WO2017199805A1

WO2017199805A1 - Thermoplastic elastomer composition, and production method therefor

Info

Publication number: WO2017199805A1
Application number: PCT/JP2017/017641
Authority: WO
Inventors: 知野　圭介; 鈴木　宏明
Original assignee: Ｊｘｔｇエネルギー株式会社
Priority date: 2016-05-17
Filing date: 2017-05-10
Publication date: 2017-11-23
Also published as: JP2017206604A; TW201815980A

Abstract

This thermoplastic elastomer composition includes: at least one elastomer component selected from the group consisting of elastomeric polymers (A) which have a side chain including a hydrogen-bonding crosslinking site having a carbonyl-containing group and/or a nitrogen-containing heterocyclic ring, and which have a glass transition point of not more than 25˚C, and elastomeric polymers (B) which include a hydrogen-bonding crosslinking site and a covalent-bonding crosslinking site in a side chain, and which have a glass transition point of not more than 25˚C; and at least one additive component selected from the group consisting of expanded graphite, carbon nanotubes, fullerene, graphene, silicate-based natural nanofibres, silsesquioxanes, and laminar titanate compounds, the content of said additive component being not more than 20 parts by mass per 100 parts by mass of the elastomer component.

Description

Thermoplastic elastomer composition and method for producing the same

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

Thermoplastic elastomer is an extremely useful material in the industry because it can be melted at the processing temperature during molding and can be molded by a known resin molding method. As such a thermoplastic elastomer, for example, in JP-A-2006-131663 (Patent Document 1), a side chain containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and a nitrogen-containing heterocyclic ring is covalently bonded. A thermoplastic elastomer composed of an elastomeric polymer having a glass transition point of 25 ° C. or less having other side chains containing a crosslinking site is disclosed. However, such a thermoplastic elastomer described in Patent Document 1 is not always sufficient in terms of tensile strength based on 100% modulus and breaking strength, and wear resistance.

JP 2006-131663 A

The present invention has been made in view of the above-mentioned problems of the prior art, and it is possible to make the tensile strength based on 100% modulus and breaking strength higher, and sufficiently high resistance. It is an object of the present invention to provide a thermoplastic elastomer composition that can be worn.

As a result of intensive studies to achieve the above object, the inventors of the present invention have a side chain containing a hydrogen-bonded bridging site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring, and a glass transition point of 25. And an elastomeric polymer (B) having a hydrogen bond crosslinking site and a covalent bond crosslinking site in the side chain and having a glass transition point of 25 ° C. or less. At least one elastomer component selected from the group, and at least one selected from the group consisting of expanded graphite, carbon nanotubes, fullerenes, graphene, silicate-based natural nanofibers, silsesquioxanes, and layered titanate compounds And an additive component whose content is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component. Therefore, the tensile strength based on the 100% modulus and the breaking strength of the obtained thermoplastic elastomer composition can be made higher, and the composition has a sufficiently high wear resistance. The present invention has been completed by finding that it is possible to have the following.

That is, the thermoplastic elastomer composition of the present invention has an elastomeric polymer having a side chain containing a hydrogen-bonding crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or lower. (A) and at least one selected from the group consisting of an elastomeric polymer (B) containing a hydrogen-bonding cross-linking site and a covalent cross-linking site in the side chain and having a glass transition point of 25 ° C. or lower. A kind of elastomer component;
It is at least one selected from the group consisting of expanded graphite, carbon nanotubes, fullerenes, graphene, silicate-based natural nanofibers, silsesquioxanes, and layered titanate compounds, and the content thereof is 100 masses of the elastomer component. An additive component that is 20 parts by mass or less relative to parts,
It contains.

In the thermoplastic elastomer composition of the present invention, the elastomer component contains the following reactants (I) to (VI):
[Reactant (I)] Among maleic anhydride-modified elastomeric polymer and triazole, hydroxyl group, thiol group and amino group which may have at least one substituent selected from hydroxyl group, thiol group and amino group Among the thiadiazole, hydroxyl group, thiol group and amino group optionally having at least one substituent of pyridine, hydroxyl group, thiol group and amino group optionally having at least one substituent group Of isocyanurate, hydroxyl group, thiol group and amino group which may have at least one substituent of imidazole, hydroxyl group, thiol group and amino group which may have at least one kind of substituent At least one of triazine, hydroxyl group, thiol group and amino group optionally having at least one substituent. A hydrocarbon compound having two or more substituents selected from hydantoin, hydroxyl group, thiol group and amino group which may have a substituent, trishydroxyethyl isocyanurate, sulfamide, and poly Reaction product with at least one compound among ether polyols [Reactant (II)] A hydroxyl group-containing elastomeric polymer, and at least one substituent selected from a carboxy group, an alkoxysilyl group and an isocyanate group Reaction product with two or more compounds [Reactant (III)] Carboxy group-containing elastomeric polymer, and a compound having two or more substituents selected from a hydroxyl group, a thiol group, and an amino group Reactant [Reactant (IV)] Amino group-containing elastomeric polymer, Reaction product [reactant (V)] with an alkoxysilyl group-containing elastomeric polymer with a compound having two or more substituents selected from a boxy group, an epoxy group, an alkoxysilyl group and an isocyanate group; Reaction product with compound having at least two substituents selected from hydroxyl group, carboxy group and amino group [reaction product (VI)] Epoxy group-containing elastomeric polymer, thiol group and amino group It is preferably at least one reactant selected from the group consisting of reactants with compounds having two or more substituents selected from at least one substituent.

Further, in the thermoplastic elastomer composition of the present invention, the main chain of the polymer contained as the elastomer component is a diene rubber, a hydrogenated diene rubber, an olefin rubber, or a hydrogenated polystyrene. It is composed of at least one selected from a polymer elastomeric polymer, a polyolefin elastomeric polymer, a polyvinyl chloride elastomeric polymer, a polyurethane elastomeric polymer, a polyester elastomeric polymer, and a polyamide elastomeric polymer Is preferred.

ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic elastomer composition which can make the tensile strength on the basis of 100% modulus and breaking strength more advanced, and can have a sufficiently high abrasion resistance. Things can be provided.

Hereinafter, the present invention will be described in detail on the basis of preferred embodiments thereof.

The thermoplastic elastomer composition of the present invention has an elastomeric polymer (A) having a side chain containing a hydrogen-bonding crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or lower. ), And at least one selected from the group consisting of an elastomeric polymer (B) having a hydrogen bond crosslinking site and a covalent bond site in the side chain and having a glass transition point of 25 ° C. or lower An elastomer component;
It is at least one selected from the group consisting of expanded graphite, carbon nanotubes, fullerenes, graphene, silicate-based natural nanofibers, silsesquioxanes, and layered titanate compounds, and the content thereof is 100 masses of the elastomer component. An additive component that is 20 parts by mass or less relative to parts,
It contains.

(Elastomer component)
Such an elastomer component is at least one selected from the group consisting of the above-mentioned elastomeric polymers (A) to (B). In such elastomeric polymers (A) to (B), “side chains” refer to side chains and terminals of the elastomeric polymer. In addition, “a side chain containing a hydrogen-bonding cross-linked site having a carbonyl-containing group and / or a nitrogen-containing heterocycle (hereinafter, sometimes referred to as“ side chain (a) ”for convenience)” means an elastomeric polymer. To the atoms (usually carbon atoms) that form the main chain (the main chain of the polymer included as the elastomer component), a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring (more preferably a carbonyl-containing group) Group and nitrogen-containing heterocycle) has a chemically stable bond (covalent bond). Further, “the side chain contains a hydrogen-bonding crosslinking site and a covalent bonding site” means a side chain having a hydrogen-bonding crosslinking site (hereinafter referred to as “side chain (a ′)” for convenience). )) And a side chain having a covalent crosslinking site (hereinafter, sometimes referred to as “side chain (b)” for the sake of convenience), the side chain of the polymer contains a hydrogen bonding crosslinking site. And a side chain having both a hydrogen bonding crosslinking site and a covalent crosslinking site (a hydrogen bonding crosslinking site and a covalent bond in one side chain). Side chains including both cross-linked sites: Hereinafter, for convenience, such side chains are sometimes referred to as “side chains (c)”. A concept that includes the case where both binding crosslink sites are contained. is there.

Such main chains of the elastomeric polymers (A) to (B) (the main chain of the polymer included as the elastomer component: the polymer forming the main chain portion) are generally known natural polymers or synthetic polymers. The molecule is not particularly limited as long as it is made of a polymer having a glass transition point of room temperature (25 ° C.) or less (it may be made of a so-called elastomer). Therefore, the elastomeric polymers (A) to (B) have, for example, an elastomeric polymer having a glass transition point of room temperature (25 ° C.) or lower such as a natural polymer or a synthetic polymer as a main chain, and a carbonyl-containing group and And / or containing a side chain (a) containing a hydrogen-bonding cross-linked moiety having a nitrogen-containing heterocycle; mainly composed of an elastomeric polymer having a glass transition point of room temperature (25 ° C.) or less, such as a natural polymer or a synthetic polymer Containing a side chain (a ′) having a hydrogen-bonding cross-linking site and a side chain (b) having a covalent cross-linking site as a side chain; glass such as a natural polymer or a synthetic polymer An elastomeric polymer having a transition point of room temperature (25 ° C.) or lower and having a side chain (c) including both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site may be used.

Examples of the main chains of the elastomeric polymers (A) to (B) (the main chain of the polymer included as the elastomer component: the polymer forming the main chain portion) include natural rubber (NR) and 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-propylene-diene rubber ( EPDM) and other hydrogenated products thereof; ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), chlorosulfonated polyethylene, acrylic rubber, fluororubber, polyethylene rubber Olef such as polypropylene rubber Examples thereof include: a tin-based rubber; an epichlorohydrin rubber; a polysulfide rubber; a silicone rubber; a urethane rubber;

The main chain of the elastomeric polymers (A) to (B) (the main chain of the polymer contained as the elastomer component: the polymer forming the main chain portion) is composed of an elastomeric polymer containing a resin component. For example, polystyrene-based elastomeric polymer (for example, SBS, SIS, SEBS, etc.) that may be hydrogenated, polyolefin-based elastomeric polymer, polyvinyl chloride-based elastomeric polymer, polyurethane-based elastomeric polymer , Polyester-based elastomeric polymers, polyamide-based elastomeric polymers, and the like.

Examples of the main chain of the elastomeric polymers (A) to (B) (the main chain of the polymer contained as the elastomer component) include diene rubber, hydrogenated diene rubber, olefin rubber, and hydrogenated. At least selected from polystyrene-based elastomeric polymer, polyolefin-based elastomeric polymer, polyvinyl chloride-based elastomeric polymer, polyurethane-based elastomeric polymer, polyester-based elastomeric polymer, and polyamide-based elastomeric polymer One is preferred. In addition, the main chain of the elastomeric polymers (A) to (B) (the main chain of the polymer contained as the elastomer component) is a diene rubber from the viewpoint that there is no double bond that tends to age. From the viewpoint of low cost and high reactivity (having many double bonds capable of ene reaction of a compound such as maleic anhydride), diene rubber is preferable. preferable.

Further, the elastomeric polymers (A) to (B) may be in a liquid or solid state, and the molecular weight thereof is not particularly limited, and uses for which the thermoplastic elastomer composition of the present invention is used, required physical properties, etc. It can be selected as appropriate according to the conditions.

When emphasizing the fluidity when the thermoplastic elastomer composition of the present invention is heated (such as decrosslinking), the elastomeric polymers (A) to (B) are preferably in a liquid state, for example, a main chain portion. Is a diene rubber such as isoprene rubber or butadiene rubber, the weight average molecular weight of the main chain portion is 1,000 to 100 in order to make the elastomeric polymers (A) to (B) liquid. , Preferably about 1,000, more preferably about 1,000 to 50,000.

On the other hand, when importance is attached to the strength of the thermoplastic elastomer composition of the present invention, the elastomeric polymers (A) to (B) are preferably in a solid state, for example, the main chain portion is isoprene rubber, butadiene rubber or the like. In order to make the elastomeric polymers (A) to (B) solid, it is preferable that the weight average molecular weight of the main chain portion is 100,000 or more. It is particularly preferably about 1,000,000 to 1,500,000.

Such a weight average molecular weight is a weight average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC). For the measurement, tetrahydrofuran (THF) is preferably used as a solvent.

In the thermoplastic elastomer composition of the present invention, the elastomeric polymers (A) to (B) can be used in combination of two or more. In this case, the mixing ratio of the respective elastomeric polymers can be set to an arbitrary ratio according to the use in which the thermoplastic elastomer composition of the present invention is used or the required physical properties.

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

The main chain of the elastomeric polymers (A) to (B) (the main chain of the polymer contained as the elastomer component) has a glass transition point of the elastomeric polymers (A) to (B) of 25 ° C. or less, Since the molded article comprising the thermoplastic elastomer composition obtained exhibits rubber-like elasticity at room temperature (25 ° C.), natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber , Diene rubbers such as styrene-butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR); ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM) And the like. Further, when an olefin rubber is used for each of the main chains of the elastomeric polymers (A) to (B), the tensile strength of the resulting thermoplastic elastomer composition is improved and there is no double bond. Degradation tends to be more sufficiently suppressed.

The amount of bound styrene of the styrene-butadiene rubber (SBR) that can be used for the elastomeric polymers (A) to (B), the hydrogenation rate of the hydrogenated elastomeric polymer, and the like are not particularly limited. The ratio can be adjusted to any ratio according to the use of the thermoplastic elastomer composition, the physical properties required of the composition, and the like.

In addition, as the main chain of the elastomeric polymers (A) to (B) (the main chain of the polymer contained as the elastomer component), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene When rubber (EPM) or ethylene-butene rubber (EBM) is used, it should have a crystallinity of less than 10% (more preferably 5 to 0%), particularly from the viewpoint of good rubbery elasticity at room temperature. Is preferred. In addition, ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), and ethylene-butene rubber (EBM) are used as the main chains of the elastomeric polymers (A) to (B). When used, the ethylene content is preferably 10 to 90 mol%, more preferably 30 to 90 mol%. If the ethylene content is within this range, it is preferable because it is excellent in compression set, mechanical strength, particularly tensile strength when it is used as a thermoplastic elastomer (composition).

Furthermore, the elastomeric polymers (A) to (B) are preferably amorphous from the viewpoint of good rubbery elasticity at room temperature. Further, such elastomeric polymers (A) to (B) may be elastomers having a crystallinity (crystal structure) in part, but even in this case, the degree of crystallinity is 10%. It is preferably less than (particularly preferably 5 to 0%). Such crystallinity is measured by using an X-ray diffractometer (for example, trade name “MiniFlex300” manufactured by Rigaku Corporation) as a measuring device, measuring a diffraction peak, and integrating a scattering peak derived from crystallinity / amorphous. It can be determined by calculating the ratio.

In addition, as described above, the elastomeric polymers (A) to (B) include, as a side chain, a side chain (a) containing a hydrogen-bonded crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle; A side chain (a ′) containing a hydrogen-bonding crosslinking site and a side chain (b) containing a covalent bonding site; and a side chain (c) containing a hydrogen-bonding crosslinking site and a covalent crosslinking site. And at least one of them. In the present invention, the side chain (c) can also be said to be a side chain that functions as a side chain (b) while functioning as a side chain (a '). Hereinafter, each side chain will be described.

<Side Chain (a ′): Side Chain Containing Hydrogen Bonding Cross-Linked Site>
The side chain (a ′) containing a hydrogen-bonding cross-linking site has a group capable of forming a cross-link by hydrogen bonding (for example, a hydroxyl group, a hydrogen-bonding cross-linking site contained in the side chain (a) described later). Any side chain that forms a hydrogen bond based on the group may be used, and the structure is not particularly limited. Here, the hydrogen bond crosslinking site is a site where polymers (elastomers) are crosslinked by hydrogen bonding. Cross-linking by hydrogen bonding includes a hydrogen acceptor (such as a group containing an atom containing a lone pair) and a hydrogen donor (such as a group including a hydrogen atom covalently bonded to an atom having a large electronegativity). Therefore, when both the hydrogen acceptor and the hydrogen donor are not present between the side chains of the elastomers, no crosslinks due to hydrogen bonds are formed. Therefore, a hydrogen bonding cross-linked site is present in the system only when both hydrogen acceptors and hydrogen donors exist between the side chains of the elastomers. In the present invention, between the side chains of the elastomers, there are both a part that can function as a hydrogen acceptor (for example, a carbonyl group) and a part that can function as a hydrogen donor (for example, a hydroxyl group). Therefore, a portion that can function as a hydrogen acceptor and a portion that can function as a donor in the side chain can be determined as a hydrogen-bonding crosslinking site.

As such a hydrogen-bonding bridging site in the side chain (a ′), a hydrogen bond having a carbonyl-containing group and / or a nitrogen-containing heterocycle described below from the viewpoint of forming a stronger hydrogen bond. It is preferable that it is an ionic crosslinking site (hydrogen bonding crosslinking site contained in the side chain (a)). That is, as the side chain (a ′), the side chain (a) described later is more preferable. From the same viewpoint, the hydrogen-bonding cross-linking site in the side chain (a ′) is more preferably a hydrogen-bonding cross-linking site having a carbonyl-containing group and a nitrogen-containing heterocycle.

<Side Chain (a): Side Chain Containing Hydrogen Bonding Crosslinkable Site Having Carbonyl-containing Group and / or Nitrogen-containing Heterocycle>
The side chain (a) containing a hydrogen-bonded bridging site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring may be any as long as it has a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring. It is not limited. As such a hydrogen bonding cross-linking site, those having a carbonyl-containing group and a nitrogen-containing heterocyclic ring are more preferred.

Such a carbonyl-containing group is not particularly limited as long as it contains a carbonyl group, and specific examples thereof include amide, ester, imide, carboxy group, carbonyl group and the like. Such a carbonyl-containing group may be a group introduced into the main chain (polymer of the main chain portion) using a compound capable of introducing a carbonyl-containing group into the main chain. The compound capable of introducing such a carbonyl-containing group into the main chain is not particularly limited, and specific examples thereof include ketones, carboxylic acids and derivatives thereof.

Examples of such carboxylic acid include organic acids having a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may be any of aliphatic, alicyclic, aromatic and the like. Specific examples of carboxylic acid derivatives include carboxylic acid anhydrides, amino acids, thiocarboxylic acids (mercapto group-containing carboxylic acids), esters, amino acids, ketones, amides, imides, dicarboxylic acids and monoesters thereof. Etc.

Specific examples of the carboxylic acid and derivatives thereof include malonic acid, maleic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, and p-hydroxybenzoic acid. Acids, carboxylic acids such as p-aminobenzoic acid and mercaptoacetic acid, and those carboxylic acids containing substituents; acids such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, propionic anhydride, benzoic anhydride Anhydrides; aliphatic esters such as maleic acid ester, malonic acid ester, succinic acid ester, glutaric acid ester and ethyl acetate; phthalic acid ester, isophthalic acid ester, terephthalic acid ester, ethyl-m-aminobenzoate, methyl-p- Aromatic esters such as hydroxybenzoate; quinone, anne Ketones such as laquinone and naphthoquinone; glycine, tyrosine, bicine, alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N- (p-aminobenzoyl) -β-alanine, etc. Amino acids; maleamide, maleamic acid (maleic monoamide), succinic monoamide, 5-hydroxyvaleramide, N-acetylethanolamine, N, N′-hexamethylenebis (acetamide), malonamide, cycloserine, 4-acetamidophenol, amides such as p-acetamidobenzoic acid; imides such as maleimide and succinimide; and the like.

Among these, the compound capable of introducing a carbonyl group (carbonyl-containing group) is preferably a cyclic acid anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride, and is maleic anhydride. It is particularly preferred.

In addition, when the side chain (a) has a nitrogen-containing heterocycle, the nitrogen-containing heterocycle may be introduced into the main chain directly or via an organic group, and the configuration thereof is particularly limited. It is not a thing. Such a nitrogen-containing heterocycle may be used even if it contains a heteroatom other than a nitrogen atom in the heterocycle, for example, a sulfur atom, an oxygen atom, a phosphorus atom, etc., as long as it contains a nitrogen atom in the heterocycle. it can. Here, in the case where a nitrogen-containing heterocyclic ring is used in the side chain (a), if it has a heterocyclic structure, the hydrogen bond forming a bridge becomes stronger, and the resulting thermoplastic elastomer composition of the present invention This is preferable because the tensile strength is further improved.

The nitrogen-containing heterocyclic ring may have a substituent, and examples of the substituent include alkyl groups such as a methyl group, an ethyl group, a (iso) propyl group, and a hexyl group; a methoxy group and an ethoxy group. Alkoxy groups such as (iso) propoxy group; groups consisting of halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; amino group; aromatic hydrocarbon group; ester group; ether group; A thioether group; and the like can be used in combination. The substitution position of these substituents is not particularly limited, and the number of substituents is not limited.

Further, the nitrogen-containing heterocycle may or may not have aromaticity, but the permanent compression of the thermoplastic elastomer composition of the present invention obtained when having aromaticity. This is preferable because strain and mechanical strength are further improved.

Further, such a nitrogen-containing heterocyclic ring is not particularly limited, but from the viewpoints that hydrogen bonds become stronger and compression set and mechanical strength are further improved, a 5-membered ring or a 6-membered ring. It is preferable that Specific examples of such nitrogen-containing heterocycle include pyrrololine, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl, phthalimidine, β -Isoindigo, monoporphyrin, diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyroerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone Hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, in , Indoline, oxylindole, carbazole, phenothiazine, indolenine, isoindole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine , Pyrazine, phenazine, tetrazine, benzoxazole, benzoisoxazole, anthranyl, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthrazolin, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline, triazine, histidine , Triazolidine, melamine, adenine, guanine, thymine, cytosine And hydroxyethyl isocyanurate and derivatives thereof. Among these, particularly for nitrogen-containing 5-membered rings, the following compounds (cyclic structures described by chemical formulas), triazole derivatives represented by the following general formula (10), and imidazole derivatives represented by the following general formula (11) Is preferably exemplified. These may have the above-described various substituents, or may be hydrogenated or eliminated.

The substituents X, Y, and Z in the general formulas (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, or 6 to 6 carbon atoms. 20 aryl groups or amino groups. Note that any one of X and Y in the general formula (10) is not a hydrogen atom, and similarly, at least one of X, Y and Z in the general formula (11) is not a hydrogen atom.

Examples of such substituents X, Y, and Z include, in addition to hydrogen atoms and amino groups, specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, dodecyl group, stearyl Linear alkyl groups such as isopropyl groups, isobutyl groups, s-butyl groups, t-butyl groups, isopentyl groups, neopentyl groups, t-pentyl groups, 1-methylbutyl groups, 1-methylheptyl groups, 2- Branched alkyl groups such as ethylhexyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group (o-, m-, p-), dimethylphenyl group, mesityl group; It is done.

Of these, the substituents X, Y, and Z are alkyl groups, particularly butyl, octyl, dodecyl, isopropyl, and 2-ethylhexyl groups. This is preferable because the processability of is improved.

The following compounds are preferably exemplified for the nitrogen-containing 6-membered ring. These may also have the above-described various substituents (for example, the substituents that the above-mentioned nitrogen-containing heterocycle may have), or may be hydrogenated or eliminated. .

In addition, a condensed product of the nitrogen-containing heterocycle and a benzene ring or a nitrogen-containing heterocycle can be used, and specific examples thereof include the following condensed rings. These condensed rings may also have the above-described various substituents, and may have hydrogen atoms added or eliminated.

Among such nitrogen-containing heterocycles, among them, the thermoplastic elastomer composition of the present invention to be obtained is excellent in recyclability, compression set, hardness and mechanical strength, particularly tensile strength. Therefore, a triazole ring, an isocyanurate ring, It is preferably at least one selected from thiadiazole ring, pyridine ring, imidazole ring, triazine ring and hydantoin ring, and at least selected from triazole ring, thiadiazole ring, pyridine ring, imidazole ring and hydantoin ring One type is preferable.

When the side chain (a) includes both the carbonyl-containing group and the nitrogen-containing heterocycle, the carbonyl-containing group and the nitrogen-containing heterocycle are introduced into the main chain as side chains independent of each other. However, it is preferable that the carbonyl-containing group and the nitrogen-containing heterocycle are introduced into the main chain as one side chain bonded through different groups. Thus, as the side chain (a), it is preferable that a side chain containing a hydrogen-bonded cross-linking site having the carbonyl-containing group and the nitrogen-containing heterocycle is introduced into the main chain as one side chain. The following general formula (1):

[In Formula (1), A is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, and a formula: NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). An amino group or a sulfur atom; or an organic group that may contain these atoms or groups. ]
It is more preferable that the side chain containing the structural part represented by is introduced into the main chain as one side chain. Thus, it is preferable that the hydrogen-bonding cross-linked site of the side chain (a) contains a structural portion represented by the general formula (1).

Here, the nitrogen-containing heterocyclic ring A in the above formula (1) specifically includes the nitrogen-containing heterocyclic rings exemplified above. Specific examples of the substituent B in the above formula (1) include, 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). (Hereinafter, for convenience, in some cases, the amino group represented by the formula: NR ′ is simply referred to as “amino group NR ′”); the number of carbon atoms that may contain these atoms or groups An alkylene group having 1 to 20 carbon atoms or an aralkylene group; an alkylene ether group having 1 to 20 carbon atoms (an alkyleneoxy group such as an —O—CH ₂ CH ₂ — group) or an alkyleneamino group having these atoms or groups as terminals. (For example, —NH—CH ₂ CH ₂ — group or the like) or alkylene thioether group (alkylene thio group, for example, —S—CH ₂ CH ₂ — group); A xylene ether group (aralkyleneoxy group), an aralkylene amino group, or an aralkylene thioether group;

Here, examples of the alkyl group having 1 to 10 carbon atoms that can be selected as R ′ in the amino group NR ′ include methyl, ethyl, propyl, butyl, pentyl, hexyl, A heptyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned. An oxygen atom, a sulfur atom and an amino group NR ′ in the substituent B in the above formula (1); and; an alkylene ether group, an alkylene amino group and an alkylene thioether having 1 to 20 carbon atoms terminated by these atoms or groups Group, or an oxygen atom such as an aralkylene ether group, an aralkylene amino group, an aralkylene thioether group, an amino group NR ′ and a sulfur atom are combined with an adjacent carbonyl group to form a conjugated ester group, amide group or imide group. It is preferable to form a thioester group or the like.

Among these, the substituent B is an oxygen atom, a sulfur atom or an amino group forming a conjugated system; an alkylene ether group having 1 to 20 carbon atoms, an alkyleneamino group or an alkylene having these atoms or groups at the terminal. It is preferably a thioether group, an amino group (NH), an alkyleneamino group (—NH—CH ₂ — group, —NH—CH ₂ CH ₂ — group, —NH—CH ₂ CH ₂ CH ₂ — group), alkylene An ether group (—O—CH ₂ — group, —O—CH ₂ CH ₂ — group, —O—CH ₂ CH ₂ CH ₂ — group) is particularly preferred.

In the case where the side chain (a) is a side chain containing a hydrogen-bonded cross-linking site having the carbonyl-containing group and the nitrogen-containing heterocycle, the hydrogen bond having the carbonyl-containing group and the nitrogen-containing heterocycle. The sex crosslinking site is more preferably a side chain introduced into the polymer main chain at the α-position or β-position as one side chain represented by the following formula (2) or (3).

[Wherein, A is a nitrogen-containing heterocyclic ring, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or A sulfur atom; or an organic group that may contain these atoms or groups. ]
Here, the nitrogen-containing heterocyclic ring A is basically the same as the nitrogen-containing heterocyclic ring A of the above formula (1), and the substituents B and D are each independently of the substituent B of the above formula (1). The same as above. However, the substituent D in the formula (3) is a single bond; an alkylene having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom among those exemplified as the substituent B in the formula (1). It is preferable to form a conjugated system of a group or an aralkylene group, and a single bond is particularly preferable. That is, it is preferable to form an alkyleneamino group or an aralkyleneamino group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom together with the imide nitrogen of the above formula (3). It is particularly preferred that the nitrogen-containing heterocycle is directly bonded to the imide nitrogen (single bond). Specifically, the substituent D includes a single bond; the above-described alkylene ether or aralkylene ether group having 1 to 20 carbon atoms having an oxygen atom, sulfur atom or amino group as a terminal; methylene including isomers; Group, ethylene group, propylene group, butylene group, hexylene group, phenylene group, xylylene group and the like.

When the side chain (a) is a side chain containing a hydrogen-bonded cross-linking site having the carbonyl-containing group and the nitrogen-containing heterocycle, the hydrogen-bond cross-linking site of the side chain (a) is Formula (101):

[In Formula (101), A is a nitrogen-containing heterocyclic ring. ]
It is preferable to contain the structural part represented by these. The nitrogen-containing heterocycle A in the formula (101) is basically the same as the nitrogen-containing heterocycle A in the formula (1). In addition, the hydrogen bond cross-linking site of such a side chain (a) is represented by the following general formula (102) from the viewpoint of high modulus and high breaking strength:

What has the structure represented by these is more preferable. Furthermore, the side chain (a) is particularly preferably a group represented by the general formula (102).

The ratio of the carbonyl-containing group and the nitrogen-containing heterocycle of the thermoplastic elastomer is not particularly limited, and is in the range of 1: 1 to 3: 1 (more preferably 1: 1, 2: 1 or 3: 1). It is preferable because it is easy to form a complementary interaction and can be easily manufactured.

The side chain (a) containing a hydrogen-bonded cross-linking site having such a carbonyl-containing group and / or a nitrogen-containing heterocycle has a ratio of 0.1 to 50 mol% with respect to 100 mol% of the main chain portion ( It is preferably introduced at a rate of 1 to 30 mol%. When the introduction rate of such side chain (a) is less than 0.1 mol%, the tensile strength at the time of crosslinking may not be sufficient. On the other hand, when it exceeds 50 mol%, the crosslinking density increases and rubber elasticity is lost. There is. That is, if the introduction rate is within the above-mentioned range, the crosslinks are efficiently formed between the molecules by the interaction between the side chains of the thermoplastic elastomer, so the tensile strength at the time of crosslinking is high and the recyclability is excellent. Therefore, it is preferable.

The introduction rate is such that the side chain (a) includes a side chain (ai) containing a hydrogen-bonded cross-linking site having the carbonyl-containing group and a hydrogen bond cross-linking site having the nitrogen-containing heterocycle. When the chain (a-ii) is independently introduced, the side chain (ai) containing the carbonyl-containing group and the side chain (ai-ii) containing the nitrogen-containing heterocyclic ring According to the ratio, these are considered as one side chain (a) and calculated. When either one of the side chains (ai) and (a-ii) is excessive, the introduction rate may be considered based on the larger side chain.

Further, the introduction rate is, for example, when the main chain portion is ethylene-propylene rubber (EPM), the amount of the monomer having the side chain portion introduced is 0.1 to 50 per 100 units of ethylene and propylene monomer units. About unit.

Further, as the side chain (a), a polymer having a cyclic acid anhydride group (more preferably a maleic anhydride group) as a functional group in a polymer (material for forming an elastomeric polymer) that forms the main chain after the reaction. A compound that forms a hydrogen bonding cross-linking site by reacting with the functional group (cyclic acid anhydride group) and the cyclic acid anhydride group using (an elastomeric polymer having a cyclic acid anhydride group in the side chain) It is preferable to react with (a compound capable of introducing a nitrogen-containing heterocycle) to form a hydrogen-bonding cross-linked site and to use the side chain of the polymer as the side chain (a). The compound capable of introducing such a nitrogen-containing heterocycle may be the nitrogen-containing heterocycle itself exemplified above, and a substituent that reacts with a cyclic acid anhydride group such as maleic anhydride (for example, hydroxyl group, thiol). A nitrogen-containing heterocycle having a group, an amino group, or the like.

Here, the bonding position of the nitrogen-containing heterocycle in the side chain (a) will be described. For convenience, the nitrogen heterocycle is referred to as “nitrogen-containing n-membered ring compound (n ≧ 3)”.

The bonding positions described below ("1st to nth positions") are based on the IUPAC nomenclature. For example, in the case of a compound having three nitrogen atoms having an unshared electron pair, the bonding position is determined by the order based on the IUPAC nomenclature. Specifically, the bonding positions are indicated on the 5-membered, 6-membered and condensed nitrogen-containing heterocycles exemplified above.

In such a side chain (a), the bonding position of the nitrogen-containing n-membered ring compound bonded to the copolymer directly or via an organic group is not particularly limited, and any bonding position (position 1 to position n) But you can. Preferably, it is the 1-position or 3-position to n-position.

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

<Side Chain (b): Side Chain Containing a Covalent Bonding Site>
In the present specification, the “side chain (b) containing a covalently bonded cross-linking site” is a covalent cross-linking site (containing an amino group described later) on an atom (usually a carbon atom) forming the main chain of the elastomeric polymer. Functional groups that can generate at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes, and thioethers by reacting with “compounds that form covalent bonds” such as compounds ) Has a chemically stable bond (covalent bond). Note that the side chain (b) is a side chain containing a covalent cross-linking site, but has a covalent bond site and a group capable of hydrogen bonding, and hydrogen bonds between the side chains. In the case of forming a cross-link by, a hydrogen donor that can be used as a side chain (c) described later (which can form a hydrogen bond between the side chains of the elastomers, and When both hydrogen acceptors are not included, for example, when only a side chain containing an ester group (—COO—) is present in the system, the ester groups (—COO—) In particular, since no hydrogen bond is formed, such a group does not function as a hydrogen-bonding cross-linking site, whereas, for example, a hydrogen-donating hydrogen donor site, such as a carboxy group or a triazole ring, and a hydrogen acceptor Part When the structures having both are included in the side chains of the elastomers, hydrogen bonds are formed between the side chains of the elastomers, so that hydrogen-bonding cross-linked sites are contained. When an ester group and a hydroxyl group coexist between the side chains and a hydrogen bond is formed between the side chains by these groups, the site where the hydrogen bond is formed becomes a hydrogen-bonding crosslinking site. The side chain (b) may be used as the side chain (c) depending on the structure itself, the structure of the side chain (b) and the type of substituents of the other side chain, etc.) . Further, the “covalent bonding crosslinking site” referred to here is a site that crosslinks polymers (elastomers) by covalent bonding.

The side chain (b) containing such a covalently cross-linked site is not particularly limited. For example, an elastomeric polymer having a functional group in the side chain (polymer for forming the main chain portion) and the functional group It is preferable to contain a covalent crosslinking site formed by reacting with a compound that reacts with a group to form a covalent crosslinking site (compound that generates a covalent bond). Crosslinking at the covalent cross-linking site of such a side chain (b) is formed by at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. Is preferred. Therefore, the functional group possessed by the polymer constituting the main chain is a functional group capable of producing at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. It is preferable.

Examples of such “compound that forms a covalent bond site (compound that forms a covalent bond)” include, for example, two or more amino groups and / or imino groups (both amino groups and imino groups are combined in one molecule). A polyamine compound having two or more of these groups in total); a polyol compound having two or more hydroxyl groups in one molecule; a polyisocyanate compound having two or more isocyanate (NCO) groups in one molecule; 1 Polythiol compound having two or more thiol groups (mercapto groups) in the molecule; polyepoxy compound having two or more epoxy groups in one molecule; polycarboxy compound having two or more carboxy groups in one molecule; And polyalkoxysilyl compounds having two or more alkoxysilyl groups. Here, the “compound that forms a covalent crosslinkable site (compound that forms a covalent bond)” refers to the type of substituent that the compound has, the degree of progress of the reaction when the compound is reacted, Depending on the above, it becomes a compound that can introduce both the hydrogen-bonding cross-linking site and the covalent-bonding cross-linking site (for example, when a cross-linking site by a covalent bond is formed using a compound having 3 or more hydroxyl groups). Depending on the progress of the reaction, two hydroxyl groups may react with the functional group of the elastomeric polymer having a functional group in the side chain, and the remaining one hydroxyl group may remain as a hydroxyl group. In that case, the site | part which forms a hydrogen bond bridge | crosslinking can also be introduce | transduced together.) Therefore, the “compound that forms a covalent bond site (compound that forms a covalent bond)” exemplified here also includes “a compound that forms both a hydrogen bond bridge site and a covalent bond site”. obtain. From this point of view, when the side chain (b) is formed, the compound is appropriately selected from “compounds that form a covalent bond site (compound that generates a covalent bond)” according to the intended design. Or the side chain (b) may be formed by appropriately controlling the degree of progress of the reaction. In addition, when the compound which forms a covalent bond crosslinkable part has a heterocyclic ring, it becomes possible to manufacture a hydrogen bondable crosslinkable part more efficiently at the same time, as a side chain (c) described later. Thus, it is possible to efficiently form a side chain having the covalent bond crosslinking site. Therefore, specific examples of the compound having such a heterocyclic ring will be described together with the side chain (c) as a suitable compound for producing the side chain (c). In addition, it can be said that side chain (c) is a suitable form of side chains, such as a side chain (a) and a side chain (b), from the structure.

Polyamine compounds that can be used as such “compound that forms a covalent bond site (compound that forms a covalent bond)” include, for example, the following alicyclic amines, aliphatic polyamines, aromatic polyamines, and the like. And nitrogen heterocyclic amines.

Specific examples of such alicyclic amines include, for example, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane, di- (Aminomethyl) cyclohexane and the like.

The aliphatic polyamine is not particularly limited, and examples thereof include methylene diamine, ethylene diamine, propylene diamine, 1,2-diaminopropane, 1,3-diaminopentane, hexamethylene diamine, diaminoheptane, diaminododecane, diethylenetriamine, Diethylaminopropylamine, N-aminoethylpiperazine, triethylenetetramine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-diisopropylethylenediamine, N, N'-dimethyl-1,3-propane Diamine, N, N'-diethyl-1,3-propanediamine, N, N'-diisopropyl-1,3-propanediamine, N, N'-dimethyl-1,6-hexanediamine, N, N'-diethyl -1, - hexanediamine, N, N ', N' '- trimethylbis (hexamethylene) triamine, and the like.

The aromatic polyamine and the nitrogen-containing heterocyclic amine are not particularly limited. For example, diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tris (dimethylaminomethyl) phenol, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenyl. Examples include sulfone and 3-amino-1,2,4-triazole.

In the polyamine compound, one or more of the hydrogen atoms may be substituted with an alkyl group, an alkylene group, an aralkylene group, an oxy group, an acyl group, a halogen atom, or the like. It may contain a hetero atom such as a sulfur atom.

Further, the polyamine compounds may be used singly or in combination of two or more. The mixing ratio when two or more types are used in combination is an arbitrary ratio depending on the use in which the thermoplastic elastomer (composition) of the present invention is used, the physical properties required for the thermoplastic elastomer (composition) of the present invention, and the like. Can be adjusted.

Of the polyamine compounds exemplified above, hexamethylene diamine, N, N′-dimethyl-1,6-hexanediamine, diaminodiphenyl sulfone and the like are preferable because of their high effect of improving compression set, mechanical strength, particularly tensile strength. .

As long as the polyol compound is a compound having two or more hydroxyl groups, the molecular weight and skeleton thereof are not particularly limited. For example, the following polyether polyols, polyester polyols, other polyols, and mixed polyols thereof may be used. Can be mentioned.

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

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

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

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

As long as the polythiol compound is a compound having two or more thiol groups, its molecular weight and skeleton are not particularly limited. Specific examples thereof include methanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, , 9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1,2-propanedithiol, 1,3-propadithiol, toluene-3,4-dithiol, 3,6-dichloro-1, 2-benzenedithiol, 1,5-naphthalenedithiol, 1,2-benzenedimethanethiol, , 3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 4,4′-thiobisbenzenethiol, 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6 -Dioxaoctane, 1,5-dimercapto-3-thiapentane, 1,3,5-triazine-2,4,6-trithiol (trimercapto-triazine), 2-di-n-butylamino-4,6- Dimercapto-s-triazine, trimethylolpropane tris (β-thiopropionate), trimethylolpropane tris (thioglycolate), polythiol (thiocol or thiol-modified polymer (resin, rubber, etc.)), tris-[(3 -Mercaptopropionyloxy) -ethyl] -isocyanurate, etc., and these can be used alone Or two or more of them may be used in combination.

The polyepoxy compound is not particularly limited in terms of molecular weight and skeleton as long as it is a compound having two or more epoxy groups. Specific examples thereof include bisphenol A diglycidyl ether (bisphenol A type epoxy resin). Bisphenol F diglycidyl ether (bisphenol F type epoxy resin), 3,4-epoxycyclohexylmethyl-3'4'-epoxycyclohexanecarboxylate, DCPD type epoxy resin, epoxy novolak resin, orthocresol novolak type epoxy resin These may be used alone or in combination of two or more.

The polycarboxy compound is not particularly limited as long as it has two or more carboxy groups, and specific examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, Examples include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, propanetricarboxylic acid, and benzenetricarboxylic acid. These may be used alone or in combination of two or more. May be.

Further, the polyalkoxysilyl compound is not particularly limited as long as it has a compound having two or more alkoxysilyl groups, and specific examples thereof include tris- (trimethoxysilylpropyl) isocyanurate. Bis (triethoxysilylpropyl) tetrasulfide, 1,6-bis (trimethoxysilyl) hexane, and bis [3- (trimethoxysilyl) propyl] amine. You may use the above together.

The functional group possessed by the polymer constituting the main chain that reacts with such a “compound that forms a covalent bond site (compound that forms a covalent bond)” includes amide, ester, lactone, urethane, and thiourethane. And a functional group capable of generating (generating: forming) at least one bond selected from the group consisting of thioethers, such as a cyclic acid anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, Preferred examples include thiol groups.

In addition, the elastomeric polymer (B) having the side chain (b) has a cross-linking at the covalent cross-linking site in the side chain (b), that is, the above-mentioned “covalent cross-linking with the functional group”. Having at least one covalent bond formed in a molecule by reaction with a compound that forms a site (compound that forms a covalent bond), and in particular, lactone, urethane, ether, thiourethane and thioether In the case where the cross-link is formed by at least one bond selected from the group consisting of: preferably 2 or more, more preferably 2 to 20, more preferably 2 to 10 More preferably.

Further, it is possible that the crosslinking at the covalent crosslinking site of the side chain (b) contains a tertiary amino bond (—N═) or an ester bond (—COO—). The compression set and mechanical strength (breaking elongation, breaking strength) of the composition) are preferable because they can be more easily improved. In this case, an elastomer having a side chain containing a group capable of forming a hydrogen bond with respect to a tertiary amino bond (—N═) and an ester bond (—COO—) is included. In some cases (for example, when another elastomer having a side chain containing a hydroxyl group or the like is present), the covalently crosslinked site can function as a side chain (c) described later. For example, in the case of the elastomeric polymer (B) having the side chain (a) as the side chain (a ′) (that is, the elastomeric polymer (B) has both side chains (a) and (b). In the case of a polymer), when the crosslinking at the covalent crosslinking site has the tertiary amino bond and / or the ester bond, these groups and the side chain (a) (carbonyl-containing group and / or nitrogen-containing group) It is considered that the crosslink density can be further improved by hydrogen bonding (interaction) with a group in the side chain having a heterocyclic ring. From the viewpoint of forming a side chain (b) having such a structure containing a tertiary amino bond (—N═) and an ester bond (—COO—), “a covalently linked cross-linking site is formed. As the compound (compound that forms a covalent bond), among those exemplified above, polyethylene glycol laurylamine (eg, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (eg, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol It may be coal stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) stearylamine). preferable.

Even if a compound that forms a covalent crosslinking site as described above (compound that forms a covalent bond) is used, depending on the degree of reaction progress, the type of substituent, the stoichiometric ratio of the raw materials used, etc. Since a hydrogen bonding crosslinking site may be introduced together, the preferred structure of the covalent crosslinking site is combined with the preferred structure of the covalent crosslinking site in the side chain (c). I will explain.

<Side Chain (c): Side Chain Containing Both Hydrogen Bonding Crosslinkage Site and Covalent Bonding Crosslinkage Site>
Such a side chain (c) is a side chain containing both a hydrogen-bonding crosslinking site and a covalent bonding site in one side chain. Such a hydrogen-bonding cross-linking site contained in the side chain (c) is the same as the hydrogen-bonding cross-linking site described in the side chain (a ′), and the hydrogen-bonding cross-linking site in the side chain (a). The thing similar to a site | part is preferable. Moreover, as a covalent crosslinkable site | part contained in a side chain (c), the thing similar to the covalent bond crosslinkable part in a side chain (b) can be utilized (The same bridge | crosslinking can also utilize the same thing. ).

Such a side chain (c) reacts with an elastomeric polymer having a functional group in the side chain (polymer for forming the main chain portion) and the functional group to form a hydrogen-bonding crosslinking site and a covalent bond. A side chain formed by reacting a compound that forms both of the crosslinking sites (a compound that introduces both a hydrogen bonding crosslinking site and a covalent bonding site) is preferable. As a compound that forms both such a hydrogen-bonding crosslinking site and a covalent-bonding crosslinking site (a compound that introduces both a hydrogen-bonding crosslinking site and a covalent-bonding crosslinking site), a heterocyclic ring (particularly preferably a nitrogen-containing compound) is used. A compound having a heterocycle) and capable of forming a covalent crosslinking site (a compound that forms a covalent bond) is preferable, among which a heterocycle-containing polyol, a heterocycle-containing polyamine, a heterocycle-containing polythiol, and the like are more preferable. preferable.

In addition, the polyol, polyamine, and polythiol containing such a heterocyclic ring may form the above-mentioned “covalently linked crosslinking site” except that it has a heterocyclic ring (particularly preferably a nitrogen-containing heterocyclic ring). The same polyols, polyamines and polythiols as described in “Possible compounds (compounds forming a covalent bond)” can be used as appropriate. Such a heterocyclic ring-containing polyol is not particularly limited, and examples thereof include bis, tris (2-hydroxyethyl) isocyanurate, kojic acid, dihydroxydithiane, and trishydroxyethyltriazine. The heterocycle-containing polyamine is not particularly limited, and examples thereof include acetoguanamine, piperazine, bis (aminopropyl) piperazine, benzoguanamine, and melamine. Further, examples of such a heterocyclic ring-containing polythiol include dimercaptothiadiazole and tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate. Thus, as the side chain (c), an elastomeric polymer having a functional group in the side chain (polymer for forming the main chain part) is reacted with a polyol, polyamine, polythiol, etc. containing a heterocyclic ring. It is preferable that the side chain is obtained.

The main chain that reacts with “a compound that forms both a hydrogen bonding crosslinking site and a covalent crosslinking site (a compound that introduces both a hydrogen bonding crosslinking site and a covalent crosslinking site)” is formed. The functional group possessed by the polymer is preferably a functional group capable of producing (generating: forming) at least one bond selected from the group consisting of amide, ester, lactone, urethane, thiourethane and thioether. Preferred examples include a cyclic acid anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, and a thiol group.

In addition, the elastomeric polymer (B) having the side chain (c) has at least one crosslink in the molecule at the covalent crosslink site in the side chain (c), In the case where a bridge is formed by at least one bond selected from the group consisting of lactone, urethane, ether, thiourethane and thioether, it preferably has 2 or more, and has 2 to 20 More preferably, 2 to 10 are more preferable. Further, it is possible that the crosslinking at the covalent crosslinking site of the side chain (c) contains a tertiary amino bond (—N═) or an ester bond (—COO—). This is preferable because the compression set and mechanical strength (breaking elongation, breaking strength) of the composition) are further improved.

(About a structure suitable as a covalent cross-linking site in side chains (b) to (c))
With respect to the side chain (b) and / or (c), the bridge at the covalent crosslinking site contains a tertiary amino bond (—N═), an ester bond (—COO—), The reason why the compression set and mechanical strength (breaking elongation, breaking strength) of the obtained thermoplastic elastomer (composition) are improved to a higher degree when these bonding sites also function as hydrogen bonding cross-linking sites. To preferred. In this way, the tertiary amino bond (—N═) or ester bond (—COO—) in the side chain having a covalent cross-linking site forms a hydrogen bond with the other side chain. In such a case, the covalent bond cross-linking site containing such a tertiary amino bond (—N═) and ester bond (—COO—) is also provided with a hydrogen bond cross-linking site, and the side chain (c) Can function.

In addition, for example, in the case of the elastomeric polymer (B) having the side chain (a) as the side chain (a ′), the share containing the tertiary amino bond and / or the ester bond is included. In the case of having a binding cross-linking site, if the tertiary amino bond and / or the ester bond forms a hydrogen bond (interaction) with a group in the side chain (a), the cross-linking density is further improved. Is considered possible. Here, a compound capable of reacting with a functional group of the polymer constituting the main chain to form a covalently crosslinked site containing the tertiary amino bond and / or the ester bond (hydrogen Examples of the compound capable of forming both a binding crosslinking site and a covalent crosslinking site include polyethylene glycol laurylamine (for example, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (Eg, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (eg, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) o Tilamine), polyethylene glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) stearylamine) Can be mentioned as suitable.

The crosslink at the covalent crosslink site of the side chain (b) and / or side chain (c) contains at least one structure represented by any of the following general formulas (4) to (6). More preferably, G in the formula contains a tertiary amino bond or an ester bond (in the following structure, when it contains a hydrogen-bonding cross-linked site, the side having that structure) The chain is used as the side chain (c)).

In the general formulas (4) to (6), E, J, K and L are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) .) Or a sulfur atom; or an organic group that may contain these atoms or groups, G may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and may have a linear, branched, or cyclic carbon number. 1 to 20 hydrocarbon groups.

Here, the substituents E, J, K, and L are each independently the same as the substituent B in the general formula (1).

Examples of the substituent G include a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, a 1,6-hexylene group, and a 1,7-heptylene group. Alkylene groups such as 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 1,11-undecylene group, 1,12-dodecylene group; N, N-diethyldodecylamine-2, 2'-diyl, N, N-dipropyldodecylamine-2,2'-diyl, N, N-diethyloctylamine-2,2'-diyl, N, N-dipropyloctylamine-2,2'- Diyl, N, N-diethylstearylamine-2,2′-diyl, N, N-dipropylstearylamine-2,2′-diyl, divinyl, bivalent group such as 1,4-cyclohexylene group Alicyclic charcoal Hydrogen group; divalent aromatic hydrocarbon group such as 1,4-phenylene group, 1,2-phenylene group, 1,3-phenylene group, 1,3-phenylenebis (methylene) group; propane-1,2 , 3-triyl, butane-1,3,4-triyl, trimethylamine-1,1 ′, 1 ″ -triyl, triethylamine-2,2 ′, 2 ″ -triyl and the like; A trivalent cyclic hydrocarbon containing an oxygen atom, sulfur atom or nitrogen atom such as a nurate group or a triazine group; a tetravalent hydrocarbon group represented by the following formulas (12) and (13); and a combination thereof And the like. Further, the substituent G in such a formula preferably has an isocyanurate group (isocyanurate ring) structure from the viewpoint of high heat resistance and high strength due to hydrogen bonding. In addition, the substituent G in such a formula is a group represented by the following general formula (111) and the following general formula (112) from the viewpoint of high heat resistance and high strength due to hydrogen bonding. It is more preferable that it is a group represented.

Further, in any one of the following formulas (7) to (9), the crosslinking at the covalent crosslinking site of the side chain (c) is bonded to the main chain of the elastomeric polymer at the α-position or β-position. It is preferable to contain at least one of the structures represented, and it is more preferred that G in the formula contains a tertiary amino group (the structures shown in the formulas (7) to (9) are a hydroxyl group and a carbonyl group. And a side chain having such a structure can function as a side chain (c)).

In the formulas (7) to (9), the substituents E, J, K and L are each independently the same as the substituents E, J, K and L in the above formulas (4) to (6). The substituent G is basically the same as the substituent G in the above formulas (4) to (6).

Further, as the structure represented by any of the formulas (7) to (9), specifically, the structures represented by the following formulas (14) to (25) are exemplified as preferable ones. The

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

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

In the side chains (b) and (c), the cross-linking at the covalent cross-linking site is preferably formed by a reaction between a cyclic acid anhydride group and a hydroxyl group or an amino group and / or an imino group. . For example, when the polymer that forms the main chain portion after the reaction has a cyclic acid anhydride group (for example, maleic anhydride group) as a functional group, the cyclic acid anhydride group of the polymer, a hydroxyl group or an amino group, and It is formed by reacting with a compound that forms the above-described covalently crosslinked site having an imino group (compound that generates a covalent bond) to form a site that is crosslinked by a covalent bond, thereby crosslinking between the polymers. Crosslinking may be used.

In such side chains (b) and (c), the crosslinking at the covalent crosslinking site is selected from the group consisting of amide, ester, lactone, urethane, ether, urea bond, thiourethane and thioether. More preferably, it is formed by at least one bond.

The side chain (a ′), the side chain (a), the side chain (b), and the side chain (c) have been described above. Each group (structure) of the side chain in such a polymer is NMR, It can be confirmed by a commonly used analytical means such as an IR spectrum.

The elastomeric polymer (A) is an elastomeric polymer having the side chain (a) and a glass transition point of 25 ° C. or less, and the elastomeric polymer (B) has a hydrogen-bonding cross-linked site in the side chain. And an elastomeric polymer having a glass transition point of 25 ° C. or less (a polymer having both side chains (a ′) and side chains (b) as side chains, side chains on side chains) A polymer containing at least one chain (c)). As such an elastomer component, one of the elastomeric polymers (A) to (B) may be used alone, or two or more of them may be used in combination. Good.

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). From the viewpoint that a stronger hydrogen bond is formed as the hydrogen bonding cross-linking site contained in the side chain of the elastomeric polymer (B), hydrogen bonding cross-linking having a carbonyl-containing group and / or a nitrogen-containing heterocycle. It is preferably a site (more preferably a hydrogen-bonding cross-linked site having a carbonyl-containing group and a nitrogen-containing heterocycle).

The at least one elastomer component selected from the group consisting of such elastomeric polymers (A) and (B) is at least one selected from the group consisting of the following reactants (I) to (VI): Preferably it is a seed.
[Reactant (I)] Maleic anhydride-modified elastomeric polymer (hereinafter simply referred to as “elastomeric polymer (E1)” for convenience) and at least one of a hydroxyl group, a thiol group, and an amino group At least one of pyridine, hydroxyl group, thiol group and amino group optionally having at least one substituent selected from triazole, hydroxyl group, thiol group and amino group optionally having substituents At least one of imidazole, hydroxyl group, thiol group and amino group optionally having at least one substituent among thiadiazole, hydroxyl group, thiol group and amino group optionally having substituents It has at least one kind of substituent among isocyanurate, hydroxyl group, thiol group and amino group which may have a substituent. At least one substituent selected from hydantoin, hydroxyl group, thiol group and amino group which may have at least one substituent selected from triazine, hydroxyl group, thiol group and amino group which may be Reaction with at least one compound of hydrocarbon compounds having two or more, trishydroxyethyl isocyanurate, sulfamide, and polyether polyol (hereinafter simply referred to as “compound (M1)” for convenience). Product [Reactant (II)] A hydroxyl group-containing elastomeric polymer (hereinafter simply referred to as “elastomeric polymer (E2)” for convenience) and a carboxy group, an alkoxysilyl group and an isocyanate group. A compound having at least two substituents (hereinafter, for convenience, Reaction product with [Compound (M2)]] [Reactant (III)] Carboxy group-containing elastomeric polymer (hereinafter simply referred to as “elastomeric polymer (E3)” for convenience). , A reaction product of a compound having two or more substituents selected from a hydroxyl group, a thiol group and an amino group (hereinafter simply referred to as “compound (M3)” for convenience) [reaction Product (IV)] An amino group-containing elastomeric polymer (hereinafter simply referred to as “elastomeric polymer (E4)” for convenience) and a carboxy group, an epoxy group, an alkoxysilyl group, and an isocyanate group. A compound having two or more substituents (hereinafter referred to simply as “compound (M4)” for convenience). (Reactant (V)) with an alkoxysilyl group-containing elastomeric polymer (hereinafter simply referred to as “elastomeric polymer (E5)” for convenience) and a hydroxyl group, a carboxy group, and an amino group. Reactant [Reactant (VI)] with compound having two or more substituents selected from the above (hereinafter simply referred to as “compound (M5)” for the sake of convenience) A polymer (hereinafter simply referred to as “elastomeric polymer (E6)” for convenience) and a compound having at least two substituents selected from a thiol group and an amino group (hereinafter referred to as convenience) , Sometimes simply referred to as “compound (M6)”).

Such elastomeric polymers (E1) to (E6) are produced by a conventional method, for example, a polymer capable of forming the main chain portion of the above-mentioned elastomer component under the usual conditions such as heating. The compound may be produced by a graft polymerization of a compound capable of introducing a functional group (for example, maleic anhydride or the like) according to the intended design by stirring the above. In addition, as such elastomeric polymers (E1) to (E6), commercially available products may be used.

In addition, the glass transition point of such elastomeric polymers (E1) to (E6) is preferably 25 ° C. or lower as in the case of the elastomer component described above. If the glass transition point of the elastomeric polymer is within this range, the resulting thermoplastic elastomer composition of the present invention will 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 weight average molecular weight of the main chain portions of the elastomeric polymers (A) and (B). This is the same as the preferred range.

Examples of the maleic anhydride-modified elastomeric polymer (E1) include maleic anhydride-modified isoprene rubbers such as LIR-403 (manufactured by Kuraray Co., Ltd.) and LIR-410A (prototype of Kuraray Co., Ltd.); Chemical Company), Yucaron (Mitsubishi Chemical Corporation), Tuffmer M (for example, MP0610 (Mitsui Chemicals), MP0620 (Mitsui Chemicals)), etc .; maleic anhydride modified ethylene-propylene rubber; Tuffmer M (for example, MA8510, MH7010, MH7020 (manufactured by Mitsui Chemicals), MH5010, MH5020 (manufactured by Mitsui Chemicals), MH5040 (manufactured by Mitsui Chemicals)), etc .; Adtex series (maleic anhydride modified EVA, Maleic anhydride modified EMA (Nippon Polyolefin )), HPR series (maleic anhydride-modified EEA, maleic anhydride-modified EVA (manufactured by Mitsui / Jupon Polyolefin)), Bond Fast series (maleic anhydride-modified EMA (manufactured by Sumitomo Chemical)), Dumiran Series (maleic anhydride modified EVOH (manufactured by Takeda Pharmaceutical Company Limited)), Bondine (ethylene / acrylic acid ester / maleic anhydride terpolymer (manufactured by Atophina)), Tuftec (maleic anhydride modified SEBS, M1943 (Asahi Kasei) Clayton (maleic anhydride modified SEBS, FG1901, FG1924 (manufactured by Kraton Polymer Co., Ltd.)), tufprene (maleic anhydride modified SBS, 912 (manufactured by Asahi Kasei)), Septon (maleic anhydride modified SEPS (Kuraray Co., Ltd.) Manufactured)), Lexpearl (maleic anhydride modified EVA) ET-182G, 224M, 234M (manufactured by Nippon Polyolefin)), maleic anhydride-modified polyethylene such as Aurorene (maleic anhydride-modified EVA, 200S, 250S (manufactured by Nippon Paper Chemicals)); Admer (for example, QB550, LF128) (Manufactured by Mitsui Chemicals)) and the like.

As the maleic anhydride-modified elastomeric polymer (E1), maleic anhydride-modified ethylene-propylene rubber and maleic anhydride-modified ethylene-butene rubber are more preferable from the viewpoint of high molecular weight and high strength.

Examples of the hydroxyl group-containing elastomeric polymer (E2) include hydroxyl group-containing BR, hydroxyl group-containing SBR, hydroxyl group-containing IR, hydroxyl group-containing natural rubber, polyvinyl alcohol, and ethylene vinyl alcohol copolymer.

Among such hydroxyl group-containing elastomeric polymers (E2), an elastomeric polymer in which both ends are hydroxyl groups is preferable from the viewpoint of being easily available industrially and excellent in physical properties. Among them, hydroxyl group-containing BR, hydroxyl group-containing IR An ethylene vinyl alcohol copolymer is more preferable, and a hydroxyl group-containing BR is more preferable.

Examples of such carboxy group-containing elastomeric polymer (E3) include carboxy group-containing BR, carboxy group-containing SBR, carboxy group-containing IR, carboxy group-containing natural rubber, polyacrylic acid, ethylene acrylic acid copolymer, poly A methacrylic acid, an ethylene methacrylic acid copolymer, etc. are mentioned.

As such a carboxy group-containing elastomeric polymer (E3), a carboxy group-containing IR, an ethylene acrylic acid copolymer, and an ethylene methacrylic acid copolymer are available from the viewpoint of being easily available industrially and having excellent physical properties. Preferably, carboxy group-containing IR is more preferable.

Furthermore, examples of the amino group-containing elastomeric polymer (E4) include amino group-containing BR, amino group-containing SBR, amino group-containing IR, amino group-containing natural rubber, amino group-containing polyethyleneimine, and the like.

As such an amino group-containing elastomeric polymer (E4), an amino group-containing polyethyleneimine is more preferable from the viewpoint of being easily industrially available and having excellent physical properties.

The amino group-containing elastomeric polymer (E4) preferably has an amine value of 1 to 50 mmol / g, more preferably 5 to 40 mmol / g, and further preferably 10 to 30 mmol / g. preferable. If the amine value is less than the lower limit, it is necessary to add a large amount, and the physical properties tend to decrease due to a decrease in the crosslinking density. On the other hand, if the upper limit is exceeded, the crosslinking density becomes too high due to the addition of a small amount. It tends to end up. As the amine value, a value measured by potentiometric titration can be used.

Examples of the alkoxysilyl group-containing elastomeric polymer (E5) include, for example, alkoxysilyl group-containing BR, alkoxysilyl group-containing SBR, alkoxysilyl group-containing IR, alkoxysilyl group-containing natural rubber, and alkoxysilyl group-containing polyethylene. And alkoxysilyl group-containing polypropylene.

Such an alkoxysilyl group-containing elastomeric polymer (E5) is more preferably an alkoxysilyl group-containing polyethylene from the viewpoint of being easily available industrially and having excellent physical properties.

Examples of the epoxy group-containing elastomeric polymer (E6) include epoxy group-containing BR, epoxy group-containing SBR, epoxy group-containing IR, and epoxy group-containing natural rubber.

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

Examples of the hydrocarbon compound having two or more substituents selected from a hydroxyl group, a thiol group and an amino group used as such a compound (M1) include the aforementioned polyol compounds and polythiol compounds. Among the polyamine compounds, those whose main skeleton is composed of a hydrocarbon compound can be mentioned. The hydrocarbon group having such a main skeleton is preferably an aliphatic hydrocarbon compound (more preferably an aliphatic hydrocarbon compound having 1 to 30 carbon atoms). Further, the hydrocarbon compound having two or more substituents selected from a hydroxyl group, a thiol group and an amino group used as such a compound (M1) can be easily obtained industrially. From the viewpoint of high crosslinking density and excellent physical properties, pentaerythritol, ethanedithiol, and ethanediamine are preferred, and pentaerythritol is more preferred.

Examples of the compound having two or more substituents selected from carboxy group, alkoxysilyl group and isocyanate group used as compound (M2) include the aforementioned polycarboxy compounds and polyalkoxysilyl compounds. Polyisocyanate compounds can be suitably used. Among them, 2,6-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, xylylene diisocyanate (XDI) can be used from the viewpoint of being easily available industrially and having excellent physical properties. Is more preferable.

Furthermore, as the compound having two or more substituents selected from the hydroxyl group, thiol group, and amino group used as the compound (M3), the aforementioned polyol compound, polythiol compound, and polyamine compound are preferable. Among them, trishydroxyethyl isocyanurate, 2,4-diamino-6-phenyl-1,3,5-triazine, tris-[( 3-mercaptopropionyloxy) -ethyl] -isocyanurate is more preferred.

Examples of the compound having two or more substituents selected from a carboxy group, an epoxy group, an alkoxysilyl group, and an isocyanate group, which are used as the compound (M4), include the above-described polycarboxy compounds, poly Epoxy compounds, polyalkoxysilyl compounds, and polyisocyanate compounds can be suitably used. Among them, 2,6-pyridinedicarboxylic acid and 2,4-pyridinedicarboxylic acid are particularly preferable from the viewpoint of being easily available industrially and having excellent physical properties. Tris- (2,3-epoxypropyl) -isocyanurate is more preferred.

In addition, as the compound (M5) used as the compound having two or more substituents selected from a hydroxyl group, a carboxy group, and an amino group, the aforementioned polyol compound and polycarboxy compound are preferably used. Among them, trishydroxyethyl isocyanurate, 2,6-pyridinedicarboxylic acid, and 2,4-pyridinedicarboxylic acid are more preferable from the viewpoint of easy industrial availability and excellent physical properties.

Furthermore, as the compound having two or more substituents selected from thiol groups and amino groups used as the compound (M6), the above-mentioned polythiol compounds and polyamine compounds can be preferably used. Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate and 2,4-diamino-6-phenyl-1,3,5-triazine are more preferred.

The main chains of the elastomeric polymers (E1) to (E6) are the same as those described as the main chains of the elastomeric polymers (A) and (B) (the preferred ones are also the same). is there.). The elastomeric polymers (E1) to (E6) used for producing each of these reactants are functional groups (maleic anhydride group, hydroxyl group, carboxy group, amino group, alkoxysilyl group, epoxy group) possessed by each polymer. ) React with the substituents of the compounds (M1) to (M6) used to produce each reactant to form a side chain having a structure derived from the main skeleton of the compounds (M1) to (M6) However, since there is basically no change in the main chain before and after the reaction, the main chains of the reactants (I) to (VI) (the main chains of the elastomeric polymers (A) and (B)) Is derived from the main chains of the elastomeric polymers (E1) to (E6).

Further, among these reactants (I) to (VI), those listed in Examples from the viewpoint of being easily available industrially and excellent in physical properties (Table 1 and Table relating to each Example described later). 2 is preferred.

In addition, as the reactant (I), from the viewpoint of being easily available industrially and capable of highly balancing mechanical strength and compression set, a maleic anhydride-modified elastomeric polymer, a hydroxyl group, a thiol group, and an amino group Pyridine, hydroxyl group, thiol group and amino group optionally having at least one substituent selected from triazole, hydroxyl group, thiol group and amino group optionally having at least one substituent Among these, thiadiazole, which may have at least one substituent, hydroxyl group, thiol group, and amino group, which may have at least one substituent among imidazole, hydroxyl group, thiol group, and amino group Of isocyanurate, hydroxyl group, thiol group and amino group optionally having at least one substituent May also have one substituent, a triazine, a hydroxyl group, a thiol group, and an amino group, a hydantoin that may have at least one substituent, trishydroxyethyl isocyanurate, sulfamide, and A reaction product with at least one compound of polyether polyols is more preferable.

In addition, the polymer contained as the elastomer component does not have a double bond, and thus is not easily deteriorated. Interaction between the isocyanurate ring and the isocyanurate ring and other hydrogen bonding sites and hydrogen bonding between the additive component and the like Therefore, 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. Examples of such a polymer in which the main chain is an olefin copolymer and the side chain has an isocyanurate ring include, for example, a maleic anhydride-modified elastomeric polymer comprising an olefin copolymer modified with maleic anhydride ( More preferred is a reaction product of maleic anhydride-modified ethylene-propylene rubber or maleic anhydride-modified ethylene-butene rubber) and trishydroxyethyl isocyanurate.

Further, when the polymer contained as the elastomer component is such that the main chain is an olefin copolymer and the side chain has an isocyanurate ring, the infrared absorption of the thermoplastic elastomer composition In the spectrum, an olefin resin (the “olefin resin” referred to herein includes an olefin copolymer of the main chain of the polymer contained as the elastomer component. An olefin-based resin having an α-olefin-based resin having no cross-linking site or a case where a plurality of polymers are contained as the elastomer component, and the main chain of one polymer is other than the olefin-based copolymer In the case of consisting of the above-mentioned “olefin resin”, all olefin resins contained in the system ( Α-olefin resins having no crosslinkable sites for chemical bonding, olefin copolymers forming a main chain, olefin resins other than olefin copolymers forming a main chain, etc.). Ratio of absorption intensity (A) of a peak near a wavelength of 2920 cm ⁻¹ derived from C—H stretching vibration to absorption intensity (B) of a peak near a wavelength of 1695 cm ⁻¹ derived from a carbonyl group in the isocyanurate ring It is preferable that ([absorption strength (B)] / [absorption strength (A)]) is 0.01 or more (more preferably 0.012 to 10, still more preferably 0.015 to 5). If the intensity ratio between the intensity of peak (A) and the intensity of peak (B) in the infrared absorption spectrum (IR spectrum) is less than the lower limit, the abundance ratio of the side chain having an isocyanurate ring in the composition is lowered. In the system, since the crosslinking density is lowered, physical properties such as mechanical strength tend to be lowered. On the other hand, if the strength ratio exceeds the upper limit, the number of branches of the elastomer component increases in the system, and the crosslinking density of the entire system decreases, so that the mechanical properties tend to deteriorate. In addition, as an infrared absorption spectrum (IR spectrum) of such a thermoplastic elastomer composition, an IR measuring device (for example, “NICOLET380” manufactured by Thermo Co.) provided with a total reflection type unit is used. 40 g of a thermoplastic elastomer composition containing (the polymer contained as the elastomer component in which the main chain is an olefin copolymer and the side chain has an isocyanurate ring) is thickened so that the surface is smooth. An infrared absorption spectrum (infrared attenuated total reflection (FTIR-ATR)) in a wave number range of 400 to 4000 cm ⁻¹ by a total reflection measurement (ATR) method using a measurement sample prepared by press molding at a thickness of 2 mm. The graph of the absorption spectrum obtained by measuring (spectrum) is used. By such measurement, the peak of the infrared absorption spectrum of the carbonyl group in the isocyanurate ring of the side chain appears in the vicinity of a wavelength of 1695 cm ⁻¹ (approximately in the range of 1690 to 1700 cm ⁻¹ ), and the olefin resin ( The peak of the infrared absorption spectrum of C—H stretching vibration of the main chain (base polymer olefin copolymer) appears in the vicinity of a wavelength of 2920 cm ⁻¹ (approximately in the range of 2910 to 2930 cm ⁻¹ ).

A maleic anhydride-modified elastomeric polymer (more preferably maleic anhydride-modified ethylene-propylene rubber or maleic anhydride-modified ethylene-butene rubber) composed of an olefin copolymer modified with maleic anhydride, and trishydroxyethylisocyanate. Taking a thermoplastic elastomer composition containing a reaction product with nurate and not containing any other olefinic resin as an example, the reaction product is a maleic anhydride-modified elastomeric polymer at the time of production of the reaction product. The side chain is formed by the reaction of the acid anhydride group therein and the hydroxyl group of trishydroxyethyl isocyanurate, and the isocyanurate ring is introduced into the side chain of the polymer. Due to the carbonyl group in the isocyanurate ring of the side chain of the (reactant) Peaks of the infrared absorption spectrum appears at a wavelength of around 1,695 cm ^-1 (range of 1690 ~ 1700 cm ^-1), while, C-H of the olefin copolymer of the polymer main chain of the (reaction) (base polymer) since a peak derived from stretching vibration appearing in the vicinity of wavelength 2920 cm ^-1 (range of 2910 ~ 2930 cm ^-1), in the above compositions comprising such reaction, the peak in the vicinity of a wavelength of 1,695 cm ^-1, wavelength 2920 cm ^-1 By calculating the ratio of the intensity of nearby peaks, the side chain in which the isocyanurate ring in the polymer (reactant) was introduced (in the case of the above example, the side chain formed is basically a hydrogen-bonding cross-linking site. And a covalent cross-linking site), the cross-linking density of the entire system can be inferred. Even when including the olefinic resin (for example, when including α- olefin resin having no chemical binding of the cross-linked site below, etc.) to another, and the peak in the vicinity of a wavelength of 1,695 cm ^-1, wavelength 2920 cm ^-1 By determining the ratio of the intensity of nearby peaks, the ratio of the side chain into which the isocyanurate ring is introduced to the total amount of olefinic resin present in the system can be determined, and the crosslinking density of the entire system can be estimated. And when such a strength ratio is not less than the lower limit, the abundance ratio of the side chain having an isocyanurate ring is sufficient, the crosslinking density of the entire system is sufficient, and the mechanical strength and the like are increased. It becomes possible to make the physical properties sufficient.

The method for producing such elastomeric polymers (A) to (B) is not particularly limited, and the side chain (a) as described above; the side chain (a ′) and the side chain (b); A known method capable of introducing at least one selected from the group consisting of the side chain (c) as a side chain of an elastomeric polymer having a glass transition point of 25 ° C. or lower can be appropriately employed. For example, as a method for producing the elastomeric polymer (B), a method described in JP-A-2006-131663 may be employed. Further, in order to obtain an elastomeric polymer (B) having the side chain (a ′) and the side chain (b) as described above, for example, a cyclic acid anhydride group (for example, a maleic anhydride group) as a functional group is used. A compound that reacts with the cyclic acid anhydride group to form a covalent bond cross-linking site (compound that forms a covalent bond) and a hydrogen bond that reacts with the cyclic acid anhydride group on the elastomeric polymer in the side chain Each side chain may be introduced at the same time using a mixture (mixed raw material) with a compound (a compound capable of introducing a nitrogen-containing heterocycle) that forms a sexually cross-linked site.

As a method for producing such elastomeric polymers (A) to (B), for example, an elastomeric polymer having a functional group (for example, a cyclic acid anhydride group) in the side chain (for example, an elastomeric polymer ( E1) to (E6) may be mentioned as preferred.) And the elastomeric polymer is reacted with the functional group to form a hydrogen-bonding cross-linked site, and the functional group is reacted with the functional group. At least one raw material compound (for example, the compounds (M1) to (M6) described above), which is a mixed raw material of a compound that forms a hydrogen bonding cross-linking site and a compound that reacts with the functional group to form a covalent cross-linking site. And elastomers having side chains (a) and side chains (a ') and elastomers having side chains (b). And / or a method of producing an elastomeric polymer having the side chain (c) (the elastomeric polymers (A) to (B)) may be employed. In addition, the conditions (temperature conditions, atmospheric conditions, etc.) employed in the case of such a reaction are not particularly limited, and the functional group and the compound that reacts with the functional group (the compound that forms a hydrogen-bonding cross-linked site and / or the covalent bond) What is necessary is just to set suitably according to the kind of compound which forms a binding bridge | crosslinking site | part. In the case of the elastomeric polymer (A), it may be produced by polymerizing a monomer having a hydrogen bonding site.

The elastomeric polymer having such a functional group (for example, cyclic acid anhydride group) in the side chain is a polymer capable of forming the main chain of the above-mentioned elastomeric polymers (A) to (B). Those having a functional group in the side chain are preferred. Here, the “elastomeric polymer containing a functional group in a side chain” means that a functional group (the above-described functional group such as a cyclic acid anhydride group) is chemically stable at an atom forming a main chain. An elastomeric polymer having a bond (covalent bond), preferably obtained by reacting an elastomeric polymer (for example, a known natural polymer or synthetic polymer) with a compound capable of introducing a functional group. Available.

Such a functional group is preferably a functional group capable of causing at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether, and among them, cyclic An anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, a thiol group and the like are preferable, and a cyclic anhydride group is particularly preferable from the viewpoint that an additive component can be more efficiently dispersed in the composition. . Further, as such a cyclic acid anhydride group, a succinic anhydride group, a maleic anhydride group, a glutaric anhydride group, and a phthalic anhydride group are preferable. Among them, it can be easily introduced into a polymer side chain and is industrially available. From the viewpoint of being easy, maleic anhydride groups are more preferable. Further, when the functional group is a cyclic acid anhydride group, examples of the compound into which the functional group can be introduced include succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and derivatives thereof. A cyclic acid anhydride may be used to introduce a functional group into an elastomeric polymer (for example, a known natural polymer or synthetic polymer).

The compound that reacts with the functional group to form a hydrogen-bonding cross-linking site is not particularly limited, but the above-mentioned “compound that forms a hydrogen-bonding cross-linking site (compound capable of introducing a nitrogen-containing heterocycle)” It is preferable to use it. Further, the compound that reacts with the functional group to form a covalent crosslinking site is not particularly limited, but the above-mentioned “compound that forms a covalent crosslinking site (compound that generates a covalent bond)” is used. Is preferred. In addition, as a compound that forms a hydrogen-bonding cross-linked site (a compound that can introduce a nitrogen-containing heterocycle) and a compound that forms a covalent-bonded cross-linked site (a compound that generates a covalent bond), the compound reacts with the functional group. Thus, compounds that form both hydrogen-bonding and covalent bonding sites (for example, polyols, polyamines, polythiols, and the like containing nitrogen-containing heterocycles) can also be suitably used.

Further, in the method for producing such an elastomer component (elastomeric polymers (A) to (B)), an elastomeric polymer having a functional group (for example, a cyclic acid anhydride group) in the side chain is used. A compound that reacts with the functional group to form a hydrogen-bonding cross-linking site, a compound that reacts with the functional group to form a hydrogen-bonding cross-linking site, and a functional group to react with a covalent bond The elastomeric polymer (A) having the side chain (a) by reacting with at least one raw material compound among the mixed raw materials of the compound forming the site, the hydrogen-bonding cross-linking site and the covalent bond in the side chain When employing the method for producing the elastomeric polymer (B) containing a cross-linked site, the elastomeric polymer having a functional group in the side chain is converted into the raw material. Before reacting with the product, the additive component and the elastomeric polymer having a functional group in the side chain are mixed, and then the raw material compound is added and reacted to form a composition simultaneously with the preparation of the elastomer component (Method of adding additive components in advance) may be employed.

In addition, since the dispersibility of the additive component is further improved and higher heat resistance can be obtained, a method of adding the additive component first when manufacturing the elastomer component (elastomeric polymers (A) to (B)) It is preferable to disperse the additive component during the preparation of the elastomer component.

Even when the reactants (I) to (VI) are produced as the elastomer components (elastomeric polymers (A) to (B)), the method is not particularly limited, and the elastomeric polymers (E1) to (E6) are not limited. ) And the compounds (M1) to (M6) to be reacted therewith are appropriately selected so that the side chains of the desired design are formed, whereby reactants (I) to (VI) are obtained. The reaction conditions (temperature conditions, atmospheric conditions, etc.) can be used as appropriate, and the functional groups and main groups of the elastomeric polymers (E1) to (E6) as raw materials for obtaining the reaction product can be used. It can be set according to the type of chain and further the types of compounds (M1) to (M6) to be reacted therewith.

When preparing such reactants (I) to (VI), for example, a polymer appropriately selected from the elastomeric polymers (E1) to (E6) is added to the pressure kneader according to the target design. Then, while stirring, the compound selected from the compounds (M1) to (M6) for reacting with the polymer may be added and reacted, and the reaction proceeds at that time. What is necessary is just to set suitably to such temperature. In preparing the reactants (I) to (VI), a polymer appropriately selected from the elastomeric polymers (E1) to (E6) used for preparing the reactants (I) to (VI) is used as the compound. Before reacting with the compound selected from (M1) to (M6), the polymer and the additive component are mixed, and then the compound is added and reacted to form the composition simultaneously with the preparation of the elastomer component. A method of forming (addition component added first) may be employed. In addition, since the dispersibility of the additive component is further improved and higher heat resistance can be obtained, the above-mentioned additive component is added in advance when producing a composition containing the reactants (I) to (VI). It is preferable to adopt the method to do.

(Additive ingredients)
The thermoplastic elastomer composition of the present invention is selected from the group consisting of expanded graphite, carbon nanotubes, fullerene, graphene, silicate natural nanofibers, silsesquioxane and layered titanate compound in combination with the elastomer component. Containing at least one additive component.

The expanded graphite used as such an additive component is not particularly limited, and known expanded graphite can be appropriately used. Here, the expanded graphite may be any graphite that expands by heat, and it is preferable to use a compound in which a compound or the like is inserted between layers of graphite (for example, natural scale-like graphite, pyrolytic graphite, quiche graphite, etc.). it can. Examples of the compound inserted between the graphite layers include acids such as sulfuric acid and nitric acid, and mixtures of these acids. As such expanded graphite, commercially available products can be used as appropriate, for example, EXP-50 series, EXP-80 series manufactured by Fuji Graphite Industries Co., Ltd., 953240 series, 9550 series, 9510 series manufactured by Ito Graphite Industries Co., Ltd .; 5099SS-3, 60CA-60 manufactured by Cole Chemical Co., Ltd .; SMF, EMF, SFF, SS; manufactured by Chuetsu Graphite Industry Co., Ltd. can be used.

Such expanded graphite is preferably in the form of powder, and the average particle size is preferably 0.1 to 100 nm, more preferably 1 to 80 nm. If the average particle size is less than the lower limit, it tends to be too fine and difficult to disperse, and the physical properties tend to decrease. Etc. tend to decrease.

Also, examples of the carbon nanotubes used as the additive component include single-walled carbon nanotubes and multi-walled carbon nanotubes. As such a carbon nanotube, a single-walled carbon nanotube is preferable from the viewpoint that higher physical properties can be expressed.

Such carbon nanotubes preferably have an average diameter of 0.1 to 100 nm (more preferably 0.4 to 50 nm). If the diameter is less than the lower limit, it tends to be too fine and difficult to disperse, and the physical properties tend to decrease. It tends to decrease. Such carbon nanotubes preferably have an average length of 1 nm to 1 mm (more preferably 10 to 100 nm). Such carbon nanotubes preferably have an aspect ratio of 1 to 1000 (more preferably 10 to 100). If the length or aspect ratio is less than the lower limit, the dispersion tends to be difficult because the dispersion is difficult, and the physical properties are lowered. There exists a tendency for tensile physical properties etc. to fall. Commercially available products can be used as such carbon nanotubes, for example, ED, EP, HP manufactured by Sakai Kogyo Co., Ltd .; EC 1.0, EC 1.5, EC 2.0 manufactured by Meijo Nano Carbon Co., Ltd .; Marubeni Information 9000, 9100, 9110 manufactured by Systems Co., Ltd .; Zeonano SG101 manufactured by Nippon Zeon Co., Ltd .; these dispersions and polymer master batch products; and the like can be used.

Further, the fullerene used as the additive component is not particularly limited, and known ones can be used as appropriate. In addition, such fullerene is a general term for a cluster composed only of a large number of carbon atoms in a closed shell cavity shape. Examples of such fullerenes include fullerenes composed of carbon clusters such as 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 preferable from the viewpoint of industrial availability and low cost, and the above fullerene mixture is particularly preferable. preferable. Moreover, as such fullerenes, commercially available products can be used as appropriate, for example, Nanom series manufactured by Frontier Carbon Co., etc. can be used.

The graphene used as the additive component is not particularly limited, and known graphene can be appropriately used. As such graphene, it is preferable to use graphene nanoparticles (graphene nanopowder) from the viewpoint of higher dispersion and higher strength. Such graphene nanoparticles preferably have an average particle size of 0.1 to 1000 nm, and more preferably 1 to 300 nm. If the average particle size is less than the lower limit, it tends to be too fine and difficult to disperse, and the physical properties tend to decrease. Etc. tend to decrease.

Further, as such graphene, commercially available products can be used as appropriate. For example, XG Graphene powder on scales manufactured by Sciences; Nano graphene aqueous solution manufactured by NanoIntegris; Graphene oxide G-GOSiO · Sol-GO manufactured by Graphos -GO: Functionalized graphene oxide manufactured by NiSiNa Materials, Rap GO, Rap bGO, Metal / GO, Rap rGO; EM Japan graphene nanopowder; Wako Yakuhin graphene;

The silicate-based natural nanofibers used as the additive component are not particularly limited, and natural nanofibers made of known silicates can be appropriately used. Such siliceous natural nanofiber, for example, the _{_{_{_{formula: SiO 2 · Al 2 O 3}}}} · 2H 2 O, silicates represented by _{_{Al 2 SiO 3 (OH) 4}} ( imogolite), wherein: Silicates (palygorskite) represented by (Mg, Al) ₂ [Si ₄ O ₁₀ ] (OH) -4H ₂ O, silicates (allophane) represented by the formula: SiO ₂ · Al ₂ O ₃ , etc. Is mentioned.

Such silicate-based natural nanofibers preferably have an average diameter (average of outer diameter) of 0.1 to 10 nm (more preferably 1 to 7 nm). In the case where the silicate-based natural nanofiber is hollow, the average inner diameter (average inner diameter) is preferably 0.1 to 8 nm (more preferably 0.3 to 6 nm). If the diameter is less than the lower limit, it tends to be too fine and difficult to disperse, and the physical properties tend to decrease. It tends to decrease. Further, such silicate-based natural nanofibers preferably have an average length of 1 nm to 5 μm (more preferably 5 nm to 3 μm). Such silicate-based natural nanofibers preferably have an aspect ratio of 1 to 1000 (more preferably 10 to 100). If the length or aspect ratio is less than the lower limit, the dispersion tends to be difficult because the dispersion is difficult, and the physical properties are lowered. There exists a tendency for tensile physical properties etc. to fall.

As such silicate-based natural nanofibers, imogolite and palygorskite are preferable, and imogolite is particularly preferable from the viewpoint of industrial availability and low cost. Moreover, as such a silicate type natural nanofiber, a commercial item can be used suitably, for example, Asron Corp. dronpa, horticultural Kanuma soil, etc. can be used.

Silsesquioxane used as the additive component is a siloxane-based compound having a main chain skeleton composed of Si—O bonds, and has the following formula:
-(RSiO _3/2 ) _n-
[Wherein, R represents an alkyl group which may have a substituent, and n represents an integer. ]
It is preferable that it has the silsesquioxane structure represented by these. Moreover, a polymer type may be sufficient. The alkyl group that can be selected as R in the formula showing such a silsesquioxane structure preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. If the number of carbon atoms is less than the lower limit, the composition tends to be unstable and easily decomposed, which tends to be difficult to mix.On the other hand, if the upper limit is exceeded, the steric hindrance is too great and the interaction with the siloxane bond falls, making dispersion difficult. In addition, molecules tend to be too large to become foreign matters and become a starting point of fracture, resulting in a tendency for tensile properties and the like to decrease. Examples of the substituent that the alkyl group that can be selected as R in the formula showing the silsesquioxane structure may include methyl, ethyl, propyl, hexyl, phenyl, vinyl, and the like.

In the formula showing the silsesquioxane structure, the integer represented by n is preferably 2 to 100, more preferably 8 to 50. If such an integer n is less than the lower limit, it tends to be liquid and the effect as a filler tends not to be obtained. It tends to decrease.

In addition, such silsesquioxane is preferably in the form of particles, and the average particle diameter is preferably 0.1 to 300 nm, more preferably 0.5 to 100 nm. If the average particle size is less than the lower limit, it tends to be too fine and difficult to disperse, and the physical properties tend to decrease. Etc. tend to decrease. As such silsesquioxanes, commercially available products can be used as appropriate. For example, KMP-590 and KMP-591 manufactured by Shin-Etsu Silicone; SST series manufactured by AMAX Co .; manufactured by Sigma-Aldrich POSS; etc. can be used.

Furthermore, it does not restrict | limit especially as a layered titanic acid compound utilized as said additional component, A well-known thing can be utilized suitably. Such layered titanate compounds have the formula:
M _l Ti _n O _m
[Wherein, M represents a metal, and l, n, and m represent an integer of 1 to 30. ]
What consists of a compound represented by these is mentioned. Such layered titanic acid compounds such as 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. Such a layered titanic acid compound is preferably in the form of particles, and the average particle diameter is preferably 0.1 to 500 nm, more preferably 0.5 to 300 nm. If the average particle size is less than the lower limit, it tends to be too fine and difficult to disperse, and the physical properties tend to decrease. Etc. tend to decrease. As such layered titanic acid compounds, commercially available products can be used as appropriate, for example, Tismo, Terrasus, Dentor WK manufactured by Otsuka Chemical Co., Ltd. SW-100, SW-300, TC manufactured by Titanium Industry Co., Ltd. -100; titanic acid compound manufactured by Fuji Titanium Industry Co., Ltd .; titanic acid compound manufactured by Sakai Chemical Industry Co., Ltd .;

Further, such additive components can be used alone or in combination of two or more. Moreover, as such an additive component, it is industrially easy to obtain and costs among expanded graphite, carbon nanotube, fullerene, graphene, silicate natural nanofiber, silsesquioxane and layered titanate compound. From the viewpoint of low, expanded graphite and layered titanate compounds are more preferable, and expanded graphite is more preferable.

(Composition)
The thermoplastic elastomer composition of the present invention contains the elastomer component and the additive component.

The reason why the thermoplastic elastomer composition of the present invention can have a sufficiently high tensile strength (tensile strength with 100% modulus and breaking strength as an index) and a sufficiently high wear resistance. Although not necessarily clear, the present inventors infer as follows. That is, first, in the present invention, the elastomer component is an elastomeric polymer containing a side chain having at least a hydrogen bonding cross-linking site (in the side chain, side chain (a); side chain (a ′) and side chain (b)). And a polymer containing at least one of the side chains (c)). First, when such an elastomeric polymer and the additive component are combined, an interaction such as hydrogen bonding is possible between the additive component and the polymer is more uniformly and highly dispersed in the polymer. Then, the surface of the component introduced as the additive component as a result of the interaction between the additive component highly dispersed in the system and the hydrogen bonding cross-linking site (formation of a new hydrogen bond, etc.) The elastomer component is surface cross-linked using As described above, any of the additive components can form a surface cross-link with a hydrogen bonding cross-linking site (so-called surface cross-linking agent). And when such surface cross-linking is formed, it becomes possible to suppress stress concentration at the cross-linking point, and higher breaking strength (until it breaks) compared to the case where the additive component is not included. (Tensile strength) can be expressed. Further, the interaction between the additive component highly dispersed in the system and the hydrogen-bonding cross-linking site interacts with each other (for example, a new hydrogen bond is formed). The present inventors speculate that the density of crosslinks formed by the process can be made more uniform, stress concentration at the crosslink points can be suppressed, and wear resistance becomes higher. To do.

On the other hand, when at least one of the elastomeric polymers (A) and (B) having a hydrogen-bonding cross-linked site in the side chain is not used as an elastomer component and only other elastomer components are used, Even if it is used in combination with the additive component, the effects as described above cannot be obtained. Considering this point, first, a general thermoplastic elastomer is a type that uses pseudo-crosslinking by physical interaction between polymer molecular chains (physical interaction is caused by interaction between polymer molecules). There are two types: a type in which a weak bond is formed) and a type in which rubber is dispersed in a thermoplastic resin matrix. Typical examples of such thermoplastic elastomers using pseudo-crosslinking include polymers having soft segments and hard segments such as block polymers and urethane elastomers. Here, without introducing a polymer having a side chain as described above, simply adding a filler such as the additive component to a thermoplastic elastomer of the type utilizing pseudo-crosslinking, interaction at the pseudo-crosslinking point ( The physical interaction between the polymer molecular chains) is hindered by the additive component, and the mechanical strength of the polymer is lowered, making it unusable for actual use as a rubber product. As described above, the conventional thermoplastic elastomer consisting only of the thermoplastic elastomer of the type utilizing pseudo-crosslinking, in the case where it is simply combined with the additive component, in the composition, on the contrary, pseudo-crosslinking. Formation is inhibited, and the mechanical strength (tensile stress, etc.) of the composition is lowered. Further, in a thermoplastic elastomer of a type in which rubber is dispersed in a thermoplastic resin matrix, the filler such as the additive component is introduced only into the matrix phase, as is apparent from the composition. Here, in a matrix made of a thermoplastic resin having no side chain, no interaction with the additive component is formed in the matrix. Therefore, even if the additive component is simply introduced, the additive component is introduced at a high concentration in a certain portion, and the additive component is not introduced at all in a certain portion. As a result, due to the difference in concentration of the additive components, a difference in hardness is generated inside the elastomer, and the mechanical strength and the like are decreased. Therefore, in a thermoplastic elastomer of a type in which rubber is dispersed in a thermoplastic resin matrix, when a polymer that does not contain a side chain is used as a hydrogen bonding cross-linked site, the additive component is simply introduced. However, the additive component cannot be sufficiently dispersed, and the mechanical strength (breaking strength, etc.) of the composition is lowered. From this point of view, when the elastomeric polymers (A) and (B) are not used as the base elastomer component, it is not only possible to form an interaction with the additive component in the first place. The present inventors infer that the presence of the additive component lowers the mechanical strength and cannot necessarily have sufficient characteristics as an elastomer (rubber).

In the present invention, when an elastomer component containing a covalent crosslinking site is contained in the side chain (for example, when containing an elastomeric polymer (B)), the side chain containing the covalent crosslinking site is more The present inventors speculate that it is possible to develop a high level of compression set resistance. Further, in the case where a hydrogen bonding crosslinking site and a covalent bonding crosslinking site are present in the elastomer component (when the elastomeric polymer (B) is contained, a mixture of the elastomeric polymer (B) and another elastomeric polymer is added. When it contains, when it contains a mixture of the elastomeric polymer (A) and the elastomeric polymer (B), the elastomeric polymer having a side chain (b) other than the elastomeric polymer (A) and the elastomeric polymer (B) In the case of using a mixture of a hydrogen bond and a covalent bond site, a higher mechanical strength due to the covalent bond and a heating due to the hydrogen bond due to the presence of the hydrogen bond crosslink site and the covalent bond site. Higher fluidity (formability) can be developed at the same time by cleaving. Therefore, the present inventors speculate that it is possible to appropriately change the composition according to the type of the side chain and to appropriately exhibit the characteristics according to the application. The elastomeric polymer having a side chain (b) other than the elastomeric polymer (B) as described above is obtained by using an elastomeric polymer having a functional group (for example, a cyclic acid anhydride group) in the side chain. By reacting a functional polymer with a compound that reacts with the functional group to form a covalently cross-linked site (compound that generates a covalent bond) to produce the elastomeric polymer having the side chain (b) It is possible to obtain. Even in this case, the above-mentioned “compound that forms a covalent crosslinking site (compound that generates a covalent bond)” is used as the compound that forms a covalent crosslinking site (a compound that generates a covalent bond). can do.

As described above, the reason why the above-described effects of the present invention can be obtained by the thermoplastic elastomer composition of the present invention has been examined. Preferred embodiments of the thermoplastic elastomer composition of the present invention (containing each component) The preferred conditions for the ratio and the like will be further described.

The thermoplastic elastomer composition of the present invention contains the elastomer component and the additive component. In the thermoplastic elastomer composition of the present invention, the content of the additive component (when two or more types are combined to include a plurality of components, the total amount thereof) is 20 with respect to 100 parts by mass of the elastomer component. It is below mass parts. If the content of such an additive component exceeds the upper limit, it is too much to easily cause a dispersion failure, resulting in a foreign matter, resulting in a decrease in tensile strength. The content (total amount) of the additive component in such a thermoplastic elastomer composition is more preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the elastomer component. More preferred is 1 to 3 parts by mass. If the content of such an additive component is less than the lower limit, the content of the additive component tends to be too small to obtain a sufficient effect.On the other hand, if the content exceeds the upper limit, the crosslinking becomes too strong. Elongation and strength are lowered, and it tends to be difficult to use for various purposes (practicality is lowered).

In addition, when such an additive component is a multilayer, it is preferably present in the composition in a single layer form. The presence of such an additive component in the form of a single layer can be confirmed by measuring the surface of the composition with a transmission electron microscope (TEM).

In addition, in the thermoplastic elastomer composition of this invention, the characteristic according to a use can also be provided suitably according to the kind of elastomer component to be used. For example, in a thermoplastic elastomer composition comprising an elastomeric polymer (A) as an elastomer component, since the properties derived from the side chain (a) can be imparted to the composition, the elongation at break, strength at break, and fluidity are particularly improved. It becomes possible to make it. Moreover, in the thermoplastic elastomer composition which uses an elastomeric polymer (B) as an elastomer component, since the characteristic derived from the covalently crosslinked site in the side chain can be imparted to the composition, it is particularly resistant to compression set. It is possible to improve (compression set resistance). In addition, in the thermoplastic elastomer composition containing the elastomeric polymer (B) as an elastomer component, in the composition, in addition to the characteristics derived from the covalent bond crosslinking site, the hydrogen bond crosslinking site (side chain (a The properties derived from the hydrogen-bonding cross-linking sites described in ') can also be imparted, so that it is possible to further improve compression set resistance while maintaining fluidity (formability), and its side chain By appropriately changing the type of the polymer, the type of the polymer (B), etc., it becomes possible to more efficiently exhibit the desired characteristics according to the application.

In the thermoplastic elastomer composition of the present invention, a thermoplastic elastomer composition containing the elastomeric polymer (A) as an elastomer component and a thermoplastic elastomer composition containing the elastomeric polymer (B) as an elastomer component, respectively. After manufacturing separately, it is good also as a thermoplastic elastomer composition which mixes this and contains the elastomeric polymers (A) and (B) as an elastomer component. In the present invention, the elastomer component only needs to contain at least the elastomeric polymers (A) and (B). However, the covalent bond can be made more efficiently by providing a covalent cross-linking site in the composition. From the viewpoint of utilizing the characteristics of the ionic crosslinkable site, other elastomeric polymers having side chains (b) other than the elastomeric polymer (B) may be used in combination. For example, when an elastomeric polymer (A) is used as the elastomer component, when another elastomeric polymer having a side chain (b) other than the elastomeric polymer (B) is used in combination, Providing substantially the same characteristics as the thermoplastic elastomer composition using the elastomeric polymer (B) containing a hydrogen bonding crosslinking site and a covalent bonding crosslinking site in the side chain derived from the side chain contained Is also possible. Moreover, when manufacturing the thermoplastic elastomer composition containing elastomeric polymers (A) and (B) as an elastomer component, side chains (b) other than the elastomeric polymer (A) and the elastomeric polymer (B) are used. When producing a thermoplastic elastomer composition containing other elastomeric polymer, the ratio of each component (for example, each component of the elastomeric polymer (A) and the elastomeric polymer (B)) is appropriately changed. It is also possible to exhibit desired characteristics as appropriate.

When the thermoplastic elastomer composition of the present invention contains the elastomeric polymers (A) and (B) as the elastomer component, the content ratio of the elastomeric polymer (A) and the elastomeric polymer (B) is mass. The ratio ([polymer (A)]: [polymer (B)]) is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. If the content ratio of such a polymer (A) is less than the lower limit, the fluidity (moldability) and mechanical strength tend to be insufficient. On the other hand, if the content ratio exceeds the upper limit, the resistance to compression set tends to decrease. It is in.

Furthermore, the thermoplastic elastomer composition of the present invention contains an elastomeric polymer (A), and other polymer having a side chain (b) other than the elastomeric polymer (B) (hereinafter referred to as “elastomer polymer”). In some cases, it is referred to as “elastomeric polymer (C)”), and the content ratio of the elastomeric polymer (A) to the elastomeric polymer (C) is a mass ratio ([elastomeric polymer (A)]). : [Elastomeric polymer (C)]), preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. If the content ratio of such a polymer (A) is less than the lower limit, the fluidity (moldability) and mechanical strength tend to be insufficient. On the other hand, if the content ratio exceeds the upper limit, the resistance to compression set tends to decrease. It is in.

In the thermoplastic elastomer composition of the present invention, when both the side chain (a ′) and the side chain (b) are present in the composition, the total amount of the side chain (a ′) and the side chain The total amount of (b) is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, based on the mass ratio. If the total amount of such side chains (a ′) is less than the lower limit, the fluidity (formability) and mechanical strength tend to be insufficient. On the other hand, if the upper limit is exceeded, the resistance to compression set is reduced. There is a tendency. Such a side chain (a ′) is a concept including the side chain (a). Therefore, even when only the side chain (a) is contained as the side chain (a ′), both the side chain (a) and the side chain (b) are present in the composition at the above-described mass ratio. Is preferred.

In addition, the thermoplastic elastomer composition of the present invention may be a polymer component other than the elastomer component (hereinafter simply referred to as “other polymer”), paraffin, as long as the purpose of the present invention is not impaired. Oil, reinforcing agent (filler), hydrogen bonding reinforcing agent (filler), filler obtained by introducing an amino group (hereinafter simply referred to as “amino group-introducing filler”), and the amino group-introducing filler Other amino group-containing compounds, compounds containing metal elements (hereinafter simply referred to as “metal salts”), maleic anhydride-modified polymers, antioxidants, antioxidants, pigments (dyes), plasticizers other than the paraffin oil , Thixotropic agents, UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, rust inhibitors, adhesion promoters, antistatic agents, clays, organoclays, antibacterials Agent, prevention Agent may contain various additives such as such as a filler. Such additives are not particularly limited, and commonly used ones (known ones) can be appropriately used. For example, as the other polymer, paraffin oil, reinforcing agent, anti-aging agent, antioxidant, pigment (dye), plasticizer and the like, the following can be appropriately used.

Examples of the other polymer include other elastomeric polymers having a side chain (b) other than the elastomeric polymer (B); α-olefin-based resins having no chemically-bonded crosslinking sites; chemically-bonded crosslinking sites A styrene block copolymer that does not have a diol can be suitably used. The “chemically-bonded cross-linked site” here refers to a site where a cross-link is formed by a chemical bond such as a hydrogen bond or a covalent bond. Therefore, “having no chemically-bonded cross-linking site” in the present invention refers to a state having no cross-link formed by a chemical bond (for example, hydrogen bond, covalent bond, etc.).

Such an α-olefin-based resin having no chemically-bonded crosslinking site (hereinafter simply referred to as “α-olefin-based resin having no chemically-bonded crosslinking site”) is a crosslink by chemical bonding. Bonding sites that do not contain functional groups (for example, hydroxyl groups, carbonyl groups, carboxyl groups, thiol groups, amide groups, and amino groups) that form points, and that directly crosslink polymer chains (covalent crosslinking) Those which do not contain a part or the like are preferably used. In addition, the α-olefin-based resin having no chemically-bonded cross-linking site includes at least the side chain (a), the side chain (a ′), the side chain (b), the side chain ( c) The polymer does not have.

Further, the “α-olefin-based resin” here refers to an α-olefin homopolymer and an α-olefin copolymer. As used herein, “α-olefin” refers to an alkene having a carbon-carbon double bond at the α-position (an alkene having a carbon-carbon double bond at the end: such an alkene may be linear. It may be branched, and preferably has 2 to 20 carbon atoms (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.

As the α-olefin-based resin having no such chemically bondable crosslinking site, an α-olefin polymer (poly α-olefin: either a homopolymer or a copolymer) may be used. There is no particular limitation, and examples thereof include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, and propylene-ethylene-butene copolymer. Among such α-olefin resins having no chemically-bonded crosslinking site, polypropylene, polyethylene, and ethylene-propylene copolymer are preferable from the viewpoint of compatibility with the base elastomer. In addition, such α-olefin-based resins having no chemically bonding cross-linking sites may be used alone or in combination of two or more.

The α-olefin resin having no chemically-bonded cross-linking site preferably has a crystallinity of 10% or more, more preferably 10 to 80%, and more preferably 10 to 75%. Further preferred. If the degree of crystallinity is less than the lower limit, the resin-like properties become dilute, so it tends to be difficult to make the mechanical properties and fluidity more advanced. Therefore, it tends to be difficult to exhibit mechanical properties in a balanced manner at a higher level. Such crystallinity is measured by using an X-ray diffractometer (for example, trade name “MiniFlex300” manufactured by Rigaku Corporation) as a measuring device, measuring a diffraction peak, and integrating a scattering peak derived from crystallinity / amorphous. It can be determined by calculating the ratio.

In addition, as an α-olefin resin not having such a chemical bonding cross-linking site, a melt flow at 190 ° C. under a load of 2.16 kg, measured according to JIS K6922-2 (issued in 2010). The rate (MFR) is preferably 40 g / 10 min or more. If such a melt flow rate (MFR) is less than the lower limit, it tends to be difficult to improve the fluidity even if blended in the composition. Such a melt flow rate (MFR) is a value measured in accordance with the method B described in JIS K6922-2 (issued in 2010). Using the name “Melt Indexer G-01”, 3 g of the α-olefin resin was added to the furnace of the apparatus, and the temperature was maintained at 190 ° C. for 5 minutes, and then maintained at 190 ° C. Measure the mass (g) of the composition flowing out in 10 minutes from the opening of a cylindrical orifice member with a diameter of 1 mm and a length of 8 mm connected to the lower part of the furnace body under the condition of loading 16 kg. (After starting the load after keeping the temperature at 190 ° C. for 5 minutes in the furnace body, the measurement of the mass of the flowing out elastomer is started). .

Furthermore, the weight average molecular weight (Mw) of the α-olefin-based resin having no chemically-bonded crosslinking site is preferably 10,000 or more and 2,000,000 or less, more preferably 30,000 or more and 1,500,000 or less. Preferably, it is 50,000 or more and 1.25 million or less. When the weight average molecular weight is less than the lower limit, the mechanical strength tends to decrease. On the other hand, when the weight average molecular weight exceeds the upper limit, the compatibility with the elastomer component decreases and the phase tends to be separated.

The number average molecular weight (Mn) of the α-olefin resin having no chemically-bonded crosslinking site is preferably 10,000 or more and 2,000,000 or less, more preferably 30,000 or more and 1,500,000 or less. Preferably, it is 50,000 or more and 1.25 million or less. If the number average molecular weight is less than the lower limit, the mechanical strength tends to decrease. On the other hand, if the number average molecular weight exceeds the upper limit, the compatibility with the elastomer component decreases, and phase separation tends to occur.

Further, the dispersion degree (Mw / Mn) of the molecular weight distribution of the α-olefin-based resin having no chemically-bonded crosslinking site is preferably 5 or less, more preferably 1 to 3. If the degree of dispersion (Mw / Mn) of the molecular weight distribution is less than the lower limit, the fluidity tends to decrease. On the other hand, if it exceeds the upper limit, the compatibility with the elastomer component tends to decrease.

The weight-average molecular weight (Mw), the number-average molecular weight (Mn), and the molecular weight distribution dispersity (Mw / Mn) of the α-olefin resin as described above are determined by a so-called gel permeation chromatography (GPC) method. Can be sought. Moreover, as a specific apparatus and conditions for measuring such molecular weight, “Prominence GPC system” manufactured by Shimadzu Corporation can be used.

In addition, the glass transition point of the α-olefin-based resin having no chemical bonding cross-linking site is preferably −150 to 5 ° C., more preferably −125 to 0 ° C. When such a glass transition point is less than the lower limit, the melting point becomes low and the heat resistance tends to be lowered. On the other hand, when the upper limit is exceeded, rubber elasticity after blending into the elastomer component tends to be lowered. The “glass transition point” here is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry) as described above. In such DSC measurement, the rate of temperature rise is preferably 10 ° C./min.

The method for producing such an α-olefin-based resin having no chemically-bonded crosslinking site is not particularly limited, and a known method can be appropriately employed. In addition, as such α-olefin resin, commercially available products may be used. For example, trade names “Tafmer” manufactured by Mitsui Chemicals, Inc .; trade names “Novatech HD”, “Novatech LD” Novatec LL, “Kernel”; Prime Polymer's trade names “Hinex” “Neozex” “Ultzex” “Evolue” “Prime Polypro” “Polyfine” “Mostron L”; May be.

When the thermoplastic elastomer composition of the present invention further contains an α-olefin resin having no chemically-bonded crosslinking site, the inclusion of the α-olefin resin not having the chemically-bonded crosslinking site The amount (content ratio) is preferably 800 parts by mass or less, more preferably 5 to 700 parts by mass, and still more preferably 10 to 600 parts by mass with respect to 100 parts by mass of the elastomer component. The amount is particularly preferably 25 to 500 parts by mass, and most preferably 50 to 400 parts by mass. If the content of the α-olefin resin not having such a chemical bonding cross-linking site is less than the lower limit, the fluidity tends to be lowered. On the other hand, if the content exceeds the upper limit, the compression set is lowered. There is a tendency.

In addition, when the thermoplastic elastomer composition of the present invention further contains an α-olefin-based resin having no chemically-bonded crosslinking site, the α-olefin-based resin not having the chemically-bonded crosslinking site. The content of is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, and still more preferably 5 to 70% by mass with respect to the total amount of the composition. If the content of the α-olefin resin not having such a chemical bonding cross-linking site is less than the lower limit, the fluidity tends to be lowered. On the other hand, if the content exceeds the upper limit, the compression set is lowered. There is a tendency.

In addition, as the other polymer, a styrene block copolymer having no chemically-bonded crosslinking site is preferable from the viewpoint that it is a component that does not interfere with the crosslinking reaction of the base elastomer. When such a styrene block copolymer is used, it basically does not interfere with the cross-linking structure of the base elastomeric polymer (the elastomer component) or the cross-linking reaction at the time of manufacture. Since the inherent physical properties of the structure are not hindered, excellent mechanical properties (particularly tensile properties, compression set, etc.) derived from the styrene block copolymer can be obtained while sufficiently maintaining the properties derived from the elastomer component. The present inventors speculate that it can be reflected (provided) in the thermoplastic elastomer composition of the present invention and can have higher properties.

The styrene block copolymer, which is a component suitably used in the thermoplastic elastomer composition of the present invention, does not have a chemically bonding cross-linked site. Here, “having no chemically-bonded cross-linking site” has the same meaning as described for the α-olefin resin. Therefore, as a styrene block copolymer having no chemically bonding crosslinking site, a functional group (for example, a hydroxyl group, a carbonyl group, a carboxyl group, a thiol group, an amide group, an amide group, which forms a crosslinking point by a chemical bond) Those that do not contain an amino group) and do not contain a binding site (such as a cross-linking site by a covalent bond) that directly cross-links polymer chains are preferably used. Further, such a styrene block copolymer having no chemically-bonded cross-linking site has at least the above-mentioned side chain (a), side chain (a ′), side chain (b), side chain ( c) The polymer does not have.

In addition, the “styrene block copolymer” herein may be a polymer having a styrene block structure at any part. In general, a styrene block copolymer has a styrene block structure, and at normal temperature, the styrene block structure part aggregates to form a physical crosslinking point (physical pseudo-crosslinking point) and is heated. Based on the fact that such a physical pseudo-crosslinking point collapses, it can be used as a material having thermoplasticity and rubber-like properties (elasticity, etc.) at room temperature.

Further, as such a styrene block copolymer having no chemically bonding cross-linking site (hereinafter, simply referred to as “styrene block copolymer having no chemical bonding cross-linking site”), rubber is used. From the viewpoint of both elasticity and thermoplasticity, styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer Polymer (SEEPS), Styrene-Butadiene-Styrene Block Copolymer (SBS), Styrene-Ethylene-Butylene-Styrene Block Copolymer (SEBS), Styrene-Isoprene-Butadiene-Styrene Block Copolymer (SIBS), These Hydrogenated products (so-called hydrogenated products) are preferred and S BS, SEEPS is more preferable. Such a styrene block copolymer may be used individually by 1 type, or may be used in combination of 2 or more type.

The styrene block copolymer having no chemically-bonded cross-linking site is a styrene block copolymer having a styrene content of 20 to 40% by mass (more preferably 25 to 37% by mass). preferable. If the styrene content is less than the lower limit, the thermoplasticity tends to decrease due to a decrease in the styrene block component. On the other hand, if the styrene content exceeds the upper limit, the rubber elasticity tends to decrease due to a decrease in the olefin component. The styrene content in such a styrene block styrene block copolymer can be measured by a method based on the IR method described in JIS K6239 (issued in 2007).

Furthermore, the weight average molecular weight (Mw) of the styrene block copolymer having no chemically-bonded crosslinking site is preferably 200,000 to 700,000, more preferably 300,000 to 600,000. Preferably, it is 350,000 or more and 550,000 or less. When the weight average molecular weight is less than the lower limit, the heat resistance tends to be reduced. On the other hand, when the weight average molecular weight exceeds the upper limit, the compatibility with the elastomeric polymer tends to be reduced.

Further, the number average molecular weight (Mn) of the styrene block copolymer having no chemically-bonded crosslinking site is preferably 100,000 or more and 600,000 or less, more preferably 150,000 or more and 550,000 or less. Preferably, it is 200,000 or more and 500,000 or less. When the number average molecular weight is less than the lower limit, the heat resistance tends to be lowered. On the other hand, when the upper limit is exceeded, the compatibility with the elastomeric polymer (the elastomer component) tends to be lowered.

Further, the dispersity (Mw / Mn) of the molecular weight distribution of the styrene block copolymer having no chemically bonding cross-linked site is preferably 5 or less, more preferably 1 to 3. The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution dispersity (Mw / Mn) can be determined by a so-called gel permeation chromatography (GPC) method. Further, as a specific apparatus and conditions for measuring such molecular weight, “Prominence GPC system” manufactured by Shimadzu Corporation can be used.

Further, the glass transition point of the styrene block copolymer having no chemically bonding cross-linking site is preferably −80 to −40 ° C., and more preferably −70 to −50. When such a glass transition point is less than the lower limit, the melting point becomes low, and thus the heat resistance tends to be lowered. On the other hand, when the upper limit is exceeded, rubber elasticity tends to be lowered. The “glass transition point” here is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry) as described above. In such DSC measurement, the rate of temperature rise is preferably 10 ° C./min.

The method for producing the styrene block copolymer having no chemical bonding cross-linking site is not particularly limited, and a known method can be appropriately employed. In addition, as such a styrene block copolymer, a commercially available product may be used. “G1651” “G1652” “G1654” “G1657” “G1660”; product names “S4055” “S4077” “S4099” “S8006” “S4044” “S8006” “S4033” “S8004” “S8007” “Kuraray” "S8076"; trade names "Tuff Tech H1041", "Tuff Tech N504", "Tuff Tech H1272", "Tuff Tech M1911", "Tuff Tech M1913", "Tuff Tech MP10" manufactured by Asahi Kasei Corporation; trade names "AR-710", "AR-720" manufactured by Aron Kasei Co., Ltd. "AR-731" "A -741 "" AR-750 "," AR-760 "," AR-770 "," AR-781 "," AR-791 "; and the like may be appropriately used.

Further, when the thermoplastic elastomer composition of the present invention further contains a styrene block copolymer having no chemically-bonded crosslinking site, the styrene block copolymer having no chemically-bonded crosslinking site is used. The content (content ratio) is preferably 10 to 400 parts by mass or less, more preferably 15 to 350 parts by mass, and more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the elastomer component. More preferred is 30 to 250 parts by mass. If the content of the styrene block copolymer having no such chemical bonding crosslinking site is less than the lower limit, the content of the styrene block copolymer having no chemical bonding crosslinking site is too small, In particular, there is a tendency that sufficient effects cannot be obtained in terms of fluidity and workability. On the other hand, when the upper limit is exceeded, the characteristics of the matrix structure (characteristics derived from the elastomer component) due to the crosslinked elastomer tend to be dilute. It is in.

Further, when the thermoplastic elastomer composition of the present invention further contains a styrene block copolymer having no chemically-bonded crosslinking site, the styrene block copolymer having no chemically-bonded crosslinking site is used. The content is preferably 5 to 60% by mass, more preferably 7 to 45% by mass, and still more preferably 10 to 30% by mass with respect to the total amount of the thermoplastic elastomer composition. If the content of the styrene block copolymer having no such chemically bondable crosslinking site is less than the lower limit, the content of the styrene block copolymer is too small, particularly in terms of fluidity and workability. On the other hand, if the upper limit is exceeded, the characteristics of the matrix structure (characteristics derived from the elastomer component) due to the crosslinked elastomer tend to be diluted.

In the thermoplastic elastomer composition of the present invention, examples of the other polymer described above include, for example, the α-olefin-based resin that does not have the chemical bond crosslinking site and the chemical bond crosslinking site. In addition to the styrene block copolymer, other types of polymers can be used as appropriate. Examples of such other types of polymers include polytetrafluoroethylene (PTFE), polyisobutylene, polymethyl methacrylate, polystearyl methacrylate, polybutyl methacrylate, polypropyl methacrylate, fluororubber, silicone rubber ( MQ), polypropylene oxide, polydimethylsiloxane, butyl rubber (IIR), polyvinyl chloride, natural rubber (NR), polyisoprene (IR: isoprene rubber), polybutadiene (BR: butadiene rubber), styrene butadiene rubber (SBR), polystyrene Is mentioned.

In addition, the paraffin oil may contain other components (additional) further contained in the thermoplastic elastomer composition of the present invention from the viewpoint that the fluidity can be further improved without deteriorating various physical properties of the composition. Agent). When such paraffin oil is used in combination with the above-mentioned styrenic block polymer, it becomes possible to absorb the oil component into the block polymer, improving the workability by adding oil (improving fluidity) and styrenic It is possible to achieve a sufficiently high level of improvement in mechanical properties due to the addition of block polymers, so that production properties such as extrusion and injection moldability are maintained while maintaining sufficient mechanical properties and heat resistance. Can be more advanced. Further, when paraffin oil is used, for example, when heated and extruded from an orifice (for example, one having an opening with a diameter of 1 mm), the string-like thermoplastic extruded from the orifice opening The shape (strand shape) of the elastomer composition has a sufficiently uniform thickness, and excellent extrudability tends to be obtained such that no fuzz is observed on the surface thereof. Such paraffin oil is not particularly limited, and known paraffin oil can be appropriately used.

In addition, as such paraffin oil, a correlation ring analysis (ndM ring analysis) based on ASTM D3238-85 is performed on the oil, and the percentage of the paraffin carbon number to the total carbon number (paraffin) Parts: C _P ), percentage of total number of naphthene carbons (naphthene part: C _N ), and percentage of total number of aromatic carbons (aromatic part: C _A ), respectively. It is preferable that the percentage (C _P ) of the paraffin carbon number to the total carbon number is 60% or more.

In addition, such a paraffin oil, is measured according to JIS K 2283 (published in 2000), it preferably has ^{^{50mm 2 / s ~ 700mm 2 /}} s kinematic viscosity at 40 ℃, 150 ~ 600mm ² / S is more preferable, and 300 to 500 mm ² / s is even more preferable. If such a kinematic viscosity (ν) is less than the lower limit, oil bleeding tends to occur. On the other hand, if it exceeds the upper limit, sufficient fluidity tends not to be imparted. As the kinematic viscosity of such paraffin oil, a value measured according to JIS K 2283 (issued in 2000) under a temperature condition of 40 ° C. is adopted. For example, JIS K 2283 (issued in 2000) The value automatically measured under a temperature condition of 40 ° C. using a Canon-Fenske viscometer (for example, trade name “SO Series” manufactured by Shibata Kagaku Co., Ltd.) may be employed.

Further, such paraffin oil preferably has an aniline point measured by the U-tube method in accordance with JIS K2256 (issued in 2013) of 80 ° C to 145 ° C, more preferably 100 to 145 ° C. Preferably, the temperature is 105 to 145 ° C. For the aniline point of such paraffin oil, a value measured by the U-shaped tube method conforming to JIS K2256 (issued in 2013) is adopted. For example, the aniline point conforming to JIS K2256 (issued in 2013) is adopted. A value measured using a measuring device (for example, trade name “aap-6” manufactured by Tanaka Scientific Instruments Co., Ltd.) may be used.

In addition, as such paraffin oil, commercially available products can be used as appropriate. For example, trade names “Super Oil M Series P200”, “Super Oil M Series P400”, “JO Nippon Mining & Energy Corporation”, “ Super Oil M Series P500S; trade names “Diana Process Oil PW90”, “Diana Process Oil PW150”, “Diana Process Oil PW380” manufactured by Idemitsu Kosan Co., Ltd .; trade names “SUNPAR Series (110, 115) , 120, 130, 150, 2100, 2280, etc.); a trade name “Gargoyle Arctic Series (1010, 1022, 1032, 1046, 1068, 1100, etc.)” manufactured by Mobil Corporation may be used as appropriate.

When the paraffin oil is further contained in the thermoplastic elastomer composition of the present invention, the content of the paraffin oil is preferably 10 to 600 parts by mass with respect to 100 parts by mass of the elastomer component. The amount is more preferably 550 parts by mass, still more preferably 75 to 500 parts by mass, and particularly preferably 100 to 400 parts by mass. If the content of such paraffin oil is less than the lower limit, the content of paraffin oil is too small, and the effect obtained by adding paraffin oil (especially the effect of improving fluidity and workability) is not always sufficient. On the other hand, when the upper limit is exceeded, bleeding of paraffin oil tends to be induced.

When the paraffin oil is further contained in the thermoplastic elastomer composition of the present invention, the content of the paraffin oil is preferably 20 to 60% by mass with respect to the total amount of the thermoplastic elastomer composition, 25 More preferably, it is -55 mass%, and still more preferably 35-55 mass%. If the content of such paraffin oil is less than the above lower limit, the content of paraffin oil is too small, and in particular, there is a tendency that sufficient effects cannot be obtained in terms of fluidity and workability, and on the other hand, the content exceeds the upper limit. In this case, paraffin oil bleed tends to be induced.

Further, the thermoplastic elastomer composition of the present invention includes an α-olefin resin not having the chemical bonding cross-linking site, the paraffin oil, and the chemical bonding cross-linking from the viewpoint of improving fluidity and mechanical properties. What contains the styrene block copolymer which does not have a site | part in combination is preferable. That is, the thermoplastic elastomer composition of the present invention includes the elastomer component, the additive component, the α-olefin resin not having the chemically-bonded crosslinking site, the paraffin oil, and the chemically-bonded crosslinking site. What contains the styrene block copolymer which does not have is more preferable.

Thus, in the case of containing the elastomer component, the additive component, the α-olefin resin, the paraffin oil, and the styrene block copolymer, wear resistance, breaking strength, and compression set resistance Etc. tend to be able to demonstrate characteristics such as etc. at a higher level in a balanced manner. The reason why such an effect is achieved is not necessarily clear, but the present inventors speculate as follows. That is, first, when the paraffin oil and the styrene block copolymer are used in combination, their compatibility is sufficiently high, so that the paraffin oil is sufficiently uniform in the system containing the styrene block copolymer. To disperse. Further, since the styrene block copolymer and the α-olefin resin are highly compatible, they are uniformly dispersed in the system. Further, in such a system containing the styrene block copolymer and the α-olefin resin, the elastomer component has high compatibility with both, so that the elastomer component is also sufficiently contained in the composition. It will be uniformly dispersed. As described above, since the elastomer component and the additive component interact to form surface crosslinking, the additive component also exists in a sufficiently dispersed state as the elastomer component is dispersed. Thus, when the elastomer component, the additive component, the α-olefin resin, the paraffin oil, and the styrene block copolymer are contained, each component is contained in a sufficiently dispersed state. Therefore, the state of the elastomer component that strongly influences the properties of the thermoplastic elastomer composition is sufficiently dispersed in a state of interacting with the additive component (a state in which a strong bond is formed by surface cross-linking). It is possible to exhibit a higher level of mechanical strength and heat resistance in a balanced manner. Further, in such a system, higher fluidity (fluidity during heating) can be achieved due to the α-olefin resin. Moreover, since the mechanical strength of the styrene block copolymer can be adjusted depending on the amount added, it can be adjusted to desired mechanical properties. Therefore, the system containing the elastomer component, the additive component, the α-olefin resin, the paraffin oil, and the styrene block copolymer has characteristics such as wear resistance, tensile strength, and compression set resistance. The present inventors speculate that the effect of being able to exhibit in a balanced manner at a higher level is obtained.

Further, examples of the reinforcing agent (filler) that can be further contained in the thermoplastic elastomer composition of the present invention include carbon black, silica, calcium carbonate, and the like. As silica, wet silica is preferably used.

In addition, as the anti-aging agent, for example, compounds such as hindered phenols, aliphatic and aromatic hindered amines can be appropriately used. Moreover, as said antioxidant, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA) etc. can be utilized suitably, for example. Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate, organic pigments such as azo pigments and copper phthalocyanine pigments. Pigments can be used as appropriate, and examples of the plasticizer include benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid. In addition to derivatives such as acids, polyesters, polyethers, epoxy resins, and the like can be used as appropriate. Further, as the plasticizer (softener), those that can be used for thermoplastic elastomers can be appropriately used from the viewpoint of further improving fluidity, and for example, oils can also be used. In addition, as such an additive etc., you may utilize suitably what is illustrated by Unexamined-Japanese-Patent No. 2006-131663.

The thermoplastic elastomer composition of the present invention has the elastomer component, the additive component, the α-olefin resin not having the chemically-bonded crosslinking site, the paraffin oil, and the chemically-bonded crosslinking site. In the case where other components other than the styrene block copolymer are contained (for example, the additive etc.), the content of the other components is not particularly limited, but polymers, reinforcing materials (filling) In the case of (agent), the amount is preferably 400 parts by mass or less, more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the elastomer component. If the content of such other components is less than the lower limit, the effect of using the other components tends to be insufficiently expressed. On the other hand, if the content exceeds the upper limit, it depends on the type of the component used. The effect of the substrate elastomer is diminished and the physical properties tend to decrease.

In the case where the above-mentioned other components are other additives (in the case of other than polymers and reinforcing materials (fillers)), the content of the other components is 100 parts by mass of the elastomer component, respectively. The amount is preferably 20 parts by mass or less, more preferably 0.1 to 10 parts by mass. If the content of such other components is less than the lower limit, the effect of using the other components tends to be insufficient, while if the upper limit is exceeded, the reaction of the substrate elastomer is adversely affected. On the other hand, physical properties tend to decrease.

The thermoplastic elastomer composition of the present invention is heated (for example, heated to 100 to 250 ° C.) to form hydrogen bonds formed at the hydrogen bond cross-linked sites and other cross-linked structures (including a styrene block copolymer). In some cases, the physical cross-linking and the like) can be dissociated and softened to impart fluidity. This is presumably because the interaction between the side chains formed between the molecules or within the molecule due to heating (mainly the interaction due to hydrogen bonding) is weakened. In the present invention, since the side chain contains an elastomer component containing at least a hydrogen-bonding cross-linked site, etc., when the fluidity is imparted by heating and left to stand, the dissociated hydrogen bond Since they are bonded and cured again, depending on the composition, the thermoplastic elastomer composition can be made to exhibit recyclability more efficiently.

Further, the thermoplastic elastomer composition of the present invention has a melt flow rate (MFR) at 230 ° C. under a load of 10 kg measured in accordance with JIS K6922-2 (issued in 2010) of 2 g / 10 min or more. Preferably, it is 4 g / 10 min or more, and more preferably 8 g / 10 min or more. If such a melt flow rate (MFR) is less than the lower limit, there may be a case where sufficient processability cannot always be exhibited. Such a melt flow rate (MFR) is a value measured in accordance with method B described in JIS K6922-2 (issued in 2010), and is a product manufactured by Toyo Seiki Seisakusho as a melt flow rate measuring device. Using the name “Melt Indexer G-01”, 3 g of the thermoplastic elastomer composition was added to the furnace of the apparatus, and the temperature was maintained at 230 ° C. for 5 minutes, and then maintained at 230 ° C. and loaded to 10 kg. The mass (g) of the elastomer flowing out in 10 minutes from the opening of a cylindrical orifice member having a diameter of 1 mm and a length of 8 mm connected to the lower part of the furnace body is measured (the furnace body The temperature is maintained at 230 ° C. for 5 minutes and then the load is started, and then the measurement of the mass of the elastomer flowing out is started. Kill.

Furthermore, in the thermoplastic elastomer composition of the present invention, the 5% weight loss temperature is preferably 320 ° C. or higher, more preferably 325 ° C. or higher. When such a 5% weight loss temperature is less than the lower limit, the heat resistance tends to be inferior. Such 5% weight loss temperature is prepared by preparing 10 mg of a thermoplastic elastomer composition as a measurement sample, and using a thermogravimetric measurement device (TGA) as a measurement device and heating at a heating rate of 10 ° C./min. It can be determined by measuring the temperature when the 5% weight is reduced from the initial weight (10 mg).

The thermoplastic elastomer composition of the present invention can be used for various rubber applications by utilizing rubber elasticity, for example. Moreover, since it can improve heat resistance and recyclability, it is preferable to use it as a hot melt adhesive or as an additive contained therein. The thermoplastic elastomer composition of the present invention comprises a hot melt adhesive or an additive contained therein, an automotive rubber part, a hose, a belt, a sheet, an anti-vibration rubber, a roller, a lining, a rubberized cloth, a sealing material, a glove, Fenders, medical rubber (syringe gaskets, tubes, catheters), gaskets (for home appliances, construction), asphalt modifiers, boots, grips, toys, shoes, sandals, keypads, gears, PET bottle caps It can be suitably used for applications such as liners, rubber parts for printers, sealing materials, paints / coating materials, and printing inks.

Specific examples of the rubber parts for automobiles include, for example, tire treads, carcass, sidewalls, inner liners, undertreads, belt portions, and other tire parts; exterior radiator grilles, side moldings, garnishes (pillars, rears) , Cowl top), aero parts (air dam, spoiler), wheel cover, weather strip, cow belt grill, air outlet louver, air scoop, hood bulge, vent parts, anti-corrosion parts (over fender, side seal panel, Malls (windows, hoods, door belts)), marks, etc .; interior window frame parts such as doors, lights, wiper weatherstrips, glass runs, glass run channels; air duct hoses, radiator hoses, brake hoses; cranks Lubricating oil system parts such as shaft seal, valve stem seal, head cover gasket, A / T oil cooler hose, mission oil seal, P / S hose, P / S oil seal; fuel hose, emission control hose, inlet filler hose, diaphragms Anti-vibration parts such as engine mounts and in-tank pump mounts; Boots such as CVJ boots, rack & pinion boots; Air-conditioning parts such as A / C hoses and A / C seals; Timing Belt parts such as belts and auxiliary belts; sealers such as windshield sealers, vinyl plastisol sealers, anaerobic sealers, body sealers, spot weld sealers; and the like.

Also, as a rubber modifier, for example, as a flow inhibitor, if it is included in a resin or rubber that causes a cold flow at room temperature, it is possible to prevent the flow during extrusion or cold flow.

The thermoplastic elastomer composition of the present invention can have higher heat resistance and can have higher tensile properties based on the breaking strength. In addition, in such a thermoplastic elastomer composition, it is possible to appropriately exhibit characteristics (for example, characteristics such as self-healing properties) required according to applications by appropriately changing the composition. In this way, by appropriately changing the composition, it is possible to appropriately exhibit the necessary characteristics in a balanced manner according to the use of the thermoplastic elastomer composition. In consideration of characteristics required according to the application, it is preferable to appropriately change the type (composition) of the components in the composition.

Although the thermoplastic elastomer composition of the present invention has been described above, a method that can be suitably used as a method for producing such a thermoplastic elastomer composition of the present invention will be described below.

As a suitable method for producing the thermoplastic elastomer composition of the present invention, for example, an elastomeric polymer (E) having a functional group in a side chain,
At least one additive selected from the group consisting of expanded graphite, carbon nanotubes, fullerenes, graphene, silicate-based natural nanofibers, silsesquioxanes and layered titanate compounds;
A first step of mixing to obtain a mixture;
Compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site in the mixture, and a covalent bond cross-linking site that reacts with the compound (I) and the cyclic acid anhydride group A thermoplastic elastomer is prepared by adding at least one raw material compound (M) among the mixed raw materials of the compound (II) forming the compound and reacting the elastomeric polymer (E) with the raw material compound (M). A second step of obtaining a composition;
Including
The thermoplastic elastomer composition obtained in the second step has a side chain containing a hydrogen-bonding cross-linked site having a carbonyl-containing group and / or a nitrogen-containing heterocycle, and has a glass transition point of 25 ° C. or lower. Selected from the group consisting of an elastomeric polymer (A) and an elastomeric polymer (B) containing a hydrogen-bonding crosslinking site and a covalent-bonding crosslinking site in the side chain and having a glass transition point of 25 ° C. or lower. At least one elastomer component,
It is at least one selected from the group consisting of expanded graphite, carbon nanotubes, fullerenes, graphene, silicate-based natural nanofibers, silsesquioxanes, and layered titanate compounds, and the content thereof is 100 masses of the elastomer component. An additive component that is 20 parts by mass or less relative to parts,
And a composition comprising
In the first step, using the additive component at a ratio such that the content of the additive component in the thermoplastic elastomer composition is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component, the elastomeric property The method of mixing a polymer (E) and the said additional component can be mentioned. Hereinafter, regarding such a method, the first step and the second step will be described separately.

(First step)
The first step is a step in which an elastomeric polymer (E) having a cyclic acid anhydride group in the side chain is mixed with the additive component to obtain a mixture.

Here, the “elastomeric polymer (E) having a functional group in its side chain” means a bond (covalent bond) in which a functional group (for example, a cyclic acid anhydride group) is chemically stable to an atom forming the main chain of the polymer. For example, a polymer capable of forming a main chain portion of the elastomeric polymers (A) to (B) and a functional group (for example, a cyclic acid anhydride group). What can be obtained by reacting with a compound capable of introducing is preferably used.

In addition, as a polymer which can form such a principal chain part, it is generally a well-known natural polymer or a synthetic polymer, The glass transition point consists of a polymer below room temperature (25 degreeC). Any material may be used as long as it is made of a so-called elastomer, and is not particularly limited.

Examples of the polymer capable of forming the main chain portion of such elastomeric polymers (A) to (B) include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1, Diene rubbers such as 2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM), and hydrogenation thereof Olefin rubbers such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), chlorosulfonated polyethylene, acrylic rubber, fluororubber, polyethylene rubber, polypropylene rubber; epichlorohydride Rubber; polysulfide rubber; Examples include ricone rubber; urethane rubber;

The polymer capable of forming the main chain portion of the elastomeric polymers (A) to (B) may be an elastomeric polymer containing a resin component, for example, hydrogenated. Polystyrene-based elastomeric polymer (for example, SBS, SIS, SEBS, etc.), polyolefin-based elastomeric polymer, polyvinyl chloride-based elastomeric polymer, polyurethane-based elastomeric polymer, polyester-based elastomeric polymer, polyamide-based elastomeric polymer Etc.

Further, polymers capable of forming the main chain portion of such elastomeric polymers (A) to (B) include diene rubber, hydrogenated diene rubber, olefin rubber, and hydrogenated. At least one selected from polystyrene-based elastomeric polymer, polyolefin-based elastomeric polymer, polyvinyl chloride-based elastomeric polymer, polyurethane-based elastomeric polymer, polyester-based elastomeric polymer, and polyamide-based elastomeric polymer It preferably consists of seeds. Further, as such a polymer, a diene rubber is preferable from the viewpoint of easy introduction of a maleic anhydride group suitable as a cyclic acid anhydride group, and an olefin rubber is preferable from the viewpoint of aging resistance. preferable.

Examples of the compound capable of introducing the functional group (for example, cyclic acid anhydride group) include cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and derivatives thereof. It is done.

When the elastomeric polymer (E) used in the first step is an elastomeric polymer having a cyclic acid anhydride group in the side chain, the cyclic acid anhydride group includes a succinic anhydride group and a maleic anhydride group. Of these, a glutaric anhydride group and a phthalic anhydride group are preferred, and among them, a maleic anhydride group is more preferred from the viewpoint of high reactivity of the raw material and industrial availability of the raw material.

Further, the elastomeric polymer having such a cyclic acid anhydride group in the side chain is converted into a polymer capable of forming the main chain portion of the elastomeric polymers (A) to (B), for example, by a usual method. Alternatively, it may be produced by a method of graft polymerization of a cyclic acid anhydride under usual conditions, for example, stirring under heating. A commercially available product may be used as the elastomeric polymer having such a cyclic acid anhydride group in the side chain.

Examples of commercially available elastomeric polymers having such a cyclic acid anhydride group in the side chain include maleic anhydride-modified isoprene rubbers such as LIR-403 (manufactured by Kuraray Co., Ltd.) and LIR-410A (prototype manufactured by Kuraray Co., Ltd.). Modified isoprene rubber such as LIR-410 (manufactured by Kuraray Co., Ltd.); carboxy-modified nitrile rubber such as Clinac 110, 221 and 231 (manufactured by Policer); CPIB (manufactured by Nisseki Chemical Co., Ltd.) Carboxy-modified polybutene such as Nucrel (made by Mitsui Dupont Polychemical), Yucaron (made by Mitsubishi Chemical), Tuffmer M (for example, MP0610 (made by Mitsui Chemicals), MP0620 (made by Mitsui Chemicals)), etc. Maleic acid-modified ethylene-propylene rubber; Toughmer M (for example, MA8510, MH701) , MH7020 (Mitsui Chemicals), MH5010, MH5020 (Mitsui Chemicals), MH5040 (Mitsui Chemicals)), etc .; Adtex series (maleic anhydride modified EVA), ethylene Methyl acrylate / maleic anhydride copolymer (manufactured by Nippon Polyolefin), HPR series (maleic anhydride modified EEA, maleic anhydride modified EVA (Mitsui / Jupon Polyolefin)), Bond Fast series (maleic anhydride modified EMA ( Sumitomo Chemical Co., Ltd.)), Dumiran series (maleic anhydride modified EVOH (manufactured by Takeda Pharmaceutical Company Limited)), Bondine (ethylene / acrylic acid ester / maleic anhydride terpolymer (manufactured by Atofina)), Tuftec ( Maleic anhydride modified SEBS, M194 (Manufactured by Asahi Kasei), Kraton (maleic anhydride modified SEBS, FG1901, FG1924 (manufactured by Kraton Polymer)), tufprene (maleic anhydride modified SBS, 912 (manufactured by Asahi Kasei)), Septon (maleic anhydride modified SEPS ( Kuraray)), Lexpearl (maleic anhydride modified EVA, ET-182G, 224M, 234M (manufactured by Nippon Polyolefin)), Aurorene (maleic anhydride modified EVA, 200S, 250S (manufactured by Nippon Paper Chemicals)) And maleic anhydride-modified polyethylene such as Admer (eg, QB550, LF128 (manufactured by Mitsui Chemicals)) and the like.

In addition, the elastomeric polymer having such a cyclic acid anhydride group in the side chain is preferably a maleic anhydride-modified elastomeric polymer (E1). Among them, from the viewpoint of high molecular weight and high strength, Maleic anhydride-modified ethylene-propylene rubber, maleic anhydride-modified ethylene-butene rubber, and ethylene / methyl acrylate / maleic anhydride copolymer are more preferable. Moreover, as an elastomeric polymer which has the said cyclic acid anhydride group in a side chain, you may utilize 1 type individually or in combination of 2 or more types.

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

Furthermore, the additive component used in the first step is the same as that described in the thermoplastic elastomer composition of the present invention (the preferred ones are also the same).

In the present invention, by reacting the elastomeric polymer (E) with a raw material compound (M) described later, an elastomer component (in the thermoplastic elastomer composition, which is the final product (target product)) ( The elastomeric polymer (A) and / or (B)) is formed, and the main chain portion of the elastomeric polymer (E) is directly used as the main chain portion of the polymer contained as the elastomer component.

In the first step, the elastomeric polymer (E) and the additive component are mixed to obtain a mixture. Here, when the additive component is added to the elastomeric polymer (E), the elastomeric polymer (E) is plasticized in advance so that the additive component is sufficiently dispersed, and then the additive component is added. It is preferable.

Thus, the method for plasticizing the elastomeric polymer (E) is not particularly limited. For example, the roll or kneader is heated at a temperature (for example, about 100 to 250 ° C.) at which these can be plasticized. A method of kneading using an extruder, a universal stirrer or the like can be appropriately employed. Conditions such as temperature at the time of plasticizing such an elastomeric polymer (E) are not particularly limited and are appropriately set according to the type of component (type of elastomeric polymer (E), etc.). do it.

Moreover, in the preparation process of such a mixture, content of the said additional component in the thermoplastic elastomer composition finally obtained is 20 mass parts or less with respect to 100 mass parts of said elastomer components (preferably 0.00. 1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, particularly preferably 1 to 3 parts by weight) using the additive component in a proportion such that the elastomeric polymer (E) and the additive component Are preferably mixed. If the content of such an additive component exceeds the upper limit, the crosslinking is too strong, and on the other hand, the elongation and the strength tend to decrease.On the other hand, if the content is less than the lower limit, the amount of the additive component is too small, and the addition There exists a tendency for the effect acquired by using a component to fall.

Further, the content of the additive component in such a mixture is preferably 20 parts by mass or less, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the elastomeric polymer (E). Is more preferably 1 to 3 parts by mass. When the content is less than the lower limit, the amount of the additive component is too small, and the effect obtained by using the additive component tends to be reduced. On the other hand, when the content exceeds the upper limit, crosslinking occurs. It is too strong and tends to decrease the elongation and strength. In addition, by using the said additive component with such content, content of the said additive component in the thermoplastic elastomer composition finally obtained becomes a value within the said range.

Furthermore, the amount of the additive component used in forming such a mixture is 0.01 g to 2.0 g (more preferably) with respect to 1 mmol of the functional group in the elastomeric polymer (E). Is preferably contained at a ratio of 0.02 to 1.0 g). If the ratio of the additive component relative to 1 mmol of the functional group in the elastomeric polymer (E) is less than the lower limit, the amount of the additive component tends to be too small and the effect tends to decrease. Crosslinking is too strong, and the elongation and strength tend to decrease. In addition, by including an additive component within the range of such a ratio, it is possible to perform an appropriate interaction with the functional group, and the dispersibility of the additive component tends to be higher. is there.

Such a mixture further has an α-olefin resin, paraffin oil, which does not have a chemical bonding crosslinking site, and a chemical bonding crosslinking site, from the viewpoint of increasing fluidity and mechanical strength. A non-styrene block copolymer or the like may be further contained. Such an α-olefin resin not having a chemical bonding crosslinking site, paraffin oil, and a styrene block copolymer having no chemical bonding crosslinking site are the thermoplastic elastomer composition of the present invention, respectively. And the same as the α-olefin resin having no chemical bonding crosslinking site, paraffin oil, and the styrene block copolymer having no chemical bonding crosslinking site (each suitable The same is true for things).

Further, in the case of further containing an α-olefin resin and / or paraffin oil and / or a styrene block copolymer not having a chemical bonding crosslinking site as described above, which does not have a chemical bonding crosslinking site. The elastomeric polymer (E), the additive component, the α-olefin resin and / or paraffin oil that does not have a chemical bonding crosslinking site, and / or the styrene block that does not have a chemical bonding crosslinking site. The order of addition with the polymer is not particularly limited, but from the viewpoint of further improving the dispersibility of the additive component, the elastomeric polymer (E), the α-olefin resin and / or the polymer. Preparing a precursor of a mixture comprising paraffin oil and / or a styrene block copolymer having no chemically-bonded crosslinking sites. After, it is preferable to add the additive ingredients in the precursor.

In addition, when the α-olefin resin (α-olefin resin having no chemically-bonded crosslinking site) is contained in the mixture, the content of the α-olefin resin is 100 masses of the elastomer component. The amount is preferably 800 parts by mass or less (more preferably 5 to 700 parts by mass, further preferably 10 to 600 parts by mass, particularly preferably 25 to 500 parts by mass, most preferably 50 to 400 parts by mass) with respect to parts. . When the content of such an α-olefin resin exceeds the upper limit, mechanical properties (breaking strength, compression set) tend to be lowered. On the other hand, when the content is less than the lower limit, fluidity tends to be lowered. The content of the α-olefin resin in such a mixture is 800 parts by mass or less (more preferably 5 to 700 parts by mass, still more preferably 10 parts by mass with respect to 100 parts by mass of the elastomeric polymer (E). To 600 parts by mass, particularly preferably 25 to 500 parts by mass, and most preferably 35 to 400 parts by mass). If such a content is less than the lower limit, mechanical properties (breaking strength, compression set) tend to decrease, and if it is less than the lower limit, fluidity tends to decrease.

When the paraffin oil is contained in the mixture, the paraffin oil content is preferably 600 parts by mass or less, more preferably 10 to 600 parts by mass with respect to 100 parts by mass of the elastomer component. 50 to 550 parts by mass, more preferably 75 to 500 parts by mass, and most preferably 100 to 400 parts by mass. In addition, when the styrene block copolymer having no chemically-bonded crosslinking site is contained in the mixture, the amount is preferably 600 parts by mass or less with respect to 100 parts by mass of the elastomer component. More preferred is 15 to 550 parts by weight, still more preferred is 20 to 500 parts by weight, and most preferred is 30 to 400 parts by weight.

Further, depending on the use of the thermoplastic elastomer composition finally obtained, the elastomer component, the α-olefin resin, and the styrene block are mixed with the mixture as long as the object of the present invention is not impaired. Polymers other than polymers, reinforcing agents (fillers), fillers introduced with amino groups (hereinafter simply referred to as “amino group-introduced fillers”), amino group-containing compounds other than the amino group-introduced fillers, Compound containing metal element (hereinafter simply referred to as “metal salt”), maleic anhydride modified polymer, antioxidant, antioxidant, pigment (dye), plasticizer, thixotropic agent, ultraviolet absorber, flame retardant Further, other components such as various additives such as a solvent, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, a rust preventive agent, an adhesion imparting agent, an antistatic agent, and a filler can be further contained. Thus, by including other components in the mixture, it is possible to appropriately include such components in the finally obtained thermoplastic elastomer composition. Such additives and the like are not particularly limited, and those commonly used can be appropriately used. Moreover, as such an additive etc., what was demonstrated in the thermoplastic-elastomer composition of the said invention can be utilized suitably.

Further, the content of such other components is preferably 500 parts by mass or less with respect to 100 parts by mass of the elastomer component when the other components are polymers and reinforcing materials (fillers). More preferred is 20 to 400 parts by mass. If the content of such other components is less than the lower limit, the effect of using the other components tends to be insufficiently expressed. On the other hand, if the content exceeds the upper limit, it depends on the type of the component used. The effect of the substrate elastomer is diminished and the physical properties tend to decrease.

Further, when the other component is other additive (in the case other than the polymers and the reinforcing material (filler)), the content of the other component is 20 with respect to 100 parts by mass of the elastomer component. The amount is preferably not more than part by mass, more preferably 0.1 to 10 parts by mass. If the content of such other components is less than the lower limit, the effect of using the other components tends to be insufficient, while if the upper limit is exceeded, the reaction of the substrate elastomer is adversely affected. On the other hand, physical properties tend to decrease.

(Second step)
In the second step, the mixture reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site, and reacts with the compound (I) and the cyclic acid anhydride group. A thermoplastic elastomer composition is obtained by adding at least one raw material compound (M) of the mixed raw materials of the compound (II) that forms a covalent cross-linking site, and reacting the polymer with the raw material compound. It is a process to obtain.

As the compound (I) that forms a hydrogen bonding cross-linking site by reacting with the cyclic acid anhydride group, a compound that forms the hydrogen bonding cross-linking site described in the thermoplastic elastomer composition of the present invention (nitrogen-containing complex). The same compounds as the compound capable of introducing a ring) can be suitably used. For example, the nitrogen-containing heterocyclic ring described in the thermoplastic elastomer composition of the present invention may be used, or the nitrogen-containing compound may be used. It may be a compound (a nitrogen-containing heterocycle having the above substituent) in which a substituent (for example, a hydroxyl group, a thiol group, an amino group, etc.) that reacts with a cyclic acid anhydride group such as maleic anhydride is bonded to the heterocyclic ring. . In addition, as such a compound (I), it is possible to introduce a compound that forms both a hydrogen bonding crosslinking site and a covalent bonding site (both hydrogen bonding crosslinking site and covalent bonding site can be introduced simultaneously). (A side chain having both a hydrogen bonding crosslinking site and a covalent bonding site can be said to be a preferred form of a side chain having a hydrogen bonding crosslinking site).

In addition, the compound (I) is not particularly limited, and the compound as described above depending on the type of side chain (side chain (a) or side chain (a ′)) in the target polymer. A suitable compound can be appropriately selected from (I). As such a compound (I), from the viewpoint that higher reactivity is obtained, triazole, pyridine, which may have at least one substituent selected from a hydroxyl group, a thiol group, and an amino group, It is preferably thiadiazole, imidazole, isocyanurate, triazine and hydantoin, and more preferably triazole, pyridine, thiadiazole, imidazole, isocyanurate, triazine and hydantoin having the above-mentioned substituents. The triazole, isocyanurate, and triazine are more preferable, and the triazole having the substituent is particularly preferable. Examples of the triazole, pyridine, thiadiazole, imidazole and hydantoin which may have such a substituent include, for example, 4H-3-amino-1,2,4-triazole, aminopyridine, aminoimidazole and aminotriazine. Aminoisocyanurate, hydroxypyridine, hydroxyethyl isocyanurate and the like.

In addition, as the compound (II) that reacts with the cyclic acid anhydride group to form a covalently crosslinked site, the “compound that forms a covalently crosslinked site” described in the thermoplastic elastomer composition of the present invention ( A compound similar to “a compound capable of forming a covalent bond” ”can be preferably used (the same applies to those suitable as the compound). In addition, as such compound (II), a compound that forms both a hydrogen bonding crosslinking site and a covalent bonding site (both hydrogen bonding crosslinking site and covalent bonding site can be introduced simultaneously. (A side chain having both a hydrogen bonding crosslinking site and a covalent crosslinking site can be said to be a preferred form of a side chain having a covalent crosslinking site).

As such compound (II), from the viewpoint of compression set resistance, trishydroxyethyl isocyanurate, sulfamide and polyether polyol are preferable, trishydroxyethyl isocyanurate and sulfamide are more preferable, and trishydroxyethyl isocyanurate is preferable. Further preferred.

In addition, as the compound (I) and / or (II), a compound having at least one substituent selected from a hydroxyl group, a thiol group, an amino group, and an imino group from the viewpoint of introducing a hydrogen-bonding crosslinking site. It is preferable to use it. Furthermore, as the compound (I) and / or (II), it is possible to introduce both the hydrogen-bonding crosslinking site and the covalent-bonding crosslinking site into the composition more efficiently. A compound that reacts with (for example, the above-mentioned cyclic acid anhydride group) to form both a hydrogen-bonding cross-linking site and a covalent cross-linking site (introducing both a hydrogen-bonding cross-linking site and a covalent cross-linking site simultaneously It is preferable to use a compound capable of As the compound that forms both the hydrogen bond crosslinking site and the covalent bond site, the heterocyclic ring-containing polyol, the heterocyclic ring-containing polyamine, and the heterocyclic ring-containing polythiol can be suitably used. Trishydroxyethyl isocyanurate is particularly preferred.

The amount of the starting compound (M) (compound (I) and / or compound (II)) added is the total amount of these compounds (if only one compound is used). ), Preferably 10 to 10 parts by weight, more preferably 0.3 to 7 parts by weight, based on 100 parts by weight of the elastomeric polymer (E) in the mixture, 0.5 More preferably, it is ˜5.0 parts by mass. If the amount of compound (I) and compound (II) added (the amount based on parts by mass) is less than the lower limit, the crosslinking density does not increase and the desired physical properties tend not to be exhibited. When it exceeds, it is too many and there exists a tendency for a branch to increase and a crosslinking density to fall.

In addition, the addition amount of the raw material compound (M) (compound (I) and / or compound (II)) (total amount of compound (I) and / or compound (II): when only one compound is used, The amount of the one compound.) Is not particularly limited, but when the compound contains active hydrogen such as amine or alcohol, the functional group (for example, the cyclic acid anhydride group) is 100 mol%. The amount of active hydrogen such as amine and alcohol in the compound is preferably 20 to 250 mol%, more preferably 50 to 150 mol%, and 80 to 120 mol%. It is more preferable that the amount is as follows. If the amount added is less than the lower limit, the amount of side chains introduced is small, it is difficult to make the crosslinking density sufficiently high, and physical properties such as tensile strength tend to be reduced. On the other hand, when the above upper limit is exceeded, the amount of the compound used is too large, the number of branches increases, and the crosslinking density tends to decrease.

In the case where both compound (I) and compound (II) are used, the order of adding compound (I) and compound (II) is not particularly limited, and either may be added first. In the case where both of the compound (I) and the compound (II) are used, the functional group of the elastomeric polymer having the functional group (for example, the cyclic acid anhydride group) in the side chain is used as the compound (I). You may make it react with a part (for example, said cyclic acid anhydride group). This makes it possible to react the compound (II) with the unreacted functional group (functional group that has not been reacted) to form a covalently crosslinked site. The part mentioned here is preferably 1 mol% or more and 50 mol% or less with respect to 100 mol% of the functional group (for example, the cyclic acid anhydride group). If it is this range, in the obtained elastomeric polymer (B), the effect of introducing a group derived from the compound (I) (for example, a nitrogen-containing heterocyclic ring) is sufficiently exhibited, and the recyclability tends to be further improved. is there. The compound (II) is preferably reacted with the cyclic acid anhydride group so that a suitable number of covalent crosslinks (for example, 1 to 3 per molecule) is obtained.

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) of the polymer and the raw material compound (M) (the compound) (I) and / or compound (II)) are chemically bonded. There are no particular restrictions on the temperature conditions for reacting the polymer (E) with the raw material compound (M) (opening the cyclic acid anhydride group), and the type of the compound and the cyclic acid anhydride group is not limited. Depending on the temperature, it may be adjusted to a temperature at which they can react, but from the viewpoint of softening and proceeding the reaction instantaneously, the temperature is preferably 100 to 250 ° C, more preferably 120 to 230 ° C.

As a result of such a reaction, at least a hydrogen-bonding cross-linking site is formed at the site where the compound (I) and the cyclic acid anhydride group are reacted. Therefore, a hydrogen-bonding cross-linking site (carbonyl group) is formed on the side chain of the polymer. A moiety having a containing group and / or a nitrogen-containing heterocyclic ring, more preferably a moiety having a carbonyl-containing group and a nitrogen-containing heterocyclic ring). The side chain formed (introduced) by such a reaction may contain a structure represented by the above formula (2) or (3).

Further, at such a site where the compound (II) and the cyclic acid anhydride group react with each other, at least a covalent crosslinking site is formed, so that the side chain of the polymer is covalently crosslinked. It is also possible to use a part containing a part (side chain (b) or side chain (c)). The side chain formed by such a reaction can also contain a structure represented by the above formulas (7) to (9).

In addition, each group (structure) of the side chain in such a polymer, that is, an unreacted cyclic acid anhydride group, a structure represented by the above formulas (2), (3) and (7) to (9) Etc. can be confirmed by commonly used analytical means such as NMR and IR spectra.

In addition, the raw material compound (M) used in such a reaction is preferably the aforementioned compounds (M1) to (M6). By using such compounds (M1) to (M6), the aforementioned reactants (I) to (VI) can be prepared.

In the present invention, the combination of the elastomeric polymer (E) having a functional group used in the reaction and the raw material compound (M) is the following combination from the viewpoint of allowing the reaction with the functional group to proceed more efficiently. (I)-(VI):
Combination (I) of maleic anhydride-modified elastomeric polymer (E1) and compound (M1); Combination (II) of hydroxyl group-containing elastomeric polymer (E2) and compound (M2); Carboxy group-containing elastomeric polymer Combination (III) of (E3) and compound (M3); Combination (IV) of amino group-containing elastomeric polymer (E4) and compound (M4); alkoxysilyl group-containing elastomeric polymer (E5) and A combination (V) with the compound (M5); and a combination (VI) of the epoxy group-containing elastomeric polymer (E6) and the compound (M6);
It is preferable that the elastomeric polymer (E) and the raw material compound (M) are selected and used so as to be any one of the above. Thus, by reacting the elastomeric polymer (E) and the raw material compound (M) in combination, the elastomer component is at least one selected from the group consisting of the reactants (I) to (VI). It can be a seed reactant.

Thus, an elastomeric polymer (A) having a side chain (a) containing a hydrogen-bonding cross-linked site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or lower, And at least one elastomer component selected from the group consisting of an elastomeric polymer (B) having a hydrogen bond crosslinking site and a covalent bond crosslinking site in the side chain and having a glass transition point of 25 ° C. or lower. When,
The additive component having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
Can be obtained.

In addition, the elastomeric polymer (A) and the elastomeric polymer (B) in the thermoplastic elastomer composition thus obtained are the side chain (a), side chain (a ′), side chain ( b) and the side chain (c) each derived from a reaction with a cyclic acid anhydride group (for example, containing structures represented by the above formulas (2), (3) and (7) to (9)) Except for the side chain and the like, the elastomeric polymer (A) and the elastomeric polymer (B) described in the thermoplastic elastomer composition of the present invention are the same.

In the present invention, from the viewpoint of easy availability and high reactivity, the elastomeric polymer having the functional group in the side chain is a maleic anhydride-modified elastomeric polymer (E1), and the raw material compound ( M) has at least one substituent selected from triazole, a hydroxyl group, a thiol group and an amino group which may have at least one substituent selected from a hydroxyl group, a thiol group and an amino group. It may have at least one substituent selected from pyridine, hydroxyl group, thiol group and amino group, and at least one substituent selected from thiadiazole, hydroxyl group, thiol group and amino group. May have at least one substituent selected from imidazole, hydroxyl group, thiol group and amino group, isocyanurate, hydroxyl group, thiol A triazine, a hydroxyl group, a thiol group and an amino group which may have at least one substituent selected from the group consisting of an amino group and an amino group. It is at least one compound of ethyl isocyanurate, sulfamide, and polyether polyol, and the elastomer component is a reaction product (reaction) of the maleic anhydride-modified elastomeric polymer (E1) and the raw material compound. Preferred embodiment of the product (I) is preferably at least one selected from the group consisting of: That is, in the present invention, the elastomer component is a maleic anhydride-modified elastomeric polymer (E1) and a triazole or hydroxyl group that may have at least one substituent selected from a hydroxyl group, a thiol group, and an amino group. , Pyridine optionally having at least one substituent of thiol group and amino group, hydroxyl group, thiadiazole optionally having at least one substituent of thiol group and amino group, hydroxyl group Imidazole optionally having at least one substituent among thiol group and amino group, isocyanurate optionally having at least one substituent selected from hydroxyl group, thiol group and amino group, Triazine, hydroxyl group, and thiyl optionally having at least one substituent selected from hydroxyl group, thiol group and amino group. And at least one compound selected from the group consisting of hydantoin, trishydroxyethyl isocyanurate, sulfamide, and polyether polyol, which may have at least one substituent selected from the group consisting of an alcohol group and an amino group (the compound (M1 It is preferably at least one selected from the group consisting of reactants with compounds selected from

In addition, from the viewpoint of high reaction efficiency and the bond formed is a hydrogen bond and a covalent bond, which can interact with the additive component to a higher degree, the elastomer component is treated with the maleic anhydride-modified elastomeric polymer (E1) and a hydroxyl group. , A reactant (I ′) with at least one of the hydrocarbon compounds having two or more substituents selected from thiol groups and amino groups, and the reactant (II) to It is preferable to use at least one reactant selected from the group consisting of (VI).

By the method including the first step and the second step, the thermoplastic elastomer composition of the present invention that can have a sufficiently high tensile strength and a sufficiently high friction resistance can be efficiently produced. Is possible.

In the present invention, for example, a thermoplastic elastomer composition containing an elastomeric polymer (A) as an elastomer component and a thermoplastic elastomer composition containing an elastomeric polymer (B) as an elastomer component were separately produced. Then, it is good also as a thermoplastic elastomer composition which mixes this and contains elastomeric polymers (A) and (B) as an elastomer component. In the case of producing a thermoplastic elastomer composition containing a combination of elastomeric polymers (A) and (B) as an elastomer component, the ratio of the elastomeric polymer (A) and the elastomeric polymer (B) is appropriately changed. Thus, desired characteristics can be exhibited by appropriately changing the ratio of the hydrogen-bonding cross-linking site and the covalent cross-linking site existing in the composition.

As mentioned above, although the manufacturing method of the thermoplastic elastomer composition of this invention which is a method suitably usable as a method for manufacturing the thermoplastic elastomer composition of this invention was demonstrated, the thermoplastic elastomer composition of this invention was demonstrated. The method for producing is not limited to the method for producing the thermoplastic elastomer composition of the present invention, and other methods may be appropriately employed. As such other methods, for example, the elastomeric polymer (D), the polymer (Z), the raw material compound, and the additive component are simultaneously added to form a mixture, and the elastomeric polymer (D) reacting the raw material compound to obtain a thermoplastic elastomer composition, forming a mixture of the elastomeric polymer (D), the polymer (Z), and the raw material compound, In the method, after reacting the elastomeric polymer (D) with the raw material compound to form an elastomer component, a method of adding the additive component to a mixture containing the elastomer component may be appropriately employed.

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, the thermoplastic elastomer composition obtained in each Example and each Comparative Example was used in an amount of 42 g, and the thermoplastic elastomer was heated at a temperature of 200 ° C. and preheated for 3 minutes. After placing in a 150 mm horizontal mold, pressure was applied by a hot press under conditions of temperature: 200 ° C., pressure: 18 MPa, pressurization time: 5 minutes, then pressure: 18 MPa, pressurization time: By applying pressure under the condition of 2 minutes and taking out from the mold, 2 mm thick sheets (thickness 2 mm, length 150 mm, width 150 mm) were formed respectively. Next, using each 2 mm-thick sheet (thickness 2 mm, length 150 mm, width 150 mm) obtained as described above, No. 3 dumbbell-shaped test pieces were prepared, respectively, at a pulling speed of 500 mm / min. The tensile strength test was conducted in accordance with JIS K6251 (issued in 2010), and the breaking strength (T _B ) [unit: MPa] and 100% modulus (M ₁₀₀ ) [MPa] were measured at room temperature (25 ° C.).

<Abrasion resistance>
First, 15 g of each of the thermoplastic elastomer compositions obtained in each Example and each Comparative Example was used, and a disk-shaped sample having a diameter of 16.0 mm and a thickness of 8 mm was respectively obtained using a dedicated mold (dedicated mold). Prepared. Next, using each of the obtained disk-shaped samples, in accordance with JIS K6264-2 (issued in 2005), a DIN abrasion tester (rotary cylindrical wear tester: trade name “DIN” manufactured by Yasuda Seiki Co., Ltd.) A wear resistance test was conducted using a wear tester under the conditions of temperature: room temperature (25 ° C.), load: 2.5 N, drum rotation speed: 40 rpm, sample lateral feed speed: 2.8 mm / sec. (Volume standard: ratio of volume worn by test with respect to total volume before wear (volume%)) The smaller the amount of wear, the higher the wear resistance.

Example 1
First, a styrene block copolymer (styrene-ethylene-butylene-styrene block copolymer (SEBS): trade name “G1633” manufactured by Clayton Co., Ltd., molecular weight: 400,000 to 500,000, styrene content: 30 mass%) 20 0.0 g was put into a pressure kneader and kneaded at 180 ° C., while paraffin oil (trade name “Super Oil M Series P500S” manufactured by JX Nippon Oil & Energy Corporation, kinematic viscosity: 472 mm ² / s, Cp value: 68.7%, aniline point: 123 ° C.) was added dropwise, and styrene-ethylene-butylene-styrene block copolymer and paraffin oil were mixed for 1 minute. Next, 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM: trade name “Toughmer MH5040”, crystallinity: 4%) manufactured by Mitsui Chemicals, Inc., α-olefin was added in the pressure kneader. Ethylene-butene copolymer (EBM: trade name “Tafmer DF7350” manufactured by Mitsui Chemicals, Inc.), crystallinity: 10%, MFR: 35 g / 10 min (2.16 kg, 190 ° C.), Mw: 100,000 ) 7.5 g and an antioxidant (trade name “AO-50” manufactured by Adeka Co., Ltd.) 0.078 g were further added, and the mixture was masticated at a temperature of 180 ° C. for 2 minutes to prepare the first mixture (PP and maleated EBM). And a mixture containing In addition, the said 1st mixture was plasticized by this mastication process. Next, 0.03 g of carbon nanotubes (trade name “Zeonano SG101” manufactured by Nippon Zeon Co., Ltd.) is further added to the first mixture in the pressure kneader, and the mixture is kneaded at 180 ° C. for 4 minutes. A mixture of was obtained. Next, 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.) is added to the second mixture in the pressure kneader, and mixed at 180 ° C. for 8 minutes. A composition was prepared.

In such a composition, the maleic anhydride group in the maleic anhydride-modified ethylene-butene copolymer reacted with trishydroxyethyl isocyanurate based on the result of infrared spectroscopic analysis of the raw material compound used. , A side chain containing a structure represented by the following formula (26) (hereinafter sometimes simply referred to as “side chain (i)”), a side chain containing a structure represented by the following formula (27) ( Hereinafter, in some cases, simply referred to as “side chain (ii)”) and a side chain containing a structure represented by the following formula (28) (hereinafter, sometimes simply referred to as “side chain (iii)”). ), An elastomeric polymer mainly having the side chain (iii) is formed (note that the side chain (i) to (iii) are stoichiometrically determined from the raw materials used). If considered, side chain (iii) is mainly formed It is clear that the side chain (i) and / or the side chain (ii) can be formed depending on the position of the side chain of the polymer, etc. Hereinafter, it is formed by reaction based on the raw materials used. In some cases, the type of the side chain that is considered to be the side chain (iii) is simply referred to as “the elastomeric polymer mainly having the side chain (iii)”. Further, it was found that such an elastomeric polymer has a glass transition point of 25 ° C. or lower because the main chain is composed of an ethylene-butene copolymer (ethylene and butene). Further, such an elastomeric polymer can be regarded as having an SP value of 8.0 from the type of raw material used (maleic anhydride-modified ethylene-butene copolymer).

[In the formulas (26) to (28), carbons represented by α and β are bonded to the main chain of the elastomeric polymer at any of the carbon positions (α-position or β-position). . ]
42 g of the thermoplastic elastomer composition thus obtained is introduced into a sheet-forming mold (thickness 2 mm, length 150 mm, width 150 mm) heated to 200 ° C., and preheated for 3 minutes without applying pressure. Then, under a condition of 200 ° C., pressurizing and molding at 16 MPa for 5 minutes, and then cooling with a water-cooled press at 16 MPa for 2 minutes, the sheet of the thermoplastic elastomer composition (thickness 2 mm, length 150 mm, 150 mm wide) was obtained. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 1.

(Example 2)
Instead of using 0.03 g of carbon nanotubes (trade name “ZeonanoSG101” manufactured by Nippon Zeon), 0.03 g of natural silicate-based nanofibers (trade name “Imogolite” manufactured by Astech) was used. In the same manner as in Example 1, a thermoplastic elastomer composition was prepared.

(Example 3)
Carbon nanotubes (Nippon Zeon Co., Ltd. under the trade name "ZeonanoSG101") to 0.03g layered titanic acid compound instead of using (Tokyo Kasei Co., Ltd. under the trade name "potassium titanate", chemical _formula: K ₂ Ti _{6 O 13,} powder A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that 0.03 g was used.

(Comparative Example 1)
Instead of using 0.03 g of carbon nanotubes (trade name “ZeonanoSG101” manufactured by Nippon Zeon Co., Ltd.), 0.03 g of carbon black (trade name “Seast KH (N339)” manufactured by Tokai Carbon Co., Ltd.) was used. 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 thus obtained are shown in Table 1.

(Comparative Example 2)
Example 1 was used except that 0.03 g of carbon nanotubes (trade name “Zeonano SG101” manufactured by Nippon Zeon Co., Ltd.) was used instead of 0.03 g of silica (trade name “Nippil AQ” manufactured by Nippon Silica Co., Ltd.). Similarly, a thermoplastic elastomer composition was prepared. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 1.

(Comparative Example 3)
Instead of using 0.03 g of carbon nanotubes (trade name “ZeonanoSG101” manufactured by Nippon Zeon Co., Ltd.), 0.03 g of titanium oxide (trade name “A-110” manufactured by Sakai Chemical Industry Co., Ltd.) was used. 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 thus obtained are shown in Table 1.

As is clear from the results shown in Table 1, when Examples 1 to 3 are compared with Comparative Examples 1 to 3, in Examples 1 to 3, additive components (carbon nanotubes, natural nanofibers, or layered titanic acid are used. In contrast, in Comparative Examples 1 to 3, the composition differs in that a so-called filler (carbon black, silica or titanium oxide) is used instead of the additive component. When the additive component is used (Examples 1 to 3), 100% modulus and breaking strength are used as a standard compared to the case where a so-called filler (carbon black, silica or titanium oxide) is used (Comparative Examples 1 to 3). It was confirmed that not only the tensile strength was higher, but also the amount of wear was reduced, and the wear resistance was higher. From these results, according to the present invention (Example 1), it is possible to make the tensile strength based on 100% modulus and breaking strength higher, and sufficiently high wear resistance. It was confirmed that it would be possible to have

Example 4
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), 0.102 g of pentaerythritol (trade name “Neuiser P” manufactured by Nippon Synthetic Chemical Co., Ltd.) is used. In addition, instead of using 0.03 g of carbon nanotubes (trade name “ZeonanoSG101” manufactured by Nippon Zeon Co., Ltd.), 0.03 g of natural nanofibers (trade name “Imogolite” manufactured by Astech Co., Ltd.) was used. 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 thus obtained are shown in Table 2.

The elastomer component becomes a reaction product of a maleic anhydride-modified ethylene-butene copolymer and pentaerythritol, and the side chain is formed by the reaction of maleic anhydride group and the hydroxy group of pentaerythritol, resulting in a carboxylate group (bonding). Part)) (having a hydrogen-bonding crosslinking site and a covalent bonding site).

(Example 5)
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), 2,4-diamino-6-phenyl-1,3,5-triazine (Nippon Shokubai Co., Ltd.) Instead of using 0.082 g of carbon nanotubes (trade name “ZeonanoSG101” manufactured by Nippon Zeon Co., Ltd.) and 0.282 g of product name “Benzoguanamine” manufactured by Nippon Kayaku Co., Ltd. the name "potassium titanate", chemical _formula: K ₂ Ti _{6 O 13,} except that the powder) was 0.03g utilized, implemented 1 was prepared a thermoplastic elastomer composition in the same manner as. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component is a reaction product of maleic anhydride-modified ethylene-butene copolymer and 2,4-diamino-6-phenyl-1,3,5-triazine, and the side chain is a maleic anhydride group and 2,4 -Formed by a reaction with an amino group (-NH ₂ ) in diamino-6-phenyl-1,3,5-triazine and having a crosslinked structure containing a triazine ring and an amide bond (formula: -CONH-) (It will have a hydrogen-bonding cross-linking site and a covalent bond cross-linking site).

(Example 6)
Instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (manufactured by SC Organic Chemical Co., Ltd.) A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that 0.527 g of the trade name “Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate”) was used. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component is a reaction product of a maleic anhydride-modified ethylene-butene copolymer and tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and the side chain is a maleic anhydride group and tris-[( 3-Mercaptopropionyloxy) -ethyl] -isocyanurate, formed by reaction with thiol group (—SH), isocyanurate ring in side chain and thioester (group represented by —CO—S—) , Having a cross-linked structure containing a carboxy group (having a hydrogen bond cross-linking site and a covalent bond cross-linking site).

(Example 7)
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Then, instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), hydroxyl-terminated polybutadiene (trade name “Polybd R-45HT”, hydroxyl equivalent: 1400, manufactured by Idemitsu Kosan Co., Ltd.) Using 10.0 g, instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), 2,6-pyridinedicarboxylic acid (trade name “2” manufactured by Air Water Co., Ltd.) , 6-pyridinedicarboxylic acid ”)), and carbon nanotubes (Nippon Zeon Corporation). In the same manner as in Example 1 except that 0.03 g of natural nanofibers (trade name “Imogolite” manufactured by Astec Co., Ltd.) was used instead of using 0.03 g of “ZeonanoSG101”). Was prepared. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component becomes a reaction product of hydroxyl-terminated polybutadiene and 2,6-pyridinedicarboxylic acid, and the side chain is formed by the reaction of the hydroxyl group and the carboxy group in 2,6-pyridinedicarboxylic acid. It has a crosslinked structure containing a ring and a carboxylic acid ester group (bonding moiety) (having a hydrogen-bonding crosslinking site and a covalent bonding site).

(Example 8)
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), carboxy group-containing polyisoprene (trade name “LIR-410” manufactured by Kuraray Co., Ltd., carboxy equivalent: 4000) 0.0 g was used, the amount of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.) was changed from 0.262 g to 0.218 g, and carbon nanotubes (trade name of Nippon Zeon Co., Ltd.) Instead of using 0.03 g of “Zeonano SG101”), a layered titanate compound (Tokyo Kasei Co., Ltd.) Trade name "Titanium potassium acid", chemical formula except that the K ₂ Ti ₆ O ₁₃ "powder) was 0.03g utilized to prepare a thermoplastic elastomer composition in the same manner as in Example 1. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component becomes a reaction product of carboxy group-containing polyisoprene and trishydroxyethyl isocyanurate, the side chain is formed by the reaction of carboxy group and the hydroxyl group of trishydroxyethyl isocyanurate, the side chain isocyanurate ring, It has a cross-linked structure containing a carboxylic acid ester group (bonding moiety) (has a hydrogen bond cross-linking site and a covalent bond cross-linking site).

Example 9
Instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), 10.0 g of carboxy group-containing polyisoprene (trade name “LIR-410” manufactured by Kuraray Co., Ltd., carboxy equivalent: 4000) is used. Furthermore, instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), pentaerythritol (trade name “Neuiser P” manufactured by Nippon Synthetic Chemical Co., Ltd.) A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that 0085 g was used. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component becomes a reaction product of carboxy group-containing polyisoprene and trishydroxyethyl isocyanurate, the side chain is formed by the reaction of the carboxy group and the hydroxyl group of pentaerythritol, and the side chain is a carboxylic acid ester group (bonding portion). (Having a hydrogen-bonding cross-linking site and a covalent bond cross-linking site).

(Example 10)
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), carboxy group-containing polyisoprene (trade name “LIR-410” manufactured by Kuraray Co., Ltd., carboxy equivalent: 4000) Instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), 0.04 g of 2,4-diamino-6-phenyl-1,3,5-triazine (Japan) 0.234g of the product name “Benzoguanamine” manufactured by Catalyst Co., Ltd. Thermoplastic elastomer in the same manner as in Example 1 except that 0.03 g of natural nanofibers (trade name “Imogolite” manufactured by Astec Co., Ltd.) was used instead of using 0.03 g of the product name “Zeonano SG101” manufactured by the company. A composition was prepared. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component is a reaction product of carboxy group-containing polyisoprene and 2,4-diamino-6-phenyl-1,3,5-triazine, and the side chain is a carboxy group and 2,4-diamino-6-phenyl-. It is formed by a reaction with an amino group (—NH ₂ ) in 1,3,5-triazine, and has a crosslinked structure containing a triazine ring and an amide bond (formula: —CONH—) (hydrogen bonding bridge) It has a site and a covalent cross-linking site.

(Example 11)
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), carboxy group-containing polyisoprene (trade name “LIR-410” manufactured by Kuraray Co., Ltd., carboxy equivalent: 4000) Instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), 0.0 g of tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (SC Organic Trade name “Tris-[(3-mercaptopropionyloxy) -ethyl] manufactured by Kagakusha -Isocyanurate ") 0.438 g, and instead of using 0.03 g of carbon nanotubes (trade name“ Zeonano SG101 ”manufactured by Nippon Zeon Co., Ltd.), a layered titanate compound (trade name“ Titanium manufactured by Tokyo Chemical Industry Co., Ltd. ”) was used. potassium acid ", chemical _formula: K ₂ Ti _{6 O 13"} and except that the powder) was 0.03g utilized in the same manner as in example 1 to prepare a thermoplastic elastomer composition. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component is a reaction product of carboxy group-containing polyisoprene and tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and the side chain is carboxy group and tris-[(3-mercaptopropionyloxy)- Ethyl] -isocyanurate is formed by reaction with a thiol group (—SH) and has a cross-linked structure containing an isocyanurate ring and a thioester (group represented by the formula —CO—S—) in the side chain. (Having a hydrogen-bonding cross-linking site and a covalent bond cross-linking site).

Example 12
Instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), an amino group-containing polyethyleneimine (trade name “Epomin SP-200” manufactured by Nippon Shokubai Co., Ltd., amine value: 18 mmol / g) 10.0 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.) instead of using 0.262 g of 2,6-pyridinedicarboxylic acid (trade name “product of Air Water” A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that 1.504 g of 2,6-pyridinedicarboxylic acid ") was used. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component becomes a reaction product of an amino group-containing polyethyleneimine and 2,6-pyridinedicarboxylic acid, and the side chain is formed by the reaction of the amino group and the carboxy group in 2,6-pyridinedicarboxylic acid. Have a crosslinked structure containing a pyridine ring and an amide bond (bonding site represented by the formula: -CONH-) (having a hydrogen bonding crosslinking site and a covalent crosslinking site).

(Example 13)
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleated EBM), amino group-containing polyethyleneimine (trade name “Epomin SP-200” manufactured by Nippon Shokubai Co., Ltd.), amine value: 18 mmol / g) is used in place of 10.0 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.) instead of 0.262 g of trisepoxypropyl isocyanurate (Tris- (2,3-epoxypropyl) ) -Isocyanurate: Product name “Tepic” manufactured by Nissan Chemical Co., Ltd.) 1.784 g In addition to using 0.03 g of carbon nanotubes (trade name “Zeonano SG101” manufactured by Nippon Zeon Co., Ltd.), 0.03 g of natural nanofibers (trade name “Imogolite” manufactured by Astech Co.) was used. 1 was used to prepare a thermoplastic elastomer composition. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component becomes a reaction product of amino group-containing polyethyleneimine and trisepoxypropyl isocyanurate, the side chain is formed by the reaction of amino group and epoxy group in trisepoxypropyl isocyanurate, and the isocyanurate ring is formed in the side chain. And a hydroxyl group and an imino bond can be formed (a side chain can be a side chain including both a hydrogen-bonding crosslinking site and a covalent bonding site). (It has a hydrogen bonding cross-linking site and a covalent bonding cross-linking site).

(Example 14)
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Then, instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), 10.0 g of alkoxysilyl group-containing polyethylene (trade name “Linkron” manufactured by Mitsubishi Chemical Corporation) was used. The amount of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.) was changed from 0.262 g to 0.087 g, and carbon nanotubes (trade name “Zeonano SG101” manufactured by Nippon Zeon Co., Ltd.) Instead of using 0.03 g, a layered titanate compound (trade name “Kali titanate manufactured by Tokyo Chemical Industry Co., Ltd.” Arm ", chemical _formula was K ₂ Ti _{6 O 13} except that the powder) was 0.03g utilized in the same manner as in Example 1 to prepare a thermoplastic elastomer composition. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component is a reaction product of an alkoxysilyl group-containing polyethylene and trishydroxyethyl isocyanurate, and the side chain is formed by the reaction of an alkoxysilyl group and a hydroxyl group (hydroxy group) in trishydroxyethyl isocyanurate. A cross-linked structure containing an isocyanurate ring and a silyloxy bond (a side chain can be a side chain containing both a hydrogen-bonded cross-linked site and a covalent-bonded cross-linked site) (It will have a hydrogen-bonding cross-linking site and a covalent bond cross-linking site).

(Example 15)
Instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), 10.0 g of alkoxysilyl group-containing polyethylene (trade name “Rychlon” manufactured by Mitsubishi Chemical Corporation) was used to obtain trishydroxy Implemented except using 0.234 g of ethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.) and using 0.034 g of pentaerythritol (trade name “Neuiser P” manufactured by Nippon Gosei Kagaku Co., Ltd.) 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 thus obtained are shown in Table 2.

The elastomer component is a reaction product of an alkoxysilyl group-containing polyethylene and pentaerythritol, and the side chain is formed by the reaction of an alkoxysilyl group and a hydroxyl group (hydroxy group) in trishydroxyethyl isocyanurate. (A side chain can be a side chain including both a hydrogen-bonded cross-link site and a covalent bond site) (hydrogen-bond cross-link site) And a covalently cross-linked site).

(Example 16)
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Then, instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), 10.0 g of alkoxysilyl group-containing polyethylene (trade name “Linkron” manufactured by Mitsubishi Chemical Corporation) was used. Instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), 2,4-diamino-6-phenyl-1,3,5-triazine (manufactured by Nippon Shokubai Co., Ltd.) 0.094g of product name "benzoguanamine") is used, and carbon nanotubes (product name "Zeo" manufactured by Nippon Zeon Co., Ltd.) are used. anoSG101 ") was except that natural nanofibers (ASTEC Co., Ltd. under the trade name" imogolite ") was 0.03g utilized in the same manner as in Example 1 to prepare a thermoplastic elastomer composition instead of 0.03g utilized. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component is a reaction product of an alkoxysilyl group-containing polyethylene and tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and the side chain is an alkoxysilyl group and tris-[(3-mercaptopropionyloxy). -Ethyl] -isocyanurate is formed by reaction with thiol group (-SH) and has a cross-linked structure containing an isocyanurate ring and a mercaptosilyl bond in the side chain (covalent bond with hydrogen-bonding cross-linking site) Having a crosslinkable site)
(Example 17)
Instead of using 7.5 g of ethylene-butene copolymer (EBM: trade name “Tuffmer DF7350” manufactured by Mitsui Chemicals), 15.0 g of high density polyethylene (HDPE: trade name “HJ590N” manufactured by Nippon Polyethylene) is used. Then, instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), an epoxidized product of styrene-butadiene block copolymer (trade name “Epofriend” manufactured by Daicel) was used. Instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), 0,4 g of 2,4-diamino-6-phenyl-1,3,5-triazine (Japan) 0.936 g of the product name “Benzoguanamine” manufactured by Catalyst Co., Ltd. is used, and carbon nanotubes (manufactured by Nippon Zeon Co., Ltd.) are used. In place of 0.03 g of a layered titanate compound (trade name “potassium titanate” manufactured by Tokyo Chemical Industry Co., Ltd., chemical formula: K ₂ Ti ₆ O ₁₃ powder) A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component is a reaction product of epoxidized styrene-butadiene block copolymer and 2,4-diamino-6-phenyl-1,3,5-triazine, and the side chain is an epoxy group and tris-[((3 -Mercaptopropionyloxy) -ethyl] -is formed by reaction with a thiol group (-SH) in isocyanurate and has a cross-linked structure containing an isocyanurate ring, a hydroxyl group and an imino bond in the side chain (hydrogen bond) Having a crosslinking site and a covalent crosslinking site).

(Example 18)
Instead of using 10.0 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM), 10.0 g of epoxidized styrene-butadiene block copolymer (trade name “Epofriend” manufactured by Daicel) is used. Instead of using 0.262 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (manufactured by SC Organic Chemical Co., Ltd.) A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that 1.75 g of the trade name “Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate”) was used. The evaluation results of the properties of the thermoplastic elastomer composition thus obtained are shown in Table 2.

The elastomer component is a reaction product of an epoxidized styrene-butadiene block copolymer and tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and the side chain is an epoxy group and tris-[(3- Mercaptopropionyloxy) -ethyl] -isocyanurate is formed by reaction with thiol group (—SH) and has a cross-linked structure containing isocyanurate ring, hydroxyl group, and thioether group in the side chain (hydrogen bond) Having a crosslinking site and a covalent crosslinking site).

As is clear from the results shown in Tables 1 and 2, the thermoplastic elastomer compositions obtained in Examples 6, 9, 12, 15, and 18 having the same composition as in Example 1 except for the type of the elastomer component. In all, the tensile strength and abrasion resistance comparable to those of Example 1 were obtained, and even higher tensile strengths were obtained compared to the thermoplastic elastomer compositions obtained in Comparative Examples 1 to 3. It was confirmed that strength and wear resistance were achieved. From these results, at least one elastomer component selected from the group consisting of the elastomeric polymer (A) and the elastomeric polymer (B) and an additive component (carbon nanotube, silicate-based natural nanofibers) It has also been found that higher tensile strength and wear resistance can be achieved by using in combination with a layered titanate compound). In addition, the thermoplastic elastomer compositions obtained in Examples 4 to 5, 7 to 8, 10 to 11, 13 to 14, and 16 to 17 are all Examples 6 and 9 having the same composition as Example 1. , 12, 15 and 18, higher tensile strength and abrasion resistance have been achieved compared to the thermoplastic elastomer compositions obtained in accordance with the present invention. It was found that the tensile strength can be made higher, and it is possible to have a sufficiently high wear resistance.

As described above, according to the present invention, it is possible to make the tensile strength based on 100% modulus and breaking strength higher, and to have sufficiently high wear resistance. It becomes possible to provide the thermoplastic elastomer composition.

Therefore, the thermoplastic elastomer composition of the present invention can exhibit various properties as described above in a well-balanced manner. For example, electrical / electronic, home appliances, chemistry, pharmaceuticals, glass, earth, steel, non-ferrous metals , Machinery, precision equipment, cosmetics, textiles, mining, pulp, paper, construction, civil engineering, construction, food and beverage, general consumer goods and services, transportation equipment, construction machinery, electrical equipment, equipment (industrial, air conditioning, hot water supply, ENE-FARM), metal, media, information, communication equipment, lighting, display, agriculture, fishery, forestry, fisheries, agribusiness, biotechnology, nanotechnology, various rubber parts (more specifically, , Products around automobiles, hoses, belts, sheets, anti-vibration rubber, rollers, linings, rubberized cloth, sealing materials, gloves, fenders, medical rubber (silin) Gaskets, tubes, catheters), gaskets (for home appliances, construction), asphalt modifiers, hot melt adhesives, boots, grips, toys, shoes, sandals, keypads, gears, PET bottle cap liners, printers It is useful as a material for manufacturing rubber parts, sealing materials, paints / coating materials, products used for printing inks, etc.).

Claims

Elastomeric polymer (A) having a side chain containing a hydrogen-bonding crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or less, and a hydrogen bond to the side chain At least one elastomer component selected from the group consisting of an elastomeric polymer (B) containing a crosslinking site and a covalent crosslinking site and having a glass transition point of 25 ° C. or lower;
It is at least one selected from the group consisting of expanded graphite, carbon nanotubes, fullerenes, graphene, silicate-based natural nanofibers, silsesquioxanes, and layered titanate compounds, and the content thereof is 100 masses of the elastomer component. An additive component that is 20 parts by mass or less relative to parts,
A thermoplastic elastomer composition comprising:
The elastomer component comprises the following reactants (I) to (VI):
[Reactant (I)] Among maleic anhydride-modified elastomeric polymer and triazole, hydroxyl group, thiol group and amino group which may have at least one substituent selected from hydroxyl group, thiol group and amino group Among the thiadiazole, hydroxyl group, thiol group and amino group optionally having at least one substituent of pyridine, hydroxyl group, thiol group and amino group optionally having at least one substituent group Of isocyanurate, hydroxyl group, thiol group and amino group which may have at least one substituent of imidazole, hydroxyl group, thiol group and amino group which may have at least one kind of substituent At least one of triazine, hydroxyl group, thiol group and amino group optionally having at least one substituent. A hydrocarbon compound having two or more substituents selected from hydantoin, hydroxyl group, thiol group and amino group which may have a substituent, trishydroxyethyl isocyanurate, sulfamide, and poly Reaction product with at least one compound among ether polyols [Reactant (II)] A hydroxyl group-containing elastomeric polymer, and at least one substituent selected from a carboxy group, an alkoxysilyl group and an isocyanate group Reaction product with two or more compounds [Reactant (III)] Carboxy group-containing elastomeric polymer, and a compound having two or more substituents selected from a hydroxyl group, a thiol group, and an amino group Reactant [Reactant (IV)] Amino group-containing elastomeric polymer, Reaction product [reactant (V)] with an alkoxysilyl group-containing elastomeric polymer with a compound having two or more substituents selected from a boxy group, an epoxy group, an alkoxysilyl group and an isocyanate group; Reaction product with compound having at least two substituents selected from hydroxyl group, carboxy group and amino group [reaction product (VI)] Epoxy group-containing elastomeric polymer, thiol group and amino group 2. The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer composition is at least one reactant selected from the group consisting of reactants with a compound having at least one substituent selected from the group consisting of two or more.
The main chain of the polymer contained as the elastomer component is diene rubber, hydrogenated diene rubber, olefin rubber, hydrogenated polystyrene elastomer polymer, polyolefin elastomer polymer, polyvinyl chloride. The thermoplastic elastomer composition according to claim 1 or 2, comprising at least one selected from a base elastomeric polymer, a polyurethane base elastomeric polymer, a polyester base elastomeric polymer, and a polyamide base elastomeric polymer.