JP2006027249A - Metal-thermoplastic material composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal-thermoplastic composite material which shows strong adhesion without using a primer and shows high recycling properties after adhesion. <P>SOLUTION: The composite material comprises a metal plate and a thermoplastic material using a thermoplastic elastomer tightly adhered on the metal plate, and the thermoplastic elastomer contains a side chain having a carbonyl-containing imino group and/or a side chain having a carbonyl group and a nitrogen-containing heterocyclic ring. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composite (metal-thermoplastic material composite) obtained by integrally fixing a metal plate and a thermoplastic material using a thermoplastic elastomer provided on the metal plate.

  Post surgery for integrating metal and rubber has been developed for a long time. For example, as seen in production examples of tires produced by vulcanizing and bonding metal tire cords and rubber, they are currently used in many fields. However, a technique for integrating a metal and a thermoplastic elastomer without using an adhesive has not been known.

Therefore, in Patent Document 1, “a modified 4-methyl-1-pentene polymer (A) modified with an unsaturated carboxylic acid and / or carboxylic anhydride is used as a thermoplastic elastomer having excellent adhesion to a metal. A composition in which particles made of a crosslinked rubber (B) and having an average particle size of 100 μm or less are dispersed in a matrix that contains 20 to 95% by weight of the matrix and 5 to 80% by weight of the particles. A "thermoplastic elastomer composition characterized in that it is contained in a proportion" has been proposed.
Further, Patent Document 2 discloses that “a metal plate integrated with good adhesion by an injection insert molding method and two thermoplastic material layers (A) and (B) sequentially provided thereon are provided. In the composite molded body in which they are integrated, a composite molded body characterized in that a mixed adhesive resin of a modified polyolefin and a modified styrene thermoplastic elastomer is used as the layer (A). Has been.
Further, Patent Document 3 states that “a processed metal shape, a coating material containing a curable resin composition coated on the surface of the metal shape, and an upper surface of the coating material are integrated with heat and pressure. There has been proposed a “composite of a metal and a thermoplastic composition comprising a thermoplastic polyester elastomer and / or a thermoplastic composition in the form of a thermoplastic polyurethane elastomer, which is affixed to a thermoplastic polyester elastomer”.

JP 2002-20562 A JP 2003-94561 A JP 2003-246209 A

However, although the thermoplastic elastomer composition described in Patent Document 1 is excellent in adhesion to metal, it may be disassembled after adhesion and repeated use of the elastomer composition (hereinafter simply referred to as “recycling”). ) Was not possible.
Further, in the composite molded body described in Patent Document 2, since two layers of thermoplastic elastomer are required, it can be seen that there is a problem that workability is inferior. Further, the composite body described in Patent Document 3 is used. However, since a coating material is required on the surface of the processed metal shaped product, it has been found that there is a problem that workability is similarly inferior.

  Therefore, an object of the present invention is to provide a metal-thermoplastic material composite having excellent adhesion to a metal plate without using a primer and having good recyclability after bonding.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic material using a thermoplastic elastomer having a side chain containing a predetermined structure has an adhesive property to a metal plate without using a primer. It has been found that it is excellent and has good recyclability even after bonding, and has achieved the present invention. That is, this invention provides the composite_body | complex described in following (I)-(IX).

(I) A composite formed by integrally fixing a metal plate and a thermoplastic material using a thermoplastic elastomer provided on the metal plate,
The composite in which the thermoplastic elastomer has a side chain containing a carbonyl-containing group and an imino group and / or a side chain containing a carbonyl-containing group and a nitrogen-containing heterocyclic ring.

  (II) The complex according to (I), wherein the side chain containing the carbonyl-containing group and the imino group contains a structure represented by the following formula (1).

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

  (III) The above side chain containing a structure represented by the following formula (2) or (3) in which the side chain containing the structure represented by the above formula (1) is bonded to the main chain at the α-position or the β-position ( The complex according to II).

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

  (IV) The complex according to any one of (I) to (III) above, wherein the side chain containing the carbonyl-containing group and the nitrogen-containing heterocycle contains a structure represented by the following formula (4).

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

  (V) The above side chain containing a structure represented by the following formula (5) or (6) in which the side chain containing the structure represented by the above formula (4) is bonded to the main chain at the α-position or β-position ( The complex according to IV).

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

  (VI) The complex according to any one of (I) to (V), wherein the nitrogen-containing heterocycle is a 5- or 6-membered ring.

  (VII) The complex according to (VI), wherein the nitrogen-containing heterocycle is a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring, or a hydantoin ring.

  (VIII) The composite according to any one of (I) to (VII), wherein the metal plate is an aluminum plate.

  (IX) The thermoplastic material according to any one of (I) to (VIII), wherein the thermoplastic material is a thermoplastic elastomer composition containing 50 parts by mass or less of a filler with respect to 100 parts by mass of the thermoplastic elastomer. Complex.

  As described below, according to the present invention, it is possible to provide a metal-thermoplastic material composite having excellent adhesion to a metal plate without using a primer and having good recyclability even after bonding. It is useful because it can.

The present invention is described in detail below.
The composite of the present invention is a composite formed by integrally fixing a metal plate and a thermoplastic material using a thermoplastic elastomer provided on the metal plate,
The thermoplastic elastomer is a composite having a side chain containing a carbonyl-containing group and an imino group and / or a side chain containing a carbonyl-containing group and a nitrogen-containing heterocyclic ring.

The reason why the composite of the present invention is excellent in adhesion to a metal plate without using a primer and has good recyclability even after adhesion is not clear in detail, but the inventor I think so.
In an embodiment having only a side chain containing a carbonyl-containing group and an imino group in the side chain of the thermoplastic elastomer, the adhesion between the metal plate and the metal plate is excellent without a primer, the interaction between the metal and the imino group, and the anchor It is thought to be because of the effect, and the recyclability is good because of the interaction such as hydrogen bonding between the carbonyl-containing group and the imino group, it is strongly cross-linked during bonding, and easily cross-linked by heating during disassembly. This is because (crosslinked structure) can be dissociated.
On the other hand, in an embodiment having only a side chain containing a carbonyl-containing group and a nitrogen-containing heterocycle, the adhesion with the metal plate is excellent without a primer because of the interaction between the metal and the nitrogen-containing heterocycle and the anchor effect. The recyclability is considered to be good because of the interaction such as hydrogen bonding between the carbonyl-containing group and the nitrogen-containing heterocycle, which causes strong cross-linking during bonding and easy cross-linking by heating during disassembly. This is because (crosslinked structure) can be dissociated.
Further, even in an embodiment having both a side chain containing a carbonyl-containing group and an imino group and a side chain containing a carbonyl-containing group and a nitrogen-containing heterocycle, the adhesion to the metal plate and the recycling are similar to the above-described action. Both properties are considered to be good.

  Below, the metal plate which comprises this invention, and the thermoplastic material using the thermoplastic elastomer provided on this metal plate are explained in full detail.

<Metal plate>
The metal plate used in the present invention is not particularly limited as long as it is a processed metal shape, and specifically, for example, cold rolled steel plate, galvanized steel plate, aluminum / zinc alloy plated steel plate, stainless steel plate, aluminum plate , An aluminum alloy plate, a magnesium plate, a magnesium alloy plate, a copper plate, etc., can be appropriately selected and used according to the application of the composite.
In addition, the thickness of the metal plate used in the present invention is appropriately selected depending on the use of the composite, but is usually in the range of 0.1 to 100 mm, preferably 0.2 to 30 mm.
In the present invention, among these, it is preferable to use an aluminum plate or a stainless steel plate having a thickness of about 0.2 to 0.5 mm because it has flexibility.

<Thermoplastic material>
The thermoplastic material used in the present invention may be the thermoplastic elastomer itself described later, or may be a thermoplastic elastomer composition containing the thermoplastic elastomer and a specific amount of filler.
Below, a thermoplastic elastomer and a thermoplastic elastomer composition are explained in full detail.

(Thermoplastic elastomer)
The thermoplastic elastomer used in the present invention is a side chain containing a carbonyl-containing group and an imino group and / or a side containing a carbonyl-containing group and a nitrogen-containing heterocyclic ring in a natural or synthetic polymer elastomeric polymer. Has a chain.
In the present invention, “side chain” refers to a side chain and a terminal of an elastomeric polymer. In addition, “having a side chain containing a carbonyl-containing group and an imino group” means that the carbonyl-containing group and the imino group are chemically stable to atoms (usually carbon atoms) that form the main chain of the elastomeric polymer. It means having a bond (for example, covalent bond, ionic bond, etc.). Similarly, “having a side chain containing a carbonyl-containing group and a nitrogen-containing heterocycle” means the main chain of the elastomeric polymer. It means that a carbonyl-containing group and a nitrogen-containing heterocycle have chemically stable bonds to the atoms to be formed.

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

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

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

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

  Such elastomeric polymers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), Diene rubber such as butyl rubber (IIR); Olefin rubber such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM); The thermoplastic material using the obtained thermoplastic elastomer is preferable because it exhibits rubber-like elasticity at room temperature. Moreover, the tensile strength of the thermoplastic material using the thermoplastic elastomer obtained when an olefin rubber is used improves.

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

  The thermoplastic elastomer used in the present invention has a side chain containing a carbonyl-containing group and an imino group and / or a side chain containing a carbonyl-containing group and a nitrogen-containing heterocycle in the elastomeric polymer.

  Here, the carbonyl-containing group is not particularly limited as long as it contains a carbonyl group, and specific examples thereof include an amide group, an ester group, an imide group, a carboxy group, and a carbonyl group. The compound into which such a group can be introduced is not particularly limited, and specific examples thereof include ketones, carboxylic acids and derivatives thereof.

Examples of the 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 the like. A monoester etc. are mentioned.
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. , Carboxylic acids such as p-aminobenzoic acid and mercaptoacetic acid, and those carboxylic acids containing substituents; acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, propionic anhydride, and benzoic anhydride Products: aliphatic esters such as maleic acid ester, malonic acid ester, succinic acid ester, glutaric acid ester, ethyl acetate; phthalic acid ester, isophthalic acid ester, terephthalic acid ester, ethyl-m-aminobenzoate, methyl-p-hydroxy Aromatic esters such as benzoate; quinone, anthraquinone, Ketones such as phthoquinone; amino acids such as glycine, tyrosine, bicine, alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N- (p-aminobenzoyl) -β-alanine; Maleamide, maleamic acid (maleic monoamide), succinic monoamide, 5-hydroxyvaleramide, N-acetylethanolamine, N, N′-hexamethylenebis (acetamide), malonamide, cycloserine, 4-acetamidophenol, p- Amides such as acetamide benzoic acid; imides such as maleimide, succinimide, and urazole (3,5-dioxo-1,2,4-triazolidine).
Of 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 or phthalic anhydride, or an imide such as urazole, Particularly preferred are maleic anhydride and urazole.

  As such a side chain containing a carbonyl-containing group and an imino group, a side chain containing a structure represented by the following formula (1) is preferably exemplified. The “side chain containing a carbonyl-containing group and an imino group” may be a side chain containing the imino group as —NH— constituting a part of the nitrogen-containing heterocyclic ring. In the specification, such a side chain is exemplified by “a side chain containing a carbonyl-containing group and a nitrogen-containing heterocycle” described later.

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

Substituent A will not be specifically limited if it is said C1-C20 alkyl group, C7-C20 aralkyl group, or C6-C20 aryl group.
Specific examples of such substituent A include, for example, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a dodecyl group, and a stearyl group; an isopropyl group Branched alkyl groups such as isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl group, 2-ethylhexyl group; benzyl group Aralkyl groups such as phenethyl group; aryl groups such as phenyl group, tolyl group (o-, m-, p-), dimethylphenyl group, mesityl group; and the like.
Among these, an alkyl group, in particular, a butyl group, an octyl group, a dodecyl group, an isopropyl group, and a 2-ethylhexyl group is preferable because the workability of the resulting thermoplastic elastomer is improved.

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

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

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

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

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

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

  The thermoplastic elastomer used in the present invention contains a “carbonyl-containing group and a nitrogen-containing heterocycle” instead of or together with the above-mentioned “side chain containing a carbonyl-containing group and an imino group” in the elastomeric polymer. It is preferable to have a “side chain” for the reason that the tensile strength of the thermoplastic material obtained is improved because the hydrogen bond forming the crosslink is strengthened, and the adhesiveness to the metal plate is further improved.

Here, the nitrogen-containing heterocycle is not particularly limited as long as it contains a nitrogen atom in the heterocycle, and has a heteroatom other than the nitrogen atom, for example, a sulfur atom, an oxygen atom, a phosphorus atom, etc. in the heterocycle. Even things can be used.
The nitrogen-containing heterocycle may have a substituent, and specific examples of the substituent include alkyl groups such as a methyl group, an ethyl group, a (iso) propyl group, and a hexyl group; Alkoxy groups such as methoxy group, ethoxy group, (iso) propoxy group; groups consisting of halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; cyano group; amino group; aromatic hydrocarbon group; ester group; An ether group; an acyl group; a thioether group; and the like can be mentioned, and these can be used in combination. The substitution position of these substituents is not particularly limited, and the number of substituents is not limited.
Further, the nitrogen-containing heterocyclic ring may or may not have aromaticity, but if it has aromaticity, the thermoplastic elastomer obtained has a higher tensile strength during crosslinking. This is preferable because it increases and mechanical strength is further improved.

The nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring.
Specific examples of such nitrogen-containing heterocycle include pyrrololine, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl, phthalimidine, β -Isoindigo, monoporphyrin, diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyroerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone Hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, in , Indoline, oxylindole, carbazole, phenothiazine, indolenine, isoindole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine , Pyrazine, phenazine, tetrazine, benzoxazole, benzoisoxazole, anthranyl, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthrazolin, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline, triazine, histidine , Triazolidine, melamine, adenine, guanine, thymine, cytosine And derivatives thereof. Of these, the nitrogen-containing 5-membered ring is preferably exemplified by the following compounds and imidazole derivatives represented by the following formula (7). These may have the above-described various substituents, or may be hydrogenated or eliminated.

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

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

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

  Among such nitrogen-containing heterocycles, triazole ring, pyridine ring, thiadiazole ring, imidazole ring and hydantoin ring indicate that the thermoplastic material using the resulting thermoplastic elastomer can be recycled, compression set, mechanical It is preferable because of its excellent strength and hardness.

Preferred examples of the side chain containing the above-mentioned carbonyl-containing group and such a nitrogen-containing heterocycle include a side chain containing a structure represented by the following formula (4).
The thermoplastic elastomer used in the present invention is represented by the following formula (5) or (6) in which a side chain containing a structure represented by the following formula (4) is bonded to the main chain at the α-position or β-position. It is preferable that it has as a side chain containing the structure made.

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

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

  The side chain containing a carbonyl-containing group and a nitrogen-containing heterocyclic ring (specifically, the side chain containing the structure represented by the above formula (4) or the above formula (5) or (6)) is It is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the polymer. If it is less than 0.1 mol%, the strength at the time of crosslinking may not be sufficient, and if it exceeds 50 mol%, the rubber elasticity of the thermoplastic material that can increase the crosslinking density may be lost. If the introduction rate is within this range, the interactions between the side chains of the elastomeric polymer occur between molecules or within the molecule, and these are formed in a well-balanced manner. Therefore, the tensile strength of the thermoplastic material using the resulting thermoplastic elastomer High strength, excellent recyclability, and good compression set. From the viewpoint that these properties are more excellent, it is more preferable that side chains are introduced at a ratio of 0.1 to 30 mol%, and side chains are introduced at a ratio of 0.5 to 20 mol%. Further preferred.

In the present invention, when both a side chain containing a carbonyl-containing group and an imino group and a side chain containing a carbonyl-containing group and a nitrogen-containing heterocycle, the side chain containing a carbonyl-containing group and a nitrogen-containing heterocycle, Totally introduced with a carbonyl-containing group and a side chain containing an imino group at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the elastomeric polymer. It is preferable that the ratio of introduction into a side chain (a side chain containing a carbonyl-containing group and a nitrogen-containing heterocyclic ring / a side chain containing a carbonyl-containing group and an imino group) is 1/99 to 99/1. It is more preferable that the ratio is 10/90 to 90/10.
If the introduction rate and the introduction ratio are within this range, the thermoplastic material using the obtained thermoplastic elastomer has high tensile strength, excellent recyclability, and further has the property of good compression set, It is preferable because mechanical strength such as tensile strength can be further improved.

  The thermoplastic elastomer used in the present invention preferably has a glass transition point of 25 ° C. or lower. When the thermoplastic elastomer has two or more glass transition points, or when two or more thermoplastic elastomers are used in combination. At least one of the glass transition points is preferably 25 ° C. or lower. A glass transition point of 25 ° C. or lower is preferable because a thermoplastic material using a thermoplastic elastomer exhibits rubber-like elasticity at room temperature.

The method for producing the thermoplastic elastomer used in the present invention is not particularly limited, and an ordinary method can be selected. Specifically, an imino group is added to an elastomeric polymer containing a cyclic acid anhydride group in the side chain. A reaction step of reacting a compound that can be introduced (hereinafter simply referred to as “reaction step A”) and / or a reaction step of reacting a compound that can introduce a nitrogen-containing heterocycle (hereinafter simply referred to as “reaction step B”). .) Is preferable.
In the case where the thermoplastic elastomer used in the present invention has both a side chain containing a carbonyl-containing group and an imino group and a side chain containing a carbonyl-containing group and a nitrogen-containing heterocyclic ring, the above reaction step A and reaction step B In this case, the reaction step B is provided as a step performed simultaneously with the reaction step A, or is provided as a pre-step or a post-step of the reaction step A. However, it is preferably provided as a pre-process of the reaction step A.

Here, “an elastomeric polymer containing a cyclic acid anhydride group in the side chain” means an elastomer in which the cyclic acid anhydride group has a chemically stable bond (covalent bond) at the atom forming the main chain. This is a polymer obtained by reacting the elastomeric polymer with a compound capable of introducing a cyclic acid anhydride group.
Specific examples of the compound capable of introducing a cyclic acid anhydride group include cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride.

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

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

In the reaction step A, the compound capable of introducing an imino group and the elastomeric polymer containing a cyclic acid anhydride group in the side chain are mixed, and the compound and the cyclic acid anhydride group can be chemically bonded. This is a step of reacting at a temperature (for example, 80 to 200 ° C.) (opening a cyclic acid anhydride group). By this reaction, the structure represented by the above formula (2) or (3) is contained in the side chain of the thermoplastic elastomer obtained.
Moreover, what is necessary is just to make the compound which can introduce | transduce an imino group react with a part or whole quantity of the cyclic acid anhydride group contained in the side chain of the said elastomeric polymer. The part is preferably 1 mol% or more, more preferably 50 mol% or more, particularly preferably 80 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. If it is this range, a high physical property (for example, fracture | rupture characteristic) will fully express. In view of excellent compression set, it is particularly preferable to react the total amount (100 mol%) of the cyclic acid anhydride group with a compound capable of introducing an imino group.

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

  In the reaction step B, a compound capable of introducing a nitrogen-containing heterocyclic ring and the elastomeric polymer containing a cyclic acid anhydride group in the side chain are mixed, and the compound and the cyclic acid anhydride group are chemically bonded. This is a step of reacting (opening a cyclic acid anhydride group) at a possible temperature (for example, 80 to 200 ° C.). By this reaction, the structure represented by the above formula (5) or (6) is contained in the side chain of the thermoplastic elastomer obtained.

  When both the side chain containing a carbonyl-containing group and an imino group and the side chain containing a carbonyl-containing group and a nitrogen-containing heterocycle are used, the reaction step B is preceded by the reaction step A, as described above. It is preferable that it is a process. In this case, the compound capable of introducing a nitrogen-containing heterocycle may be reacted with a part of the cyclic acid anhydride group contained in the side chain of the elastomeric polymer. The part is preferably 1 to 99 mol%, more preferably 1 to 90 mol%, and still more preferably 50 to 90 mol% with respect to 100 mol% of the cyclic acid anhydride group. If it is this range, the effect which introduce | transduced the nitrogen-containing heterocyclic ring will express, and mechanical strength, such as the tensile strength at the time of bridge | crosslinking, will increase more.

  In the above production method, each group (structure) of the side chain of the thermoplastic elastomer, that is, an unreacted cyclic acid anhydride group, specifically, the above formulas (2), (3), (5) and The structure represented by (6) can be confirmed by commonly used analytical means such as NMR and IR spectrum.

The bonding position of the nitrogen-containing heterocycle in the case where the thermoplastic elastomer used in the present invention has a side chain containing the nitrogen-containing heterocycle will be described. For convenience, the nitrogen-containing heterocycle is referred to as “nitrogen-containing n-membered ring compound (n ≧ 3)”.
The bonding positions described below ("positions 1 to n") are based on the IUPAC nomenclature. For example, in the case of a compound having three nitrogen atoms having an unshared electron pair, the bonding position is determined by the order based on the IUPAC nomenclature. Specifically, the bonding positions are indicated on the 5-membered, 6-membered and condensed nitrogen-containing heterocycles exemplified above.
In the thermoplastic elastomer used in the present invention, 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 may be any bonding position (position 1 to position n). . Preferably, it is the 1-position or 3-position to n-position.

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

(Thermoplastic elastomer composition)
The thermoplastic elastomer composition used in the present invention is a composition containing 50 parts by mass or less, preferably 30 parts by mass or less, more preferably 10 parts by mass or less of the filler with respect to 100 parts by mass of the thermoplastic elastomer described above. is there.
Here, the thermoplastic elastomer in the thermoplastic elastomer composition may be used alone or in combination of two or more. The mixing ratio when two or more types are used in combination can be set to any ratio depending on the use of the composite of the present invention, the physical properties required of the composite, and the like.

  Specific examples of the filler include carbon black, silica, iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, kaolin clay. , Calcined clay, fillers introduced with amino groups (hereinafter simply referred to as “amino group-introduced fillers”), and the like. Among these, carbon black, silica, and amino group-introduced fillers are used. preferable.

  The type of carbon black is appropriately selected according to the application. Generally, carbon black is classified into hard carbon and soft carbon based on the particle diameter. Soft carbon has low reinforcement to rubber, and hard carbon has strong reinforcement to rubber. In the present invention, it is particularly preferable to use hard carbon having strong reinforcing properties.

The silica is not particularly limited, and specific examples include fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, diatomaceous earth, and the like, and among these, precipitated silica is preferable.
When silica is used as the filler, a silane coupling agent can be used in combination. Examples of the silane coupling agent include bis (triethoxysilylpropyl) tetrasulfide (Si69), bis (triethoxysilylpropyl) disulfide (Si75), γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and the like. Moreover, the aminosilane compound mentioned later can also be used.

  Examples of the filler that serves as the base for the amino group-introducing filler (hereinafter sometimes simply referred to as “filler that serves as the base”) include the various fillers exemplified above. Silica, carbon black, and calcium carbonate are preferable, and silica is more preferable from the viewpoint of easy adjustment of the introduction ratio (introduction ratio) and the like.

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

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

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

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

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

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

  The amino group-introduced fillers may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the use of the composite of the present invention, the physical properties required for the composite of the present invention, and the like.

  If necessary, the thermoplastic elastomer composition used in the present invention may be a polymer other than a thermoplastic elastomer, an amino group-containing compound, a compound containing a metal element (hereinafter simply referred to as “metal”, as long as the object of the present invention is not impaired. Salt "), maleic anhydride modified polymer, anti-aging agent, antioxidant, pigment (dye), plasticizer, UV absorber, flame retardant, solvent, surfactant (including leveling agent), dispersant, Various additives, such as a dehydrating agent, a rust preventive agent, an adhesion imparting agent, an antistatic agent, and a filler, can be contained.

As the additive and the like, commonly used ones can be used, and specific examples thereof are shown below, but are not limited to those exemplified.
As the polymer other than the thermoplastic elastomer, a polymer having a glass transition temperature of 25 ° C. or lower is preferable for the same reason as described above. Specifically, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butyl rubber ( IIR), ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), etc., and particularly the unsaturated bond of IIR, EPM, EBM. Polymers that do not have them or polymers with low unsaturated bonds (eg EPDM) are preferred. A polymer having a site capable of hydrogen bonding is also preferable, and examples thereof include polyester, polylactone, and polyamide.
In the thermoplastic elastomer composition used in the present invention, the polymer other than the thermoplastic elastomer may contain one kind or two or more kinds, and the content of the polymer is based on 100 parts by mass of the thermoplastic elastomer. 0.1 to 100 parts by mass, and more preferably 1 to 50 parts by mass.

The said amino group containing compound is demonstrated.
The amino group in the amino group-containing compound is basically the same as that described in the amino group-introduced filler, and is not particularly limited as long as the amino group content is 1 or more. It is preferable that the number is at least one because two or more cross-linking bonds can be formed with the thermoplastic elastomer, and the effect of improving the physical properties is excellent.

The series of the amino group in the amino group-containing compound is not particularly limited, and is the same as the amino group in the amino group-introduced filler, primary (—NH ₂ ), secondary (imino group,> NH), tertiary ( > N-) or quaternary (> N ⁺ <), and may be arbitrarily selected according to physical properties such as recyclability, compression set, mechanical strength and hardness required for the thermoplastic elastomer composition. You can choose. When a secondary amino group is selected, mechanical strength tends to be excellent, and when a tertiary amino group is selected, recyclability tends to be excellent. In particular, it is preferable to have two secondary amino groups because the thermoplastic material using the thermoplastic elastomer composition obtained is excellent in recyclability and compression set, and also in the balance of physical properties.
In the case where the amino group-containing compound contains two or more amino groups, the number of primary amino groups in the amino group-containing compound is preferably 2 or less, and 1 or less. More preferably. When there are 3 or more primary amino groups, the (crosslinking) bond formed by the amino groups and the functional groups in the thermoplastic elastomer (particularly carboxy groups, which are carbonyl-containing groups) is strengthened and has excellent recyclability. May be damaged.

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

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

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

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

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

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

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

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

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

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

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

  Among these, from the viewpoint of further improving the compression set of the thermoplastic material using the thermoplastic elastomer composition obtained, Ti, Al, Zn is preferable as the metal element, and these acetates as the metal salt, C1-C20 saturated fatty acid salts such as stearates, metal alkoxides (reactants with alcohols having 1 to 12 carbons), oxides, hydroxides, complexes with diketones are preferred, such as stearates A saturated fatty acid salt having 1 to 20 carbon atoms, a metal alkoxide (a reaction product with an alcohol having 1 to 12 carbon atoms), and a complex with a diketone are particularly preferable.

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

  The content of the metal salt is preferably 0.05 to 3.0 equivalents, more preferably 0.1 to 2.0 equivalents, based on the carbonyl group contained in the thermoplastic elastomer. It is especially preferable that it is 2-1.0 equivalent. If the content of the metal salt is within this range, it is preferable because physical properties such as compression set, mechanical strength and hardness of the thermoplastic material using the thermoplastic elastomer composition obtained are improved.

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

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

The maleic anhydride residue is introduced (modified) into the side chain or terminal of the elastomeric polymer and is not introduced into the main chain of the elastomeric polymer. The maleic anhydride residue is a cyclic acid anhydride group, and the cyclic acid anhydride group (part) does not open.
Therefore, as the maleic anhydride-modified thermoplastic polymer, for example, as shown in the following formula (8), a cyclic acid in the side chain obtained by reacting an ethylenically unsaturated bond portion of maleic anhydride with an elastomeric polymer is used. Examples include thermoplastic elastomers having an anhydride group and no nitrogen-containing heterocycle, and specific examples thereof include those exemplified for the above-described elastomeric polymer containing a cyclic acid anhydride group in the side chain. .

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

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

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

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

The content of the maleic anhydride-modified polymer is preferably 1 to 100 parts by mass and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. If the content of the maleic anhydride-modified polymer is within this range, the processability and mechanical strength of the resulting thermoplastic elastomer composition are improved, which is preferable.
When the thermoplastic elastomer used in the present invention is produced, specifically, in the above-described reaction step A or B, when an elastomeric polymer containing a cyclic acid anhydride group in the side chain remains as an unreacted product. Further, without removing the remaining carbonyl-containing group-modified elastomer, it can be contained in the thermoplastic elastomer composition as it is.

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

Specific examples of the plasticizer include benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid, and other polyesters. , Polyether, epoxy and the like.
Specific examples of the thixotropic agent include benton, silicic anhydride, silicic acid derivatives, urea derivatives, and the like.
Specific examples of the ultraviolet absorber include 2-hydroxybenzophenone, benzotriazole, and salicylic acid ester.
Specific examples of the flame retardant include phosphorus-based materials such as TCP, halogen-based materials such as chlorinated paraffin and perchlorpentacyclodecane, antimony-based materials such as antimony oxide, and aluminum hydroxide.

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

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

  The content of the plasticizer is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. The content of other additives is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.

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

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

  The method for producing the thermoplastic elastomer composition used in the present invention is not particularly limited. For example, a thermoplastic elastomer and various additives that may be contained as needed are rolled, kneader, extruder, universal agitator. What is necessary is just to mix by etc.

  Curing conditions for crosslinking the thermoplastic elastomer composition (with a vulcanizing agent) can be appropriately selected according to various components to be blended, and are not particularly limited. For example, curing conditions for curing at a temperature of 130 to 200 ° C. for 5 to 60 minutes are preferable.

The composite of the present invention is a composite formed by integrally bonding the above-described metal plate and the thermoplastic material using the above-described thermoplastic elastomer or thermoplastic elastomer composition provided on the metal plate. .
Here, “fixed integrally” means that the thermoplastic material is placed on the metal plate so that at least part of the thermoplastic material is in contact with the metal plate, and then the thermoplastic material is used at 150 to 250 ° C. It shows that the metal plate and the thermoplastic material are bonded together while forming a bridge in the material.
Specifically, as shown in the examples described later, the above-described thermoplastic elastomer or thermoplastic elastomer composition is sandwiched between two aluminum plates, and then heated at 180 ° C. for 5 minutes from above and below the aluminum plate. The mode etc. which carry out pressure bonding are illustrated suitably.

In addition, the composite of the present invention obtained by integrally fixing the metal plate and the thermoplastic material described above is reheated to about 80 to 200 ° C., so that the three-dimensional cross-linking in the thermoplastic material is performed. (Crosslinked structure) is dissociated and softened to impart fluidity. This is considered to be because the interaction between the side chains formed between the molecules or within the molecule is weakened.
The thermoplastic material softened and fluidized can be easily separated from the metal plate and recovered. In the present invention, the thermoplastic material recovered in this way is used for fixing to the metal plate again because the thermoplastic elastomer or thermoplastic elastomer composition used for the thermoplastic material is excellent in recyclability as described above. Can be used and the composite can be reshaped.

EXAMPLES Next, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited to these.
<Thermoplastic elastomer (1)>
A pressure kneader heated to 190 ° C. was charged with 300.0 g of maleic anhydride EPM (prototype manufactured by Mitsui Chemicals) and masticated for 3 minutes, and then 2.49 g of 3-amino-1,2,4-triazole. (0.03 mol) was added and kneaded for 20 minutes to prepare a thermoplastic elastomer (1). An IR analysis of the kneaded product confirmed that the rubber had a triazole ring introduced.

<Thermoplastic elastomer composition (2)>
A thermoplastic elastomer composition is obtained by kneading, with a Banbury mixer, 10 parts by mass of carbon black (Seast V, manufactured by Mitsubishi Chemical Corporation) with respect to 100 parts by mass of the thermoplastic elastomer (1). (2) was prepared.

<Thermoplastic elastomer composition (3)>
A thermoplastic elastomer composition (3) was prepared in the same manner as the thermoplastic elastomer composition (2) except that 30 parts by mass of carbon black (Seast V, manufactured by Mitsubishi Chemical Corporation) was added.

(Examples 1 to 3 and Comparative Example 1)
As shown in FIG. 1A, between the two aluminum plates 1 (size: width 25 mm × length 100 mm × thickness 0.2 mm), the thermoplastic elastomer (1) obtained above, thermoplasticity After sandwiching the elastomer composition (2) or the thermoplastic elastomer composition (3) 2 so as to have a thickness of 2 mm, each aluminum plate 1 was pressed from above and below at 180 ° C. for 5 minutes, so that Examples 1-3 As a composite, a metal-thermoplastic composite with a thickness of 2 mm was produced. As Comparative Example 1, a double-sided tape (foam double-sided tape, manufactured by Nitto Denko Corporation) was used to prepare a composite that was sandwiched and bonded with the same aluminum plate.
Further, as shown in FIG. 1B, between the two aluminum plates 1 (size: width 25 mm × length 100 mm × thickness 0.2 mm), the thermoplastic elastomer (1) obtained above, After sandwiching the thermoplastic elastomer composition (2) or the thermoplastic elastomer composition (3) 2 so as to have a thickness of 2 mm (adhesion area: 10 mm × 25 mm), the aluminum plate 1 is vertically heated at 180 ° C. for 5 minutes. By pressing, a metal-thermoplastic material composite having a thickness of 2 mm was produced as the composite of Examples 1 to 3. As Comparative Example 1, a double-sided tape having the same size (foam double-sided tape, manufactured by Nitto Denko Corporation) was used to produce a composite that was sandwiched and bonded with the same aluminum plate.

  FIG. 1 (A) is a perspective view showing a composite for use in a 180 degree peel adhesion strength test, and FIG. 1 (B) is a perspective view showing a composite for use in a tensile shear bond strength test.

These composites were subjected to 180 degree peel adhesion strength test and tensile shear adhesion strength test. The results are shown in Table 1 below.
The 180 degree peel adhesion strength test was performed by separating the ends of two aluminum plates in the direction of the arrow in FIG. 1A at a peel rate of 50 mm / min at room temperature (25 ° C.). The shear bond strength test was performed by pulling the ends of two aluminum plates at a speed of 500 mm / min in the direction of the arrow in FIG. 1B at room temperature (25 ° C.).

About the composite of Example 2 using the thermoplastic elastomer composition (2) obtained above, the 180 ° peel adhesion strength test and the tensile shear adhesive strength of the composite recycled and remolded by the following method The test was conducted.
Recycling was performed by reheating the composite of Example 2 to 180 ° C., peeling the softened thermoplastic elastomer composition (2) from the aluminum plate, and remolding it using the re-kneaded composition. As Example 4, a composite using a composition subjected to recycling twice was prepared, and as Example 5, a composite using a composition subjected to recycling four times was prepared. A peel adhesion strength test and a tensile shear bond strength test were conducted. The results are shown in Table 2 below.

  As is clear from Tables 1 and 2 above, the composites of Examples 1 to 3 have both peeling adhesive strength and shear adhesive strength compared to the composite of Conventional Example 1 which is an example of a conventional product using a double-sided tape. It turned out that it was excellent, and also about the composite after a recycling, it turned out that both the peeling adhesive force and the shearing adhesive force are maintained favorable.

FIG. 1 (A) is a perspective view showing a composite for use in a 180 degree peel adhesion strength test, and FIG. 1 (B) is a perspective view showing a composite for use in a tensile shear bond strength test.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Aluminum plate 2 Thermoplastic elastomer (1), thermoplastic elastomer composition (2), or thermoplastic elastomer composition (3)

Claims (9)

It is a composite formed by integrally fixing a metal plate and a thermoplastic material using a thermoplastic elastomer provided on the metal plate,
The composite in which the thermoplastic elastomer has a side chain containing a carbonyl-containing group and an imino group and / or a side chain containing a carbonyl-containing group and a nitrogen-containing heterocyclic ring. The complex according to claim 1, wherein the side chain containing the carbonyl-containing group and the imino group contains a structure represented by the following formula (1).

Wherein A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups. The side chain containing the structure represented by the formula (1) contains a structure represented by the following formula (2) or (3) bonded to the main chain at the α-position or the β-position. Complex.

Wherein A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups. The complex according to any one of claims 1 to 3, wherein the side chain containing the carbonyl-containing group and the nitrogen-containing heterocycle contains a structure represented by the following formula (4).

Wherein E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; An organic group that may contain any atom or group of The side chain containing the structure represented by said Formula (4) contains the structure represented by following formula (5) or (6) couple | bonded with a principal chain in (alpha) position or (beta) position. Complex.

(Wherein E is a nitrogen-containing heterocyclic ring, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)) or A sulfur atom; or an organic group that may contain these atoms or groups.)   The complex according to any one of claims 1 to 5, wherein the nitrogen-containing heterocycle is a 5- or 6-membered ring.   The complex according to claim 6, wherein the nitrogen-containing heterocycle is a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring or a hydantoin ring.   The composite according to any one of claims 1 to 7, wherein the metal plate is an aluminum plate.   The composite according to any one of claims 1 to 8, wherein the thermoplastic material is a thermoplastic elastomer composition containing 50 parts by mass or less of a filler with respect to 100 parts by mass of the thermoplastic elastomer.

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