned styrene-butadiene rubber (SBR) used in the elastomeric polymers (A) to (B), or the hydrogenation rate of the hydrogenated elastomeric polymer. It is particularly limited, and it can be adjusted to an arbitrary ratio according to the application used for the thermoplastic elastomer composition of the present invention, or the physical properties required for the composition.

The main chains of the elastomeric polymers (A) to (B) (the elastomer component contained as the polymer main chain) are ethylene-propylene-diene rubber (EPDM) and ethylene-acrylic rubber. (AEM), ethylene-propylene rubber (EPM), and ethylene-butene rubber (EBM), from the viewpoint of good rubber-like elasticity at room temperature, especially when the degree of crystallization is less than 10% (better) 5 ~ 0%). The main chains of the elastomeric polymers (A) to (B) are used in ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), and ethylene- In the case of butene rubber (EBM), its vinyl content is preferably 10 to 90 mol%, and more preferably 30 to 90 mol%. When the content of the vinyl group is within this range, the compression set and the mechanical strength of the thermoplastic elastomer (composition) can be improved, and in particular, the tensile strength can be made better.

In addition, the aforementioned elastomeric polymers (A) to (B) are preferably non-crystalline from the viewpoint that good rubber-like elasticity can be produced at room temperature. In addition, these elastomeric polymers (A) to (B) may be partially crystalline (crystalline structures) elastomers. In this case, the degree of crystallinity is also less than 10% (particularly as 5 ~ 0%) is better. These crystallinity degrees are measured using an X-ray diffraction device (for example, a measurement device manufactured by Scientific Corporation under the trade name "MiniFlex300") to measure diffraction peaks and calculate the number of scattering peaks due to crystallinity / amorphity. Points can be obtained.

In addition, as described above, the elastomeric polymers (A) to (B) have a side chain having, as described above, a side containing "a hydrogen-bonding crosslinking site having a carbonyl group-containing group and / or a nitrogen-containing heterocyclic ring". Chain (a); a side chain (a ') containing a hydrogen-bondable cross-linking site and a side chain (b) containing a covalent-bondable cross-linking site; and a chain containing a hydrogen-bondable cross-linking site and a covalent-bond cross-linking Site side chain (c); at least one of them. In the present invention, the side chain (c) may also be referred to as a side chain having a function of a side chain (a ') and a function of a side chain (b). Hereinafter, the contents of each side chain will be described.

     <Side chain (a '): a side chain containing a hydrogen-bondable crosslinking site>     

The side chain (a ') containing a hydrogen-bonding cross-linking site has a group that forms a cross-link via hydrogen bonding (for example, a hydroxyl group, a hydrogen-bonding cross-linking site contained in a side chain (a) described later, etc.), The structure is not particularly limited as long as it is a side chain capable of forming a hydrogen bond based on this group. Here, the hydrogen-bondable cross-linking site refers to a site where the polymers (the elastomers) are cross-linked by hydrogen bonding. In addition, the crosslinks generated by hydrogen bonding are acceptors (including radicals containing atoms with independent electron pairs, etc.), and hydrogen donors (with covalent bonds with atoms with a higher degree of electrical negativeness). The base of the hydrogen atom, etc.) begins to form after contact. Therefore, when there is no hydrogen acceptor and hydrogen donor between the side chains of the elastomer, the intersection generated by the hydrogen bond cannot be formed. Link. Therefore, when the side chains between the elastomers pass through both the acceptor of hydrogen and the donor of hydrogen, the hydrogen-bonding cross-linking site starts to exist in the reaction system. In addition, in the present invention, between the side chains between the elastomers, there is a part having a function as a hydrogen acceptor (for example, a carbonyl group), and a part having a function as a hydrogen donor (for example, a carbonyl group). In the case of both hydroxyl groups, etc., the part of the side chain having a function as an acceptor of hydrogen and the part functioning as a donor can be judged to be hydrogen-bonding cross-linking sites.

In view of the fact that the hydrogen-bonding cross-linking sites in the side chains (a ') can form stronger hydrogen bonds, the "hydrogen bond having a carbonyl group-containing group and / or a nitrogen-containing heterocyclic ring" described below is described. A "sexual cross-linking site" (a hydrogen-bonding cross-linking site contained in the side chain (a)) is preferred. That is, the side chain (a ') described later is more preferable. From the same viewpoint, the hydrogen-bonding crosslinking site in the side chain (a ') is more preferably a hydrogen-bonding crosslinking site having a carbonyl group-containing group and a nitrogen-containing heterocyclic ring.

     <Side chain (a): a side chain containing "a hydrogen-bonding crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring">     

The side chain (a) containing "a hydrogen-bonding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring" may be any other structure as long as it has a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring. The content is not specifically limited. These hydrogen-bondable crosslinking sites are more preferably those having a carbonyl-containing group and a nitrogen-containing heterocyclic ring.

These carbonyl group-containing groups are not particularly limited as long as they include a carbonyl group, and specific examples thereof include amidine, ester, amidine, carboxyl, and carbonyl. These carbonyl group-containing groups may be compounds obtained by introducing a carbonyl group-containing group into the aforementioned main chain, or a group introduced into the aforementioned main chain (a polymer in the main chain portion). The compounds obtained by introducing a carbonyl group-containing group into the main chain are not particularly limited, and specific examples thereof include ketones, carboxylic acids, and derivatives thereof.

These carboxylic acids are, for example, organic acids having a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may be any of an aliphatic group, an alicyclic group, and an aromatic group. Specific examples of the carboxylic acid derivative include a carboxylic acid anhydride, an amino acid, a thiocarboxylic acid (a hydrogen sulfur-containing carboxylic acid), an ester, an amino acid, a ketone, amidines, and fluorene. Amines, dicarboxylic acids and their monoesters.

Examples of the carboxylic acid and its derivatives include malonic acid, maleic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, and p- Carboxylic acids such as phenyldiacetic acid, p-hydroxybenzoic acid, p-aminobenzoic acid, hydrothioacetic acid, and these carboxylic acids containing substituents; succinic anhydride, maleic anhydride, glutaric anhydride, benzene dicarboxylic acid Anhydrides of formic anhydride, propionic anhydride, benzoic anhydride, etc .; fatty esters of maleate, malonate, succinate, glutarate, ethyl acetate, etc .; phthalate, isophthalate Aromatic esters of esters, terephthalates, ethyl-m-aminobenzoates, methyl-p-hydroxybenzoates, etc .; ketones such as quinone, anthraquinone, naphthoquinone, etc. Amino acid, tyrosine, diglycine, alanine, valine (Valine), leucine, serine, threonine, lysine, aspartic acid, glutamic acid, hemi Cysteine, Methionine, Proline, N- (p-Aminobenzylidene) -β-Alanine, etc .; Maleic acid, maleic acid Amino acid (maleimide) Monoammonium succinate, 5-hydroxypentamidine, N-ethylammonium ethanolamine, N, N'-hexamethylbis (acetamidamine), malondiamine, cycloserine, 4-acetaminophen, p-ethyl Amidoamines such as ammonium benzoic acid; amines such as maleimide and succinimide; etc.

Among these, compounds obtained by introducing a carbonyl group (a carbonyl group-containing group) are preferably cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride, and particularly preferably maleic anhydride.

When the side chain (a) has a nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring may be one which is introduced into the main chain directly or through an organic group, and the constitution and the like are not particularly limited. As long as these nitrogen-containing heterocyclic rings contain a nitrogen atom in the heterocyclic ring, a ring having a heteroatom other than a nitrogen atom in the heterocyclic ring, for example, a sulfur atom, an oxygen atom, a phosphorus atom, or the like may be used. Wherein, when a nitrogen-containing heterocyclic ring is used in the aforementioned side chain (a), having a heterocyclic structure can strengthen the hydrogen bond that forms a crosslink, and further improve the tensile strength of the obtained thermoplastic elastomer composition of the present invention. Lift up and better.

The nitrogen-containing heterocyclic ring may have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, (iso) propyl, and hexyl; methoxy, ethoxy, and (iso) propoxy Alkoxy groups such as radicals; radicals formed by halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; cyano; amine; aromatic hydrocarbon groups; ester groups; ether groups; fluorenyl groups; thioether groups; These can also be used in combination. The substitution positions of the substituents are not particularly limited, and the number of the substituents is also not limited.

In addition, the nitrogen-containing heterocyclic ring may be aromatic or non-aromatic, but when it is aromatic, the obtained thermoplastic elastomer composition of the present invention can be permanently deformed by compression or mechanical strength. Lift up, and better.

In addition, these nitrogen-containing heterocycles are not particularly limited in view of making hydrogen bonds stronger and improving compression set or mechanical strength, and 5-membered rings and 6-membered rings are preferred. Specific examples of the nitrogen-containing heterocyclic ring include pyrroline, pyrrolidone, oxindole (2-oxindole), and indoxyl (3 -Oxindole, dioxindole, isatin, indolyl, phthalimidine, β-isoindigo, monoporphyrin, doporphyrin Phthaloline, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, chlorophyll, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, Benzotriazole, imidazoline, imidazolone, imidazolidone, hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, and indole Indole (pyridoindole), purine, cinnoline, pyrrole, pyrroline, indole, indolinoline, indolone, carbazole, phenothialine (phenothiazine), pseudoindole (indolenine), isoindole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxaline Benzox 呔 Pyridine, pyridine ,coffee ,four , Benzoxazole, benzoisoxazole, anthranilic (acid), benzothiazole, furazan, pyridine, quinoline, isoquinoline, acridine , Pyrididine, anthrazoline, 1,5-naphthyridine, thiophene ,despair , Pyrimidine, quinazoline, quinoxaline, three , Histidine, trisazolysine, melamine, adenine, guanine, thymine, Cytosine, hydroxyethyl isocyanurate, and derivatives thereof. Among these, the nitrogen-containing 5-membered ring is particularly represented by the following compound (cyclic structure described by chemical formula), a triazole derivative represented by the following general formula (10), and the following general formula (11) The imidazole derivative is a preferable example. These substituents may have various kinds of substituents as described above, and may be hydrogenated or dissociated.

The substituents X, Y, and Z in the general formulae (10) and (11) are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and 6 to 20 carbon atoms. Aryl or amine. In addition, any one of X and Y in the general formula (10) is not a hydrogen atom. Similarly, at least one of X, Y, and Z in the general formula (11) is not a hydrogen atom.

These substituents X, Y, and Z are other than a hydrogen atom and an amine group, and specifically, for example, methyl, ethyl, propyl, butyl, pentyl, octyl, dodecyl, and stearyl Equivalent linear alkyl groups; isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, t-pentyl, 1-methylbutyl, 1-methyl Branched alkyl groups such as heptyl, 2-ethylhexyl; aralkyl groups such as benzyl, phenethyl; phenyl, tolyl (o-, m-, p-), xylyl, xylene And other aryl groups; etc.

Among these, when the substituents X, Y, and Z are alkyl groups, especially when butyl, octyl, dodecyl, isopropyl, and 2-ethylhexyl are used, the thermoplasticity of the present invention can be obtained by using them. The elastomer composition is preferred because it has good processability.

The nitrogen-containing 6-membered ring is preferably exemplified by the following compounds. Among these, it may have the various substituents mentioned above (for example, the substituent which the said nitrogen-containing heterocyclic ring may have), and a hydrogenation or dissociation may be sufficient.

In addition, those in which the nitrogen-containing heterocyclic ring and the benzene ring or nitrogen-containing heterocyclic ring are condensed with each other may be used. Specifically, the following condensed ring is a preferred example. These condensed rings may have various kinds of substituents as described above, and may be hydrogenated or dissociated.

For these nitrogen-containing heterocyclic rings, the obtained thermoplastic elastomer composition of the present invention has excellent recyclability, compression set, hardness, and mechanical strength, especially for the purpose of tensile strength. Polycyanate ring, thiadiazole ring, pyridine ring, imidazole ring, three At least one selected from a ring and a hydantoin ring is preferable, and at least one selected from a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring, and a hydantoin ring is preferable.

When the side chain (a) contains both the carbonyl-containing group and the nitrogen-containing heterocyclic ring, the carbonyl-containing group and the nitrogen-containing heterocyclic ring may be introduced into the main chain as mutually independent side chains. However, it is preferable to introduce the main chain by way of a side chain that is bonded via the carbonyl-containing group and the nitrogen-containing heterocyclic ring as a different group. Therefore, it is preferable that the side chain (a) is introduced into the main chain as a side chain from a side chain having a carbonyl group and a nitrogen-containing heterocyclic ring containing a hydrogen bonding cross-linking site. The side chain of the structural part represented by the following general formula (1) is preferably introduced as a side chain into the main chain:

[In formula (1), A is a nitrogen-containing heterocyclic ring, and B is a single bond; an oxygen atom, and an amine or sulfur atom represented by NR '(R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) Or an organic group which may contain these atoms or groups].

As described above, it is preferable that the hydrogen-bonding cross-linking site of the side chain (a) contains a structural portion represented by the general formula (1).

Among them, the nitrogen-containing heterocyclic ring A in the formula (1) specifically includes, for example, the nitrogen-containing heterocyclic ring exemplified above. Further, the substituent B in the above formula (1) specifically includes, for example, a single bond; an oxygen atom, a sulfur atom, or a formula: NR '(R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) The amine group represented (also, hereinafter, simply, depending on the situation, the formula: the amine group represented by NR 'is also simply referred to as "amino group NR'"); the number of carbons that can contain these atoms or groups is 1 ~ 20 alkylene or aralkylene; 1-20 alkylene ether groups (alkoxyl, for example, -O-CH ₂ CH ₂ -yl), Alkylamino (for example, -NH-CH ₂ CH ₂ -group, etc.) or alkylene sulfide (alkylene thio group, for example, -S-CH ₂ CH ₂ -group); the terminal has these carbon number 1 ~ 20 aralkylene ether group (arylene alkoxy group), aralkylene group or aralkyl sulfide group; etc.

Among them, the alkyl group having 1 to 10 carbon atoms selected as R ′ in the amine group NR ′ includes an isomer thereof, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, Heptyl, octyl, nonyl, decyl, etc. Oxygen atom, sulfur atom and amine group NR ′ in the substituent B in the above formula (1); and an alkylene ether group, alkyleneamine group, alkylene group having 1 to 20 carbon atoms having these atoms or groups at the terminal Alkyl sulfide groups, or oxygen atoms such as aralkylene ether groups, aralkylene amine groups, aralkyl sulfide groups, amine groups NR 'and sulfur atoms, can be combined with adjacent carbonyl groups to form a conjugated system Ester group, amido group, amido group, thioester group and the like are preferred.

Among these, the aforementioned substituent B is an oxygen atom, a sulfur atom, or an amine group which can form a conjugated system; an alkylene ether group, an alkyleneamine group, or an alkylene group having 1 to 20 carbon atoms having these atoms or groups at the terminal or An alkylene sulfide group is preferable, and an amino group (NH), an alkylene group (-NH-CH ₂ -group, -NH-CH ₂ CH ₂ -group, -NH-CH ₂ CH ₂ CH ₂ -group) An alkylene ether group (-O-CH ₂ -yl, -O-CH ₂ CH ₂ -yl, -O-CH ₂ CH ₂ CH ₂ -yl) is particularly preferred.

When the side chain (a) is a side chain containing a hydrogen-bonding crosslinkable site having the carbonyl-containing group and the nitrogen-containing heterocyclic ring, the side chain (a) has the hydrogen bond having the carbonyl-containing group and the nitrogen-containing heterocyclic ring. The tie-crosslinking site is preferably one side chain represented by the following formula (2) or (3), and a side chain introduced into the polymer main chain at the α position or the β position is more preferred.

[In the formula, A is a nitrogen-containing heterocyclic ring, and B and D are each independently a single bond; an oxygen atom, an amine group NR '(R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or may contain Those atoms or radicals].

Among them, the nitrogen-containing heterocyclic ring A is substantially the same as the nitrogen-containing heterocyclic ring A of the formula (1), and the substituents B and D are each independently substantially the same as the substituent B of the formula (1). However, the substituent D in the above formula (3) is a single bond in the content exemplified by the substituent B in the above formula (1); it may have a carbon number of 1 to 20 containing an oxygen atom, a nitrogen atom, or a sulfur atom. A conjugated system of an alkylene or an alkylene is more preferred, and a single bond is particularly preferred. That is, it is preferred to form an alkylene or aralkylamino group having 1 to 20 carbon atoms containing an oxygen atom, a nitrogen atom, or a sulfur atom together with the azaimine of the formula (3). It is particularly preferred that the impurity is directly bonded (single bond) to the azaimine of the formula (3). Specifically, the above-mentioned substituent D is, for example, a single bond; the above-mentioned alkylene ether or alkylene ether group having 1 to 20 carbon atoms having an oxygen atom, a sulfur atom, or an amine group at the terminal, etc .; Examples include methyl, ethyl, propyl, butyl, hexyl, phenyl, xylyl, and the like.

When the side chain (a) is a side chain containing a hydrogen-bondable cross-linking site having the carbonyl-containing group and the nitrogen-containing heterocyclic ring, the hydrogen-bondable cross-linking site of the side chain (a) is It is preferable to include a structural part represented by the following general formula (101):

[In formula (101), A is a nitrogen-containing heterocyclic ring].

The nitrogen-containing heterocyclic ring A in the formula (101) is basically the same as the nitrogen-containing heterocyclic ring A in the formula (1). In addition, the aforementioned hydrogen-bondable crosslinking sites of these side chains (a) are more preferably those having a structure represented by the following general formula (102) from the viewpoint of high modulus and high breaking strength:

The side chain (a) is particularly preferably a group represented by the general formula (102).

The ratio of the carbonyl group-containing group to the nitrogen-containing heterocyclic ring of the thermoplastic elastomer is not particularly limited, and is generally in the range of 1: 1 to 3: 1 (more preferably 1: 1, 2: 1 Or 3: 1), it is easy to form complementary interactions, and it is more preferable because it is easy to manufacture.

The side chains (a) containing "hydrogen-bonding crosslinking sites having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring" are introduced in an amount of 0.1 to 50 mol% relative to 100 mol% of the main chain portion. The ratio (introduction rate) is better, and the ratio of 1-30 mol% is more preferable. When the introduction rate of these side chains (a) is less than 0.1 mol%, the tensile strength may be insufficient during cross-linking. In addition, when it exceeds 50 mol%, the crosslink density is too high, The rubber elasticity may be lost. That is, when the introduction rate is within the above range, the side chains of the thermoplastic elastomer interact with each other to efficiently cross-link between the molecules, thereby improving the tensile strength during cross-linking and excellent recyclability. And better.

The above introduction rate is that each side chain (a) independently introduces a side chain (ai) containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and a hydrogen-bonding cross-linking site containing a nitrogen-containing heterocyclic ring. In the case of the side chain (a-ii), these are set as a group according to the ratio of the side chain (ai) containing the carbonyl group to the side chain (a-ii) containing the nitrogen-containing heterocyclic ring. On the other hand, it is calculated as one side chain (a). In addition, when any one of the side chains (a-i) and (a-ii) is excessive, one of the side chains may be used as a reference to calculate the introduction rate.

In addition, for the above introduction rate, for example, when the main chain portion is ethylene-propylene rubber (EPM), when the unit of ethylenic and propylene monomers is set to 100 units, the amount of monomers introduced into the side chain portion is approximately It is about 0.1 to 50 units.

The side chain (a) is a polymer (material for forming an elastomeric polymer) that forms the main chain after the reaction, and a cyclic anhydride group (more preferably, a maleic anhydride group) is used as a functional group. ) Polymer (an elastomeric polymer having a cyclic acid anhydride group in the side chain), a compound in which the functional group (cyclic acid anhydride group) reacts with the cyclic acid anhydride group to form a hydrogen-bondable crosslinking site (A compound obtained by introducing a nitrogen-containing heterocyclic ring) is preferably reacted to form a hydrogen-bondable crosslinking site, and the side chain of the polymer is preferably a side chain (a). The compounds obtained by introducing a nitrogen-containing heterocyclic ring may be the nitrogen-containing heterocyclic ring exemplified above, and may have a substituent (for example, a hydroxyl group, a thiol group) that can react with a cyclic acid anhydride group such as maleic anhydride. , Amine groups, etc.) may be nitrogen-containing heterocyclic rings.

Hereinafter, the bonding position of the nitrogen-containing heterocyclic ring in the side chain (a) will be described. The nitrogen heterocyclic ring is also referred to simply as "nitrogen-containing n-membered ring compound (n ≧ 3)".

The bond positions ("1 ~ n digits") described below are those marked according to the IUPAC nomenclature. For example, a compound having three nitrogen atoms with non-covalent electron pairs is based on the IUPAC nomenclature and determines the bonding position according to the order. Specifically, for example, the bonding positions indicated on the nitrogen-containing heterocycles of the 5-membered ring, the 6-membered ring, and the condensed ring illustrated above.

In these side chains (a), the bonding position of the nitrogen-containing n-membered ring compound directly or via an organic group and the copolymer is not particularly limited, and it may be any bonding position (1 position) ~ n digits). Preferably, it is 1 or 3 to n bits.

When the nitrogen atom contained in the nitrogen-containing n-membered ring compound is one (for example, a pyridine ring, etc.), it is easy to form a chelate compound, and when used as a composition, the physical properties such as tensile strength can be more excellent. It is preferable to use 3 to (n-1) digits. When the bonding position of the nitrogen-containing n-membered ring compound is selected, the elastomeric polymer can be easily formed between the molecules of the elastomeric polymer through hydrogen bonding, ionic bonding, coordination bonding, and the like. Cross-linking tends to improve recycling properties and mechanical properties, especially tensile strength.

     <Side chain (b): a side chain containing a covalently bonded cross-linking site>     

In the present specification, "a side chain (b) containing a covalently-bondable cross-linking site" means a covalently-bondable cross-linking site on an atom (usually a carbon atom) forming the main chain of the elastomeric polymer. (By reacting with the "formation of covalently-bonded compounds" and the like described later with amine-containing compounds, etc., amines, esters, lactones, urethanes, ethers, and thiocarbamates are formed. And at least one functional group selected from the group consisting of thioethers and the like to form a chemically stable bond (covalent bond). The side chain (b) is a side chain containing a covalently-bondable cross-linking site. In addition to the covalently-bondable site, the side-chain (b) may further have a hydrogen-bondable base, and hydrogen bonds between the side chains. In the case of forming a cross-link, it can be used as a side chain (c) described later (in addition, the side chain between the elastomers does not contain a hydrogen donor capable of forming a hydrogen bond, a hydrogen acceptor, etc. In the case of both, for example, when only a side chain containing an ester group (-COO-) is present in the reaction system, the ester groups (-COO-) do not particularly form hydrogen bonds with each other, so the group does not have hydrogen as The function of a bondable cross-linking site. For example, as a carboxyl group or a triazole ring, each side chain of the elastomer contains a site having a hydrogen donor as a hydrogen bond, and a site receiving hydrogen as a hydrogen acceptor. In the structure of both parts, such as hydrogen bonds are formed between the side chains of elastomers, hydrogen-bondable cross-linked sites are formed. For example, side chains of elastomers Since the ester group and the hydroxyl group coexist, the hydrogen bond is formed between the side chains through these groups. Position is the hydrogen-bonding cross-linking site. Therefore, it can be determined according to the structure of the side chain (b) itself, or the structure of the side chain (b) and the kind of substituents of other side chains. Used as a side chain (c)). The "covalently bonded cross-linking site" referred to herein refers to a site where polymers (cross-linked elastomers) are cross-linked through covalent bonding.

The side chain (b) containing the covalently-bonded cross-linking site is not particularly limited, and examples thereof include an elastomeric polymer having a functional group in a side chain (a polymer forming the main chain portion). ) To react with a compound that can react with the aforementioned functional group to form a covalently-bonded cross-linking site (a compound that forms a covalently-bonded link). The cross-links in the aforementioned covalently-bondable cross-linking sites of the side chains (b) are formed by amidine, ester, lactone, urethane, ether, thiocarbamate, and thioether. It is preferred that at least one bond formed by the group is formed. Therefore, the functional groups included in the polymer constituting the main chain are selected from the group consisting of amidine, ester, lactone, urethane, ether, thiocarbamate, and thioether. Preferably, at least one functional group is bonded.

These "compounds forming covalently-bonded crosslink sites (compounds that form covalently-bonded compounds)", for example, have two or more amine groups and / or imine groups (having both amine groups and In the case of an amine group, these groups are two or more polyamine compounds; a polyalcohol compound having two or more hydroxyl groups in one molecule; and a polyisocyanate compound having two or more isocyanate (NCO) groups in one molecule. ; Polythiol compound having two or more thiol groups (hydrothio groups) in one molecule; Polyepoxide compound having two or more epoxy groups in one molecule; One having two or more carboxyl groups in one molecule Polycarboxy compounds; polyalkoxysilyl compounds having two or more alkoxysilyl groups in one molecule; etc. Among them, the "compound that forms a covalently-bondable cross-linking site (compound that forms a covalently-bonded compound)" is, depending on the kind of substituents the compound has, or the degree of the reaction when the compound is used for the reaction, A compound obtained by introducing both the hydrogen-bondable cross-linking site and the covalently-bondable cross-linking site (for example, when a compound having three or more hydroxyl groups is used to form a cross-linked site through covalent bonding) Depending on the degree of reaction, the functional group of the elastomeric polymer having a functional group on the side chain reacts with two hydroxyl groups, and the remaining one hydroxyl group remains as a hydroxyl group. In this case, In addition, hydrogen-bondable cross-linking sites may be introduced together). Therefore, the "compounds that form covalently-bondable cross-linking sites (compounds that form covalently-bonded sites)" exemplified therein also include both "formation of hydrogen-bondable cross-linked sites and covalently-bonded cross-linked sites" compound of". Based on these viewpoints, in the case of forming a side chain (b), the compound can be appropriately selected according to the design of the target from "the compound that forms a covalently-bonded cross-linking site (the compound that forms a covalently-bonded compound)" in accordance with the purpose design. It is only necessary to form the side chain (b) by controlling the degree to which the reaction proceeds or the like. In addition, when the compound forming the covalently-bondable cross-linking site has a heterocyclic ring, a hydrogen-bondable cross-linking site can be efficiently produced at the same time, and the side chain (c) described later can also efficiently form the above-mentioned The side chain of the valence-bonding cross-linking site. Therefore, specific examples of the compound having the heterocyclic ring will be described in the side chain (c) together with the content of a compound suitable for producing the side chain (c). In addition, the side chain (c) can be referred to as a preferred form of a side chain such as a side chain (a) or a side chain (b) in terms of its structural content.

These polyamine compounds that can be used as "compounds that form covalently-bondable cross-linking sites (compounds that form covalently-bonded bonds)" include, for example, cycloaliphatic amines, aliphatic polyamines, and aromatics shown below. Polyamines, nitrogen-containing heterocyclic amines, etc.

Specific examples of these alicyclic amines include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane and bis- (4-aminocyclohexyl) Methane, diaminocyclohexane, bis- (aminomethyl) cyclohexane, and the like.

The aliphatic polyamine is not particularly limited, and examples thereof include methylenediamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, and 1,3-diamine. Pentane, hexamethyldiamine, diaminoheptane, diaminododecane, diethylenetriamine, diethylaminopropylamine, N-aminoethylpiperazine, triethylenetetramine , N, N'-dimethyl ethylenediamine, N, N'-diethyl ethylene diamine, N, N'-diisopropyl ethylene diamine, 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 (hexamethyl) triamine, and the like.

The aromatic polyamine and the nitrogen-containing heterocyclic amine are not particularly limited, and examples thereof include diaminotoluene, diaminoxylene, tetramethylxylenediamine, and ginsyl (dimethylaminomethyl) Phenol), m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylphosphonium, 3-amino-1,2,4-triazole, and the like.

In the polyamine compound, one or more hydrogen atoms may be substituted by an alkyl group, an alkylene group, an alkylene group, an oxy group, a fluorenyl group, a halogen atom, or the like, and the skeleton may contain oxygen. Atoms, sulfur atoms, and other heteroatoms.

Moreover, the said polyamine compound may be used individually by 1 type, and may use 2 or more types together. The mixing ratio when two or more types are used in combination can be adjusted to an arbitrary ratio in accordance with the application used for the thermoplastic elastomer (composition) of the present invention, and the physical properties required for the thermoplastic elastomer (composition) of the present invention.

Among the polyamine compounds exemplified above, hexamethyldiamine, N, N'-dimethyl-1,6-hexanediamine, diaminodiphenylphosphonium, etc., have high compression set. The mechanical strength, especially the improvement effect of tensile strength, is better.

The polyalcohol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups. For example, polyether polyalcohol, polyester polyalcohol, other polyalcohols, And these mixed polyols.

Specific examples of these polyether polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, 1,1,1-trimethylolpropane, 1,2, 5-hexanetriol, 1,3-butanediol, 1,4-butanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxyphenylmethane, pentaerythritol, etc. Polyol selected from at least one kind, and polyoxyl alcohol obtained by adding at least one selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc .; polyoxytetramethylene oxidation These can 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- One or more of trimethylolpropane and other low-molecular-weight polyols, and glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, and isophthalic acid , Dimer acid and other low-molecular carboxylic acid or oligomer acid condensation polymer obtained from one or two or more; ring-opening polymers such as pentolactone, valerolactone; etc., these They can be used alone or in combination of two or more.

Specific examples of other polyols include polymer polyols and polycarbonate polyols; polybutadiene polyols; hydrogenated polybutadiene polyols; acrylic polyols; ethylene glycol and diethylene glycol. Alcohol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, polyethylene glycol laurylamine (e.g., N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol lauryl Amines (e.g., N, N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamines (e.g., N, N-bis (2-hydroxyethyl) octylamine), Polypropylene glycol octylamine (for example, 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-bis (2-methyl-2-hydroxyethyl) stearylamine) and other low molecular weight polyols; etc., these can be used alone , Or a combination of two or more.

Examples of the polyisocyanate compound include 2,4-tolyl diisocyanate (2,4-TDI), 2,6-tolyl diisocyanate (2,6-TDI), and 4,4'-diphenyl. Methane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylene diisocyanate (XDI) Aromatic polyisocyanates such as tetramethylxylene diisocyanate (TMXDI), toluidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), hexamethyldiisocyanate (HDI), trimethyl Aliphatic polyisocyanates such as hexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (NBDI), transcyclohexane-1,4-diisocyanate, isophorone Diisocyanate compounds such as alicyclic polyisocyanates such as diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (hydrogenated MDI), H ₆ TDI (hydrogenated TDI); polymethylated polyphenylene Polyisocyanate compounds such as polyisocyanates; carbodiimide-modified polyisocyanates of these isocyanate compounds; isotricyanates of these isocyanate compounds Polyisocyanates; urethane prepolymers obtained by reacting these isocyanate compounds with the above-exemplified polyol compounds; etc., these can be used alone or in combination of two or more .

The polythiol compound is not particularly limited as long as it is a compound having two or more thiol groups, and specific examples thereof include methanedithiol and 1,3-butane Dithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol , 1,10-decane dithiol, 1,2-ethane dithiol, 1,6-hexane dithiol, 1,9-nonane dithiol, 1,8-octane dithiol , 1,5-pentanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, toluene-3,4-dithiol, 3,6-dichloro-1,2- Benzene dithiol, 1,5-naphthalene dithiol, 1,2-benzyl dimethane thiol, 1,3-benzyl dimethane thiol, 1,4-benzene dimethane thiol, 4,4'-sulfur Diphenylthiol, 2,5-dihydrothio-1,3,4-thiadiazole, 1,8-dihydrothio-3,6-dioxaoctane, 1,5-dihydro Thio-3-thiopentane, 1,3,5-tri -2,4,6-trithiol (trihydrothio-tri ), 2-di-n-butylamino-4,6-dihydrothio-s-tri , Trimethylolpropane ginseng (β-sulfur propionate), trimethylolpropane ginseng (sulfide glycolate), polythiol (thiol or thiol-denatured polymer (resin, rubber, etc.)), three -[(3-Hydroxythiopropionyloxy) -ethyl] -isocyanurate, etc. These may be used alone or in combination of two or more.

The molecular weight and backbone of the polyepoxide compound are not particularly limited as long as the compound has two or more epoxy groups. Specific examples thereof include bisphenol A diglycidyl ether ( Bisphenol A epoxy resin), bisphenol F diglycidyl ether (bisphenol F epoxy resin), 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane Carboxylic acid esters, DCPD epoxy resins, epoxy novolac resins, o-cresol-phenol novolac epoxy resins, etc. These may be used alone or in combination of two or more.

The polycarboxyl compound is not particularly limited as long as it has a compound having two or more carboxyl groups. Specific examples thereof include oxalic acid, malonic acid, succinic acid, and glutaric acid. Acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, propanetricarboxylic acid, benzenetricarboxylic acid, etc. One type may be used alone, or two or more types may be used in combination.

In addition, when the polyalkoxysilyl compound is a compound containing two or more alkoxysilyl groups, the molecular weight and skeleton thereof are not particularly limited, and specific examples thereof include tris- (trimethoxy Silylpropyl) isotricyanate, bis (triethoxysilylpropyl) tetrasulfide, 1,6-bis (trimethoxysilyl) hexane, bis (3- (trimethoxy) These may be used alone or in combination of two or more kinds.

The functional groups of the polymer constituting the main chain that can be reacted with the compound that forms a covalently-bondable cross-linking site (a compound that forms a covalently-bonded site) are formed (formed: formed) by It is preferred that at least one functional group selected from the group consisting of amidine, ester, lactone, urethane, thiocarbamate, and thioether is bonded. The functional group is cyclic An acid anhydride group, a hydroxyl group, an amine group, a carboxyl group, an isocyanate group, a thiol group, and the like are preferable examples.

The elastomeric polymer (B) having the side chain (b) is a crosslink in the part of the side chain (b) in the covalently-bondable crosslinking site, that is, in one molecule. It has at least one crosslink formed by a covalent bond formed by a reaction between the aforementioned functional group and the above-mentioned "compound that forms a covalent bonding crosslinkable compound (a compound that forms a covalent bond)", and in particular, via When the lactone, urethane, ether, thiocarbamate, and thioether form a crosslink formed by at least one bond selected from the group consisting of two or more, It is more preferable to have 2-20, and it is more preferable to have 2-10.

In addition, the cross-linking in the covalently-bonding cross-linking site of the side chain (b) contains a tertiary amine bond (-N =) and an ester bond (-COO-), and it is easier to improve The obtained thermoplastic elastomer (composition) is preferred for reasons such as compression set and mechanical strength (elongation at break, breaking strength). In this case, the tertiary amine bond (-N =) and the ester bond (-COO-) include an elastomer having a side chain containing a group capable of forming a hydrogen bond (for example, There may be an elastomer having a side chain containing a hydroxyl group or the like), and the aforementioned covalently-bondable cross-linking site has a function as a side chain (c) described later. For example, when the elastomeric polymer (B) has the side chain (a) as the side chain (a ') (that is, the elastomeric polymer (B) has side chains (a) and (b) In the case of an elastomeric polymer such as the two), when the cross-linking in the covalently-bondable cross-linking site has the aforementioned tertiary amine bond and / or the aforementioned ester bond, these groups, and The groups in the side chain (a) (having a carbonyl-containing group and / or a nitrogen-containing heterocyclic side chain) will form hydrogen bonds (interactions), which can further increase the crosslinking density. From the viewpoint of forming a side chain (b) of a structure containing these tertiary amine bond (-N =) and ester bond (-COO-), "the compound that forms a covalently-bonded cross-linking site ( To form covalently bonded compounds) ", in the above-exemplified content, 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 Octylamine (e.g., N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (e.g., N, N-bis (2-hydroxyethyl) stearate Amine) and polypropylene glycol stearylamine (for example, N, N-bis (2-methyl-2-hydroxyethyl) stearylamine) are preferred.

In addition, even if a compound that forms a covalently-bonded cross-linking site (a compound that forms a covalently-bonded compound) is used as described above, the degree of progress of the compounding reaction, the type of substituents, the stoichiometric ratio of the raw materials used, etc. The case of hydrogen-bondable cross-linking sites is also introduced together. Therefore, regarding the preferred structure of the aforementioned covalently-bondable cross-linking sites, it is better to incorporate the covalently-bondable cross-linking sites in the side chain (c) together. Explanation in the structure.

     <Side chain (c): a side chain containing both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site>     

These side chains (c) are side chains containing both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site in one side chain. The hydrogen-bonding cross-linking sites contained in the side chains (c) are the same as the hydrogen-bonding cross-linking sites described in the side chain (a '), and are similar to the hydrogen bonds in the side chain (a). It is preferable that the cross-linking sites have the same content. In addition, the covalently-bondable cross-linking site contained in the side chain (c) can have the same content as the covalently-bondable cross-linking site in the side chain (b) (the preferred cross-linking is also the same content) ).

The side chains (c) are composed of an elastomeric polymer (a polymer forming the main chain part) having a functional group in the side chain, and can react with the functional group to form a hydrogen-bonding cross-linking site. Compounds (such as compounds that introduce both hydrogen-bondable cross-linking sites and covalent-bondable cross-linking sites) and covalently-bonded cross-linking sites are preferred to form side chains.

These compounds that form both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site (compounds that introduce both a hydrogen-bondable cross-linking site and a covalently-bond cross-linking site) and have a heterocyclic ring The compound (especially a nitrogen-containing heterocyclic ring) is preferably a compound capable of forming a covalently bonded cross-linking site (a compound that forms a covalent bond). Among them, a heterocyclic-containing polyalcohol and a heterocyclic-containing polyamine And heterocyclic-containing polythiols are preferred.

In addition, the polyalcohols, polyamines, and polythiols containing these heterocycles, in addition to those having heterocycles (particularly, nitrogen-containing heterocycles), may be appropriately used in combination with the above-mentioned "covalent bondable cross-linking". Polyols, polyamines, and polythiols described in "Site Compounds (Compounds Forming Covalent Bonds)" have the same contents. In addition, these heterocyclic-containing polyols are not particularly limited, and examples thereof include bis and ginseng (2-hydroxyethyl) isotricyanates, kojic acid, and dihydroxydithia. Dithiane, trihydroxyethyltri Wait. The heterocyclic-containing polyamine is not particularly limited, and examples thereof include ethylguanidine , Piperazine, bis (aminopropyl) piperazine, benzoguanidine , Melamine, etc. Examples of the heterocyclic-containing polythiols include dihydrothiothiadiazole and tri-[(3-hydrothiopropionyloxy) -ethyl] -isotricyanate. As mentioned above, the side chain (c) is composed of an elastomeric polymer (a polymer forming the main chain part) having a functional group in the side chain, and a polyalcohol, a polyamine, and a polythiol containing a heterocyclic ring. The reaction is carried out, and the side chain prepared is better.

In addition, it reacts with "compounds that form both hydrogen-bondable cross-linked sites and covalently-bonded cross-linked sites (compounds that introduce both hydrogen-bondable cross-linked sites and covalently-bonded cross-linked sites)" The functional group of the polymer constituting the main chain can form (form: form) a group consisting of amidine, ester, lactone, urethane, thiocarbamate, and thioether. The selected at least one bonded functional group is preferred, and these functional groups are preferably exemplified by a cyclic acid anhydride group, a hydroxyl group, an amine group, a carboxyl group, an isocyanate group, and a thiol group.

Moreover, the elastomeric polymer (B) having the aforementioned side chain (c) has at least one of the aforementioned covalently-bondable crosslinking sites in one part of the side chain (c). In particular, when a crosslink is formed by at least one bond selected from the group consisting of a lactone, a urethane, an ether, a thiocarbamate, and a thioether, it has a 2 It is more preferable to have two or more, it is more preferable to have two to twenty, and it is more preferable to have two to ten. In addition, the cross-linking in the covalently-bondable cross-linking site of the side chain (c) contains a tertiary amine bond (-N =) and an ester bond (-COO-), which can improve the obtained thermoplasticity. Elastomers (compositions) are preferred for reasons such as compression set and mechanical strength (elongation at break, breaking strength).

     (Preferred structure of covalently bonded cross-linking sites in side chains (b) to (c))     

For side chains (b) and / or (c), the cross-linking in the covalently-bonded cross-linking site includes a tertiary amine bond (-N =) and an ester bond (-COO-). When these bonding sites have a function as hydrogen-bondable cross-linking sites, it is possible to highly improve the compression set and mechanical strength (elongation at break, breaking strength) of the obtained thermoplastic elastomer (composition). good. As mentioned above, a tertiary amine bond (-N =) or an ester bond (-COO-) in a side chain having a covalently bonded cross-linking site forms a hydrogen bond with another side chain. At the time of bonding, the covalently bonded cross-linking site containing the tertiary amine bond (-N =) and the ester bond (-COO-) also has a hydrogen-bond cross-linking site, so it has a side chain ( c) function.

In addition, for example, the elastomeric polymer (B) having the side chain (a) as the side chain (a ') has a covalent bond with the tertiary amine bond and / or the ester bond. In the case of a bonding cross-linking site, when the tertiary amine bond and / or the ester bond form a hydrogen bond (interaction) with a group in the side chain (a), the crosslinking density can be re-established Lift up. Among them, a compound which can react with a functional group of the polymer constituting the main chain to form a covalently-bondable cross-linking site containing the tertiary amine bond and / or the ester bond (which can form hydrogen) Compounds such as a bonding cross-linking site and a covalent bonding cross-linking site) include, for example, polyethylene glycol laurylamine (for example, N, N-bis (2-hydroxyethyl) laurylamine), poly Propylene 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 octylamine (for example, N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (for example, N, N-bis (2-hydroxyethyl) Group) stearylamine) and polypropylene glycol stearylamine (for example, N, N-bis (2-methyl-2-hydroxyethyl) stearylamine) are preferred examples.

The cross-linking in the covalently-bondable cross-linking site of the side chain (b) and / or the side chain (c) is represented by containing at least one of the following general formulae (4) to (6) The structure is better, and G in the formula is preferably one containing a tertiary amine bond or an ester bond (also, in the following structure, when a hydrogen-bondable cross-linking site is included, a side chain having the structure is provided. Can be used as a side chain (c)).

In the above general formulae (4) to (6), E, J, K and L are each independently a single bond; an oxygen atom, an amine group NR '(R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or sulfur An atom; or an organic group which may contain these atoms or groups; G is a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom.

Among them, the substituents E, J, K, and L are independent of each other, and basically have the same contents as the substituent B of the general formula (1).

The substituent G is, for example, methyl, ethyl, 1,3-propyl, 1,4-butyl, 1,5-pentyl, 1,6-hexyl, 1,7. -Heptyl, 1,8-octyl, 1,9-endonyl, 1,10-decyl, 1,11-undecyl, 1,12-dodecyl, etc. Alkyl; N, N-diethyldodecylamine-2,2'-diyl, N, N-dipropyldodecylamine-2,2'-diyl, N, N-diethyl Octylamine-2,2'-diyl, N, N-dipropyloctylamine-2,2'-diyl, N, N-diethylstearylamine-2,2'-diyl, N , N-dipropylstearylamine-2,2'-diyl;vinylidene; 1,4-cyclohexyl and other bivalent alicyclic hydrocarbon groups; 1,4-phenylene, 1,2 -Divalent aromatic hydrocarbon groups such as phenylene, 1,3-phenylene, 1,3-phenylene bis (methylene); propane-1,2,3-triyl, butane- 1,3,4-triyl, trimethylamine-1,1 ', 1 "-triyl, triethylamine-2,2', 2" -triyl and other trivalent hydrocarbon groups; isocyanurates Base, three A trivalent cyclic hydrocarbon containing an oxygen atom, a sulfur atom, or a nitrogen atom; a tetravalent hydrocarbon group represented by the following formulae (12) and (13); and a substituent formed by these combinations; and the like. In addition, the substituent G in these formulas has a structure having an isotricyanate group (isotricyanate ring) from the viewpoint of having high heat resistance and high strength through hydrogen bonding. Better. In addition, the substituent G in these formulas is represented by the following formula (111) and the following formula (112) from the viewpoint of having high heat resistance and high strength through hydrogen bonding. The basis is better.

In addition, the cross-linking in the covalently-bondable cross-linking site of the side chain (c) includes at least one α- or β-position bonded to the main chain of the above-mentioned elastomeric polymer as follows The structure represented by any one of formulas (7) to (9) is preferred, and G in the formula is preferably one containing a tertiary amine group (the structure shown in formulas (7) to (9) contains a hydroxyl group It has a structure containing both a carbonyl group and a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site. The side chain having the structure has a function as a side chain (c)).

In the formulae (7) to (9), the substituents E, J, K, and L are independent of each other, and are basically the same as the substituents E, J, K, and L of the formulae (4) to (6). The group G is basically the same as the substituent G in the formulae (4) to (6).

The structures represented by any of the formulae (7) to (9) are specifically exemplified by the structures represented by the following formulae (14) to (25).

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

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

In the side chains (b) and (c), the crosslinks in the covalently-bondable crosslinkable sites are formed by reacting a cyclic acid anhydride group with a hydroxyl group, an amine group, and / or an imine group. Better. For example, when a polymer that forms a main chain portion after the reaction has a cyclic acid anhydride group (for example, a maleic anhydride group) as a functional group, the cyclic acid anhydride group of the polymer may have a hydroxyl group or an amine group. And / or the imine group forming a covalently-bonded cross-linking compound (a compound forming a covalent-bond) reacts to cause cross-linking between polymers that form a cross-linking site through covalent bonding. Way, as the crosslinks formed.

In addition, in these side chains (b) and (c), the cross-linking in the covalently-bondable cross-linking site is linked by amidine, ester, lactone, carbamate, ether, urea, It is preferable that at least one selected bond is formed by a group formed by a thiocarbamate and a thioether.

The above is the description of the side chain (a '), the side chain (a), the side chain (b), the side chain (c), and the like. The groups (structures) and the like of the side chain in these polymers may be Confirmation is performed using commonly used analytical methods such as NMR and IR spectra.

The elastomeric polymer (A) is an elastomeric polymer having a glass transition point of the side chain (a) of 25 ° C. or lower, and the elastomeric polymer (B) is a polymer having a side chain. Elastomer polymer with a glass transition point of 25 ° C or lower at the hydrogen-bondable cross-linking site and the covalently-bondable cross-linking site (with side chains (a ') and (b)) Polymers, or polymers containing at least one side chain (c) on the side chain). These elastomer components may be used alone or as a mixture of two or more of these elastomeric polymers (A) to (B).

The elastomeric polymer (B) may be a polymer having both a side chain (a ') and a side chain (b), or a polymer having a side chain (c). These elastomers The hydrogen-bonding cross-linking site contained in the side chain of the polymer (B) can form a stronger hydrogen-bonding point, and "H-bonding with a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring A "crosslinking site" (more preferably a hydrogen-bonding crosslinkable site having a carbonyl group and a nitrogen-containing heterocyclic ring) is more preferred.

In addition, at least one type of elastomer component selected from the group formed by the elastomeric polymers (A) and (B) is selected from the group formed by the following reactants (I) to (VI). At least one is preferred.

     [Reactant (I)]     

A maleic anhydride-denatured elastomeric polymer (hereinafter, also referred to as "elastomeric polymer (E1)" depending on the situation), and is composed of at least one of a hydroxyl group, a thiol group, and an amine group. Triazole as a substituent, pyridine that may have at least one of a hydroxyl group, a thiol group, and an amine group, thiadiazole that may have at least one kind of a substituent on a hydroxyl group, a thiol group, and an amine group, may have Imidazole, a substituent of at least one of a hydroxyl group, a thiol group, and an amine group, an isocyanurate which may have at least one kind of a substituent of a hydroxyl group, a thiol group, and an amine group, may have a hydroxyl group, a thiol group And at least one of the substituents in the amine group Hydantoin which may have at least one kind of substituents of a hydroxyl group, a thiol group and an amine group, and a hydrocarbon compound having at least one kind of substituents selected from a hydroxyl group, a thiol group and an amine group , Trihydroxyethyl isotricyanate, Thiamine, and a reactant of at least one compound (hereinafter, also referred to as "compound (M1)" in some cases) among polyether polyols

     [Reactant (II)]     

Hydroxyl-containing elastomeric polymer (hereinafter, also referred to as "elastomeric polymer (E2)" depending on the situation), and has two or more selected from carboxyl, alkoxysilyl, and isocyanate groups Reactants of at least one selected compound (hereinafter, also referred to as "compound (M2)" depending on the situation)

     [Reactant (III)]     

Elastomer polymer containing carboxyl group (hereinafter also referred to as "elastomeric polymer (E3)" depending on the situation), and has two or more selected from hydroxyl, thiol and amine groups Reactant of at least one kind of substituent compound (hereinafter, referred to as "compound (M3)" depending on the situation)

     [Reactant (IV)]     

Elastomer polymers containing amine groups (hereinafter, also referred to as "elastomeric polymers (E4)" depending on the situation), and have two or more carboxyl, epoxy, and alkoxysilyl groups And a reactant of at least one selected from isocyanate groups (hereinafter, referred to as "compound (M4)" depending on the case)

     [Reactant (V)]     

An alkoxysilyl-containing elastomeric polymer (hereinafter, also referred to as "elastomeric polymer (E5)" depending on the situation), and has more than two hydroxyl groups, carboxyl groups, and amine groups. Reactants of at least one selected compound (hereinafter, referred to as "compound (M5)" depending on the situation)

[Reactant (VI)] An epoxy-containing elastomeric polymer (hereinafter, referred to as "elastomeric polymer (E6)" depending on the situation), and has two or more thiol groups And a reactant of a compound selected from at least one of the amine groups (hereinafter, referred to as "compound (M6)" depending on the case).

The elastomeric polymers (E1) to (E6) can be performed according to a usual method, for example, on a polymer that can form the main chain part of the above-mentioned elastomer component, according to the usual conditions, for example, via Stirring under heating, etc., can be prepared by introducing a functional group-compatible compound (for example, maleic anhydride, etc.) according to the purpose design, and performing graft polymerization. These elastomeric polymers (E1) to (E6) can also be used in the market.

The glass transition points of the elastomeric polymers (E1) to (E6) are the same as those of the aforementioned elastomer, and preferably 25 ° C or lower. When the glass transition point of the elastomeric polymer is within this range, the obtained thermoplastic elastomer composition of the present invention can exhibit rubber-like elasticity at room temperature. The preferred range of the weight average molecular weight of the main chain portions of the elastomeric polymers (E1) to (E6) is the same as that of the main chain portions of the aforementioned elastomeric polymers (A) and (B). The preferred range of the weight average molecular weight is the same.

These maleic anhydride-denatured elastomeric polymers (E1) are, for example, maleic anhydride-denatured isoprene rubbers such as LIR-403 (manufactured by Kurare), LIR-410A (trial by Kurare), and Nucrel (Mitsui DuPont Poly Chemicals Co., Ltd.), Ukuron (Mitsubishi Chemical Co., Ltd.), Tafmer M (for example, MP0610 (Mitsui Chemical Co., Ltd.), MP0620 (Mitsui Chemical Co., Ltd.)), maleic anhydride modified ethylene-propylene rubber; Tafmer M ( For example, MA8510, MH7010, MH7020 (manufactured by Mitsui Chemicals), MH5010, MH5020 (manufactured by Mitsui Chemicals), MH5040 (manufactured by Mitsui Chemicals), etc., maleic anhydride-denatured ethylene-butene rubber; Adtex series (maleic anhydride Modified EVA, maleic anhydride modified EMA (manufactured by Japan Polyolefin Corporation)), HPR series (maleic anhydride modified EEA, maleic anhydride modified EVA (manufactured by Mitsui ‧ DuPont Polyolefins)), Bondfast series (maleic anhydride modified EMA (Manufactured by Sumitomo Chemical Co., Ltd.)), Dumine series (maleic anhydride modified EVOH (manufactured by Takeda Pharmaceutical Industry Co., Ltd.)), Bondine (ethylene, acrylate, maleic anhydride terpolymer (manufactured by Adfina)), Tuftec (Malay (Anhydride denatured SEBS, M1943 (manufactured by Asahi Kasei Corporation)) Kuradon (maleic anhydride-denatured SEBS, FG1901, FG1924 (manufactured by Kuradon Polymers)), Tufprene (maleic anhydride-denatured SBS, 912 (manufactured by Asahi Kasei Corporation)), Septon (maleic anhydride-denatured SEPS (manufactured by Kurare)), Luxpal (maleic anhydride denatured EVA, ET-182G, 224M, 234M (manufactured by Japan Polyolefin Corporation)), Aurrene (maleic anhydride denatured EVA, 200S, 250S (manufactured by Nippon Paper Chemical Co., Ltd.)), etc. Ethylene; maleic anhydride-denatured polypropylene such as Admer (for example, QB550, LF128 (manufactured by Mitsui Chemicals)); and the like.

In addition, these maleic anhydride-denatured elastomeric polymers (E1) are preferably a maleic anhydride-denatured ethylene-propylene rubber and a maleic anhydride-denatured ethylene-butene rubber from the viewpoint of high molecular weight and high strength.

The hydroxyl-containing elastomeric polymer (E2) is, for example, a hydroxyl-containing BR, a hydroxyl-containing SBR, a hydroxyl-containing IR, a hydroxyl-containing natural rubber, a polyvinyl alcohol, an ethylene vinyl alcohol copolymer, and the like.

Among these hydroxyl-containing elastomeric polymers (E2), from the viewpoint of industrial availability and excellent physical properties, elastomeric polymers that form hydroxyl groups at both ends are preferred. Among them, hydroxyl-containing BR A hydroxyl-containing IR or ethylene vinyl alcohol copolymer is preferred, and a hydroxyl-containing BR is more preferred.

The carboxyl group-containing elastomeric polymers (E3), for example, carboxyl group-containing BR, carboxyl group-containing SBR, carboxyl group-containing IR, carboxyl group-containing natural rubber, polyacrylic acid, ethylidene acrylic copolymer, polymethyl Acrylic acid, ethylene methacrylic acid copolymer, etc.

These carboxyl group-containing elastomeric polymers (E3) are preferably industrially available and have excellent physical properties. The carboxyl group-containing IR, ethyl methacrylate copolymer, and ethylene methacrylic acid copolymer are preferred. The IR of the carboxyl group is preferred.

In addition, the amine group-containing elastomeric polymers (E4) include, for example, amine group-containing BR, amine group-containing SBR, amine group-containing IR, amine group-containing natural rubber, and amine group-containing Polyethyleneimine and so on.

The amine group-containing elastomeric polymer (E4) is preferably an amine group-containing polyethyleneimine from the viewpoint of being easily obtained industrially and having excellent physical properties.

The amine group-containing elastomeric polymer (E4) has an amine value of preferably 1 to 50 mmol / g, more preferably 5 to 40 mmol / g, and even more preferably 10 to 30 mmol / g. When these amine values do not reach the aforementioned lower limit, they must be added in a large amount, and the physical properties tend to be lowered due to a decrease in the crosslink density. In addition, when the amine value is exceeded, the addition of only a small amount tends to cause the crosslink density to become too high. As these amine valences, values measured by a potentiometric titration method can be used.

The alkoxysilyl group-containing elastomeric polymers (E5) include, for example, alkoxysilyl group-containing BR, alkoxysilyl group-containing SBR, alkoxysilyl group-containing IR, Natural rubber of alkoxysilyl group, polyethylene containing alkoxysilyl group, polypropylene containing alkoxysilyl group, etc.

The alkoxysilyl group-containing elastomeric polymer (E5) is preferably an alkoxysilyl group-containing polyethylene from the viewpoint of industrial availability and excellent physical properties.

The epoxy-based elastomeric polymers (E6) are, for example, epoxy-containing BR, epoxy-containing SBR, epoxy-containing IR, epoxy-containing natural rubber, and the like.

The epoxy group-containing elastomeric polymer (E6) is preferably an epoxy group-containing SBR from the viewpoint of being easily obtained industrially and having excellent physical properties.

In addition, as the hydrocarbon compounds having at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, and an amine group, these compounds (M1) include, for example, the aforementioned polyalcohol compound, polythiol compound, polyalcohol Among the amine compounds, the main skeleton is formed from a hydrocarbon compound. The hydrocarbon group of these main skeletons is preferably an aliphatic hydrocarbon compound (more preferably, an aliphatic hydrocarbon compound having 1 to 30 carbon atoms). In addition, as these hydrocarbon compounds (M1), hydrocarbon compounds having at least one kind of substituent selected from a hydroxyl group, a thiol group, and an amine group are easily obtained industrially and have excellent high cross-linking density. From the viewpoint, pentaerythritol, ethanedithiol, and ethanediamine are preferred, and pentaerythritol is more preferred.

In addition, as the compound (M2), the compound having at least one substituent selected from the group consisting of a carboxyl group, an alkoxysilyl group, and an isocyanate group, the aforementioned polycarboxyl compound and polyalkoxysilyl group can be suitably used. Of the compounds and polyisocyanate compounds, 2,6-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, and xylene diisocyanate (XDI) are preferred from the viewpoint of being easily available industrially and having excellent physical properties.

In addition, as the compound (M3), the above-mentioned polyalcohol compound, polythiol compound, polythiol compound, polythiol compound, polythiol compound, or polyhydric compound may be suitably used as the compound having at least one kind of substituent selected from a hydroxyl group, a thiol group, and an amine group. Among the amine compounds, trihydroxyethyl isocyanurate, 2,4-diamino-6-phenyl-1,3,5-trisyl are commercially available and have excellent physical properties. Tri-[(3-hydrothiopropylammoniumoxy) -ethyl] -isotricyanate is preferred.

As the compound (M4), the compound having at least one substituent selected from the group consisting of a carboxyl group, an epoxy group, an alkoxysilyl group, and an isocyanate group, the aforementioned polycarboxyl compound, poly Among the epoxy compounds, polyalkoxysilyl compounds, and polyisocyanate compounds, 2,6-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, and tri- (2,3-Epoxypropyl) -isotricyanate is preferred.

As the compound (M5), the above-mentioned polyalcohol compound and polycarboxyl compound can be suitably used as a compound having at least one kind of substituent selected from a hydroxyl group, a carboxyl group, and an amine group. Among them, industrially, From the viewpoint of easy availability and excellent physical properties, trihydroxyethyl isocyanurate, 2,6-pyridinedicarboxylic acid, and 2,4-pyridinedicarboxylic acid are preferred.

In addition, as the compound (M6), the compound having two or more substituents selected from at least one of a thiol group and an amine group, the aforementioned polythiol compound and polyamine compound can be suitably used, and further, Tris-[(3-Hydroxythiopropionyloxy) -ethyl] -isotricyanate, 2,4-diamino-6-phenyl-1,3,5-tris Is better.

The main chains of the elastomeric polymers (E1) to (E6) are the same as the descriptions of the main chains of the elastomeric polymers (A) and (B) (the better ones are also the same). Content). Among the elastomeric polymers (E1) to (E6) used in the production of each of these reactants, the functional group (maleic anhydride group, hydroxyl group, carboxyl group, amine group, alkoxysilyl group) of each polymer, Epoxy group) reacts with the substituents of the compounds (M1) to (M6) used in the production of each reactant to form a compound derived from the main skeleton of the compounds (M1) to (M6) The structure of the side chain has no change in the main chain before and after the basic reaction, so the main chains of the aforementioned reactants (I) to (VI) (the main chains of the aforementioned elastomeric polymers (A) and (B)) , Is produced from the main chain of the elastomeric polymers (E1) to (E6).

In addition, among these reactants (I) to (VI), from the viewpoint of being easily obtained industrially and having excellent physical properties, the contents are listed in the examples (in each of the examples described later, Tables 1 and 2 are described). Elastomer component) is preferred.

In addition, the aforementioned reactant (I) is industrially easy to obtain, and has a high balance of mechanical strength and compression set. In order to use a maleic anhydride-denatured elastomeric polymer, it may have a hydroxyl group or a thiol group. Triazole with at least one kind of substituent in amine group, pyridine which may have at least one kind of substituent in hydroxyl group, thiol group and amine group, substitution with at least one kind of hydroxyl group, thiol group and amine group Thiadiazole, imidazole which may have at least one kind of substituent of hydroxyl group, thiol group and amine group, isotricyanate which may have at least one kind of substituent group of hydroxyl group, thiol group and amine group Three of the substituents which may have at least one of a hydroxyl group, a thiol group and an amine group Hydantoin, trihydroxyethyl isocyanurate, thiocarbamide, and polyether polyalcohol, which may have at least one of a hydroxyl group, a thiol group, and an amine group as a substituent. The reactants of the compounds are preferred.

In addition, since the polymer contained in the aforementioned elastomer component does not have a double bond, it is not easily deteriorated, causing isocyanurate rings to each other and the isocyanurate ring and other hydrogen bonding sites, or From the viewpoints of interaction with the aforementioned hydrogen-bonding components and the like, it is preferable that the main chain of the polymer is an olefin copolymer, and the side chain of the polymer has an isocyanurate ring. The polymers whose main chain is an olefin-based copolymer and whose side chain has an isocyanurate ring, for example, maleic anhydride-denatured elastomeric polymer formed from an olefin-based copolymer obtained by denaturing maleic anhydride The reactants (more preferably maleic anhydride-denatured ethylene-propylene rubber, maleic anhydride-denatured ethylene-butene rubber) and the reaction product of trihydroxyethyl isotricyanate are preferred examples.

When the polymer contained in the elastomer component is as described above, when the main chain is an olefin-based copolymer and the side chain has an isotricyanate ring, the polymer is included in the infrared absorption spectrum of the thermoplastic elastomer composition. An olefin-based resin (herein referred to as an "olefin-based resin" is an olefin-based copolymer containing the aforementioned elastomer component as a polymer main chain. For example, as an additive component, it does not have chemical bonding properties. In the case of an α-olefin-based resin at a coupling site, or in a case where the elastomer component contains a plurality of polymers and the main chain of one of the polymers is formed from an olefin-based resin other than an olefin-based copolymer, the aforementioned "olefin-based resin "Resin" includes all olefin-based resins included in the reaction system (a-olefin-based resins having no cross-linking sites having chemical bonding properties, olefin-based copolymers forming a main chain, and olefin-based copolymers forming a main chain). Absorptive intensity (A) of a peak near a wavelength of 2920 cm ^-1 derived from CH stretching vibration of an olefin-based resin, etc.), and a wavelength of 1695 cm derived from a carbonyl group in the aforementioned isocyanurate ring The ratio of the absorption intensity (B) of the peak near ^-1 ([Absorption intensity (B)] / [Absorption intensity (A)]) is 0.01 or more (more preferably 0.012 to 10, more preferably 0.015 to 5) as good. If the intensity ratio of the intensity of the peak (A) to the intensity of the peak (B) in these infrared absorption spectra (IR spectra) does not reach the aforementioned lower limit, the side chain having an isotricyanate ring in the composition will be reduced. There is a ratio, and because the crosslink density in the reaction system decreases, physical properties such as mechanical strength tend to decrease. When the strength ratio exceeds the upper limit, too many branches of the elastomer component in the reaction system cause the crosslink density of the entire reaction system to decrease, which tends to lower the mechanical properties. In addition, the infrared absorption spectrum (IR spectrum) of these thermoplastic elastomer compositions is an IR measurement device (for example, "NICOLET380" manufactured by Thermo Co., Ltd.) having a total reflection unit, and the polymer (mainly A polymer having a chain of an olefin-based copolymer and an isotricyanate ring in a side chain. The thermoplastic elastomer composition (40 g of the polymer contained in the aforementioned elastomer component) is added with a thickness of 2 mm in order to smooth the surface. The measurement sample prepared by compression molding is determined by measuring the infrared absorption spectrum (infrared attenuated total reflection (FTIR-ATR) spectrum) of the wave number value of 400 to 4000 cm ^-1 using the total reflection measurement (ATR) method. The pattern of the obtained absorption spectrum. Through the plurality of measured, infrared iso cyanurate ring in the side chain carbonyl group absorption spectrum a peak appeared in the vicinity of a wavelength of 1695cm ^-1 (approximate range of 1690 ~ 1700cm ^-1), the composition of the olefin-based composition The peak of the infrared absorption spectrum of the CH stretching vibration of the resin (the olefin-based copolymer including the main chain (base polymer) described above) appears at a wavelength of around 2920 cm ^-1 (a range of approximately 2910 to 2930 cm ^-1 ).

In addition, a maleic anhydride-denatured elastomeric polymer (more preferably a maleic anhydride-denatured ethylene-propylene rubber or a maleic anhydride-denatured ethylene-butene rubber) formed from a maleic anhydride-denatured olefin-based copolymer, and As an example, a reaction product of trihydroxyethyl isocyanurate and a thermoplastic elastomer composition not containing other olefin resins will be described as an example. In the production of the reaction product, maleic anhydride-denatured elastomer properties The acid anhydride group in the polymer reacts with the hydroxyl group of trihydroxyethyl isocyanurate to form a side chain, which is formed by introducing an isocyanurate ring on the side chain of the polymer, but as described above generally, the peak due to infrared iso cyanurate ring in the side chain of the polymer (reaction product) of the carbonyl group of the derivative absorption spectrum appears in wavelength around 1695cm ^-1 (1690 ~ ^-1 range of 1700 cm), additionally , derived from the CH stretching vibrations of the polymer (reaction product) of the backbone (the base polymer) of the olefin-based copolymer wavelength peaks appeared in the vicinity of 2920cm ^-1 (2910 ~ ^-1 range of 2930 cm), containing the so In the aforementioned composition of the reactant, obtain a wavelength of 1695c. When the intensity ratio of a peak near m ^-1 to a peak near wavelength 2920 cm ^-1 is obtained, it can be known that a side chain of an isocyanurate ring is introduced into the aforementioned polymer (reactant) (in the case exemplified above, Basically, the side chain formed is a ratio having both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site, etc., and the cross-link density of the entire reaction system can be analogized by this method. In addition, other circumstances containing olefin resin (e.g., containing the later case α- olefin-based resin having no crosslinked by chemical bonding of the parts, etc.), is obtained in the vicinity of the peak wavelength of 1695cm ^-1, a wavelength 2920cm ^{- When} the intensity ratio of the peaks near ¹ is known, the ratio of the side chain with an isotricyanate ring introduced relative to the total amount of the olefin resin present in the reaction system can be obtained, and the reaction system can be analogized. Crosslink density of the whole. Therefore, when these strength ratios are higher than the aforementioned lower limit, the proportion of the side chains having isocyanurate rings is extremely sufficient, and the reaction system as a whole can have a sufficient crosslinking density, so that it can be obtained Physical properties such as sufficient mechanical strength.

The method for manufacturing the elastomeric polymers (A) to (B) is not particularly limited. As described above, the side chain (a); the side chain (a ') and the side chain (b); And, at least one selected from the side chain (c); a known method that can be introduced as a side chain of an elastomeric polymer having a glass transition point of 25 ° C. or lower as appropriate. For example, a method described in JP-A-2006-131663 for producing an elastomeric polymer (B) can be used. When the elastomeric polymer (B) having a side chain (a ') and a side chain (b) is to be prepared as described above, for example, the side chain may have a cyclic acid anhydride group as a functional group. (E.g., maleic anhydride group), an elastomeric polymer, and a compound that reacts with the cyclic acid anhydride group to form a covalently-bondable cross-linking site (a compound that forms a covalently-bonded), and The method in which the cyclic acid anhydride group reacts to form a mixture (mixed raw material) of a compound (compound obtained by introducing a nitrogen-containing heterocyclic ring) at a hydrogen-bondable cross-linking site, and simultaneously introduces each side chain.

Further, as a method for producing these elastomeric polymers (A) to (B), for example, an elastomeric polymer having a functional group (for example, a cyclic acid anhydride group) in a side chain (for example, an elastomer Polymers (E1) to (E6) are preferred examples), and the elastomeric polymer can react with the aforementioned functional group to form a hydrogen-bondable cross-linking site compound, and can interact with the aforementioned functional group At least one kind of raw material compound (e.g., the aforementioned compound (M1) among compounds that react to form a hydrogen-bondable cross-linking site and a compound that can react with the functional group to form a covalently-bondable cross-linking site. ) ~ (M6) are preferred examples) to react to produce the elastomeric polymer having the aforementioned side chain (a); the elastomeric polymer having the side chain (a ') and the side chain (b); and And / or a method of an elastomeric polymer (the aforementioned elastomeric polymers (A) to (B)) having the side chain (c). In addition, the conditions (temperature conditions, environmental conditions, etc.) used in these reactions are not particularly limited, and they can be combined with a functional group or a compound that reacts with the functional group (a compound that forms a hydrogen-bondable crosslinking site and The type of the compound that forms a covalently-bondable cross-linking site may be appropriately set. In the case of the aforementioned elastomeric polymer (A), a monomer having a hydrogen bonding site may be polymerized to obtain the polymer.

An elastomeric polymer having these functional groups (such as a cyclic acid anhydride group) on its side chain to form a polymer of the main chain of the aforementioned elastomeric polymers (A) to (B), and the side chain has a functional group Those are better. The "elastomeric polymer containing a functional group in its side chain" means that the atoms forming the main chain form a chemically stable bond (covalent bond) with a functional group (such as the above-mentioned functional group, such as a cyclic acid anhydride group). The meaning of the elastomeric polymer is also a polymer obtained by reacting an elastomeric polymer (such as a known natural polymer or a synthetic polymer) with a compound obtained by introducing a functional group.

In addition, these functional groups are bonded to form at least one selected from the group consisting of amidine, ester, lactone, urethane, ether, thiocarbamate, and thioether. Functional groups are preferred, among which cyclic acid anhydride groups, hydroxyl groups, amine groups, carboxyl groups, isocyanate groups, and thiol groups are preferred. From the viewpoint that the components added to the composition can be more efficiently dispersed, It is particularly preferable to use a cyclic acid anhydride group. These cyclic acid anhydride groups are preferably succinic acid anhydride groups, maleic acid anhydride groups, glutaric acid anhydride groups, and phthalic acid anhydride groups. Among them, it is easy to introduce polymer side chains, and it is easy to obtain them industrially. Maleic anhydride groups are preferred. In the case where the functional group is a cyclic acid anhydride group, for example, a cyclic acid anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and derivatives thereof can be used as the compound into which the functional group is introduced. It is also possible to introduce a functional group into an elastomeric polymer (for example, a known natural polymer or synthetic polymer).

The compound capable of reacting with the functional group to form a hydrogen-bondable cross-linking site is not particularly limited, and the above-mentioned "a compound that forms a hydrogen-bondable cross-linking site (a compound obtained by introducing a nitrogen-containing heterocyclic ring) is used. Better. In addition, the compound that can react with the functional group to form a covalently-bondable cross-linking site is not particularly limited, and the above-mentioned "a compound that forms a covalently-bondable cross-linking site (a compound that forms a covalently-bonded link)" is used. Better. Compounds that form hydrogen-bonding cross-linking sites (compounds obtained by introducing nitrogen-containing heterocycles) and compounds that form covalently-bonding cross-linking sites (compounds that form covalent bonds) can also be used as appropriate. A compound that reacts with the functional group to form both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site (for example, a polyalcohol, a polyamine, and a polythiol containing a nitrogen-containing heterocyclic ring).

Furthermore, in the method for producing these elastomer components (elastomer polymers (A) to (B)), an elastomer polymer having a functional group (for example, a cyclic acid anhydride group) in a side chain is used, and the elastomer Polymer, and a compound capable of reacting with the aforementioned functional group to form a hydrogen-bondable crosslinking site, and a compound capable of reacting with the aforementioned functional group to form a hydrogen-bondable crosslinking site, and capable of reacting with the aforementioned functional group At least one of the raw material compounds among the mixed raw materials of the compounds forming the covalently-bondable cross-linking site is reacted to prepare the elastomeric polymer (A) having the side chain (a). In the method of the above-mentioned elastomeric polymer (B) having a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site, an elastomeric polymer having a functional group in a side chain may be used to react with the aforementioned raw material compound. Previously, a method of mixing an additive component with an elastomeric polymer having a functional group in a side chain, and then adding the aforementioned raw material compound to perform a reaction to form an elastomer while producing an elastomer component (adding an additive component first Methods).

In addition, from the viewpoint of improving the dispersibility of the added ingredients and obtaining a higher degree of heat resistance, when manufacturing elastomer components (elastomer polymers (A) to (B)), the added ingredients can be used first. It is better to disperse the added ingredients when manufacturing the elastomer components.

When manufacturing the aforementioned reactants (I) to (VI) as the aforementioned elastomer component (elastomer polymers (A) to (B)), the method is not particularly limited, and it can be appropriately used, for example, appropriately The elastomeric polymers (E1) to (E6) are selected appropriately, and the compounds (M1) to (M6) that react with them are reacted in an appropriate manner to form a side chain of the intended design to obtain a reactant (I). Method of (VI). These reaction conditions (temperature conditions, environmental conditions, etc.) can be combined with the functional groups or main chains of the elastomeric polymers (E1) to (E6) as raw materials of the reactants to be prepared. The type can be appropriately set according to the types of the compounds (M1) to (M6) to be reacted.

When producing these reactants (I) to (VI), for example, according to the purpose design, a polymer appropriately selected from elastomeric polymers (E1) to (E6) is added to a pressure kneader and stirred. In addition, a compound appropriately selected from the compounds (M1) to (M6) used for the reaction with the polymer is added, and the reaction is performed to obtain the compound. At this time, the temperature used for the reaction can be appropriately adjusted. Just set it. When producing the above-mentioned reactants (I) to (VI), a polymer appropriately selected from the elastomeric polymers (E1) to (E6) used for producing the reactants (I) to (VI) may be used. Before reacting with the compound selected from the aforementioned compounds (M1) to (M6), the polymer is mixed with the added ingredients, and then the aforementioned compounds are added to make the reaction, and the elastomer component can be manufactured at the same time , The method of forming the composition (the method of adding ingredients first). From the viewpoint of further improving the dispersibility of the additive components and obtaining higher heat resistance, in the case of manufacturing a composition containing the reactants (I) to (VI), it is also necessary to use the first addition of the aforementioned additive components. The method is better.

     (Add ingredients)     

The thermoplastic elastomer composition of the present invention, in combination with the aforementioned elastomer components, contains expanded graphite, carbon nanotubes, fullerene, graphene, silicate-based natural nanofibers, and silsesquioxane. At least one selected additive ingredient in a group of alkane and layered titanate compounds.

The expanded graphite used as an additive is not particularly limited, and a known expanded graphite can be used. Among them, the expanded graphite may be a graphite that expands when subjected to heat, and it may be suitably used as an intercalation compound that can be intercalated in graphite (for example, natural scaly graphite, pyrolytic graphite, kish graphite, etc.). And other substances. Compounds that can be inserted between these graphite layers include, for example, acids such as sulfuric acid and nitric acid, or mixtures of these acids. For these expanded graphites, commercially available products can be used as appropriate. For example, EXP-50 series and EXP-80 series manufactured by Fuji Graphite Industry Co., Ltd .; 953240 series, 9550 series, and 9510 series manufactured by Ito Graphite Industry Co., Ltd .; Kore Chemical 5099SS-3, 60CA-60 manufactured by the company; SMF, EMF, SFF, SS manufactured by Sino-Vietnam Graphite Industry Corporation; etc.

The expanded graphite is preferably powdered, and its average particle diameter is preferably 0.1 to 100 nm, and more preferably 1 to 80 nm. When these average particle diameters do not reach the aforementioned lower limit, they tend to be difficult to disperse due to excessive fineness, which tends to reduce physical properties. On the other hand, when they exceed the aforementioned upper limit, foreign matter may be formed due to excessively large particles, and a source of damage may be formed. On the other hand, there is a tendency that the physical properties such as stretching are lowered.

In addition, the nano carbon tube as the additive component includes, for example, a single-walled carbon nanotube and a multi-walled carbon nanotube. From the viewpoint of producing higher physical properties, these nano carbon tubes are preferably single-walled carbon tubes.

The nano carbon tubes are preferably those having an average diameter of 0.1 to 100 nm (more preferably 0.4 to 50 nm). When these average particle diameters do not reach the aforementioned lower limit, they tend to be difficult to disperse due to excessive fineness, which tends to reduce physical properties. On the other hand, when they exceed the aforementioned upper limit, foreign matter may be formed due to excessively large particles, and a source of damage may be formed. On the other hand, there is a tendency that the physical properties such as stretching are lowered. The nano-carbon tubes are preferably those having an average length of 1 nm to 1 mm (more preferably 10 to 100 nm). The nano-carbon tubes preferably have a length-to-diameter ratio of 1 to 1000 (more preferably 10 to 100). When the length or aspect ratio does not reach the aforementioned lower limit, it is difficult to disperse due to excessive fineness, and physical properties tend to decrease. On the other hand, when it exceeds the aforementioned upper limit, foreign matter may be formed due to excessively large amounts, and a source of damage may be formed. Point, there is a tendency that the physical properties such as stretching are lowered. These nano carbon tubes can be appropriately used commercially, for example, ED, EP, HP manufactured by Ba Industry Co., Ltd .; EC1.0, EC1.5, EC2.0 manufactured by Mingcheng Nano Carbon Co., Ltd .; Marubeni Information 9000, 9100, 9110 manufactured by System Corporation; Zeonano SG101 manufactured by Zeon Corporation of Japan; these dispersions or polymer master batches; etc.

In addition, the aforementioned fullerene as an additive is not particularly limited, and a known substance can be appropriately used. These fullerenes are composed of only a large number of carbon atoms forming a closed-cell cavity, and are collectively referred to as clusters. The fullerenes are, for example, fullerenes formed by carbon clusters of C60, C70, C76, C78, C82, C84, C90, C94, and C96. Among these fullerenes, C60 fullerene, C70 fullerene, and a mixture of the above fullerenes (a mixture of C60 fullerene and C70 fullerene) are considered from the viewpoint of industrial availability and low cost. Preferably, a mixture of the aforementioned fullerenes is particularly preferred. In addition, as these fullerenes, commercially available products can be appropriately used, and for example, nano series made by Frontier Carbon can be used.

The aforementioned graphene as an additive component is not particularly limited, and a known graphene can be appropriately used. From the viewpoint of high dispersibility and higher strength of these graphene, it is preferable to use graphene nano particles (graphene nano powder). The average particle diameter of these graphene nano particles is preferably 0.1 to 1000 nm, and more preferably 1 to 300 nm. When these average particle diameters do not reach the aforementioned lower limit, they tend to be difficult to disperse due to excessive fineness, which tends to reduce physical properties. On the other hand, when they exceed the aforementioned upper limit, foreign matter may be formed due to excessively large particles, and a source of damage may be formed. On the other hand, there is a tendency that the physical properties such as stretching are lowered.

In addition, as for these graphene, commercially available articles can be appropriately used, for example, graphene powder on scales manufactured by XG Sciences; nanographene aqueous solution manufactured by NanoIntegris; graphene oxide G-GOSiO‧ manufactured by Graphos; Sol-GO‧GO; functional graphene oxides Rap GO, Rap bGO, Metal / GO, Rap rGO manufactured by NiSiNa Materials; graphene nano powder manufactured by EM Japan; graphene manufactured by Wako Pharmaceuticals; etc.

The aforementioned silicate-based natural nanofibers as an additive component are not particularly limited, and natural nanofibers formed from a well-known silicate can be appropriately used. These silicates are natural nanofibers, for example, silicates (filament alumina (Imogolite)) represented by the formula: SiO ₂ ‧Al ₂ O ₃ ‧2H ₂ O, Al ₂ SiO ₃ (OH) ₄ ), Formula: (Mg, Al) ₂ [Si ₄ O ₁₀ ] (OH) -4H ₂ O silicate (Palygorskite), formula: SiO ₂ ‧Al ₂ O ₃ Silicate (Allophane) and the like.

These silicate-based natural nanofibers are preferably those having an average diameter (average outer diameter) of 0.1 to 10 nm (more preferably 1 to 7 nm). When the silicate-based natural nanofibers have a hollow shape, the average diameter of the inner diameter (average of the inner diameter) is preferably 0.1 to 8 nm (more preferably 0.3 to 6 nm). When the diameters do not reach the aforementioned lower limit, they tend to be difficult to disperse due to excessive fineness, which tends to reduce physical properties. On the other hand, when the diameter exceeds the aforementioned upper limit, foreign matter may be formed due to excessively large diameters, and a source of damage may be formed. There is a tendency to cause reduction in stretched physical properties and the like. The silicate-based natural nanofibers are preferably those having an average length of 1 nm to 5 μm (more preferably 5 nm to 3 μm). The silicate-based natural nanofibers preferably have a length to diameter ratio of 1 to 1,000 (more preferably 10 to 100). When the length or aspect ratio does not reach the aforementioned lower limit, it is difficult to disperse due to excessive fineness, and physical properties tend to decrease. On the other hand, when it exceeds the aforementioned upper limit, foreign matter may be formed due to excessively large amounts, and a source of damage may be formed. Point, there is a tendency that the physical properties such as stretching are lowered.

These silicate-based natural nanofibers are preferably made of filiform alumina (Imogolite), palygorskite (palygorskite), and filiform alumina (Imogolite) from the viewpoint of industrial availability and low cost. ) Is particularly good. In addition, these silicate-based natural nanofibers can be appropriately used in the market. For example, Trompa manufactured by Astec, deer marsh for gardening, and the like can be used.

The aforementioned silsesquioxane as an additive component is a siloxane-based compound having a main chain skeleton formed of Si-O bonds, and preferably has a silsesquioxane structure represented by the following formula. -(RSiO _3/2 ) _n- [In the formula, R represents an alkyl group which may have a substituent, and n represents an integer].

It may also be in the form of a polymer. The alkyl groups as R in the formulas in these silsesquioxane structures are preferably those having 1 to 30 carbon atoms, and more preferably those having 1 to 20 carbon atoms. When these carbon numbers do not reach the aforementioned lower limit, they tend to decompose due to instability and tend to be difficult to cooperate. On the other hand, when the carbon number exceeds the aforementioned upper limit, the steric hindrance is too large, which reduces the interaction with the siloxane bond. It is not easy to disperse, and when the molecule is too large, the source of foreign matter formation and damage will be formed, and there will be a tendency to reduce tensile properties and the like. Examples of the substituents of the alkyl group as R in the formulas in these silsesquioxane structures include methyl, ethyl, propyl, hexyl, phenyl, and vinyl.

In addition, the integer represented by n in these silsesquioxane structures is preferably 2 to 100, and more preferably 8 to 50. When these integers n do not reach the aforementioned lower limit, they will form a liquid, and they will not function as fillers. On the other hand, when they exceed the aforementioned upper limit, foreign matter will be formed due to excessively large amounts, and the source of damage will be formed. There is a tendency to cause deterioration of stretched physical properties and the like.

The silsesquioxane is preferably in the form of particles, and its average particle diameter is preferably 0.1 to 300 nm, and more preferably 0.5 to 100 nm. When these average particle diameters do not reach the aforementioned lower limit, they tend to be difficult to disperse due to excessive fineness, which tends to reduce physical properties. On the other hand, when they exceed the aforementioned upper limit, foreign matter may be formed due to excessively large particles, and a source of damage may be formed. On the other hand, there is a tendency that the physical properties such as stretching are lowered. These silsesquioxanes can be appropriately used in the market. For example, KMP-590 and KMP-591 manufactured by Shin-Etsu Polysilicon; SST series manufactured by Azmax; and Sigma-Aldrich manufactured POSS; etc.

In addition, the aforementioned layered titanic acid compound as an additive is not particularly limited, and a known substance can be appropriately used. Examples of these layered titanic acid compounds include compounds represented by the following formula: M _l Ti _n O _m [wherein M represents a metal and l, n, and m represent an integer of 1 to 30].

The plurality of layered titanic acid compound, e.g., potassium titanate K ₂ Ti ₆ O _13, barium titanate BaTiO _3, strontium titanate SrTiO _3, calcium titanate CaTiO _3, magnesium titanate MgTiO _3, lead titanate PbTiO _3, Aluminum titanate Al ₂ TiO ₅ , lithium titanate Li ₄ Ti ₅ O ₁₂ and the like. These layered titanic acid compounds are preferably particles, and the average particle diameter is preferably 0.1 to 500 nm, and more preferably 0.5 to 300 nm. When these average particle diameters do not reach the aforementioned lower limit, they tend to be difficult to disperse due to excessive fineness, which tends to reduce physical properties. On the other hand, when they exceed the aforementioned upper limit, foreign matter may be formed due to excessively large particles, and a source of damage may be formed. On the other hand, there is a tendency that the physical properties such as stretching are lowered. In addition, as for these layered titanic acid compounds, commercially available products can be suitably used, for example, Tismo, Terras, and DentellWK manufactured by Otsuka Chemical Co., Ltd .; SW-100, SW-300, TC-100 manufactured by Titanium Industry Co., Ltd. can be used; Titanic acid compounds manufactured by Fuji Titanium Industries; titanic acid compounds manufactured by Koji Chemical Industries; etc.

These additional ingredients may be used singly or in combination of two or more kinds. Among these expanded graphites, carbon nanotubes, fullerenes, graphene, silicate-based natural nanofibers, silsesquioxane, and layered titanic acid compounds, it is industrially easy. From the viewpoints of acquisition, low cost, etc., expanded graphite and layered titanate compounds are preferred, and expanded graphite is more preferred.

     (Composition)     

The thermoplastic elastomer composition of the present invention includes the aforementioned elastomer component and the aforementioned additive component.

In addition, the thermoplastic elastomer composition of the present invention has extremely high tensile strength (tensile strength using 100% modulus and breaking strength as indicators), and the reason for having extremely high abrasion resistance is still Although it is not clear, the present inventors speculate that it is as follows. That is, the inventors speculated that, first, in the present invention, the elastomer component is an elastomeric polymer containing at least a side chain having a hydrogen-bondable cross-linking site (the side chain contains a side chain (a); the side Chain (a ') and side chain (b); and a polymer of at least one of side chain (c)). Therefore, first of all, these elastomeric polymers can be combined with the aforementioned additive components, or interactions between the additive components via hydrogen bonding, etc., can be more uniformly and highly dispersed in the polymer. Therefore, in these reaction systems, the aforementioned additive component which is highly dispersed and the hydrogen-bondable cross-linking site interact with the elastomer by introducing the surface of the aforementioned component as an additive component through interaction (formation of a new hydrogen bond, etc.). The ingredients form surface cross-links. As mentioned above, the aforementioned added components are those in which any one can form a surface cross-linking between the hydrogen-bondable cross-linking sites (a so-called surface cross-linking agent). Therefore, when these surface cross-links are formed, stress concentration at the cross-linking points can be suppressed, and when compared with the case where the aforementioned additive component is not contained, a higher breaking strength (tensile strength until breaking) can be obtained. In addition, as shown above, the interaction with the hydrogen-bondable cross-linking site (formation of a new hydrogen-bond, etc.) through the aforementioned highly dispersed additive component in the reaction system enables interaction with the hydrogen-bondable cross-linking site. The formed crosslinking density is more uniform, and stress concentration at the crosslinking point can be suppressed, and a composition with higher abrasion resistance can be formed.

On the other hand, if at least one of the elastomeric polymers (A) and (B) having a hydrogen-bonding crosslinking site in the side chain is not used as the elastomer component, and only other elastomer components are used For example, when used in combination with the aforementioned added ingredients, as mentioned above, effective effects cannot be obtained. When researching and reviewing this point, first, general thermoplastic elastomers can be distinguished into the form of pseudo-crosslinking (interactions via intermolecular forces of polymers, etc.) caused by physical interactions between polymer molecular chains. Forms with weak physical bonds) and two forms of dispersed rubber in the matrix of thermoplastic resin. Typical objects using these pseudo-crosslinked thermoplastic elastomers are, for example, polymers with soft segments and hard segments, such as block polymers or urethane elastomers. Among them, as described above, when a polymer having a side chain is not introduced, but only a thermoplastic elastomer having a pseudo-crosslinking form is used, when the filler such as the aforementioned additive component is added, the interaction at the pseudo-crosslinking point (high The physical interaction between molecules and molecular chains) is hindered by the aforementioned added components, but it will cause the mechanical strength of the polymer to decrease, and cannot reach the level of use as a rubber product. As described above, when a conventional thermoplastic elastomer formed of a thermoplastic elastomer using only pseudo-crosslinked form is simply combined with the aforementioned additive component, the composition will hinder the pseudo-crosslinking. Formation while reducing the mechanical strength (tensile stress, etc.) of the composition. Moreover, in the matrix of a thermoplastic resin, in the form of a rubber-dispersed thermoplastic elastomer, it is known from this composition that fillers such as the aforementioned additive components can be introduced only in the form of a matrix phase. Among them, a matrix formed of a thermoplastic resin without the above-mentioned side chains does not form an interaction with the aforementioned added components in the matrix. Therefore, simply introducing the aforementioned added ingredients will result in a state where a high concentration of the aforementioned added ingredients is introduced in one part, while another part is not introduced at all. As a result, based on the difference in the concentration of the added components, a difference in hardness will be generated inside the elastomer, and the mechanical strength and the like will be reduced instead. Therefore, in the case of a thermoplastic elastomer in which a rubber is dispersed in the matrix of the thermoplastic resin, when the side chain does not contain a polymer having a hydrogen-bondable cross-linking site, even when the aforementioned additive component is simply introduced, the aforementioned additive component In addition, it cannot be sufficiently dispersed, and the mechanical strength (such as breaking strength) of the composition is reduced. Based on these viewpoints, the present inventors speculate that when the elastomeric polymers (A) and (B) are not used as the elastomer component of the matrix, no interaction will occur except for the aforementioned added components. In addition, due to the presence of the aforementioned additive components, the mechanical strength is reduced, and it is impossible to achieve sufficient characteristics as an elastomer (rubber).

In addition, in the present invention, the present inventors have discovered that when the side chain contains an elastomer component containing a covalently-bondable cross-linking site (for example, when the elastomeric polymer (B) is contained), the covalent-bondable cross-linking is included. When the side chain of the part, it can produce a higher level of compression and permanent deformation resistance. In addition, when there are hydrogen-bondable cross-linked sites and covalently-bonded cross-linked sites in the elastomer component (in the case where the elastomeric polymer (B) is contained, the elastomeric polymer (B) and other elastomeric properties are included) In the case of a mixture of polymers, in the case of a mixture containing an elastomeric polymer (A) and an elastomeric polymer (B), the use of a polymer other than the elastomeric polymer (A) and the elastomeric polymer (B) In the case of a mixture of an elastomeric polymer having a side chain (b), etc., based on the existence of a hydrogen-bondable cross-linked site and a covalently-bonded cross-linked site, a covalent bond can be generated at the same time during use. The higher mechanical strength generated by the junction and the higher fluidity (moldability) produced by the hydrogen bonding through cracking upon heating. Therefore, the present inventors speculate that the composition can be appropriately changed according to the type of the side chain, and the characteristics required for the combined use can be appropriately exhibited. As described above, the elastomeric polymer having a side chain (b) other than the elastomeric polymer (B) may be an elastomeric polymer having a functional group (for example, a cyclic acid anhydride group) in the side chain. By reacting the elastomeric polymer with a compound that can react with the functional group to form a covalently-bondable cross-linking site (a compound that forms a covalent bond) to produce a polymer having the side chain (b) It can be prepared by the aforementioned method of an elastomeric polymer. In this case, as the compound that forms a covalently-bonded cross-linking site (a compound that forms a covalent bond), the aforementioned "a compound that forms a covalently-bond cross-linking site (a compound that forms a covalent bond) can be used. ".

In the above, in order to explain the reasons for the effect of the present invention that can be achieved through the thermoplastic elastomer composition of the present invention, the preferred embodiment of the thermoplastic elastomer composition of the present invention (appropriate conditions for the content ratio of each component) will be described below. Etc.).

The thermoplastic elastomer composition of the present invention includes the aforementioned elastomer component and the aforementioned additive component. Among them, in the thermoplastic elastomer composition of the present invention, the content of the aforementioned additive component (when it contains a plurality of components in a combination of two or more types is the total amount of these components), relative to 100 parts by mass of the aforementioned elastomer component, is 20 parts by mass or less. When the content of these added components exceeds the above-mentioned upper limit, excessive dispersion may easily cause poor dispersion or the formation of foreign matter, which may cause reduction in tensile strength and the like. The content (total amount) of the added components in these thermoplastic elastomer compositions is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and 1 to 100 parts by mass of the aforementioned elastomer component. ~ 3 parts by mass are particularly good. When the content of these added ingredients does not reach the aforementioned lower limit, there is a tendency that a sufficient effect cannot be obtained because the content of the added ingredients is too small. On the other hand, when the content exceeds the aforementioned upper limit, the crosslinking will be too strong, which will result in elongation. The degree or strength is reduced, and it is difficult to be used for various applications (the practicality is lowered).

In addition, when the added ingredients are multi-layered ingredients, it is preferable that they are present in the composition in the form of a single layer. The existence state of these single-layered added components can be confirmed by measuring the surface of the composition using a transmission electron microscope (TEM).

In addition, the thermoplastic elastomer composition of the present invention can be appropriately blended with the type of the elastomer component to be used to impart properties to the application. For example, when a thermoplastic elastomer composition using an elastomeric polymer (A) as an elastomer component can impart properties derived from the side chain (a) to the composition, in particular, it can increase the elongation at break, the strength at break, Liquidity, etc. In addition, when an elastomeric polymer (B) is used as a thermoplastic elastomer composition of the elastomer component, the properties derived from the covalently-bondable cross-linking sites in the side chains can be imparted to the composition, so that it can be particularly improved. Resistance to compression set (resistance to compression set). In addition, in the case of a thermoplastic elastomer composition containing an elastomeric polymer (B) as an elastomer component, in addition to the characteristics derived from the covalently-bondable cross-linking site in the composition, hydrogen-bondable cross-linking can also be imparted. The properties derived from the site (the hydrogen-bondable cross-linking site described in the side chain (a ')) can be maintained in the state of fluidity (formability), and the compression permanent deformation resistance can be further increased, which can increase the By appropriately changing the type of the side chain or the type of the polymer (B), the characteristics expected from the application can be utilized more efficiently.

In addition, the thermoplastic elastomer composition of the present invention can separately produce a thermoplastic elastomer composition using an elastomeric polymer (A) as an elastomer component and a thermoplastic elastomer composition using an elastomeric polymer (B) as an elastomer component. After the thermoplastic elastomer composition, these are mixed, and the elastomer component is a thermoplastic elastomer composition containing elastomeric polymers (A) and (B). In the present invention, the elastomer component is only required to contain at least the elastomeric polymers (A) and (B), but there are covalently bonded cross-linking sites in the composition, and the co-efficient From the viewpoint of the characteristics of the valence-bondable crosslinking site, it may be used in combination with other elastomeric polymers having side chains (b) other than the elastomeric polymer (B). For example, when a combination of an elastomeric polymer (A) with an elastomer component and another elastomeric polymer having a side chain (b) other than the elastomeric polymer (B) is used, and its use A thermoplastic elastomer composition containing an elastomeric polymer (B) having a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site in a side chain derived from a side chain contained in the composition can give almost the same Of characteristics. In addition, when the elastomer component is produced as a thermoplastic elastomer composition containing the elastomeric polymers (A) and (B), or when it is produced other than the elastomeric polymer (A) and the elastomeric polymer (B) In the case of a thermoplastic elastomer composition of another elastomeric polymer having a side chain (b), each component (e.g., the elastomeric polymer (A) and the elastomeric polymer (B) Ratio of each component) to properly exhibit desired characteristics.

In the case where the thermoplastic elastomer composition of the present invention contains the elastomeric polymers (A) and (B) as an elastomer component, the elastomeric polymers (A) and the elastomeric polymers (B) The content ratio is preferably 1: 9 to 9: 1, and more preferably 2: 8 to 8: 2 according to the mass ratio ([Polymer (A)]: [Polymer (B)]). When the content of these polymers (A) does not reach the aforementioned lower limit, the fluidity (moldability) and mechanical strength tend to be inadequate. In addition, when the content exceeds the aforementioned upper limit, the resistance to compression set is reduced. tendency.

In addition, the thermoplastic elastomer composition of the present invention is an elastomer having a side chain (b) other than the elastomeric polymer (B) containing the elastomeric polymer (A) and further containing another polymer. In the case of an elastomeric polymer (hereinafter, also referred to as "elastomeric polymer (C)" depending on the situation), the content ratio of the elastomeric polymer (A) to the elastomeric polymer (C) depends on the quality The ratio ([elastomeric polymer (A)]: [elastomeric polymer (C)]) is preferably 1: 9 to 9: 1, and more preferably 2: 8 to 8: 2. When the content ratio of these polymers (A) does not reach the aforementioned lower limit, the fluidity (moldability) and mechanical strength tend to be inadequate. On the other hand, when it exceeds the aforementioned upper limit, the resistance to permanent compression deformation may become insufficient. Declining tendency.

In addition, in the thermoplastic elastomer composition of the present invention, there may be both a side chain (a ') and a side chain (b) in the composition, and the total amount of the side chain (a') and the amount of the side chain (b) The total amount is based on the mass ratio, preferably 1: 9 ~ 9: 1, and more preferably 2: 8 ~ 8: 2. When the total amount of these side chains (a ') does not reach the aforementioned lower limit, the fluidity (moldability) and mechanical strength tend to be inadequate. On the other hand, when the aforementioned upper limit is exceeded, the resistance to permanent compression deformation may become insufficient. Declining tendency. In addition, these side chains (a ') are a concept including a side chain (a). Therefore, when only the side chain (a) of the side chain (a ') is contained, it is preferable that the above-mentioned mass ratio is such that both the side chain (a) and the side chain (b) are present in the composition.

In addition, the thermoplastic elastomer composition of the present invention can be blended with necessity to contain polymer components other than the aforementioned elastomer component (hereinafter, also simply referred to as "his polymer"), paraffin, as long as the purpose of the present invention is not impaired. Oil, reinforcing agent (filler), hydrogen-bonding reinforcing agent (filler), fillers obtained by introducing amine groups (hereinafter, also referred to as "amine-based introduction fillers"), and fillers introduced into the same Compounds containing amine groups, compounds containing metal elements (hereinafter also simply referred to as "metal salts"), maleic anhydride-denatured polymers, anti-aging agents, antioxidants, pigments (dye), other than the aforementioned paraffin oils Plasticizers, shakers, UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, rust inhibitors, adhesives, antistatic agents, clays, organic clays, Various additives such as antibacterial agents, antifungal agents, fillers, etc. These additives and the like are not particularly limited, and generally used ingredients (known ingredients) can be appropriately used. For example, the paraffin oil, the reinforcing agent, the anti-aging agent, the antioxidant, the pigment (dye), the plasticizer, and the like of the other polymers mentioned above can suitably use the components described below.

As the other polymers, other elastomeric polymers having a side chain (b) other than the elastomeric polymer (B) can be used as appropriate; an α-olefin resin having no chemically bonding cross-linking site ; A styrene block copolymer having no cross-linking site for chemical bonding; etc. The "chemically-bonded cross-linking site" as used herein refers to a site where cross-linking is formed by chemical bonding such as hydrogen bonding or covalent bonding. Therefore, the term “crosslinking site having no chemical bonding” as used in the present invention refers to a state in which no crosslink is formed through chemical bonding (for example, hydrogen bonding, covalent bonding, etc.).

These α-olefin-based resins having no chemically-bonded cross-linking sites (hereinafter also referred to simply as "α-olefin-based resins without chemically-bonding cross-linking sites") can be suitably used through chemical bonding. And the formation of the cross-linking point does not contain functional groups (for example, hydroxyl, carbonyl, carboxyl, thiol, amido, and amine), and does not contain bonding sites (via Valence bonds, etc.). In addition, these α-olefin-based resins having no chemically-bondable cross-linking sites do not have at least the side chain (a), the side chain (a '), the side chain (b), and the side chain ( c) and other polymers.

The "α-olefin resin" referred to herein means a homopolymer of an α-olefin and a copolymer of an α-olefin. The term "α-olefin" refers to an olefin having a carbon-carbon double bond at the α position (an olefin having a carbon-carbon double bond at the end: the olefin may be linear or branched). It is also possible to use a carbon number of 2 to 20 (more preferably 2 to 10), for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -Octene, 1-nonene, 1-decene and the like.

These α-olefin-based resins having no cross-linking sites having chemical bonding properties are not limited as long as they are polymers of α-olefins (polyα-olefins: either homopolymers or copolymers). There are special restrictions, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, propylene-ethylene-butene copolymer, and the like. Among these α-olefin-based resins having no chemically-bondable cross-linking sites, polypropylene, polyethylene, and ethylene-propylene copolymers are preferred from the viewpoint of compatibility with the elastomer as a matrix. These α-olefin-based resins having no chemically-bonding crosslinking sites may be used alone or in combination of two or more.

These α-olefin resins having no cross-linking sites having chemical bonding properties are preferably those having a crystallinity of 10% or more, more preferably 10 to 80%, and even more preferably 10 to 75%. When the degree of crystallization does not reach the aforementioned lower limit, the properties of the resin are extremely low. Therefore, it is difficult to use it to produce a higher degree of mechanical properties and fluidity. On the other hand, when it exceeds the aforementioned upper limit, due to the resin The properties are too strong, so there is a tendency that it is not easy to make mechanical properties balanced and fully exerted at a higher level. These crystallinity degrees are measured using an X-ray diffraction device (for example, a measurement device manufactured by Scientific Corporation under the trade name "MiniFlex300") to measure diffraction peaks and calculate the number of scattering peaks due to crystallinity / amorphity. Points can be obtained.

The α-olefin-based resins having no chemically bonded cross-linking sites have a melt flow rate (MFR) of 190 ° C and a load of 2.16 kg measured based on JIS K6922-2 (issued in 2010). ) Is preferably 40 g / 10 minutes or more. When the melt flow rate (MFR) does not reach the aforementioned lower limit, even if it is added to the composition, it tends to be difficult to improve the fluidity. The melt flow rate (MFR) is a value measured based on the B method described in JIS K6922-2 (issued in 2010). The melt flow rate measurement device is a product name manufactured by Toyo Seiki. "Melt Indexer G-01", after adding 3 g of the aforementioned α-olefin-based resin to the furnace of the device, the temperature was maintained at 190 ° C for 5 minutes, and then maintained at 190 ° C under the condition of a load of 2.16 kg. At the opening of a cylindrical opening member with a diameter of 1 mm and a length of 8 mm at the bottom of the furnace body, the mass (g) of the composition flowing out within 10 minutes was measured (in the furnace body, the temperature was 190 ° C). After holding for 5 minutes, the load was started, and the mass of the flowing elastomer was measured.

In addition, the weight-average molecular weight (Mw) of the α-olefin-based resin having the aforementioned cross-linking site having no chemical bonding is preferably 10,000 or more and 2 million or less, and more preferably 30,000 or more and 1.5 million or less. More than 50,000 and less than 1.25 million are more preferred. When these weight average molecular weights do not reach the aforementioned lower limit, their mechanical strength tends to decrease. On the other hand, when they exceed the aforementioned upper limit, the compatibility with the elastomer components is reduced, and phase separation tends to occur easily.

The number-average molecular weight (Mn) of the α-olefin-based resin having no cross-linking site having a chemical bond is preferably 10,000 or more and 2 million or less, and more preferably 30,000 or more and 1.5 million or less. More than 50,000 and less than 1.25 million are more preferred. When the number average molecular weight does not reach the aforementioned lower limit, the mechanical strength tends to decrease. On the other hand, when it exceeds the aforementioned upper limit, the compatibility with elastomer components is reduced, and phase separation tends to occur easily.

In addition, the dispersion degree (Mw / Mn) of the molecular weight distribution of the α-olefin resin having the aforementioned cross-linking site having no chemical bondability is preferably 5 or less, and more preferably 1 to 3. When the values of the dispersion (Mw / Mn) of these molecular weight distributions do not reach the aforementioned lower limit, the fluidity tends to decrease. On the other hand, when the aforementioned upper limit is exceeded, the compatibility with the elastomer component tends to decrease.

In addition, as described above, the so-called gel permeation chromatography (GPC) of the weight average molecular weight (Mw) of the α-olefin resin or the number average molecular weight (Mn) and the dispersion (Mw / Mn) of the molecular weight distribution can be used. ) Method. The specific apparatus and conditions for measuring these molecular weights and the like are those using a "Prominence GPC system" manufactured by Shimadzu Corporation.

The glass transition point of the aforementioned α-olefin-based resin having no chemically-bonded crosslinking site is preferably -150 to 5 ° C, and more preferably -125 to 0 ° C. When the glass transition point does not reach the aforementioned lower limit, the heat resistance tends to decrease due to the melting point being too low. On the other hand, when it exceeds the aforementioned upper limit, the rubber elasticity after the addition of the elastomer component tends to decrease easily. . The "glass transition point" referred to herein is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry), as described above. In these DSC measurements, the temperature increase rate is preferably 10 ° C / min.

There is no particular limitation on the method for producing these α-olefin-based resins having no chemically-bonded crosslinking sites, and known methods can be suitably used. These α-olefin-based resins may also be commercially available products. For example, a brand name "Tafmer" manufactured by Mitsui Chemicals Co., Ltd., and a product name "Novatec HD" "Novatec LD" manufactured by Japan Polyethylene Corporation may be appropriately used. "Novatec LL" "Kernel"; trade names "Hynex", "Neonex", "Ult-Zex", "Evolue", "Primepolypro", "Polyfine" and "Moston L" manufactured by Prime Polymer Corporation; PP manufactured by Sunallomer, etc.

In the case where the thermoplastic elastomer composition of the present invention further contains the aforementioned α-olefin-based resin having no cross-linking site having chemical bonding, the content of the aforementioned α-olefin-based resin having no cross-linking site having chemical bonding ( Content ratio), with respect to 100 parts by mass of the aforementioned elastomer component, preferably 800 parts by mass or less, more preferably 5 to 700 parts by mass, even more preferably 10 to 600 parts by mass, and 25 to 500 parts by mass Good, preferably 50 to 400 parts by mass. When the content of the α-olefin-based resin having no chemically-bonded crosslinking sites does not reach the aforementioned lower limit, the fluidity tends to decrease. On the other hand, when it exceeds the aforementioned upper limit, the compression set tends to decrease. .

In the case where the thermoplastic elastomer composition of the present invention further contains the aforementioned α-olefin-based resin having no chemically-bondable cross-linking site, the above-mentioned α-olefin-based resin without the chemically-bondable cross-linking site. The content is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, and even more preferably 5 to 70% by mass relative to the total amount of the foregoing composition. When the content of the α-olefin-based resin having no chemically-bonded crosslinking sites does not reach the aforementioned lower limit, the fluidity tends to decrease. On the other hand, when it exceeds the aforementioned upper limit, the compression set tends to decrease. .

In addition, the other polymers described above are preferably styrene block copolymers having a cross-linking site having no chemical bonding, from the viewpoint that they are components that do not interfere with the cross-linking reaction of the elastomer as a matrix. In addition, the present inventors believe that when these styrene block copolymers are used, they basically do not interfere with the cross-linked structure of the elastomeric polymer (the aforementioned elastomer component) as a matrix or the cross-linking during manufacture. Reaction, etc., so it will not hinder the original physical properties of the crosslinked elastomer structure as the parent, but can maintain the state derived from the aforementioned elastomer components sufficiently, so that the Excellent mechanical properties (especially tensile properties, compression set, etc.) are reflected (contributed) to the thermoplastic elastomer composition of the present invention, and polymers with higher properties can be produced.

The aforementioned styrenic block copolymers which are suitable as a component of the thermoplastic elastomer composition of the present invention are those having no cross-linking sites having chemical bonding properties. The term “without a chemically-bonding cross-linking site” herein has the same meaning as that described in the aforementioned α-olefin resin. Therefore, as the styrene block copolymer having no cross-linking site having chemical bonding properties, a functional group (for example, a hydroxyl group, a carbonyl group, a carboxyl group, a thiol group, a fluorene group, or a fluorene group) that does not have a cross-linking point through chemical bonding can be suitably used. Amine group, amine group), and does not contain a bonding site (such as a cross-linking site via a covalent bond) where the polymer chains are directly cross-linked to each other. In addition, these styrene block copolymers which do not have a crosslinkable site having chemical bonding properties have at least no side chains (a), (a '), (b), and side chains as described above. (c) and other polymers.

The "styrene block copolymer" referred to herein may be a polymer having a styrene block structure at any position. In general, a styrene block copolymer may have a styrene block structure, and at normal temperature, the styrene block structure is aggregated to form a physical cross-linking point (pseudo-physical cross-linking point). In addition, upon heating, the pseudo-physical cross-linking point is thermoplastic and has rubber-like properties (elasticity, etc.) at room temperature.

In addition, these styrene block copolymers that do not have chemically-bonded cross-linking sites (hereinafter, depending on the situation, are also simply referred to as "styrene block copolymers that do not have chemically-bonded cross-link sites" ), From the viewpoint of both rubber elasticity and thermoplasticity, styrene-isoprene-styrene block copolymer (SIS), styrene-vinyl-propylene-styrene block copolymer (SEPS), Styrene-vinyl-vinyl-propenyl-styrene block copolymer (SEEPS), styrene-butadiene-styrene block copolymer (SBS), styrene-vinyl-butenyl-benzene Ethylene block copolymers (SEBS), styrene-isoprene-butadiene-styrene block copolymers (SIBS), and these hydrides (ie, hydrides) are preferred. SEBS and SEEPS are preferred. Better. These styrene block copolymers may be used singly or in combination of two or more kinds.

The styrene block copolymer having a cross-linking site having no chemical bond is preferably a styrene block copolymer having a styrene content of 20 to 40% by mass (more preferably 25 to 37% by mass). When the styrene content does not reach the aforementioned lower limit, the thermoplasticity tends to decrease due to a decrease in the styrene block component. On the other hand, when it exceeds the aforementioned upper limit, the rubber elasticity tends to decrease due to the decrease in the olefin component. The styrene content in these styrene block styrene block copolymers can be measured by a method based on the IR method described in JIS K6239 (issued in 2007).

In addition, the weight average molecular weight (Mw) of the aforementioned styrene block copolymer having no cross-linking site having chemical bonding properties is preferably 200,000 or more and 700,000 or less, and more preferably 300,000 or 600,000 or less, More than 350,000 and less than 550,000 are more preferred. When these weight average molecular weights do not reach the aforementioned lower limit, the heat resistance tends to decrease. On the other hand, when they exceed the aforementioned upper limit, the compatibility with the elastomeric polymer tends to decrease.

The number average molecular weight (Mn) of the aforementioned styrene block copolymer having no cross-linking site having chemical bonding properties is preferably 100,000 or more and 600,000 or less, and more preferably 150,000 or more and 550,000 or less. More than 200,000 and less than 500,000 is more preferable. When the number average molecular weight does not reach the aforementioned lower limit, the heat resistance tends to decrease. On the other hand, when it exceeds the aforementioned upper limit, the compatibility with the elastomeric polymer (the elastomer component) tends to decrease.

The molecular weight distribution dispersion (Mw / Mn) of the aforementioned styrene block copolymer having no crosslinkable site having chemical bonding is preferably 5 or less, and more preferably 1 to 3. The weight average molecular weight (Mw) or the number average molecular weight (Mn) and the dispersion (Mw / Mn) of the molecular weight distribution can be obtained by a gel permeation chromatography (GPC) method. For specific devices or conditions for measuring such molecular weights, the "Prominence GPC system" manufactured by Shimadzu Corporation can be used.

In addition, the glass transition point of the aforementioned styrene block copolymer having no cross-linking site having chemical bonding properties is preferably -80 to -40 ° C, and more preferably -70 to -50. When these glass transition points do not reach the aforementioned lower limit, the heat resistance tends to decrease due to the melting point being too low. On the other hand, when the aforementioned upper limit is exceeded, the rubber elasticity tends to decrease. The "glass transition point" referred to herein is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry), as described above. In these DSC measurements, the temperature increase rate is preferably 10 ° C / min.

The method for producing the aforementioned styrene block copolymer having no cross-linking site having chemical bonding properties is not particularly limited, and a known method can be suitably used. These styrenic block copolymers may also be commercially available. For example, the product names "G1633", "G1640", "G1641", "G1642", "G1643", "G1645", "G1650") manufactured by Kuradon Corporation can be used as appropriate. "G1651" "G1652" "G1654" "G1657" "G1660"; Kurare's product names "S4055" "S4077" "S4099" "S8006" "S4044" "S8006" "S4033" "S8004" "S8007" "S8076"; product names "TuftecH1041" "TuftecN504" "TuftecH1272" "TuftecM1911" "TuftecM1913" "TuftecMP10" manufactured by Asahi Kasei Corporation; "AR-710" "AR-720" "AR-731" manufactured by Aron Kasei Corporation "AR-741" "AR-750" "AR-760" "AR-770" "AR-781" "AR-791"; etc.

In addition, when the thermoplastic elastomer composition of the present invention further contains the aforementioned styrene block copolymer having no cross-linking site having chemical bonding, the aforementioned styrene block copolymer having no cross-linking site having chemical bonding The content (content ratio) is preferably 10 to 400 parts by mass, more preferably 15 to 350 parts by mass, more preferably 20 to 300 parts by mass, and 30 to 100 parts by mass of the aforementioned elastomer component. 250 parts by mass is particularly good. When the content of these styrene block copolymers having no chemically bonded cross-linking sites does not reach the aforementioned lower limit, the content of the styrene block copolymers having no cross-linking sites with no chemical bonding is too small, especially From the viewpoint of fluidity and processability, there is a tendency that a sufficient effect cannot be obtained. On the other hand, when the above-mentioned upper limit is exceeded, the characteristics of the matrix structure formed by the elastomer obtained by cross-linking (derived from the aforementioned elastomer components) Characteristics) tends to decrease.

In addition, in the thermoplastic elastomer composition of the present invention, when the aforementioned styrene block copolymer having no cross-linking site having chemical bonding properties is still contained, the aforementioned styrene block copolymer having no cross-linking site having chemical bonding properties The content is preferably 5 to 60% by mass, more preferably 7 to 45% by mass, and even more preferably 10 to 30% by mass relative to the total amount of the thermoplastic elastomer composition. When the content of these styrene block copolymers which do not have chemically bonded cross-linking sites does not reach the aforementioned lower limit, the content of the aforementioned styrene block copolymer is too small, especially from the viewpoint of flowability and processability. There is a tendency that a sufficient effect cannot be obtained. On the other hand, when the above-mentioned upper limit is exceeded, the characteristics of the matrix structure formed by the elastomer obtained by crosslinking (the characteristics derived from the aforementioned elastomer component) tend to decrease.

In the thermoplastic elastomer composition of the present invention, the other polymer is, for example, the α-olefin-based resin having no cross-linking site having chemical bonding properties and the styrene having no cross-linking site having chemical bonding properties. In addition to the block copolymer, other types of polymers may be appropriately used. These other kinds of polymers, for example, polytetrafluoroethylene (PTFE), polyisobutylene, polymethyl methacrylate, polystearyl methacrylate, polybutyl methacrylate, polypropyl methacrylate, Fluorine rubber, polysiloxane (MQ), oxidized polypropylene, polydimethylsiloxane, butyl rubber (IIR), polyvinyl chloride, natural rubber (NR), polyisoprene (IR: isoprene Diene rubber), polybutadiene (BR: butadiene rubber), styrene butadiene rubber (SBR), polystyrene, and the like.

In addition, the aforementioned paraffin oil can be used as other components (additives) contained in the thermoplastic elastomer composition of the present invention from the viewpoints that various physical properties of the composition are not reduced and fluidity is further improved. In addition, when these paraffin oils are used in combination with the aforementioned styrenic block polymer, the oil component can be absorbed into the block polymer, and the processability can be improved by simultaneously adding oil at a very high level (improved Fluidity), and improved mechanical properties with the addition of styrenic block polymers to maintain the mechanical properties or heat resistance more fully, resulting in higher levels of extrusion processability and injection moldability Sex thing. When paraffin oil is used, for example, the shape of the twisted thermoplastic elastomer composition (strand) extruded from the opening of the orifice when it is extruded from a heated orifice (for example, having a 1 mm diameter opening). (Strand shape) has sufficient uniform thickness, so it has a tendency to obtain excellent extrusion processability without surface fluffing. These paraffin oils are not particularly limited, and known paraffin oils can be appropriately used.

Moreover, with respect to these paraffin oils, relative ring analysis (ndM ring analysis) can be performed according to ASTM D3238-85 as a reference, and the percentages of the total carbon number of paraffin carbon numbers (paraffin wax) unit: C _P), the percentage of naphthenic carbon atoms whole number of carbon (cycloalkyl portion: C _N), and, on the percentage of aromatic carbon atoms whole number of carbon (aromatic portion: case C _a) of the It is preferable that the percentage (C _P ) of the total carbon number of the paraffin carbon number is 60% or more.

The paraffin oil has a kinematic viscosity at 40 ° C measured in accordance with JIS K 2283 (issued in 2000), preferably 50 mm ² / s to 700 mm ² / s, and 150 to 600 mm ² / s. It is more preferable, and 300 to 500 mm ² / s is more preferable. When these dynamic viscosities (ν) do not reach the aforementioned lower limit, there is a tendency that oil oozing tends to be caused. On the other hand, when they exceed the aforementioned upper limit, there is a tendency that sufficient fluidity cannot be imparted. The dynamic viscosity of these paraffin oils is a value measured in accordance with JIS K 2283 (issued in 2000) at a temperature of 40 ° C. For example, JIS K 2283 (issued in 2000) can be used as A standard Cannon-Fenske viscometer (for example, "SO series" manufactured by Shibata Scientific Co., Ltd.) automatically measures the value obtained at a temperature of 40 ° C.

The aniline point of these paraffin oils measured using the U-tube method based on JIS K2256 (issued in 2013) is preferably 80 ° C to 145 ° C, more preferably 100 to 145 ° C, and 105 ° C. ~ 145 ° C is better. The aniline point of these paraffin oils is a value measured using the U-tube method based on JIS K2256 (issued in 2013). For example, an aniline point measurement device based on JIS K2256 (issued in 2013) can be used. (E.g., the trade name "aap-6" manufactured by Tanaka Scientific Instruments).

These paraffin oils can be appropriately used in the market. For example, JX Nippon Nissei Energy Co., Ltd.'s trade names "Super-Oil M-series P200", "Super-Oil M-series P400", "Super-Oil M Series P500S"; Idemitsu Kosan's product names "Diana Process Oil PW90", "Diana Process Oil PW150", "Diana Process Oil PW380"; Japan Sun Petroleum Corporation product name "SUNPAR Series ( 110, 115, 120, 130, 150, 2100, 2280, etc. ";" Gargoyle_Arcti series (1010, 1022, 1032, 1046, 1068, 1100, etc.) "made by Mobile; etc .;

In the thermoplastic elastomer composition of the present invention, when the paraffin oil is further contained, the content of the paraffin oil is preferably 10 to 600 parts by mass and 50 to 550 parts by mass relative to 100 parts by mass of the elastomer component. For the better, 75 to 500 parts by mass is more preferred, and 100 to 400 parts by mass is particularly preferred. When the content of these paraffin oils does not reach the aforementioned lower limit, and when the content of paraffin oils is too small, the effects obtained by adding paraffin oils (especially the effects of improving flowability and processability) may not be fully obtained. On the other hand, when the above-mentioned upper limit is exceeded, there is a tendency for paraffin oil to easily bleed out.

In addition, in the thermoplastic elastomer composition of the present invention, when the paraffin oil is further contained, the content of the paraffin oil is preferably 20 to 60% by mass and 25 to 55% by mass relative to the total amount of the thermoplastic elastomer composition. % Is more preferable, and 35 to 55 mass% is more preferable. When the content of these paraffin oils does not reach the aforementioned lower limit, the content of paraffin oil is too small, especially from the viewpoint of fluidity and processability, and there may be a tendency to fail to obtain a sufficient effect. There is a tendency to easily cause paraffin oil to ooze out.

In addition, the thermoplastic elastomer composition of the present invention is, from the viewpoint of improving fluidity and mechanical properties, the α-olefin-based resin containing the aforementioned cross-linking site having no chemical bonding property, the paraffin oil, and the non-chemically bonding property. A combination of styrene block copolymers at the crosslinking site is preferred. That is, the thermoplastic elastomer composition of the present invention includes the α-olefin-based resin containing the elastomer component, the additive component, the cross-linking site having no chemical bonding property, the paraffin oil, and the non-chemically bonding property. A styrene block copolymer at a crosslinking site is preferred.

As described above, when it contains the elastomer component, the additive component, the α-olefin resin, the paraffin oil, and the styrene block copolymer, it has abrasion resistance, breaking strength, and compression resistance. The characteristics such as permanent deformability tend to be exhibited at a higher level and in a balanced manner. Although the reasons for achieving these effects have not yet been confirmed, the inventors speculate that the reasons are as follows. That is, the present inventors speculated that, first, when the paraffin oil and the styrene block copolymer are used in combination, since these are extremely compatible, the reaction system containing the styrene block copolymer includes paraffin oil. Can be fully and uniformly dispersed. In addition, since the styrene block copolymer and the α-olefin-based resin are highly compatible, they can be uniformly dispersed in the reaction system. In the reaction system containing the styrene block copolymer and the α-olefin-based resin, the elastomer component is highly compatible with both, so that the elastomer component is formed in the composition. Fully and evenly dispersed ingredients. In addition, as mentioned above, since the elastomer component and the additive component interact to form surface cross-linking, the additive component may exist in a fully dispersed state with the dispersion of the elastomer component. As described above, in the case where the aforementioned elastomer component, the aforementioned additive component, the aforementioned α-olefin resin, the aforementioned paraffin oil, and the aforementioned styrene block copolymer are contained, each component can be formed in a more fully dispersed state. Therefore, the state of the aforementioned elastomer component, which has a strong influence on the properties of the thermoplastic elastomer composition, can be sufficiently dispersed in a state where the aforementioned added components interact (a state in which a stronger bond is formed through surface cross-linking), thereby achieving Balanced and full use of higher mechanical strength or heat resistance. In addition, in these reaction systems, a higher degree of fluidity (fluidity during heating) can be achieved by the reason of the aforementioned α-olefin-based resin. The mechanical strength of the styrene block copolymer can be adjusted to the desired mechanical properties because the mechanical strength can be adjusted through the amount of addition. Therefore, in the reaction system containing the elastomer component, the additive component, the α-olefin-based resin, the paraffin oil, and the styrene block copolymer, it is possible to obtain a sufficiently high level and achieve a balanced performance. Effects such as abrasion resistance, tensile strength, compression set resistance, etc.

The thermoplastic elastomer composition of the present invention may further include the aforementioned reinforcing agent (filler), and examples thereof include carbon black, silicon dioxide, and calcium carbonate. Silica dioxide is preferred to use wet silica.

As the anti-aging agent, for example, compounds such as hindered phenol, aliphatic and aromatic hindered amines can be suitably used. As the antioxidant, for example, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), and the like can be suitably used. In addition, as the pigment, for example, inorganic pigments such as titanium oxide, zinc oxide, ultramarine, iron oxide red, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate can be suitably used. Organic pigments such as azo pigments, copper phthalocyanine pigments, etc., and the aforementioned plasticizers, for example, benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, decyl Derivatives such as diacid, fumaric acid, maleic acid, itaconic acid, citric acid, etc., to polyesters, polyethers, epoxy systems, etc. In addition, the plasticizer (softener) can appropriately use a component that can be used for a thermoplastic elastomer from the viewpoint of further improving fluidity, for example, an oil can be used. These additives and the like can be appropriately used as exemplified in Japanese Patent Application Laid-Open No. 2006-131663.

In addition, the thermoplastic elastomer composition of the present invention comprises an α-olefin-based resin containing the elastomer component, the additive component, the cross-linking site having no chemical bondability, the paraffin oil, and the compound having no chemical bondability. In the case of components other than the styrene block copolymer at the crosslinking site (for example, the aforementioned additives, etc.), the content of the aforementioned other components is not particularly limited. In the case of polymers or reinforcing materials (fillers), With respect to 100 parts by mass of the aforementioned elastomer component, it is preferably 400 parts by mass or less, and more preferably 20 to 300 parts by mass. When the content of these other ingredients does not reach the aforementioned lower limit, there is a tendency that the effect cannot be fully achieved when other ingredients are used. On the other hand, when it exceeds the aforementioned upper limit, although it varies depending on the types of ingredients used, but There is still a tendency that the effect of the matrix elastomer is reduced, and the physical properties are reduced.

When the other components mentioned above are other additives (in the case of components other than polymers and reinforcing materials (fillers)), the content of the other components is 20 parts by mass relative to 100 parts by mass of the elastomer component, respectively. It is preferably less than or equal to 0.1 parts, and more preferably 0.1 to 10 parts by mass. When the content of these other ingredients does not reach the aforementioned lower limit, there is a tendency that the effect cannot be fully achieved when using other ingredients. On the other hand, when the aforementioned upper limit is exceeded, the reaction to the elastomer of the matrix will have an adverse effect, instead There is a tendency to cause deterioration of physical properties.

After the thermoplastic elastomer composition of the present invention is heated (for example, heated to 100 to 250 ° C.), hydrogen bonding formed at the hydrogen-bondable cross-linking site or other cross-linked structures (including styrene intercalation) In the case of a segmented copolymer, it is softened due to physical dissociation, etc.), and fluidity is imparted. The reason is presumed to be the result of reducing the interaction between the molecules or the side chains formed within the molecule (mainly hydrogen bonding interactions) due to heating. In addition, in the present invention, since the side chain contains at least an elastomer component and the like containing a hydrogen-bondable cross-linking site, after the fluidity is imparted by heating, the hydrogen bond is re-formed due to dissociation when it is left to stand. Bonding and hardening, when having this composition content, the thermoplastic elastomer composition can more efficiently generate recyclability.

In addition, the thermoplastic elastomer composition of the present invention preferably has a melt flow rate (MFR) of 230 g at a load of 10 kg measured at JIS K6922-2 (issued in 2010) of 2 g / 10 minutes or more. It is preferably 4 g / 10 minutes or more, and more preferably 8 g / 10 minutes or more. When the melt flow rate (MFR) does not reach the aforementioned lower limit, there is a tendency that sufficient processability cannot be produced. The melt flow rate (MFR) is a value measured based on the B method described in JIS K6922-2 (issued in 2010). The melt flow rate measurement device is a product name manufactured by Toyo Seiki. "Melt Indexer G-01", after adding 3g of thermoplastic elastomer composition to the furnace of the device, set the temperature to 230 ° C, hold it for 5 minutes, and maintain 230 ° C under the condition of 10kg load by connecting to The opening of a cylindrical opening member with a diameter of 1 mm and a length of 8 mm at the bottom of the furnace body was measured (in the furnace body, the temperature was set to 230 ° C., the load was started after 5 minutes, and the outflow was measured. The mass of the elastomer) was obtained as the mass (g) of the elastomer flowing out within 10 minutes.

In addition, in the thermoplastic elastomer composition of the present invention, the temperature when the weight is reduced by 5% is preferably 320 ° C or more, and more preferably 325 ° C or more. When the temperature at which these weight reductions are reduced by 5% does not reach the aforementioned lower limit, the heat resistance tends to deteriorate. The temperature at which the weight is reduced by 5% can be obtained in the following manner. 10 mg of a thermoplastic elastomer composition is prepared as a measurement sample, and a thermogravimetric measurement device (TGA) is used as the measurement device, and the temperature rise rate is 10 ° C / Heating was performed under the condition of min, and it was measured by measuring the temperature when the initial weight (10 mg) was reduced by 5%.

The thermoplastic elastomer composition of the present invention can be used for various rubber applications by activating rubber elasticity. When it is used as a hot-melt adhesive, or when an additive containing the same is used, heat resistance and recyclability can be improved, which is preferable. The thermoplastic elastomer composition of the present invention can be applied to: hot-melt adhesives or additives containing the same, rubber parts for automobiles, rubber tubes, belts, sheets, shock-resistant rubber, rollers, linings, rubber cloths, sealing materials, Tote bags, cushioning materials, medical rubber (syringe gaskets, sleeves, catheters), gaskets (for home appliances, construction), asphalt modifiers, footwear, jigs, toys, boots, sandals, key pads, gears, PET bottle cap mats, rubber parts for photocopiers, mat materials, coatings, coating materials, printing coatings and other applications.

Specific examples of the aforementioned rubber parts for automatic vehicles include tire parts such as tire treads, automobile frames, sidewalls, linings, pads, and belt parts; radiator grilles for exteriors, side bumpers, Decoration (pillar, rear frame, top of fairing), aero leather kit (air dam, spoiler), wheel cover, air tight strip, belt strip, exhaust seam, air inlet, expansion hood, air vent Parts, anti-collision parts (fenders, side trims, other (windows, covers, belts)), signs; doors, lights, wipers, airtight strips, glass chute, glass chute, etc. Built-in window frame parts; air-conducting rubber tube, cooling rubber tube, brake rubber tube; crankshaft cover, door lever cover, top washer, A / T oil-cooled rubber tube, transmission oil, P / S rubber tube, Lubricating oil parts such as P / S oil seals; fuel rubber parts such as fuel rubber hoses, emission control rubber hoses, feed rubber hoses, diaphragms, etc .; anti-vibration parts such as engine feet and gasoline pump feet; CVJ Sleeves of sleeves, racks, pinion sleeves, etc .; A / C rubber tubes, A / C seals, etc .; Belts, belts and other strip-like parts engine; primer window seal, a vinyl plastisol primer, anaerobic primer, the primer body, like the spot primer based primer; and the like.

In addition, rubber modifiers, such as resins or rubbers that cause cold flow at room temperature or anti-flow agents, can prevent flow or cold flow during extrusion.

The thermoplastic elastomer composition of the present invention has higher tensile properties when it has higher heat resistance and is based on the breaking strength. In addition, in these thermoplastic elastomer compositions, when the composition is changed, necessary characteristics (for example, characteristics such as self-healing properties) suitable for use can be appropriately exhibited. As described above, when the composition is appropriately changed, the use of the thermoplastic elastomer composition can be combined with the necessary characteristics to be properly exerted in a balanced manner. Therefore, as described above, when used in various applications, it can be used in various applications. In accordance with the necessary characteristics required for the application, it is preferable to appropriately change and use the types (compositions) of the components in the composition.

The above is an explanation of the thermoplastic elastomer composition of the present invention. The following content will describe a method that is more suitable for use in the method of manufacturing the thermoplastic elastomer composition of the present invention.

A method suitable for producing the thermoplastic elastomer composition of the present invention includes, for example, an elastomeric polymer (E) having a functional group in a side chain, and an expanded graphite, a carbon nanotube, a fullerene, a graphene, The first step of preparing a mixture by mixing at least one selected ingredient selected from the group consisting of natural nano-fiber, silsesquioxane, and layered titanic acid compound, and in the aforementioned mixture, A compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bondable cross-linking site, and a compound that reacts with the compound (I) and the cyclic acid-anhydride group to form a covalently-bondable cross-linking site ( II) at least one of the raw material compounds (M) in the mixed raw materials, a second step of preparing a thermoplastic elastomer composition through the reaction of the aforementioned elastomeric polymer (E) with the aforementioned raw material compounds (M); Wherein, the aforementioned thermoplastic elastomer composition obtained in the aforementioned second step contains, has a side chain containing "a hydrogen-bondable cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring", and the glass transition point is Elastomers below 25 ℃ The polymer (A) and the group of elastomeric polymers (B) whose side chains contain hydrogen-bondable cross-linking sites and covalently-bondable cross-linking sites and whose glass transition point is 25 ° C or lower are selected At least one kind of elastomer component, and a group consisting of expanded graphite, carbon nanotubes, fullerene, graphene, silicate natural nanofibers, silsesquioxane, and layered titanate compounds A composition selected from at least one selected from the group consisting of 20 parts by mass or less based on 100 parts by mass of the elastomer component, and in the first step, the thermoplastic elastomer The content of the aforementioned additive component in the body composition is in a proportion of 20 parts by mass or less relative to 100 parts by mass of the aforementioned elastomer component. A method of mixing the aforementioned elastomeric polymer (E) with the aforementioned additive component using the aforementioned additive component, etc. . In the following, the methods are divided into the first step and the second step.

     (First step)     

The first step is a step of preparing a mixture by mixing the elastomeric polymer (E) having a cyclic acid anhydride group in a side chain with the aforementioned additive component.

The "elastomeric polymer (E) having a functional group in the side chain" means that a functional group (for example, a cyclic acid anhydride group) on an atom forming a main chain of the polymer forms a chemically stable bond (covalent bond) The meaning of the elastomeric polymer is, for example, a polymer that can form the main chain part of the aforementioned elastomeric polymers (A) to (B), and the introduction of a functional group (for example, a cyclic acid anhydride) may be appropriately used. Group) can be prepared by a method of reacting the compound.

In addition, the polymer that can form these main chain portions may be formed by a polymer that is generally known natural or synthetic polymers and has a glass transition point of room temperature (25 ° C) or lower ( That is, it may be formed by a so-called elastic body), and there is no particular limitation.

Polymers that can form the main chain part of these elastomeric polymers (A) ~ (B), such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene -Diene rubbers such as propylene-diene rubber (EPDM) and their hydrides; ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), chlorosulfonation Polyethylene, acrylic-based rubber, fluororubber, polyethylene rubber, polypropylene rubber and other olefin-based rubber; epichlorohydrin rubber; polysulfide rubber; polysiloxane rubber; urethane rubber; etc.

In addition, the polymers that can form the main chain portion of these elastomeric polymers (A) to (B) can also be elastomeric polymers containing a resin component, for example, hydrogenated polystyrene Elastomer polymers (e.g., SBS, SIS, SEBS, etc.), polyolefin elastomer polymers, polyvinyl chloride elastomer polymers, polyurethane elastomer polymers, polyesters Based elastomeric polymers, polyamine based elastomeric polymers, and the like.

In addition, the polymers that can form the main chain portion of these elastomeric polymers (A) to (B) are composed of diene rubber, diene rubber hydride, olefin rubber, and hydrogenatable polymer. Styrene-based elastomeric polymer, polyolefin-based elastomeric polymer, polyvinyl chloride-based elastomeric polymer, polyurethane-based elastomeric polymer, polyester-based elastomeric polymer, In addition, it is preferable that at least one selected from the polyamide-based elastomeric polymers is formed. In addition, these polymers are preferably a diene rubber from the viewpoint of easy introduction of a maleic anhydride group suitable as a cyclic acid anhydride group, and are preferably an olefin rubber from the viewpoint of aging resistance.

In addition, a compound having the aforementioned functional group (for example, a cyclic acid anhydride group) may be introduced, such as cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and derivatives thereof.

When the elastomeric polymer (E) used in the first step is an elastomeric polymer having a cyclic acid anhydride group in a side chain, the cyclic acid anhydride group includes a succinic anhydride group, a maleic anhydride group, and glutaric acid. An acid anhydride group and a phthalic anhydride group are preferable. Among them, a maleic anhydride group is preferable from the viewpoints of having high reactivity with raw materials and easy availability of industrial raw materials.

In addition, the elastomeric polymer having cyclic acid anhydride groups in the side chain can be carried out according to a conventional method, for example, a polymer that can form a main chain part of the elastomeric polymers (A) to (B). It can be prepared by graft polymerization of a cyclic acid anhydride by stirring under heating under normal conditions, for example. Moreover, as for this elastomeric polymer which has some cyclic acid anhydride group in a side chain, a commercial item can also be used.

Commercially available articles of elastomeric polymers having cyclic acid anhydride groups in this side chain, for example, maleic anhydride-modified isoprene such as LIR-403 (manufactured by Kurare), LIR-410A (trial by Kurare) Rubber; LIR-410 (manufactured by Kurare) and other modified isoprene rubber; Krynac 110, 221, 231 (manufactured by Polysa) and other carboxyl modified nitrile rubber; CPIB (manufactured by Nissho Chemical Co.); HRPIB (Nippon Petrochemical) Carbide-modified polybutene, etc .; Nucrel (manufactured by Mitsui Chemicals Co., Ltd.), Ukuron (manufactured by Mitsubishi Chemical Corporation), Tafmer M (e.g., MP0610 (manufactured by Mitsui Chemicals), MP0620 (Mitsui Chemical Co., Ltd.) )) And other maleic anhydride-denatured ethylene-propylene rubber; Tafmer M (for example, MA8510, MH7010, MH7020 (made by Mitsui Chemicals), MH5010, MH5020 (made by Mitsui Chemicals), MH5040 (made by Mitsui Chemicals)), etc. Maleic anhydride modified ethylene-butene rubber; Adtex series (maleic anhydride modified EVA), ethylene ‧ methacrylate ‧ maleic anhydride copolymer (made by Japan Polyolefin Corporation), HPR series (maleic anhydride modified EEA, Maleic anhydride modified EVA (Mitsui‧DuPont Polyolefin (Manufactured)), Bondfast series (maleic anhydride denatured EMA (manufactured by Sumitomo Chemical Co., Ltd.)), Dumine series (maleic anhydride denatured EVOH (manufactured by Takeda Pharmaceutical Industry Co., Ltd.)), Bondine (ethylene, acrylate, maleic anhydride ternary copolymerization (Adfina company)), Tuftec (maleic anhydride denatured SEBS, M1943 (manufactured by Asahi Kasei Corporation)), Kuradon (maleic anhydride denatured SEBS, FG1901, FG1924 (Kuradon polymer company)), Tufprene (maleic anhydride denatured) SBS, 912 (manufactured by Asahi Kasei Corporation)), Septon (maleic anhydride denatured SEPS (manufactured by Kurare)), Luxpal (maleic anhydride denatured EVA, ET-182G, 224M, 234M (manufactured by Japan Polyolefin Corporation)), Aurrene ( Maleic anhydride modified polyethylene such as maleic anhydride modified EVA, 200S, 250S (manufactured by Nippon Paper Chemical Co., Ltd.); maleic anhydride modified polypropylene such as Admer (e.g., QB550, LF128 (manufactured by Mitsui Chemicals)); etc. .

The elastomeric polymer having cyclic acid anhydride groups in the side chain is preferably a maleic anhydride-denatured elastomeric polymer (E1). Among them, maleic anhydride-denatured polymers are modified from the viewpoint of high molecular weight and high strength. Ethylene-propylene rubber, maleic anhydride-denatured ethylene-butene rubber, and ethylene-methacrylate-maleic anhydride copolymers are preferred. Moreover, the elastomeric polymer which has the said cyclic acid anhydride group in a side chain may be used individually by 1 type, and may use 2 or more types together.

The elastomeric polymer (E) used in the first step is preferably the aforementioned elastomeric polymers (E1) to (E6).

In addition, the aforementioned added ingredients used in the first step are the same as those described in the thermoplastic elastomer composition of the present invention (the better ones are also the same).

In the present invention, as a result of the reaction between the elastomeric polymer (E) and the raw material compound (M) described later, an elastomer component (elastomeric polymer) in the thermoplastic elastomer composition of the final product (target product) is formed. (A) and / or (B)), the main chain portion of the aforementioned elastomeric polymer (E) may be included in the main chain portion of the polymer in the form of the elastomer component.

In the first step, a mixture obtained by mixing the above-mentioned elastomeric polymer (E) and the above-mentioned added components is obtained. When the additive component is added to the elastomeric polymer (E), in order to fully disperse the additive component, the elastomeric polymer (E) may be plasticized in advance, and then the additive component may be added. The method is better.

As mentioned above, the method for plasticizing the aforementioned elastomeric polymer (E) is not particularly limited. For example, it can be appropriately performed at a temperature at which plasticization can be performed (for example, about 100 to 250 ° C). Next, use a roller, kneader, extruder, universal mixer, etc. for simple kneading. The conditions such as the temperature at which these elastomeric polymers (E) are plasticized are not particularly limited, and they can be combined with the types of ingredients (such as the types of elastomeric polymers (E)), etc. , Make the appropriate settings.

In addition, in the manufacturing steps of these mixtures, the content of the aforementioned added components in the finally obtained thermoplastic elastomer composition is 20 parts by mass or less (more preferably 0.1 to 10 parts by mass) relative to 100 parts by mass of the elastomer component. , More preferably 0.5 to 5 parts by mass, particularly preferably 1 to 3 parts by mass), it is preferable to use the aforementioned additive component and mix the aforementioned elastomeric polymer (E) with the aforementioned additive component. When the content of these added ingredients exceeds the aforementioned upper limit, there is a tendency that the elongation or strength will decrease due to excessive cross-linking. On the other hand, when the aforementioned lower limit is not reached, the amount of the aforementioned added ingredients will be too small, and there will be This tends to reduce the effect that can be achieved by using the aforementioned added ingredients.

In addition, in these mixtures, the content of the aforementioned additive components is preferably 20 parts by mass or less, more preferably 0.5 to 5 parts by mass, and 1 to 3 parts by mass relative to 100 parts by mass of the elastomeric polymer (E). Mass parts are better. When these contents do not reach the aforementioned lower limit, the amount of the aforementioned additive component is too small, which tends to reduce the effect that can be achieved by using the aforementioned additive component. On the other hand, when the above-mentioned upper limit is exceeded, the cross-linking is too strong, and the elongation or strength tends to decrease. In addition, when the content of the aforementioned additive components is used, the content of the aforementioned additive components in the finally obtained thermoplastic elastomer composition can be a value within the aforementioned range.

In addition, the amount of the aforementioned additive component used in forming these mixtures is 0.01 g to 2.0 g (more preferably 0.02 to 1.0 g) relative to 1 mmol of the functional group in the elastomeric polymer (E). ) Is preferred. With respect to 1 mmol of the functional groups in these elastomeric polymers (E), when the proportion of the added component does not reach the aforementioned lower limit, the amount of the added component is too small, and the effect tends to decrease. On the other hand, when the above-mentioned upper limit is exceeded, the cross-linking is too strong, and the elongation or strength tends to decrease. In addition, when the content of the additive component is within the range of these ratios, there may be interaction with the functional group guide, and the dispersibility of the aforementioned additive component may be higher.

In addition, in these mixtures, from the viewpoint of increasing fluidity and mechanical strength, an α-olefin-based resin having no crosslinking site having chemical bonding properties, paraffin oil, and a crosslinking site having no chemical binding properties may be further contained. Styrene block copolymer and the like. The α-olefin resin, the paraffin oil and the styrene block copolymer having no chemically-bondable cross-linking sites are respectively related to the above-mentioned thermoplastic elastomer composition of the present invention. The α-olefin resin, paraffin oil, and styrene block copolymers having no chemically-bonded cross-linking sites are the same as described (each of the preferred examples is also Same content).

In addition, as described above, when the α-olefin-based resin and / or paraffin oil and / or the styrene block copolymer having no chemically-bonded crosslinking site are further contained, In the above, the elastomeric polymer (E), the aforementioned additive component, and the α-olefin-based resin and / or paraffin oil and / or the cross-linking site having no chemical bonding There is no particular limitation on the order of addition of the styrene block copolymer. From the viewpoint of increasing the dispersibility of the aforementioned added components, the elastomeric polymer (E) and the α-olefin are prepared. It is preferable that a mixture of the resin and / or the paraffin oil and / or the styrene block copolymer having the cross-linking site having no chemical bonding property is added to the precursor after the precursor.

When the α-olefin-based resin (α-olefin-based resin having no cross-linking site having chemical bonding properties) is contained in the mixture, the content of the α-olefin-based resin is 100 parts by mass relative to the elastomer component, It is preferably 800 parts by mass or less (more preferably 5 to 700 parts by mass, more preferably 10 to 600 parts by mass, particularly preferably 25 to 500 parts by mass, and most preferably 50 to 400 parts by mass). When the content of these α-olefin-based resins exceeds the above-mentioned upper limit, the mechanical properties (breaking strength, compression set) tend to decrease. On the other hand, when the above-mentioned lower limit is not reached, the fluidity tends to decrease. The content of the α-olefin resin in these mixtures is 800 parts by mass or less (more preferably 5 to 700 parts by mass, and more preferably 10 parts by mass) based on 100 parts by mass of the elastomeric polymer (E). ~ 600 parts by mass, particularly preferably 25 ~ 500 parts by mass, and most preferably 35 ~ 400 parts by mass). When the content is less than the aforementioned lower limit, the mechanical properties (fracture strength and compression set) tend to decrease. On the other hand, when the content is below the aforementioned lower limit, the fluidity tends to decrease.

When the paraffin oil is contained in the mixture, the content of paraffin oil is preferably 600 parts by mass or less, more preferably 10 to 600 parts by mass, and 50 to 550 parts by mass relative to 100 parts by mass of the elastomer component. More preferably, 75 to 500 parts by mass is particularly preferred, and 100 to 400 parts by mass is most preferred. In the case where the mixture contains the styrene block copolymer having a cross-linking site having no chemical bondability, it is preferably 600 parts by mass or less, and 10 to 600 parts by mass based on 100 parts by mass of the elastomer component. Preferably, 15 to 550 parts by mass is more preferred, 20 to 500 parts by mass is particularly preferred, and 30 to 400 parts by mass is most preferred.

In addition, when the application of the finally obtained thermoplastic elastomer composition is blended, the compound may further contain the elastomer component, the α-olefin-based resin, and the styrene block as long as the purpose of the present invention is not impaired. Polymers other than copolymers, reinforcing agents (fillers), fillers obtained by introducing amine groups (hereinafter, also referred to simply as "amine-based introduction fillers"), amine-containing groups other than fillers into which amine groups are introduced Compounds, compounds containing metal elements (hereinafter also simply referred to as "metal salts"), maleic anhydride-denatured polymers, anti-aging agents, antioxidants, pigments (dyes), plasticizers, shakers, ultraviolet absorbers , Flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, antirust agents, adhesives, antistatic agents, fillers and other additives and other ingredients. As mentioned above, when other components are contained in the aforementioned mixture, these components can be appropriately contained in the thermoplastic elastomer composition finally obtained. In addition, these additives and the like are not particularly limited, and commonly used ingredients can be appropriately used. In addition, as for these additives, the components described in the thermoplastic elastomer composition of the present invention can be appropriately used.

In addition, when the content of the other components is a polymer or a reinforcing material (filler), it is preferably 500 parts by mass or less, and 20 to 400 parts relative to 100 parts by mass of the elastomer component. Mass parts are preferred. When the content of these other ingredients does not reach the aforementioned lower limit, there is a tendency that the effect cannot be fully achieved when other ingredients are used. On the other hand, when it exceeds the aforementioned upper limit, although it varies depending on the types of ingredients used, but There is still a tendency that the effect of the matrix elastomer is reduced, and the physical properties are reduced.

In addition, when other components are other additives (in the case of components other than polymers and reinforcing materials (fillers)), the content of the other components relative to 100 parts by mass of the elastomer component is 20 parts by mass or less. It is preferably 0.1 to 10 parts by mass. When the content of these other ingredients does not reach the aforementioned lower limit, there is a tendency that the effect cannot be fully achieved when using other ingredients. On the other hand, when the aforementioned upper limit is exceeded, the reaction to the elastomer of the matrix will have an adverse effect, instead There is a tendency to cause deterioration of physical properties.

     (Second step)     

The second step is to add the compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bondable cross-linking site in the mixture, and react with the compound (I) and the cyclic acid anhydride group to form A step of preparing a thermoplastic elastomer composition by reacting at least one of the raw material compound (M) in the mixed raw material of the compound (II) at the covalently-bonded cross-linking site with the aforementioned polymer and the aforementioned raw material compound. .

The compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bondable cross-linking site can be suitably used with the compound that forms a hydrogen-bondable cross-linking site as described in the thermoplastic elastomer composition of the present invention ( The compound obtained by introducing a nitrogen-containing heterocyclic ring) is the same compound. For example, it may be the nitrogen-containing heterocyclic compound described in the thermoplastic elastomer composition of the present invention described above, or the nitrogen-containing heterocyclic ring may A compound (a nitrogen-containing heterocyclic ring having the aforementioned substituent) bonded to a substituent (for example, a hydroxyl group, a thiol group, an amino group, or the like) that reacts with a cyclic acid anhydride group such as an acid anhydride may be used. In addition, as these compounds (I), compounds that form both a hydrogen-bondable cross-linked site and a covalent-bondable cross-linked site can be used (a hydrogen-bondable cross-linked site, a covalently-bonded cross-linked site, etc. can be simultaneously introduced). Compounds of both) (A side chain having both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site can also be referred to as one of the preferred forms of a side-chain having a hydrogen-bondable cross-linking site. ).

In addition, the content of these compounds (I) is not particularly limited, and it can be compatible with the type of side chain (side chain (a) or side chain (a ')) in the target polymer, as described above, A suitable compound selected from Compound (I) can be appropriately used. These compounds (I) are highly reactive, and from the viewpoint of triazole, pyridine, thiadiazole, imidazole, and heterotrimer which may have at least one of a hydroxyl group, a thiol group, and an amine group as a substituent. Cyanate And hydantoin are preferred, and triazole, pyridine, thiadiazole, imidazole, isotricyanate, and And hydantoin are preferred, and triazole, isotricyanate, More preferably, triazole having the aforementioned substituent is particularly preferred. Triazole, pyridine, thiadiazole, imidazole, and hydantoin which may have these substituents, for example, 4H-3-amino-1,2,4-triazole, aminopyridine, and aminoimidazole Amine three , Amino isocyanurate, hydroxypyridine, hydroxyethyl isocyanurate, etc.

The compound (II) that reacts with the cyclic acid anhydride group to form a covalently-bondable cross-linking site can be suitably used with the "formation of a covalent bond" described in the thermoplastic elastomer composition of the present invention. Sexual cross-linking sites (compounds that form covalent bonds) "are the same compounds (the same applies to those who are suitable as such compounds). As these compounds (II), compounds that form both hydrogen-bondable cross-linked sites and covalently-bondable cross-linked sites can be used (two hydrogen-bondable cross-linked sites and covalently-bonded cross-linked sites can be introduced simultaneously). (Compound compounds) (A side chain having both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site can also be referred to as one of the preferred forms of a side-chain having a covalently-bondable cross-linking site. ).

Among these compounds (II), from the viewpoint of resistance to compression set, trihydroxyethyl isocyanurate, thiamine, and polyether polyols are preferred, and trihydroxyethyl isocyanurate is preferred. Thiamin is more preferred, and trihydroxyethyl isocyanurate is more preferred.

Moreover, the said compound (I) and / or (II) uses the compound which has a substituent of at least 1 sort (s) of a hydroxyl group, a thiol group, an amine group, and an imine group from a viewpoint of introducing a hydrogen-bondable crosslinking site. Better. In addition, the aforementioned compounds (I) and / or (II) can more efficiently introduce both hydrogen-bondable cross-linked sites and covalently-bondable cross-linked sites into the composition. A compound that reacts with a functional group (such as the cyclic acid anhydride group described above) to form both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site (can simultaneously introduce a hydrogen-bondable cross-linking site and a covalently-bonded cross-linking site) Compounds of the two are preferred. As these compounds that form both a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site, the heterocyclic-containing polyalcohol, the heterocyclic-containing polyamine, and the heterocyclic-containing polysulfide can be suitably used. Among these alcohols, trihydroxyethyl isocyanurate is particularly preferred.

In addition, the total amount of the raw material compound (M) (compound (I) and / or compound (II)) added (when only one compound is used, the amount of the one compound), With respect to 100 parts by mass of the elastomeric polymer (E) in the aforementioned mixture, it is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and even more preferably 0.5 to 5.0 parts by mass. When the amount of these compounds (I) and compound (II) added (based on mass parts) does not reach the aforementioned lower limit, the crosslink density cannot be increased because the amount is too small, and the desired physical properties tend to fail. On the other hand, when the above-mentioned upper limit is exceeded, too many branches cause excessive branching, and the crosslink density tends to decrease.

In addition, the addition amount of the aforementioned raw compound (M) (compound (I) and / or compound (II)) (total amount of compound (I) and / or compound (II): when only one compound is used, it is The amount of the one compound) is not particularly limited. In the case where the compound contains active hydrogen such as amine, alcohol, etc., the compound is 100 mol% relative to the aforementioned functional group (for example, the aforementioned cyclic acid anhydride group). Active amines such as amines and alcohols are preferably in an amount of 20 to 250 mol%, more preferably 50 to 150 mol%, and more preferably 80 to 120 mol%. When the amount of these additions does not reach the aforementioned lower limit, the amount of side chains to be introduced is reduced, and it is not easy to obtain a product with a very high crosslinking density, so physical properties such as tensile strength tend to decrease. On the other hand, When it exceeds the aforementioned upper limit, the amount of the compound to be used is too large, resulting in too many branches, but tends to decrease the crosslinking density.

In the case where both the compound (I) and the compound (II) are used, the order of adding the compound (I) and the compound (II) is not particularly limited, and any of them may be added first. When both the compound (I) and the compound (II) are used, the compound (I) and the functional group in the elastomeric polymer having the functional group (for example, the cyclic acid anhydride group) in the side chain may be used as the functional group. (Such as the aforementioned cyclic acid anhydride group). In this way, the unreacted functional group (unreacted functional group) can form a covalently-bondable crosslinking site by reacting with the compound (II). A part referred to herein is preferably 1 mol% or more and 50 mol% or less with respect to 100 mol% of a functional group (for example, the aforementioned cyclic acid anhydride group). Within this range, the obtained elastomeric polymer (B) can fully exhibit the effect of introducing a group (for example, a nitrogen-containing heterocyclic ring) derived from the compound (I), and can have recyclability. The tendency to ascend further. In addition, the compound (II) is preferably one that reacts with the cyclic acid anhydride group in a manner capable of achieving an appropriate number of cross-links generated by covalent bonding (for example, 1 to 3 in one molecule).

When the polymer and the raw material compound (compound (I) and / or compound (II)) are reacted, the functional group (for example, the cyclic acid anhydride group) that the polymer has and the raw material compound (M) can be made. (The aforementioned compound (I) and / or compound (II)) form a chemical bond. The temperature conditions when the aforementioned polymer (E) reacts with the aforementioned raw material compound (M) to ring-open the cyclic acid anhydride group are not particularly limited, and can be adjusted according to the types of the aforementioned compound and cyclic acid anhydride group. The temperature at which these reactions can be performed is sufficient, and from the viewpoint that the softening reaction can be performed instantaneously, 100 to 250 ° C is preferable, and 120 to 230 ° C is more preferable.

Through these reactions, at least the hydrogen-bondable cross-linking site can be formed where the compound (I) reacts with the cyclic acid anhydride group. Therefore, the side-chain of the polymer can contain hydrogen-bondable cross-linking. Site (a site having a carbonyl group and / or a nitrogen-containing heterocyclic ring, more preferably a site having a carbonyl group and a nitrogen-containing heterocyclic ring). The side chain formed (introduced) through these reactions may also include a structure represented by the formula (2) or (3).

In addition, through these reactions, at least a covalently-bondable cross-linking site is formed in a site where the compound (II) reacts with a cyclic acid anhydride group, so that the side chain of the polymer can be formed to contain a covalent bond. Those with a cross-linked portion (side chain (b) or side chain (c)). Subsequently, through these reactions, the formed side chain can be formed to contain a structure represented by the formulae (7) to (9).

In addition, each group (structure) of a side chain in these polymers, that is, an unreacted cyclic acid anhydride group, a structure represented by the above formulae (2), (3), and (7) to (9), etc., It can be confirmed by a commonly used analysis means such as NMR and IR spectrum.

In addition, the aforementioned starting compound (M) used in these reactions is preferably the aforementioned compounds (M1) to (M6). When these compounds (M1) to (M6) are used, the aforementioned reactants (I) to (VI) can be prepared.

In addition, in the present invention, from the viewpoint that the reaction with the functional group can be performed more efficiently, the elastomeric polymer (E) having the functional group used in the reaction may be combined with the raw material compound (M). The following combinations (I) to (VI): the combination (I) of the maleic anhydride-denatured elastomeric polymer (E1) and the aforementioned compound (M1); the hydroxyl-containing elastomeric polymer (E2) and the aforementioned compound (M2) combination (II); carboxyl group-containing elastomeric polymer (E3) and the aforementioned compound (M3) (III); amine group-containing elastomeric polymer (E4) and the aforementioned compound (M4) Combination (IV); combination (V) of an alkoxysilyl group-containing elastomeric polymer (E5) and the aforementioned compound (M5); and epoxy group-containing elastomeric polymer (E6) and the aforementioned compound In the case of any one of the combination (VI); (M6), it is preferable to use the above-mentioned elastomeric polymer (E) and the raw material compound (M). In this way, when the elastomeric polymer (E) is reacted with the raw material compound (M) in combination, the elastomer component can be selected from the group consisting of the reactants (I) to (VI). At least one reactant.

In this way, a side chain (a) containing: a side chain (a) containing "a hydrogen-bonding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring" and having a glass transition point of 25 ° C or lower can be obtained. An elastomeric polymer (A) and an elastomeric polymer (B) having a side chain containing a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site and having a glass transition point of 25 ° C or lower A composition obtained by selecting at least one type of elastomer component from the group and the aforementioned additive component in a proportion of 20 parts by mass or less based on 100 parts by mass of the elastomer component.

In addition, the elastomeric polymer (A) and the elastomeric polymer (B) in the thermoplastic elastomer composition prepared in this way, and the side chains (a) and (a ') of each polymer ), Side chain (b), and side chain (c) are side chains derived by reacting with a cyclic acid anhydride group, respectively (for example, those containing the above formulas (2), (3), and (7) to (9) The structure other than the side chain shown) is the same as the elastomeric polymer (A) and the elastomeric polymer (B) described in the thermoplastic elastomer composition of the present invention.

In addition, in the present invention, the elastomeric polymer having a functional group in the side chain is a maleic anhydride-denatured elastomeric polymer (E1); and the raw material compound (M) ) Is: triazole which may have at least one kind of substituents of hydroxyl group, thiol group and amine group, pyridine which may have at least one kind of substituent group of hydroxyl group, thiol group and amine group, may have hydroxyl group, thiol group Thiadiazole, which may have at least one kind of substituent of amino group and amine group, imidazole, which may have at least one kind of substituent of hydroxyl group, thiol group and amine group, and at least one kind of hydroxy group, thiol group and amine group Isocyanurate, which may have at least one of a hydroxyl group, a thiol group, and an amine group Hydantoin, trihydroxyethyl isocyanurate, thiocarbamide, and polyether polyalcohol, which may have at least one of a hydroxyl group, a thiol group, and an amine group as a substituent. And the aforementioned elastomer component is selected from the group consisting of the reactant (the preferred embodiment of the reactant (I)) of the aforementioned maleic anhydride-denatured elastomeric polymer (E1) and the aforementioned raw material compound. At least one is preferred. That is, in the present invention, the elastomer component is a maleic anhydride-denatured elastomeric polymer (E1), and triazole, which may have a substituent of at least one of a hydroxyl group, a thiol group, and an amine group, may be A pyridine having at least one kind of a substituent of a hydroxyl group, a thiol group, and an amine group, a thiadiazole having a kind of a substituent of at least one type of a hydroxyl group, a thiol group, and an amine group, and a hydroxyl group, a thiol group, and an amine group Imidazole with at least one kind of substituent, isocyanurate which may have at least one kind of substituent among hydroxyl group, thiol group and amine group, at least one kind of hydroxy group, thiol group and amine group Three of the substituents Hydantoin, trihydroxyethyl isocyanurate, thiocarbamide, and polyether polyalcohol, which may have at least one of a hydroxyl group, a thiol group, and an amine group as a substituent. Preferably, at least one selected from the group consisting of the reactants of the compound (the compound selected from the aforementioned compound (M1)) is used.

In addition, from the viewpoint of having high reaction efficiency, the formed bonds are hydrogen bonds and covalent bonds, and can have a higher degree of interaction with the added components, the aforementioned elastomer components are modified by maleic anhydride Reactant (I ') of a polymer (E1) with a compound of at least one kind of a hydrocarbon compound having at least one substituent selected from a hydroxyl group, a thiol group, and an amine group, and the aforementioned reactant Preferably, at least one of the reactants selected from the group (II) to (VI) is selected.

By using the method including the first step and the second step, the thermoplastic elastomer composition of the present invention having extremely high tensile strength and extremely high friction resistance can be efficiently produced.

In the present invention, for example,

The thermoplastic elastomer composition using the elastomeric polymer (A) as the elastomer component and the thermoplastic elastomer composition using the elastomeric polymer (B) as the elastomer component are mixed to prepare a composition containing the thermoplastic elastomer composition. The thermoplastic elastomer composition of the elastomeric polymers (A) and (B) as an elastomer component. When producing a thermoplastic elastomer composition containing a combination of elastomeric polymers (A) and (B) as an elastomer component, the elastomeric polymer (A) and the elastomeric polymer ( The ratio of B) can exhibit desired characteristics by appropriately changing the ratio of the hydrogen-bondable cross-linked site and the covalently-bondable cross-linked site present in the composition.

The above is one of the preferred examples of the method for manufacturing the thermoplastic elastomer composition of the present invention, as the description of the method for manufacturing the thermoplastic elastomer composition of the present invention, but the method of manufacturing the thermoplastic elastomer composition of the present invention It is not limited to the above-mentioned manufacturing method of the thermoplastic elastomer composition of the present invention, and other suitable methods may also be used. For these other methods, for example, the elastomeric polymer (D), the polymer (Z), the raw material compound, and the additive component may be added together to form a mixture, so that the elastomeric polymer may be appropriately used. (D) a method for preparing a thermoplastic elastomer composition by reacting with the aforementioned raw material compound; forming a mixture of the aforementioned elastomeric polymer (D), the aforementioned polymer (Z), and the aforementioned raw material compound in the mixture, A method of reacting the elastomeric polymer (D) with the raw material compound to form an elastomer component, and then adding the aforementioned additive component to a mixture containing the elastomer component.

    [Example]    

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

First, a method for evaluating the characteristics of the thermoplastic elastomer composition obtained in each example and each comparative example will be described.

    <Measurement of breaking strength and 100% modulus>    

First, 42 g of the thermoplastic elastomer composition obtained in each example and each comparative example were used, and the thermoplastic elastomer was placed at a thickness of 2 mm, a length of 150 mm, and a width of 200 mm, which were heated under conditions of 200 ° C. and preheating for 3 minutes. After the inside of a 150 mm mold, the temperature was 200 ° C., the pressure was 18 MPa, and the pressurization time was 5 minutes under heating and pressurizing conditions. Then, the water was cooled and pressurized under pressure: 18 MPa and the pressurization time: 2 Pressure was applied on the condition of minutes, and then taken out from the mold to form 2 mm thick sheets (thickness 2 mm, length 150 mm, width 150 mm). Next, using the 2 mm thick sheets (thickness 2 mm, 150 mm in length, and 150 mm in width) obtained in the above manner, a dumbbell-shaped test piece No. 3 was prepared, and the tensile speed was 500 mm in accordance with JIS K6251 (issued in 2010). A tensile test per minute was performed to determine the breaking strength (T _B ) [unit: MPa] and 100% modulus (M ₁₀₀ ) [MPa] at room temperature (25 ° C).

    <Abrasion resistance>    

First, 15 g of the thermoplastic elastomer composition obtained in each example and each comparative example were used, and a special mold (special mold) was used to prepare disc-shaped samples having a diameter of 16.0 mm and a thickness of 8 mm. Next, the obtained disc-shaped samples were used in accordance with JIS K6264-2 (issued in 2005) as a reference, and a DIN abrasion tester (rotary cylindrical abrasion tester: Yasuda Seiki Co., Ltd., trade name "DIN Abrasion Tester" was used. Under the conditions of temperature: room temperature (25 ° C), load: 2.5N, rotary drum rotation speed: 40rpm, and sample lateral conveying speed: 2.8mm / sec, the wear resistance test is performed and the amount of wear (volume basis) is measured : The ratio of the volume worn out after the test (volume%) relative to the total volume before the abrasion. Also, the smaller the abrasion amount, the higher the abrasion resistance.

    (Example 1)    

First, a styrene block copolymer (styrene-vinyl-butenyl-styrene block copolymer (SEBS): trade name "G1633" manufactured by Kuradon Corporation, molecular weight: 400,000 to 500,000, styrene Content: 30% by mass) 20.0g is put into a pressure kneader and kneaded at 180 ° C. The paraffin oil ("Super-Oil M Series P500S" manufactured by JX Nippon Nissei Energy Co., Ltd.) is used. Viscosity: 472 mm ² / s, Cp value: 68.7%, aniline point: 123 ° C.) 40.0 g is dropped into the aforementioned pressure kneader to make styrene-vinyl-butenyl-styrene block copolymer and paraffin oil Mix for 1 minute. Next, 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (Malaysian Chemical EBM: trade name "Tafmer MH5040" manufactured by Mitsui Chemicals Co., Ltd., 4%) was added to the pressure kneader. Α-olefin resin ethylene-butene copolymer (EBM: "Tafmer DF7350" by Mitsui Chemicals Co., Ltd., degree of crystallinity: 10%, MFR: 35 g / 10 minutes (2.16 kg, 190 ° C), Mw : 100,000) 7.5g and anti-aging agent (trade name "AO-50" manufactured by Adeka Corporation) 0.078g, the temperature was set at 180 ° C, and the mixture was simply kneaded for 2 minutes to prepare a first mixture (containing PP and Malay). A mixture of tritiated EBM). In addition, through the simple kneading step, the first mixture is plasticized. Next, 0.03 g of a nano carbon tube (trade name "ZeonanoSG101" manufactured by Zeon Corporation of Japan) was added to the first mixture in the pressure kneader, and kneaded at 180 ° C for 4 minutes to obtain the first Two mixtures. Next, 0.262 g of trihydroxyethyl isotricyanate (trade name "Tanac" manufactured by Nissei Industrial Co., Ltd.) was added to the second mixture in the pressure kneader, and mixed at 180 ° C for 8 minutes. A thermoplastic elastomer composition was obtained.

In addition, as a result of infrared spectroscopic analysis of the raw material compounds used in these compositions, it was found that the maleic anhydride group in the ethylene-butene copolymer modified with maleic anhydride was reacted with trihydroxyethyl isocyanurate. Reaction to form a side chain containing a structure represented by the following formula (26) (hereinafter, it may also be referred to as "side chain (i)" depending on the situation) and a structure represented by the following formula (27) Side chains (hereinafter, also referred to as "side chain (ii)" depending on the situation), and side chains containing the structure represented by the following formula (28) (hereinafter, depending on the situation, only (Referred to as "side chain (iii)"), an elastomeric polymer having the above-mentioned side chain (iii) as a main component (these side chains (i) to (iii) are considered, and the raw materials used are considered In the stoichiometry, it is clearly known that it mainly forms side chains (iii), but forms side chains (i) and / or side chains (ii) depending on the position of the polymer side chains, etc. Hereinafter, via the raw materials used In the case of an elastomeric polymer having a side chain (iii) whose main type of side chain is formed through the reaction, depending on the situation, it is also simply referred to as "having Chain (iii) -based elastomeric polymer "). In addition, since these elastomeric polymers have a main chain formed of an ethylene-butene copolymer (ethylene and butene), they are known to have a glass transition point of 25 ° C or lower. These elastomeric polymers are known from the types of raw materials used (maleic anhydride-denatured ethylene-butene copolymers), and they can be regarded as having an SP value of 8.0.

[In the formulae (26) to (28), the carbons represented by α and β are any of the positions (α position or β position) of these carbons, and are bonded to the elastomeric polymer. The meaning of the main chain].

42 g of the thermoplastic elastomeric composition obtained in this way was introduced into a mold for forming a sheet (thickness 2 mm, length 150 mm, width 150 mm) heated to 200 ° C, and preheated for 3 minutes without applying pressure. Secondly, it was molded under pressure of 16 MPa and 5 minutes at 200 ° C. Secondly, the sheet of the thermoplastic elastomer composition (thickness 2 mm, length 150 mm in length) was prepared by using water cooling and pressure and cooling at 16 MPa for 2 minutes. , Horizontal 150mm). Table 1 shows the results of the evaluation of the properties of the thermoplastic elastomer composition prepared in this manner.

    (Example 2)    

In addition to using silicate-based natural nanofibers (trade name "Imogolite" manufactured by Astec Corporation) 0.03g instead of nanocarbon tubes (trade name "ZeonanoSG101" manufactured by Zeon Corporation of Japan) 0.03g Other than that, a thermoplastic elastomer composition was obtained in the same manner as in Example 1.

    (Example 3)    

In addition to using a layered titanate compound (trade name "potassium titanate" manufactured by Tokyo Chemical Industry Co., Ltd., chemical formula: K ₂ Ti ₆ O ₁₃ , powder form) 0.03 g instead of a nano carbon tube (trade name "ZeonanoSG101" manufactured by Japan Zeon Corporation) ") Except 0.03 g, the thermoplastic elastomer composition was prepared in the same manner as in Example 1.

    (Comparative example 1)    

Except that 0.03 g of carbon black (trade name "Seasuto KH (N339)" manufactured by Tokai Graphite Co., Ltd.) was used instead of 0.03 g of nano carbon tube (trade name "Zeonano SG101" manufactured by Zeon Corporation of Japan), everything else was in accordance with Example 1. A thermoplastic elastomer composition was obtained in the same manner. Table 1 shows the results of the evaluation of the properties of the thermoplastic elastomer composition prepared in this manner.

    (Comparative example 2)    

Except the use of 0.03 g of silicon dioxide (trade name "Nipusil AQ" manufactured by Japan Silicon Dioxide Corporation) instead of 0.03 g of carbon nanotubes (trade name "Zeonano SG101" manufactured by Japan Zeon Corporation), the rest are in accordance with Example 1. A thermoplastic elastomer composition was obtained in the same manner. Table 1 shows the results of the evaluation of the properties of the thermoplastic elastomer composition prepared in this manner.

    (Comparative example 3)    

Except that 0.03 g of titanium oxide (trade name "A-110" manufactured by Sakai Chemical Industry Co., Ltd.) was used instead of 0.03 g of nano carbon tube (trade name "Zeonano SG101" manufactured by Zeon Corporation of Japan), other examples were followed. 1 A thermoplastic elastomer composition was obtained in the same manner. Table 1 shows the results of the evaluation of the properties of the thermoplastic elastomer composition prepared in this manner.

According to the results shown in Table 1, when comparing Examples 1 to 3 and Comparative Examples 1 to 3, compared with the additive components (nano carbon tubes, natural nano fibers, or , Layered titanic acid compound), the content of the filler (carbon black, silicon dioxide, or titanium oxide) used in Comparative Examples 1 to 3 in place of the aforementioned additive component is different, so the case of using the aforementioned additive component ( Examples 1 to 3) Compared with the case of using fillers (carbon black, silicon dioxide, or titanium oxide) (Comparative Examples 1 to 3), it was not only confirmed that the 100% modulus and the breaking strength were used as the reference. In addition to those having a higher tensile strength, the abrasion amount is lower, so it is confirmed that they have higher abrasion resistance. From these results, it was confirmed that the present invention (Example 1) is a person who can improve the tensile strength based on the modulus and the breaking strength based on 100%, and can have a sufficiently high abrasion resistance.

    (Example 4)    

In addition to using 7.5 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), pentaerythritol ( 0.102 g of the brand name "Neulizer P" manufactured by Japan Synthetic Chemical Co., Ltd. replaces 0.262 g of trihydroxyethyl isocyanurate (trade name of "Tanac" manufactured by Nissei Industrial Co., Ltd.), and then use natural nanofiber (Astec Except for 0.03 g of the company's brand name "filiform aluminite (Imogolite)" instead of 0.03 g of carbon nanotubes (trade name "Zeonano SG101" manufactured by Japan's Zeon Corporation), the rest were prepared in the same manner as in Example 1. Thermoplastic elastomer composition. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed by a reaction product of maleic anhydride-denatured ethylene-butene copolymer and pentaerythritol, and the side chain is formed by reacting a maleic anhydride group with a hydroxyl group of pentaerythritol and having a carboxylic acid ester group (bond). The crosslinked structure (formed by a hydrogen-bondable crosslinked site and a covalently-bonded crosslinked site).

    (Example 5)    

In addition to using 15.0 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), 2, 4-diamino-6-phenyl-1,3,5-tri (Brand name made by Japan Catalyst Corporation, "benzoguanidine ") 0.282 g instead of 0.262 g of trihydroxyethyl isotricyanate (trade name" Tanac "manufactured by Nissei Industrial Co., Ltd.), and a layered titanate compound (trade name" potassium titanate manufactured by Tokyo Chemical Industry Co., Ltd. ""Chemical formula: K ₂ Ti ₆ O ₁₃ , powder form) 0.03 g instead of 0.03 g of carbon nanotubes (trade name" ZeonanoSG101 "manufactured by Zeon Corporation of Japan), the thermoplastic elasticity was obtained in the same manner as in Example 1.体 组合 物 Body composition. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

The elastomer component is a maleic anhydride-denatured ethylene-butene copolymer and 2,4-diamino-6-phenyl-1,3,5-tri It is formed by a reactant with a side chain consisting of a maleic anhydride group and 2,4-diamino-6-phenyl-1,3,5-tris Amine group (-NH ₂ ) A cross-linking structure (formed by a hydrogen-bondable cross-linking site and a covalent-bondable cross-linking site) of a ring and amidine bond (formula: -CONH-).

    (Example 6)    

In addition to the use of tri-[(3-hydrothiopropanoyloxy) -ethyl] -isotricyanate (trade name "Tri-[(3-hydrothiopropanoyloxy))" manufactured by SC Organic Chemical Co., Ltd.- Ethyl] -isotricyanate ") 0.527 g instead of 0.262 g of trihydroxyethyl isocyanurate (trade name" Tanac "manufactured by Nisshin Sangyo Co., Ltd.), the rest are the same as in Example 1. The method produces a thermoplastic elastomer composition. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed by the reaction product of maleic anhydride-denatured ethylene-butene copolymer and tri-[(3-hydrothiopropionyloxy) -ethyl] -isocyanurate, and the side chain is The side chain formed by the reaction of a maleic anhydride group with a thiol group (-SH) in tri-[(3-hydrothiopropionyloxy) -ethyl] -isocyanurate has an iso group Crosslinking structure of cyanurate ring with thioester (formula: -CO-S-) and carboxyl group (formed by hydrogen-bondable cross-linked sites and those with covalently-bonded cross-linked sites ).

    (Example 7)    

In addition to using 7.5 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), using hydroxyl two 10.0 g of terminal polybutadiene (trade name "Polybd R-45HT", manufactured by Idemitsu Kosan Co., Ltd., hydroxyl equivalent: 1400) is used instead of 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM). 0.597 g of 2,6-pyridine dicarboxylic acid (trade name "2,6-pyridine dicarboxylic acid" made by Air‧Water) instead of trihydroxyethyl isocyanurate (trade name made by Nisshin Industries) "Tanac") 0.262g, and then use natural nanofibers (trade name "filament aluminite (Imogolite)" manufactured by Astec) 0.03g instead of nano carbon tubes (trade name "ZeonanoSG101" manufactured by Zeon Japan) Except for 0.03 g, the thermoplastic elastomer composition was obtained in the same manner as in Example 1. The evaluation results of the properties of the thermoplastic elastomer composition obtained in this manner are shown in Table 2.

In addition, the elastomer component is formed by reacting polybutadiene at both ends of the hydroxyl group with 2,6-pyridinedicarboxylic acid, and the side chain is formed by reacting the hydroxyl group with a carboxyl group in 2,6-pyridinedicarboxylic acid. On the side chain, there is a crosslinked structure having a pyridine ring and a carboxylic acid ester group (bonded portion) (formed by a hydrogen-bondable crosslinked site and a covalently-bonded crosslinked site).

    (Example 8)    

In addition to using 7.5 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), use of carboxyl group 10.0 g of polyisoprene (trade name "LIR-410" manufactured by Kurare, carboxy equivalent: 4000) was substituted for maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM) 10.0 g, and trihydroxy The amount of ethyl isotricyanate (trade name "Tanac" manufactured by Nissei Sangyo Co., Ltd.) was changed from 0.262 g to 0.218 g, and a layered titanate compound (trade name "Titanic acid manufactured by Tokyo Chemical Industry Co., Ltd." was used) Potassium ”, chemical formula: K ₂ Ti ₆ O ₁₃ ” powdered) 0.03 g instead of 0.03 g of carbon nanotubes (trade name “ZeonanoSG101” manufactured by Zeon Corporation of Japan), and thermoplastics were prepared in the same manner as in Example 1. Elastomer composition. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed from the reactant of carboxyl-containing polyisoprene and trihydroxyethyl isocyanurate, and the side chain is composed of the hydroxyl group of carboxyl and trihydroxyethyl isocyanurate Formed by the reaction and having a cross-linking structure with an isocyanurate-containing ring on the side chain and a carboxylic acid ester group (bonding portion) (having a hydrogen-bondable cross-linking site and a covalent-bonded intercourse Linked sites are formed).

    (Example 9)    

In addition to using 10.0 g of polyisoprene containing a carboxyl group (trade name "LIR-410" manufactured by Kurare, carboxy equivalent: 4000) instead of 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM) And use 0.0085 g of pentaerythritol (trade name "Neulizer P" manufactured by Nippon Synthetic Chemical Co., Ltd.) instead of 0.262 g of trihydroxyethyl isotricyanate (trade name "Tanac" manufactured by Nisshin Industrial Co., Ltd.), others The thermoplastic elastomer composition was prepared in the same manner as in Example 1. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed from a reactant of carboxyl-containing polyisoprene and trihydroxyethyl isocyanurate, and the side chain is formed by reacting a carboxyl group with a hydroxyl group of pentaerythritol. Crosslinked structure of carboxylic acid ester group (bonded portion) (formed by hydrogen-bonded crosslinked sites and those with covalently bonded crosslinked sites).

    (Example 10)    

In addition to using 7.5 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), use of carboxyl group 10.0 g of polyisoprene (trade name "LIR-410" manufactured by Kurare, carboxy equivalent: 4000) was used instead of 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM). 4-diamino-6-phenyl-1,3,5-tri (Brand name made by Japan Catalyst Corporation, "benzoguanidine ”) 0.234 g instead of 0.262 g of trihydroxyethyl isocyanurate (trade name“ Tanac ”manufactured by Nissei Industrial Co., Ltd.), and then use natural nanofiber (trade name“ filament alumina ”manufactured by Astec Corporation) (Imogolite) ") 0.03 g instead of 0.03 g of a nano carbon tube (trade name" ZeonanoSG101 "manufactured by Zeon Corporation of Japan), a thermoplastic elastomer composition was prepared in the same manner as in Example 1. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

The elastomer component is composed of carboxyl-containing polyisoprene and 2,4-diamino-6-phenyl-1,3,5-tris It is formed by a reactant with a side chain consisting of a carboxyl group and 2,4-diamino-6-phenyl-1,3,5-tris Amine group (-NH ₂ ) A cross-linking structure (formed by -CONH-) of a ring and amidine bond (formed by a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site.

    (Example 11)    

In addition to using 7.5 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), use of carboxyl group 10.0 g of polyisoprene (trade name "LIR-410" manufactured by Kurare, carboxy equivalent: 4000) was used instead of 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM). [(3-Hydroxythiopropionyloxy) -ethyl] -isocyanurate (trade name manufactured by SC Organic Chemical Co., Ltd. "Tri-[(3-Hydroxythiopropionyloxy) -ethyl]- 0.438 g of isotricyanate ") instead of 0.262 g of trihydroxyethyl isocyanurate (trade name" Tanac "manufactured by Nisshin Kogyo Co., Ltd.), and a layered titanate compound (manufactured by Tokyo Chemical Industry Co., Ltd.) Trade name "potassium titanate", chemical formula: K ₂ Ti ₆ O ₁₃ ", powder form) 0.03 g instead of 0.03 g of carbon nanotubes (trade name" ZeonanoSG101 "manufactured by Zeon Corporation of Japan). 1 A thermoplastic elastomer composition was obtained in the same manner. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed from a reactant of a carboxyl group-containing polyisoprene and tri-[(3-hydrothiopropionyloxy) -ethyl] -isotricyanate, and the side chain is derived from Isocyanuric group-containing side chains formed by the reaction of a carboxyl group with a thiol group (-SH) in tri-[(3-hydrothiopropionyloxy) -ethyl] -isocyanurate The ester ring is a cross-linked structure (formed by a hydrogen-bondable cross-linking site and a covalent-bondable cross-linking site) with a thioester (formula: -CO-S-).

    (Example 12)    

In addition to using 10.0 g of polyimide containing amino groups (trade name "epoxy SP-200" manufactured by Japan Catalyst Corporation, amine value: 18 mmol / g) instead of maleic anhydride-denatured ethylene-butene copolymer (Malay 10.0 g of tritiated EBM, and 1.504 g of 2,6-pyridinedicarboxylic acid (trade name "2,6-pyridinedicarboxylic acid" manufactured by Air‧Water) was used instead of trihydroxyethyl isocyanurate ( Except for 0.262 g of the product name "Tanac" manufactured by Nissei Industrial Co., Ltd., the thermoplastic elastomer composition was prepared in the same manner as in Example 1. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed by the reactant of amine-containing polyethyleneimine and 2,6-pyridinedicarboxylic acid, and the side chain is formed by the reaction of the amine group with the carboxyl group in 2,6-pyridinedicarboxylic acid. The formed side chain has a cross-linking structure (containing a hydrogen-bondable cross-linking site and a covalent-bondable cross-linking site containing a pyridine ring and amidine linkage (formula: -CONH-)). Formed).

    (Example 13)    

In addition to using 7.5 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), use of amine-containing 10.0 g of polyethyleneimine (trade name "Epoxy SP-200" manufactured by Japan Catalyst Corporation, amine value: 18 mmol / g) instead of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM) 10.0 g, using triepoxypropyl isocyanurate (tri- (2,3-epoxypropyl) -isocyanurate: trade name "Tepic" made by Nissan Chemical Co., Ltd.) 1.784 g instead of 0.262 g of trihydroxyethyl isotricyanate (trade name "Tanac" manufactured by Nissei Industries), using natural nanofiber (trade name "Imogolite" manufactured by Astec Corporation) ") Except for 0.03 g of 0.03 g of carbon nanotubes (trade name" ZeonanoSG101 "manufactured by Zeon Corporation of Japan), a thermoplastic elastomer composition was prepared in the same manner as in Example 1. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed from the reactant of polyethyleneimine containing amine group and triepoxypropyl isocyanurate, and the side chain is composed of amine group and triepoxypropyl isotrimer. The side chain formed by the reaction of an epoxy group in a cyanate ester has a crosslinked structure containing an isotricyanate ring containing a bond with a hydroxyl group and an imine (the side chain is formed by a hydrogen-containing crosslinkable site) Cross-linking structure (formed by a hydrogen-bondable cross-linking site and a covalent-bondable cross-linking site) with a cross-linking structure formed by both side chains such as a covalently-bondable cross-linking site.

    (Example 14)    

In addition to using 7.5 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), use alkane-containing 10.0 g of oxysilyl polyethylene (trade name "Linklon" manufactured by Mitsubishi Chemical Corporation) replaces 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM), and trihydroxyethyl isotrimerizes The amount of cyanate ester (trade name "Tanac" manufactured by Nissei Industrial Co., Ltd.) was changed from 0.262 g to 0.087 g, and then a layered titanate compound (trade name "potassium titanate" manufactured by Tokyo Chemical Industry Co., Ltd.) was used. Chemical formula: K ₂ Ti ₆ O ₁₃ powder) 0.03 g instead of 0.03 g of a nano carbon tube (trade name "ZeonanoSG101" manufactured by Zeon Corporation of Japan), a thermoplastic elastomer composition was prepared in the same manner as in Example 1. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed by the reaction product of polyethylene containing alkoxysilyl group and trihydroxyethyl isotricyanate, and the side chain is isotrimerized with alkoxysilyl group and trihydroxyethyl isocyanurate. The side chain formed by the reaction of a hydroxyl group (hydroxyl group) in a cyanate ester has a crosslinked structure containing an isotricyanate ring containing a silicon-oxygen bond (the side chain is formed by a hydrogen-containing crosslinkable site and Covalently-bonded cross-linking sites (formed by both side chains) and cross-linking structures (formed by hydrogen-bondable cross-linking sites and those with covalently-bondable cross-linking sites).

    (Example 15)    

Instead of using 10.0 g of alkoxysilyl-containing polyethylene (trade name "Linklon" manufactured by Mitsubishi Chemical Corporation) instead of 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM), use pentaerythritol (Japan The same as in Example 1 except that 0.234 g of the trade name "Neulizer P" (manufactured by Synthetic Chemical Co., Ltd.) was substituted for trihydroxyethyl isocyanurate (trade name "Tanac" manufactured by Nisshin Industrial Co., Ltd.). The method produces a thermoplastic elastomer composition. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed by the reactant of polyethylene containing alkoxysilyl group and pentaerythritol, and the side chain is the hydroxyl group (hydroxyl group) in alkoxysilyl group and trihydroxyethyl isocyanurate. The side chain formed by the reaction has a crosslinked structure containing a silicon-containing oxygen bond (the side chain is formed by a side chain containing both a hydrogen-bondable crosslink site and a covalently-bond crosslink site, etc.) Cross-linking structure (formed by a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site).

    (Example 16)    

In addition to using 7.5 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), use alkane-containing 10.0 g of oxysilyl polyethylene (trade name "Linklon" manufactured by Mitsubishi Chemical Corporation) replaces 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM) and uses 2,4-diamine groups -6-phenyl-1,3,5-tri (Brand name made by Japan Catalyst Corporation, "benzoguanidine '') 0.094 g instead of 0.262 g of trihydroxyethyl isocyanurate (trade name "Tanac" manufactured by Nissei Industrial Co., Ltd.), and then use natural nanofiber (trade name "filament alumina" manufactured by Astec Corporation) (Imogolite) ") 0.03 g instead of 0.03 g of a nano carbon tube (trade name" ZeonanoSG101 "manufactured by Zeon Corporation of Japan), a thermoplastic elastomer composition was prepared in the same manner as in Example 1. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is formed by the reaction product of polyethylene containing alkoxysilyl group and tri-[(3-hydrothiopropionyloxy) -ethyl] -isotricyanate, and the side chain is The side chain formed by the reaction of an alkoxysilyl group with a thiol group (-SH) in tri-[(3-hydrothiopropionyloxy) -ethyl] -isocyanurate has an isopropyl group. A cross-linked structure of a cyanurate ring and a hydrogenthiosilane bond (formed by a hydrogen-bondable cross-linking site and a covalently-bondable cross-linking site).

    (Example 17)    

In addition to using 7.5 g of high-density polyethylene (HDPE: Japanese polyethylene product name "HJ590N") instead of ethylene-butene copolymer (EBM: Mitsui Chemicals company product name "Tafmer DF7350"), using styrene -10.0 g of epoxide of butadiene block copolymer (trade name "Epolando" manufactured by Daicel) instead of 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM), using 2,4 -Diamino-6-phenyl-1,3,5-tri (Brand name made by Japan Catalyst Corporation, "benzoguanidine ") 0.936 g instead of 0.262 g of trihydroxyethyl isotricyanate (trade name" Tanac "manufactured by Nissei Industrial Co., Ltd.), and then a layered titanate compound (trade name" potassium titanate manufactured by Tokyo Chemical Industry Co., Ltd. ""Chemical formula: K ₂ Ti ₆ O ₁₃ powder) 0.03 g instead of 0.03 g of carbon nanotubes (trade name" ZeonanoSG101 "manufactured by Zeon Corporation of Japan), the thermoplastic elastomer was prepared in the same manner as in Example 1.组合 物。 Composition. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

The elastomer component is composed of an epoxide of a styrene-butadiene block copolymer and 2,4-diamino-6-phenyl-1,3,5-tri The side chain is formed by reacting an epoxy group with a thiol group (-SH) in tri-[(3-hydrothiopropionyloxy) -ethyl] -isotricyanate. The formed side chain has a cross-linked structure containing an isocyanurate ring, a hydroxyl group, and an imine bond (formed by a hydrogen-bondable cross-linking site and a covalent-bondable cross-linking site).

    (Example 18)    

In addition to using 10.0 g of an epoxide (trade name "Epolando" manufactured by Daicel Corporation) of a styrene-butadiene block copolymer instead of 10.0 g of maleic anhydride-denatured ethylene-butene copolymer (maleimide EBM), Tri-[(3-Hydroxythiopropionyloxy) -ethyl] -isotricyanate (trade name "Tri-[(3-Hydroxythiopropionyloxy) -ethyl" manufactured by SC Organic Chemical Co., Ltd. was used. Group] -isocyanurate ") 1.75 g instead of 0.262 g of trihydroxyethyl isocyanurate (trade name" Tanac "manufactured by Nissei Industrial Co., Ltd.). A thermoplastic elastomer composition was obtained. The evaluation results of the properties of the thermoplastic elastomer composition prepared in this manner are shown in Table 2.

In addition, the elastomer component is a reaction product of an epoxide of a styrene-butadiene block copolymer and tri-[(3-hydrothiopropionyloxy) -ethyl] -isotricyanate. Formed, the side chain is a side chain formed by the reaction of an epoxy group with a thiol group (-SH) in tri-[(3-hydrothiopropionyloxy) -ethyl] -isotricyanate Those having an isocyanurate ring-containing cross-linking structure with a hydroxyl group and a thioether group (formed by a hydrogen-bondable cross-linking site and a covalent-bondable cross-linking site).

From the results shown in Tables 1 and 2, it is clear that the thermoplastic elastomer compositions obtained in Examples 6, 9, 12, 15, 18 having the same composition as in Example 1 except for the types of elastomer components In either case, tensile strength and abrasion resistance equivalent to those in Example 1 were obtained. In addition, when compared with the thermoplastic elastomer composition obtained in Comparative Examples 1 to 3, it was also confirmed that a higher height was achieved. Tensile strength and abrasion resistance. Based on these results, it was confirmed that at least one kind of elastomer component selected by combining the above-mentioned elastomeric polymer (A) and the above-mentioned elastomeric polymer (B), and an additive component (nanocarbon tube) , Silicate-based natural nanofibers or layered titanic acid compounds), can achieve higher tensile strength and wear resistance. In addition, the thermoplastic elastomer composition obtained in Examples 4 to 5, 7 to 8, 10 to 11, 13 to 14, and 16 to 17 has the same composition as that in Example 1 in any of Examples 6 and 6. When compared with the thermoplastic elastomer composition obtained from 9, 12, 12, 15, 18, all of them can achieve higher tensile strength and abrasion resistance. Therefore, according to the present invention, it can provide a 100% increase in modulus (modulus) and tensile strength based on tensile strength, and can have a sufficiently high abrasion resistance.

    [Industrial availability]    

As explained above, according to the present invention, it is possible to provide a thermoplastic elastomer composition which can improve the tensile strength based on 100% modulus and breaking strength, and can have a high degree of abrasion resistance. Thing.

Therefore, the thermoplastic elastomer composition of the present invention, as described above, can exert various properties in a balanced and sufficient manner, and is therefore very suitable for use in the manufacture of, for example, electrical and electronics, home appliances, chemicals, pharmaceuticals, glass, earth, stone, Iron and steel, non-ferrous metals, machinery, precision machinery, cosmetics, fiber, mining, pulp, paper, construction, civil engineering, construction, food, beverages, general consumer goods, services, transportation machinery, construction machinery, electrical equipment, equipment (industry , Air conditioning, water supply, household fuel cells (Ene-Farm)), metals, media, information, communications equipment, lighting, displays, agriculture, fisheries, forestry, aquaculture, agricultural enterprises, biotechnology, nanotechnology, etc. Various rubber parts used (more specifically, products around the automobile, rubber tubes, belts, sheets, shock-resistant rubber, rollers, linings, rubber cloths, sealing materials, handbags, cushioning materials, medical rubber (syringes Gaskets, sleeves, ducts), gaskets (for household appliances, construction), asphalt modifiers, hot melt adhesives, footwear, jigs, toys, boots, Rubber parts shoes, key pads, gears, PET pad caps, photocopying machine, the mat, ‧ per sheet coating is applied, a printing product uses of coatings, etc.) material.

Claims (3)

    A thermoplastic elastomer composition characterized by containing an elastomer having a side chain containing a "hydrogen-bondable cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring" and having a glass transition point of 25 ° C or lower Polymer (A), and a group of elastomeric polymers (B) with side chains containing hydrogen-bondable cross-linking sites and covalently-bondable cross-linking sites, and having a glass transition point of 25 ° C or lower At least one selected elastomer component is made of expanded graphite, carbon nanotubes, fullerene, graphene, silicate natural nanofibers, silsesquioxane, and layered titanic acid compounds. At least one selected from the group, and its content is an added component of 20 parts by mass or less based on 100 parts by mass of the elastomer component.     For example, the thermoplastic elastomer composition of claim 1, wherein the aforementioned elastomer component is at least one kind of reactant selected from the group consisting of the following reactants (I) to (VI): [Reactant (I) ] Maleic anhydride-denatured elastomeric polymers, and triazoles which may have at least one kind of substituents of a hydroxyl group, a thiol group and an amine group, and those which may have at least one kind of a hydroxyl group, a thiol group and an amine group Pyridine as a substituent, thiadiazole which may have at least one of a hydroxyl group, a thiol group and an amine group, imidazole which may have a substituent of at least one kind of a hydroxyl group, a thiol group and an amine group, and may have a hydroxyl group 3, isocyanurate of at least one kind of substituent of thiol group and amine group, three of substituents which may have at least one kind of hydroxyl group, thiol group and amine group Hydantoin which may have at least one kind of substituents of a hydroxyl group, a thiol group and an amine group, and a hydrocarbon compound having at least one kind of substituents selected from a hydroxyl group, a thiol group and an amine group , Trihydroxyethyl isotricyanate, thiamidine, and a reactant of at least one compound in a polyether polyol; [reactant (II)] a hydroxyl-containing elastomeric polymer, and Reactant of a compound having two or more substituents selected from carboxyl, alkoxysilyl, and isocyanate groups; [Reactant (III)] a carboxyl-containing elastomeric polymer, and A reactant of a compound of at least one selected from the group consisting of a hydroxyl group, a thiol group, and an amine group; [reactant (IV)] an elastomeric polymer containing an amine group, and Reactant of a compound of at least one selected from carboxyl, epoxy, alkoxysilyl and isocyanate groups; [reactant (V)] an elastomeric polymer containing an alkoxysilyl group, With two or more substituents selected from at least one selected from hydroxyl, carboxyl and amine groups [Reactant (VI)] an epoxy-containing elastomeric polymer, and a compound having at least one substituent selected from thiol and amine groups Reactant.     The thermoplastic elastomer composition according to claim 1 or 2, wherein the aforementioned elastomer component contained as the polymer main chain is a diene rubber, a diene rubber hydride, an olefin rubber, or a hydrogenatable polymer. Polystyrene-based elastomeric polymer, Polyolefin-based elastomeric polymer, Polyvinyl chloride-based elastomeric polymer, Polyurethane-based elastomeric polymer, Polyester-based elastomeric polymer And formed of at least one selected from the polyamine-based elastomeric polymers.