JP2017057393A - Thermoplastic elastomer composition, manufacturing method therefor and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition capable of improving heat resistance and breaking strength.SOLUTION: There is provided a thermoplastic elastomer composition containing at least one elastomer component selected from a group consisting of an elastomer polymer (A) having a side chain (a) containing a hydrogen bond crosslinked site having a carbonyl-containing group and/or a nitrogen-containing heterocycle and glass transition point of 25°C or less and an elastomer polymer (B) containing a hydrogen bond crosslinked site and a covalent crosslinked site in a side chain and glass transition point of 25°C or less, clay with percentage content of 20 pts.mass or less based on 100 pts.mass of the elastomer component, and a styrene block copolymer having no chemical bond crosslinked site.SELECTED DRAWING: None

Description

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

  A thermoplastic elastomer is an extremely useful material in the industry because it melts at the processing temperature during the molding process and can be molded by a known resin molding method.

  As such a thermoplastic elastomer, for example, in Japanese Patent Application Laid-Open No. 2006-131663 (Patent Document 1), a side chain containing a hydrogen-bonding crosslinking site having a carbonyl-containing group and a nitrogen-containing heterocyclic ring is covalently bonded. A thermoplastic elastomer comprising an elastomeric polymer having a glass transition point of 25 ° C. or lower and having other side chains containing a functional crosslinking site is disclosed. However, such a thermoplastic elastomer described in Patent Document 1 is not always sufficient in terms of heat resistance and breaking strength.

JP 2006-131663 A

  The present invention has been made in view of the above-described problems of the prior art, and provides a thermoplastic elastomer composition capable of further improving heat resistance and breaking strength, and a method for producing the same. With the goal. Moreover, an object of this invention is to provide the laminated body which can make the adhesive strength between a metal layer and an elastomer layer sufficient.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have a side chain (a) containing a hydrogen-bonding bridging site having a carbonyl-containing group and / or a nitrogen-containing heterocycle, and a glass transition. An elastomeric polymer (A) having a point of 25 ° C. or lower, and an elastomeric polymer (B) containing a hydrogen-bonding crosslinking site and a covalent bonding site in the side chain and having a glass transition point of 25 ° C. or lower ) At least one elastomer component selected from the group consisting of: a clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component; and a styrene block copolymer having no chemically-bonded cross-linking site. By incorporating the coalesced, it is possible not only to make the resulting thermoplastic elastomer composition have higher heat resistance, but also to break It found that degree it is possible to be made more sophisticated, and have completed the present invention.

That is, the thermoplastic elastomer composition of the present invention has a side chain (a) containing a hydrogen-bonding crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring, 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,
Clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
A styrene block copolymer having no chemically-bonded crosslinking site;
It is characterized by containing.

  In the thermoplastic elastomer composition of the present invention, the content ratio of the styrene block copolymer is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the elastomer component.

  In the thermoplastic elastomer composition of the present invention, the styrene block copolymer is a styrene-isoprene-styrene block copolymer (SIS), a styrene-ethylene-propylene-styrene block copolymer (SEPS), Styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-butadiene -It is preferable that it is at least 1 sort (s) selected from the group which consists of a styrene block copolymer (SIBS) and these hydrogenated substances.

  Moreover, in the thermoplastic elastomer composition of the present invention, the styrene block copolymer is preferably a styrene block copolymer having a styrene content of 20 to 40% by mass.

  Furthermore, in the thermoplastic elastomer composition of the present invention, it is preferable that the styrene block copolymer has a weight average molecular weight of 200,000 to 700,000.

  Further, in the thermoplastic elastomer composition of the present invention, the hydrogen bonding cross-linking site contained in the side chain of the elastomeric polymer (B) has hydrogen bonding properties having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring. A crosslinking site is preferred.

  In the thermoplastic elastomer composition of the present invention, the clay is preferably at least one selected from the group consisting of clays containing silicon and magnesium as main components, and organic clays, More preferred is clay.

  Furthermore, in the thermoplastic elastomer composition of the present invention, the crosslinking at the covalent crosslinking site contained in the side chain of the elastomeric polymer (B) is amide, ester, lactone, urethane, ether, thiourethane. And at least one bond selected from the group consisting of thioethers.

  In the thermoplastic elastomer composition of the present invention, the hydrogen-bonding cross-linked site of the side chain (a) is represented by 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 preferable to contain the structural part represented by these.

  Moreover, in the thermoplastic elastomer composition of the present invention, the nitrogen-containing heterocycle is preferably a 5-membered ring and / or a 6-membered ring.

  Furthermore, in the thermoplastic elastomer composition of the present invention, the nitrogen-containing heterocycle is at least one selected from a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring, a triazine ring, an isocyanurate ring, and a hydantoin ring. It is preferable that

  In the thermoplastic elastomer composition of the present invention, the main chains of the elastomeric polymers (A) to (B) are respectively 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 It is preferable to consist of one type.

Further, a method for producing a thermoplastic elastomer composition of the present invention (first production method: hereinafter, for convenience, “first production method”, “manufacturing method of first thermoplastic elastomer composition of the present invention” in some cases. Is a mixture obtained by mixing an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and a styrene block copolymer having no chemically-bonded crosslinking site. Process,
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 second step of obtaining a thermoplastic elastomer composition by adding at least one raw material compound among the mixed raw materials of the compound (II) that forms the compound, and reacting the polymer and the raw material compound;
Including,
The thermoplastic elastomer composition obtained in the second step has a side chain (a) containing a hydrogen-bonded crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle, and has a glass transition point of 25 ° C. A group consisting of the following elastomeric polymer (A) and 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. At least one elastomer component selected from:
The clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
The styrene block copolymer;
And a composition comprising
In the first step, the cyclic acid anhydride is used by using the clay in such a proportion that the content of the clay in the thermoplastic elastomer composition is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component. Mixing the elastomeric polymer having a group in the side chain, the clay, and the styrene block copolymer;
It is the method characterized by this.

  In the method for producing the thermoplastic elastomer composition of the present invention (first production method), the elastomeric polymer having the cyclic acid anhydride group in the side chain is preferably a maleic anhydride-modified elastomeric polymer.

  Moreover, in the manufacturing method (1st manufacturing method) of the said thermoplastic elastomer composition of this invention, it reacts with the said cyclic acid anhydride group as said compound (I) and / or (II), and hydrogen bonding property It is preferable to use a compound that forms both a crosslinking site and a covalent crosslinking site.

  Moreover, in the manufacturing method (1st manufacturing method) of the thermoplastic-elastomer composition of the said invention, as said compound (I) and / or (II), a hydroxyl group, a thiol group, an amino group, and an imino group It is preferable to use a compound having at least one substituent.

Further, a method for producing the thermoplastic elastomer composition of the present invention (second production method: hereinafter, for convenience, “second production method” and “production method of the second thermoplastic elastomer composition of the present invention” as the case may be. And so on).
An elastomeric polymer having a cyclic acid anhydride group in the side chain;
With clay,
A styrene block copolymer having no chemically-bonded crosslinking site;
Compound (I) which reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site, and compound which reacts with the compound (I) and the cyclic acid anhydride group to form a covalent-bonding cross-linking site At least one raw material compound of the mixed raw materials of (II);
And a process of obtaining a thermoplastic elastomer composition by reacting the elastomeric polymer having the cyclic acid anhydride group in the side chain with the raw material compound,
The thermoplastic elastomer composition has an elastomeric polymer (a) having a side chain (a) 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 ( A) and at least one selected from the group consisting of 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 An elastomer component of
The clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
The styrene block copolymer;
And a composition comprising
Using the clay in such a proportion that the content of the clay in the thermoplastic elastomer composition is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
It is the method characterized by this.

The laminate of the present invention includes a metal layer,
An elastomer layer comprising the thermoplastic elastomer composition of the present invention;
It is characterized by providing.

  In the laminate of the present invention, it is preferable that an adhesive layer is further provided between the metal layer and the elastomer layer.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the thermoplastic elastomer composition which can make heat resistance and breaking strength more advanced, and its manufacturing method. Moreover, according to this invention, it becomes possible to provide the laminated body which can make the adhesive strength between a metal layer and an elastomer layer sufficient.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Thermoplastic elastomer composition]
The thermoplastic elastomer composition of the present invention has an elastomeric property having a side chain (a) 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. At least selected from the group consisting of a polymer (A) and 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. One elastomer component;
Clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
A styrene block copolymer having no chemically-bonded crosslinking site;
It is characterized by containing.

(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 chain” refers to side chains and terminals of the elastomeric polymer. In addition, the “side chain (a) containing a hydrogen-bonding cross-linked site having a carbonyl-containing group and / or a nitrogen-containing heterocycle” refers to an atom (usually a carbon atom) that forms the main chain of the elastomeric polymer. It means that a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring (more preferably a carbonyl-containing group and a nitrogen-containing heterocyclic ring) as a hydrogen-bonding crosslinking site 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 an elastomeric polymer (A) to (B) main chain (polymer forming the main chain portion) is generally a known natural polymer or synthetic polymer, and has a glass transition point of room temperature ( 25 ° C.) or lower polymer (so long as it is made of so-called elastomer), it is not particularly limited. Therefore, the elastomeric polymers (A) to (B) include, 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, 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 (polymers 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; Rubber, urethane rubber, and the like.

  The main chain of the elastomeric polymers (A) to (B) (polymer forming the main chain portion) may be composed of 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.

  The main chain of such elastomeric polymers (A) to (B) includes diene rubber, hydrogenated diene rubber, olefin rubber, hydrogenated polystyrene elastomeric polymer, polyolefin At least one selected from an elastomeric polymer, a polyvinyl chloride-based elastomeric polymer, a polyurethane-based elastomeric polymer, a polyester-based elastomeric polymer, and a polyamide-based elastomeric polymer is preferable. In addition, as the main chain of the elastomeric polymers (A) to (B), a hydrogenated diene rubber and an olefin rubber are preferable from the viewpoint that there is no aging double bond. From the viewpoint of low and high reactivity (having many double bonds capable of ene reaction of a compound such as maleic anhydride), a diene rubber is preferable.

  Furthermore, the elastomeric polymers (A) to (B) may be liquid or solid, and the molecular weight thereof is not particularly limited, and uses and required physical properties for which the thermoplastic elastomer composition of the present invention is used. 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 (decrosslinked or the like), the elastomeric polymers (A) to (B) are preferably liquid, 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. Is preferably about 1,000 to 50,000, particularly 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 solid, 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 especially preferable that it is about 1,000,500,000.

  Such a 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 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.

  Moreover, the glass transition point of the said elastomeric polymers (A)-(B) is 25 degrees C or less as mentioned 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 such elastomeric polymers (A) to (B) has a glass transition point of 25 ° C. or less of the elastomeric polymers (A) to (B), and a molded product made of the resulting thermoplastic elastomer composition. Since it exhibits rubber-like elasticity at room temperature (25 ° C.), natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), ethylene-propylene -Diene rubbers such as diene rubber (EPDM) and butyl rubber (IIR); and olefin rubbers such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), and ethylene-butene rubber (EBM). Moreover, when olefin rubber is used for 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.

  Further, as the main chain of the elastomeric polymers (A) to (B), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), and ethylene-butene rubber (EBM) are used. When used, it is particularly preferable that the crystallinity is less than 10% (more preferably 5 to 0%) from the viewpoint of good rubbery elasticity at room temperature. Further, as the main chain of the elastomeric polymers (A) to (B), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), and ethylene-butene rubber (EBM) are used. 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).

  Further, the elastomeric polymers (A) to (B) are preferably amorphous from the viewpoint of good rubbery elasticity at room temperature. Moreover, as such elastomeric polymers (A) to (B), an elastomer having a crystallinity (crystal structure) in part may be used, 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 acids 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, and benzoic anhydride Anhydrides; 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- Aromatic esters such as hydroxybenzoate; quinone, ant Ketones such as quinone 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 group such as isopropyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl group, 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 and mesityl group; It is done.

  Among these, as the substituents X, Y and Z, the thermoplastic elastomer composition of the present invention to be obtained is an alkyl group, in particular, a butyl group, an octyl group, a dodecyl group, an isopropyl group or a 2-ethylhexyl group. This is preferable because the processability of is improved.

  Moreover, about a nitrogen-containing 6-membered ring, the following compound is illustrated preferably. These may also have the above-mentioned various substituents (for example, the substituent that the above-mentioned nitrogen-containing heterocyclic ring may have), 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, 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. In addition, as the substituent B in the above formula (1), specifically, for example, a single bond; oxygen atom, sulfur atom or 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 1-20 alkylene group or 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 at its end (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 an isomer, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 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 alkyleneamino group, an alkylenethioether having 1 to 20 carbon atoms terminated with these atoms or groups Group, oxygen atom such as aralkylene ether group, aralkylene amino group, aralkylene thioether group, amino group NR ′ and sulfur atom are combined with the adjacent carbonyl group to form a conjugated ester group, amide group, 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 terminals. 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 Particularly preferred is an ether group (—O—CH ₂ — group, —O—CH ₂ CH ₂ — group, —O—CH ₂ CH ₂ CH ₂ — group).

  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 said Formula (3) is a C1-C20 alkylene which may contain a single bond; an oxygen atom, a nitrogen atom, or a sulfur atom among what was illustrated by the substituent B of the said 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 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 is a single bond; an alkylene ether or aralkylene ether group having 1 to 20 carbon atoms having an oxygen atom, a sulfur atom or an 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 between the carbonyl-containing group and the nitrogen-containing heterocycle of the thermoplastic elastomer is not particularly limited, and 2: 1 is preferable because it tends to form a complementary interaction and can be easily produced. .

  The side chain (a) containing such a carbonyl-containing group and / or a hydrogen-bonding cross-linked site having 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 preferable that it is 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) contains a side chain (ai) containing a hydrogen bondable 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 (a-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.

  The introduction ratio is, for example, when the main chain portion is ethylene-propylene rubber (EPM), the monomer having the side chain portion introduced per 100 units of ethylene and propylene monomer units is 0.1-50. 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 ("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 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 And polythiol compounds having two or more thiol groups (mercapto groups) in the molecule. 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 amine include, for example, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane, di- (Aminomethyl) cyclohexane and the like.

  In addition, the aliphatic polyamine is not particularly limited, but for example, methylenediamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, 1,3-diaminopentane, hexamethylenediamine, diaminoheptane, diaminododecane, diethylenetriamine, Diethylaminopropylamine, N-aminoethylpiperazine, triethylenetetramine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-dimethyl-1,3-propane Diamine, N, N′-diethyl-1,3-propanediamine, N, N′-diisopropyl-1,3-propanediamine, N, N′-dimethyl-1,6-hexanediamine, N, N′-diethyl -1,6 Hexanediamine, N, N ', N' '- trimethylbis (hexamethylene) triamine, and the like.

  The aromatic polyamine and the nitrogen-containing heterocyclic amine are not particularly limited. For example, diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tris (dimethylaminomethyl) phenol, metaphenylenediamine, diaminodiphenylmethane, 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.

  Moreover, the said polyamine compound may be used individually by 1 type, or may use 2 or more types together. 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.

  Among the polyamine compounds exemplified above, hexamethylenediamine, N, N′-dimethyl-1,6-hexanediamine, diaminodiphenylsulfone and the like are preferable because they have a 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 (for example, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (for example, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine) Polyethylene glycol octylamine (for example, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octyl Amines (eg, N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine ( For example, low molecular polyols such as N, N-bis (2-methyl-2-hydroxyethyl) stearylamine) may be used, and these may be used alone or in combination of two or more.

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, 1 3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 4,4′-thiobisbenzenethiol, 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6- Dioxaoctane, 1,5-dimercapto-3-thiapentane, 1,3,5-triazine-2,4,6-trithiol (trimercapto-triazine), 2-di-n-butylamino-4,6-dimercapto -S-triazine, trimethylolpropane tris (β-thiopropionate), trimethylolpropane tris (thioglycolate), polythiol (thiocol or thiol-modified polymer (resin, rubber, etc.)) and the like. You may use individually by 1 type or may use 2 or more types together.

  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.

  Moreover, the thermoplastic elastomer obtained by the bridge | crosslinking in the covalent bond bridge | crosslinking site | part of the said side chain (b) containing a tertiary amino bond (-N =) and 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—), As the compound (compound that forms a covalent bond), among those exemplified above, polyethylene glycol laurylamine (for example, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (for example, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (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 (for example, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine (for example, 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 Bond 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. Furthermore, 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 It is more preferable to have 2-10. Further, the thermoplastic elastomer obtained from the fact that the crosslinking at the covalent crosslinking site of the side chain (c) contains a tertiary amino bond (—N═) and 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-bonding cross-linking site in the side chains (b) to (c))
For the side chain (b) and / or (c), the crosslink at the covalent crosslink 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. As described above, the tertiary amino bond (—N═) or the ester bond (—COO—) in the side chain having a covalent bond crosslinking site forms a hydrogen bond with another side chain. In such a case, the covalently linked cross-linking site containing such tertiary amino bond (—N═) and ester bond (—COO—) will also be provided with a hydrogen-bonding cross-linked site, and as a 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. (For example, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (for example, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octylamine (for example, N, N-bis (2-methyl-2-hydroxyethyl) 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 of 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. 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 1,11-undecylene group, 1,12-dodecylene group and other alkylene groups; 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, divalent, such as vinylene group, 1,4-cyclohexylene group Alicyclic carbonization Elemental 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.

  Furthermore, in the following formulas (7) to (9), the crosslinking at the covalent bond 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 structure 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 formula (4).

  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 examples. 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.

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

  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 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 mixed and used. 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 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); and 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.

  In addition, 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 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 An elastomeric polymer having the side chain (a ′) and side chain (b) by reacting with at least one raw material compound among the mixed raw materials of the compound forming the site; 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, a cyclic acid anhydride group) in the side chain is a polymer capable of forming the main chain of the elastomeric polymers (A) to (B) described above. 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 acid anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, a thiol group, and the like are preferable. From the viewpoint that clay can be more efficiently dispersed in the composition, a cyclic acid anhydride group is particularly preferable. preferable. 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 to produce the elastomeric component. 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, an elastomeric polymer having a functional group in the side chain is added to the raw material compound. Before reacting with clay and mixing an elastomeric polymer having a functional group in the side chain, and then adding and reacting the raw material compound to form a composition simultaneously with the preparation of the elastomer component (clay May be employed.

  In addition, since the dispersibility of clay improves further and higher heat resistance is obtained, when manufacturing an elastomer component (elastomeric polymers (A) to (B)), a method of adding the above clay in advance The composition is preferably prepared simultaneously with the preparation of the elastomer component. Moreover, as a method of adding such clay in advance, it is more preferable to employ the method for producing a thermoplastic elastomer composition of the present invention described later.

(Clay)
The clay according to the present invention is not particularly limited, and a known clay (clay mineral or the like) can be appropriately used. Examples of such clay include natural clay, synthetic clay, and organic clay. Examples of such clays include montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, mica, fluorinated mica, kaolinite, pyrophyllolite, smectite, sericite. Sites (sericite), illite, groconite (sea green stone), chlorite (chlorite), talc (talc), zeolite (zeolite), hydrotalcite and the like.

  Among such clays, at least one selected from the group consisting of clays containing silicon and magnesium as main components and organic clays is preferable.

  In the present invention, the clay mainly composed of silicon and magnesium refers to a clay in which the metal main component of the metal oxide, which is a constituent component of clay, is silicon (Si) and magnesium (Mg). Metal oxides (aluminum (Al), iron (Fe), etc.) may be included as subcomponents. The clay containing silicon and magnesium as main components is not particularly limited, and a known clay can be appropriately used. By using clay mainly composed of silicon and magnesium, the particle size is small, so that the reinforcing property can be enhanced. Moreover, as a clay which has such a silicon and magnesium as a main component, the clay which has a smectite structure from a viewpoint of availability is preferable.

  Examples of the clay mainly composed of silicon and magnesium include stevensite, hectorite, saponite, and talc. It is more preferable to use light or saponite.

  Moreover, as a clay which has silicon and magnesium as a main component, a synthetic clay is preferable. As such synthetic clay, commercially available ones may be used. For example, trade names “Smecton SA” and “Smecton ST” manufactured by Kunimine Industry Co., Ltd., trade names “Ionite” manufactured by Mizusawa Chemical Industry Co., Ltd., Corp. A trade name “Lucentite” manufactured by Chemical Co., Ltd. can be used as appropriate.

  Moreover, although the said organized clay is not restrict | limited in particular, It is preferable that a clay is formed by organicizing with an organic agent. Such clay before being organized is not particularly limited and may be a so-called clay mineral, for example, montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, mica, Fluorinated mica, kaolinite, pyrophyllolite, smectite, sericite, illite, glowconite, chlorite, talc, zeolite (zeolite) ), Hydrotalcite and the like. Such clay may be a natural product or a synthetic product.

  Further, the organic agent is not particularly limited, and a known organic agent capable of organicizing clay can be appropriately used. For example, hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion , Dodecyl ammonium ion, lauryl ammonium ion, octadecyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion, dioctadecyl dimethyl ammonium ion, trioctyl ammonium ion, dioctadecyl dimethyl ammonium ion, trioctadecyl ammonium ion, etc. can be used. .

  Further, as such an organized clay, a quaternary ammonium salt of clay can be suitably used from the viewpoint of monolayer dispersibility. The quaternary ammonium salt of such an organized clay is not particularly limited, and examples thereof include trimethyl stearyl ammonium salt, oleyl bis (2-hydroxylethyl) salt, methyl ammonium salt, dimethyl stearyl benzyl ammonium salt, and dimethyl octadecyl ammonium salt. , And a mixture of two or more of these can be suitably used. As the quaternary ammonium salt of such an organized clay, dimethylstearylbenzylammonium salt, dimethyloctadecylammonium salt, and mixtures thereof can be more suitably used from the viewpoint of improving tensile strength and heat resistance. A mixture of stearylbenzylammonium salt and dimethyloctadecylammonium salt can be more suitably used.

  Moreover, as such an organized clay, commercially available ones may be used, for example, trade names “Kunifil-D36”, “Kunifil-B1”, “Kunifil-HY”, etc. manufactured by Kunimine Industries, Ltd. The product name “Esven series (C, E, W, WX, N-400, NX, NX80, NZ, NZ70, NE, NEZ, NO12S, NO12”, “Organite series (D, T), manufactured by Hojun Co., Ltd.” Among such commercially available organic clays, the product name “Kunifil-D36” manufactured by Kunimine Industries Co., Ltd. and the product name “Esven series WX” manufactured by Hojun Co. can be suitably used. .

  Thus, as the clay according to the present invention, from the viewpoint of high dispersibility, clays and organoclays mainly composed of silicon and magnesium are preferable, and among them, higher tensile stress (modulus) can be obtained. It is particularly preferable to use an organized clay.

(Styrene block copolymer that does not have a chemical bonding cross-linking site)
The styrene block copolymer according to the present invention does not have a chemical bonding crosslinking site. “Chemical bond cross-linking site” means hydrogen bond, covalent bond, metal ion-polar functional group chelation, σ-π interaction between metal-unsaturated bond (double bond, triple bond) The site | part in which bridge | crosslinking is formed by chemical bonds, such as the bond formed by (1). Therefore, “having no chemically-bonded crosslinking site” in the present invention means the hydrogen bond, covalent bond, metal ion-polar functional group chelation, metal-unsaturated bond (double bond) described above. , A triple bond) means a state having no chemical bond formed by a bond formed by σ-π interaction. As such a styrene block copolymer having no chemically-bonded crosslinking site, a functional group (for example, a hydroxyl group, a carbonyl group, a carboxyl group, a thiol group, an amide group) that forms a crosslinking point by a chemical bond. , Amino groups) and those not containing a binding site (such as a cross-linking site due to a covalent bond) that directly cross-links the polymer chains. 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.

  In addition, as the styrene block copolymer having no chemically bonded cross-linking site, from the viewpoint of achieving both rubber elasticity and thermoplasticity, styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene- Propylene-styrene block copolymer (SEPS), Styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), Styrene-butadiene-styrene block copolymer (SBS), Styrene-ethylene-butylene-styrene block copolymer A polymer (SEBS), a styrene-isoprene-butadiene-styrene block copolymer (SIBS), and hydrogenated products thereof (so-called hydrogenated products) are preferable, and SEBS and SEEPS are 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.

  Moreover, as a styrene block copolymer which does not have a chemical bonding bridge | crosslinking site | part, it is a styrene block copolymer whose styrene content is 20-40 mass% (more preferably 25-37 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. In addition, 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 (the elastomer component) 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, and 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.

  The glass transition point of the styrene block copolymer having no chemically bonding cross-linked site is preferably −80 to −40 ° C., 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” referred to 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 chemically bonded crosslinking 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”; Kuraray's product names “S4055” “S4077” “S4099” “S8006” “S4044” “S8006” “S4033” “S8004” “S8007” “ "S8076"; Asahi Kasei's product names "Tuftec H1041", "Tuftech N504", "Tuftech H1272", "Tuftech M1911", "Tuftech M1913", "Tufftech MP10"; Product names "AR-710" "AR-720" manufactured by Aron Kasei “AR-731” “AR-741” “AR-750” “AR-760” “AR-770” “AR-781” “AR-791”;

(Composition)
The thermoplastic elastomer composition of the present invention contains the elastomer component, the clay, and a styrene block copolymer having no chemically-bonded crosslinking site.

  The reason why the thermoplastic elastomer composition of the present invention can achieve both a sufficiently high level of heat resistance and a sufficiently high breaking strength is not necessarily clear, but the present inventors speculate as follows. . That is, first, in the present invention, the elastomer component comprises an elastomeric polymer containing at least a side chain having a hydrogen-bonding cross-linking site (on 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 clay are combined, the clay interacts with the hydrogen-bonding cross-linked site (for example, a new hydrogen bond is formed), and the elastomer is utilized using the surface of the clay. The components are cross-linked. And when such surface bridge | crosslinking is formed, it will become possible to express sufficiently high heat resistance derived from the structure. Further, when such surface cross-linking is formed, it becomes possible to suppress stress concentration at the cross-linking point, and higher rupture strength (tensile strength until rupture) than when no clay is contained. The present inventors speculate that it is possible to express the above). In particular, as described in the side chain (a), the hydrogen-bonding cross-linking site is “a hydrogen-bonding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle (more preferably, a carbonyl-containing group and a nitrogen-containing heterocycle). Hydrogen bonding cross-linkable sites) ”, it is possible to bond hydrogen at more points, and in addition to hydrogen bonding at more points between elastomers, there are more hydrogen bonds with clay. Since hydrogen bonding occurs at a point, it is possible to cross-link the surface more strongly, and a higher effect tends to be obtained in terms of tensile strength and heat resistance.

  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 another elastomer component is used, for example, Even when used in combination with clay, 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, when a filler such as clay is simply blended with a thermoplastic elastomer of a type utilizing pseudo-crosslinking, an interaction at the pseudo-crosslinking point (polymer The physical interaction between the molecular chains) is hindered by the clay, and the mechanical strength of the polymer is lowered, making it unusable for actual use as a rubber product. In this way, conventional thermoplastic elastomers consisting only of thermoplastic elastomers of the type utilizing pseudo-crosslinking, in combination with clay, form pseudo-crosslinks in the composition instead. Is inhibited, and the mechanical strength (such as tensile stress) of the composition is lowered. In addition, in a thermoplastic elastomer of a type in which rubber is dispersed in a thermoplastic resin matrix, as is apparent from the composition, fillers such as clay are introduced only into the matrix phase. Here, in a matrix made of a thermoplastic resin having no side chain, no interaction with clay is formed in the matrix. Therefore, even if the filler is simply introduced, the filler is introduced at a high concentration in a certain portion, and the filler is not introduced at all in the certain portion. As a result, due to the difference in the concentration of the filler, a difference in hardness is generated inside the elastomer, and the mechanical strength and the like are reduced. Therefore, in a thermoplastic elastomer of a type in which rubber is dispersed in a thermoplastic resin matrix, when using a polymer that does not contain a hydrogen bonding cross-linked site in the side chain, even if clay is simply introduced, Clay cannot be sufficiently dispersed, and the mechanical strength (such as tensile stress) of the composition is lowered. From this point of view, when the elastomeric polymers (A) and (B) are not used as the elastomer component, an interaction cannot be formed with the clay, and the presence of the clay The present inventors infer that the mechanical strength is lowered and the elastomer (rubber) cannot always have sufficient characteristics.

  Further, in the present invention, the content of the clay is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component, but even with such a content ratio (sufficiently low ratio), heat resistance A sufficiently high effect can be obtained. Regarding this point, as described above, the clay is sufficiently uniformly dispersed in the composition, and it is possible to sufficiently form the surface cross-linkage (in addition, the proportion dispersed in a single layer). If it is higher, it tends to be possible to form more surface crosslinks in the elastomer, and it can be said that this is a more preferable form.) Even if the content is as small as 20 parts by mass or less, The present inventors speculate that it is possible to exhibit sufficiently high tensile stress and sufficiently high heat resistance.

  In addition, the thermoplastic elastomer composition of the present invention contains a styrene block copolymer having no chemically-bonded cross-linking site together with the thermoplastic elastomer composition and clay. In the case of containing a styrene block copolymer having no functional crosslinking site, it does not interfere with the crosslinking reaction of the elastomer component. It is possible to further reflect the excellent mechanical properties of the block copolymer. Therefore, in the thermoplastic elastomer composition of the present invention, it is possible to achieve improvement in tensile properties (particularly breaking strength) derived from a styrene block copolymer having no chemically bonding cross-linked site. Furthermore, the present inventors speculate that it is possible to improve mechanical properties such as compression set according to the type of styrene block copolymer. Further, in the present invention, clay is used in combination with the styrene block copolymer, but since the cross-linked structure of the base elastomer is highly polar, the clay is sufficiently dispersed, but the cross-linked structure of the base elastomer is used. Because the interaction between the clay and the clay is large, the clay does not inhibit the formation of pseudo-crosslinks in the styrene block copolymer used together with the elastomer component, and the composition of the styrene block copolymer is sufficient for the composition. The present inventors speculate that it can be imparted to the above. In the present invention, rubber properties and fluidity (moldability) can be sufficiently retained by hydrogen bonds formed by hydrogen-bonding cross-linked sites in the side chain contained in the elastomer component. The present inventors speculate. That is, even if the hydrogen bond disappears once during the heat processing, the hydrogen bond is formed again during the curing, so that the rubber characteristics and fluidity (moldability) can be sufficiently maintained. In addition, the styrene block copolymer contained together with the elastomer component can also exhibit fluidity due to collapse of the pseudo-crosslinking point (physical crosslinking point) by heating, and the elastomer component and the styrene block When used in combination with a copolymer, it is possible to sufficiently maintain the workability during heating. Moreover, in the composition of this invention, it is also possible to express sufficient hardness etc. which can be utilized as rubber | gum by containing each said component.

  Furthermore, 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, the clay, and a styrene block copolymer having no chemically bonding cross-linked site, and the content of the clay is: It is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component. When the content of such clay exceeds the upper limit, heat resistance and breaking strength are lowered. As content of the clay in such a thermoplastic elastomer composition, it is more preferable that it is 0.1-10 mass parts with respect to 100 mass parts of said elastomer components, and it is 0.5-5 mass parts. More preferably, it is 1 to 3 parts by mass. If the clay content is less than the lower limit, the clay content tends to be too low to obtain a sufficient effect, whereas if the upper limit is exceeded, the crosslinking becomes too strong, and the elongation and strength are rather high. However, it tends to be difficult to use in various applications (practicality is reduced).

  Moreover, as such a clay, it is preferable that the clay of a single layer form (single layer clay) exists in a composition. Presence of such a single-layered clay can be confirmed by measuring the surface of the composition with a transmission electron microscope (TEM).

Furthermore, in the thermoplastic elastomer composition of the present invention, measurement points having a size of 5.63 μm ² above any three points on the surface of the thermoplastic elastomer composition were measured by a transmission electron microscope (TEM). In all cases, at all measurement points, 50% or more (more preferably 70% or more, more preferably 80 to 100%, particularly preferably 85 to 100%) of the total clay is based on the number of the single clay. It is preferable to exist as If the abundance of the single-layer clay is less than the lower limit, the elongation at break and the strength at break tend to decrease. When measuring the abundance (ratio) of such a single-layer clay, the thermoplastic elastomer was used as a sample using a transmission electron microscope (for example, trade name “JEM-2010” manufactured by JEOL Ltd.). 10 g of the composition was prepared, and three or more measurement points having a size of 5.63 μm ² on the surface of the thermoplastic elastomer composition were measured. In each TEM image obtained by such measurement, a single layer of clay was measured. By calculating the number and the number of multi-layered clays, and calculating the abundance (ratio) of single-layer clay among all the clays for each measurement point (each TEM image) based on the number. Can be sought. In the case of a multilayer structure before the formation of a single layer, the interlayer distance of montmorillonite is about 9.8 angstroms, and the interlayer distance of general organic clay is about 20-40 angstroms (2-4 nm). is there. In addition, when a general organic clay is dispersed in an organic solvent to form a single layer, the interlayer distance is 50 angstroms (> 5 nm) or more, so the interlayer distance of each layer that can be confirmed by a TEM image is Based on the fact that the distance is larger than the interlayer distance, it may be determined as a single layer. Thus, although it depends on the type of clay, for example, it may be determined that there is a single layer state when there is a gap of 5 nm or more, and in some cases, there is a gap of several tens of nm or more. It may be determined that the state is a single layer.

  In addition, when a single layer of clay was contained in the composition in the above-described proportion (existence), the clay was more dispersed and contained than the multilayered clay was dispersed as it was. Since it becomes a state (because the multilayered clay is decomposed to form a single-layered clay), the clay can be dispersed in the composition with higher dispersibility. In this way, the clay has higher dispersibility when the monolayer is present in the above ratio than the multi-layered composition in the composition, and has higher heat resistance and breaking strength. Can be. Therefore, it is more preferable to contain the clay in a single layer at the ratio as described above, whereby the clay is more dispersed and the heat resistance and the breaking strength can be improved more efficiently. Further, the method for containing the single-layered clay in the above-described proportion (existence ratio) is not particularly limited, but the method for producing the thermoplastic elastomer composition of the present invention to be described later is adopted to provide the thermoplastic elastomer composition. It becomes possible to contain a single layer of clay at the above ratio more efficiently.

Further, in the thermoplastic elastomer composition of the present invention, when measuring a measuring point of size of 5.63 μm ² of any three or more points on the surface of the thermoplastic elastomer composition with a transmission electron microscope, It is preferable that 1 to 100 (more preferably 3 to 80, more preferably 5 to 50) are dispersed per 1 μm ^{2 at} all measurement points. If the number of such single-layer clays is less than the lower limit, the amount of clay is too small and sufficient effects tend not to be obtained. The number of single-layer clays can be determined by confirming a TEM image in the same manner as the measurement of the abundance (ratio) of single-layer clay.

  In the thermoplastic elastomer composition of the present invention, the content of the styrene block copolymer having no chemically-bonded cross-linked site is 10 to 400 parts by mass with respect to 100 parts by mass of the elastomer component. Is preferably 15 to 350 parts by mass, more preferably 20 to 300 parts by mass, and particularly preferably 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, in the thermoplastic elastomer composition of the present invention, the content of the styrene block copolymer having no chemically bonding cross-linked site is 5 to 60% by mass with respect to the total amount of the thermoplastic elastomer composition. It is preferably 7 to 45% by mass, more preferably 10 to 30% by mass. 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 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, and 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 has, as an elastomer component, an elastomeric polymer (A) and another elastomeric polymer having a side chain (b) other than the elastomeric polymer (B) (hereinafter referred to as “elastomer” in some cases). The content ratio of the elastomeric polymer (A) and the elastomeric polymer (C) is a mass ratio ([elastomeric polymer (A)]: [elastomeric]. The polymer (C)]) is preferably 1: 9 to 9: 1, and 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.

  If necessary, the thermoplastic elastomer composition of the present invention is a polymer other than the elastomer component and the styrene block copolymer (for example, the styrene block copolymer) as long as the object of the present invention is not impaired. (Other polymers that do not contain a styrene block structure) and that do not have a chemically bonding cross-linking site), reinforcing agents (fillers), hydrogen bonding reinforcing agents (fillers), A filler obtained by introducing an amino group (hereinafter simply referred to as “amino group-introducing filler”), an amino group-containing compound other than the amino group-introducing filler, and a compound containing a metal element (hereinafter simply referred to as “metal salt”) ), Maleic anhydride-modified polymer, anti-aging agent, antioxidant, pigment (dye), plasticizer (including so-called softener), thixotropic agent, ultraviolet absorber, flame retardant, solvent, surface activity Agents (including leveling agents), dispersants, dehydrating agents, may contain rust inhibitors, adhesion promoters, antistatic agents, 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 anti-aging agent, antioxidant, pigment (dye), and plasticizer, those described below can be used as appropriate.

  As the polymer other than the elastomer component, another elastomeric polymer having a side chain (b) other than the elastomeric polymer (B) can be suitably used.

  In addition, as the polymer other than the elastomer component, a known polymer that is appropriately used from the viewpoint of adjusting the hardness and maintaining the mechanical properties can be appropriately used in the thermoplastic elastomer field, and is not particularly limited. An α-olefin-based resin that does not have a crosslinking site may be used as appropriate.

  In addition, the polymer other than the elastomer component is preferably an α-olefin-based resin having no chemically-bonded cross-linked site from the viewpoint of not interfering with the cross-linking reaction of the elastomer which becomes a base during blending. An α-olefin resin (polypropylene, ethylene-propylene copolymer, polyethylene, polybutene, etc.) having a degree of conversion of 10% or more can be suitably used.

  Moreover, as such a reinforcing agent (filler), carbon black, silica, calcium carbonate, etc. can be raised. As carbon black, wet silica is used as silica, and calcium carbonate is preferably used.

  As such an anti-aging agent, for example, a hindered phenol-based, aliphatic and aromatic hindered amine-based compound 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 the thermoplastic elastomer can be appropriately used from the viewpoint of further improving the fluidity. For example, oils (more preferably paraffin oil) are used. be able to. In addition, as such an additive etc., you may utilize suitably what is illustrated by Unexamined-Japanese-Patent No. 2006-131663.

  In addition, the thermoplastic elastomer composition of the present invention contains other components (for example, the additive and the like) other than the elastomer component, the clay, and the styrene block copolymer having no chemically bonding cross-linked site. In this case, the content of the other component is not particularly limited, but in the case of polymers and reinforcing materials (fillers), the total amount thereof is 400 mass with respect to 100 mass parts of the elastomer component. Part or less, preferably 20 to 300 parts by weight. 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.

  When the other component is the plasticizer (including a softening agent), the content is preferably 600 parts by mass or less with respect to 100 parts by mass of the elastomer component, and 10 to 600 parts by mass. More preferably, it is more preferably 50 to 550 parts by mass, particularly preferably 75 to 500 parts by mass, and most preferably 100 to 400 parts by mass. If the content of the plasticizer (including the softener) is less than the lower limit, the fluidity and workability tend to decrease. On the other hand, if the content exceeds the upper limit, the plasticizer (including the softener). Bleed tends to be induced. In addition, in the case where the above-mentioned other components are other additives (in the case other than the polymers, the reinforcing material (filler) and the plasticizer), the contents of the other components are respectively The amount is preferably 20 parts by mass or less, more preferably 0.1 to 10 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 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 or other cross-linked structures (in the styrene block copolymer). (Such as physical cross-linking) 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 and the styrene block copolymer is used, fluidity is obtained by heating. After being imparted, when left standing, the dissociated hydrogen bonds are recombined and cured, or physical crosslinks between the styrene block structure sites are formed again, depending on the composition, the thermoplastic elastomer composition, It is also possible to express recyclability more efficiently.

  Further, the thermoplastic elastomer composition of the present invention has a melt flow rate (MFR) at 230 ° C. and 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 minutes or more, more preferably 8 g / 10 minutes or more. When such a melt flow rate (MFR) is less than the lower limit, sufficient processability tends not to be exhibited. In addition, such a melt flow rate (MFR) is a value measured based on the B method described in JIS K6922-2 (2010 issue), 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 into 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 flowing out elastomer is started.). That.

  Furthermore, the thermoplastic elastomer composition of the present invention preferably has a 5% weight loss temperature of 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 obtained 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 utilizing, for example, rubber elasticity. 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 includes automotive rubber parts, hoses, belts, sheets, anti-vibration rubbers, rollers, linings, rubberized cloths, sealing materials, gloves, fenders, medical rubbers (syringe gaskets, tubes). , Catheters), gaskets (for home appliances, construction), asphalt modifiers, hot melt adhesives, boots, grips, toys, shoes, sandals, keypads, gears, PET bottle cap liners, etc. Used.

  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 weather strips, glass runs, glass run channels, etc .; air duct hoses, radiator hoses, brake hoses; Lubricating oil system parts such as ft 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.

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

  The thermoplastic elastomer composition of the present invention can have higher heat resistance depending on its composition, and has higher tensile properties based on breaking strength and breaking elongation. It is also possible to have a sufficiently high level of compression set resistance. In addition, in such a thermoplastic elastomer composition, it is possible to appropriately exhibit characteristics (for example, characteristics such as self-healing properties) required depending on the application 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 view of the characteristics required according to the application, it is preferable to appropriately change the type (composition) of the components in the composition.

  The thermoplastic elastomer composition of the present invention has been described above. In the following, the thermoplastic resin of the present invention that can be suitably used as a method for producing such a thermoplastic elastomer composition of the present invention. The manufacturing method (first manufacturing method and second manufacturing method) of the elastomer composition will be described.

[Method for producing thermoplastic elastomer composition (first production method)]
The method for producing a thermoplastic elastomer composition of the present invention (the first method for producing a thermoplastic elastomer composition of the present invention) comprises an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and chemical bonding properties. A first step of mixing a styrene block copolymer having no crosslinking site 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 second step of obtaining a thermoplastic elastomer composition by adding at least one raw material compound among the mixed raw materials of the compound (II) that forms the compound, and reacting the polymer and the raw material compound;
Including,
The thermoplastic elastomer composition obtained in the second step has a side chain (a) containing a hydrogen-bonded crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle, and has a glass transition point of 25 ° C. A group consisting of the following elastomeric polymer (A) and 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. At least one elastomer component selected from:
The clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
The styrene block copolymer;
And a composition comprising
In the first step, the cyclic acid anhydride is used by using the clay in such a proportion that the content of the clay in the thermoplastic elastomer composition is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component. Mixing the elastomeric polymer having a group in the side chain, the clay, and the styrene block copolymer;
It is the method characterized by this. Hereinafter, the first step and the second step will be described separately.

(First step)
The first step is a step of obtaining a mixture by mixing an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and a styrene block copolymer having no chemically bonding crosslinking site.

  Here, “an elastomeric polymer having a cyclic acid anhydride group in the side chain” means that the cyclic acid anhydride group has a chemically stable bond (covalent bond) at the atom forming the main chain of the polymer. Refers to an elastomeric polymer, for example, reacting a polymer capable of forming the main chain portion of the elastomeric polymers (A) to (B) with a compound capable of introducing a cyclic acid anhydride group. Can be suitably used.

  The polymer capable of forming such a main chain portion is a generally known natural polymer or synthetic polymer, and has a glass transition point of room temperature (25 ° C.) or lower. 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 the 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; Corn rubber; urethane rubber; and the like.

  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 into which the cyclic acid anhydride group can be introduced include cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and derivatives thereof.

  In addition, as the cyclic acid anhydride group of the elastomeric polymer having a cyclic acid anhydride group in the side chain used in the first step, succinic anhydride group, maleic anhydride group, glutaric anhydride group, phthalic anhydride group Among them, a maleic anhydride group is more preferable from the viewpoint of high reactivity of the raw material and industrial availability of the raw material.

  Furthermore, the elastomeric polymer having a cyclic acid anhydride group in the side chain used in the first step can form the main chain portion of the elastomeric polymer (A) to (B), for example, a commonly performed method. Such a polymer may be produced by a method in which a cyclic acid anhydride is graft-polymerized under the usual conditions, for example, stirring under heating. Moreover, you may use a commercial item as an elastomeric polymer which has a cyclic acid anhydride group used for a 1st process in a side chain.

  Examples of commercially available elastomeric polymers having 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 Nippon Oil Chemical Co., Ltd.), HRPIB (manufactured by Nippon Oil 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, 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 (manufactured by Nippon Polyolefin Co., Ltd.)), 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 Co., Ltd.)), Dumiran series (maleic anhydride modified EVOH (manufactured by Takeda Pharmaceutical Co., Ltd.)), Bondine (ethylene / acrylic acid ester / maleic anhydride terpolymer (manufactured by Atofina)), Tuftec (maleic anhydride modified SEBS, M1943) (Manufactured by 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 Co., Ltd.)), Septon (maleic anhydride-modified SEPS (manufactured by Kuraray Co., Ltd.)), Lexpearl ( Maleic anhydride modified EVA, ET-182G, 224M, 234M (manufactured by Nippon Polyolefin Co., Ltd.), maleic anhydride modified polyethylene such as Aurorene (maleic anhydride modified EVA, 200S, 250S (manufactured by Nippon Paper Chemical Co., Ltd.)); Admer (Eg, maleic anhydride-modified polypropylene such as QB550, LF128 (manufactured by Mitsui Chemicals)); and the like.

  The elastomeric polymer having a cyclic acid anhydride group in the side chain is more preferably maleic anhydride-modified ethylene-propylene rubber or maleic anhydride-modified ethylene-butene rubber from the viewpoint of high molecular weight and high strength.

  Furthermore, the clay used in the first step is the same as the clay described in the thermoplastic elastomer composition of the present invention (the preferred one is also the same). Further, the styrene block copolymer having no chemically-bonded crosslinking site used in the first step is a styrene block having no chemically-bonded crosslinking site described in the thermoplastic elastomer composition of the present invention. It is the same as the copolymer (the preferred one is also the same).

  In the first step, an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and a styrene block copolymer having no chemically-bonded crosslinking site are mixed to obtain a mixture. In the preparation process of such a mixture, the order of addition of the elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and the styrene block copolymer is not particularly limited, but the dispersion of clay is not limited. From the viewpoint of further improving the property, after preparing a precursor of a mixture containing the styrene block copolymer and an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay is added to the precursor. It is preferable.

  In addition, when adding clay to obtain the mixture, the clay should be added after plasticizing an elastomeric polymer having a cyclic acid anhydride group in the side chain in advance so that the clay is sufficiently dispersed. It is preferable to plasticize the mixture precursor and add clay to it.

  Thus, the method of plasticizing the elastomeric polymer having a cyclic acid anhydride group in the side chain and the mixture precursor is not particularly limited, and for example, a temperature (that enables plasticizing them) ( For example, a method of kneading using a roll, a kneader, an extruder, a universal stirrer, or the like can be appropriately employed. Conditions such as temperature at the time of plasticizing the elastomeric polymer having such a cyclic acid anhydride group in the side chain and the mixture precursor are not particularly limited, and the type of component (for example, cyclic acid anhydride) What is necessary is just to set suitably according to the kind etc. of the elastomeric polymer which has a physical group in a side chain.

  Moreover, in the preparation process of such a mixture, content of the clay in the thermoplastic elastomer composition finally obtained is 20 parts by mass or less (more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the elastomer component). 10 parts by mass, more preferably 0.5 to 5 parts by mass, particularly preferably 1 to 3 parts by mass) using the clay in an amount of the elastomeric polymer having the cyclic acid anhydride group in the side chain. It is preferable to mix the clay and the styrene block copolymer having no chemically-bonded crosslinking site. When the content of such clay exceeds the upper limit, crosslinking is too strong, and the elongation and strength tend to decrease.On the other hand, when the content is lower than the lower limit, the amount of clay is too small, and the clay is used. There exists a tendency for the obtained effect to fall.

  Moreover, as content of the clay in such a mixture, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of elastomeric polymers which have a cyclic acid anhydride group in a side chain, 0.5-5 masses Is more preferably 1 to 3 parts by mass. If the content is less than the lower limit, the amount of clay is too small, and the effect obtained by using clay tends to be reduced.On the other hand, if the upper limit is exceeded, crosslinking is too strong, On the other hand, the elongation and strength tend to decrease. In addition, by using clay with such content, content of the clay in the thermoplastic elastomer composition finally obtained becomes a value within the said range.

  Furthermore, as the amount of clay used in forming such a mixture, the clay is 0.01 g to 1 mmol of the cyclic acid anhydride group in the elastomeric polymer having the cyclic acid anhydride group in the side chain. The content is preferably 2.0 g (more preferably 0.02 to 1.0 g). If the ratio of the clay to the acid anhydride group is less than the lower limit, the effect tends to be too low, whereas if the upper limit is exceeded, the crosslinking is too strong, and the elongation and strength tend to decrease. It is in. In addition, by including clay within the range of such a ratio, the clay contained in the mixture can be efficiently decomposed, and a single-layer clay can be efficiently produced, and the dispersibility of the clay is further improved. It tends to be advanced.

  In the preparation process of such a mixture, the content of the styrene block copolymer (the styrene block copolymer having no chemically-bonded cross-linking site) in the finally obtained thermoplastic elastomer composition Is styrene at a ratio such that it is 400 parts by weight or less (more preferably 15 to 350 parts by weight, more preferably 20 to 300 parts by weight, particularly preferably 30 to 250 parts by weight) with respect to 100 parts by weight of the elastomer component. It is preferable to mix the elastomeric polymer having the cyclic acid anhydride group in the side chain, the clay, and the styrene block copolymer using a block copolymer. If the content of such a styrene block copolymer exceeds the upper limit, the characteristics of the matrix structure due to the crosslinked elastomer (characteristics derived from the elastomer component) tend to be dilute. There is a tendency that sufficient effects cannot be obtained in terms of workability and workability.

  Further, the content of the styrene block copolymer in such a mixture is 400 parts by mass or less (more preferably 10 to 400 parts per 100 parts by mass of the elastomeric polymer having a cyclic acid anhydride group in the side chain. Mass parts, more preferably 15 to 350 parts by mass, particularly preferably 20 to 300 parts by mass, and most preferably 30 to 250 parts by mass). If the content is less than the lower limit, sufficient effects in terms of fluidity and workability tend not to be obtained. On the other hand, if the content is lower than the lower limit, the characteristics of the matrix structure of the crosslinked elastomer (the elastomer component Tend to be diluted.

  Moreover, the mixing method for obtaining such a mixture is not particularly limited, and a known method or the like can be appropriately employed. For example, a method of mixing with a roll, a kneader, an extruder, a universal stirrer, or the like is employed. be able to.

  In such a mixture, a polymer other than the elastomer component, a reinforcing agent (filler), and a filler obtained by introducing an amino group (hereinafter simply referred to as “amino group” within the range not impairing the object of the present invention. Introducing fillers ”), amino group-containing compounds other than the amino group-introducing fillers, compounds containing metal elements (hereinafter simply referred to as“ metal salts ”), maleic anhydride-modified polymers, anti-aging agents, antioxidants Agents, pigments (dyes), plasticizers, thixotropic agents, UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, rust inhibitors, adhesion promoters, antistatic agents Other components such as various additives such as an agent and a filler can be contained. Such additives and the like are not particularly limited, and those commonly used can be appropriately used.

  When the other component is a polymer or a reinforcing material (filler), 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. More preferably, it is 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.

  When the other component is the plasticizer (including a softener), the content is preferably 600 parts by mass or less, and 10 to 600 parts by mass with respect to 100 parts by mass of the elastomer component. It is more preferable that it is 50-550 mass parts, it is still more preferable that it is 75-500 mass parts, and it is most preferable that it is 100-400 mass parts. Further, when the other component is other additive (in the case other than the polymers, the reinforcing material (filler) and the plasticizer), the content of the other component is 100 parts by mass of the elastomer component. Is preferably 20 parts by mass or less, and 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. In the step of obtaining a thermoplastic elastomer composition by adding at least one raw material compound of the mixed raw materials of the compound (II) that forms a covalent cross-linking site and reacting the polymer and the raw material compound. is there.

  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, 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 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 that generates a covalent bond” ”can be preferably used (the same is true for 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. Further, as the compound (I) and / or (II), it is possible to more efficiently introduce both a hydrogen-bonding crosslinking site and a covalent-bonding crosslinking site into the composition. A compound that reacts with an anhydride group to form both a hydrogen bonding crosslinking site and a covalent crosslinking site (compound capable of simultaneously introducing both a hydrogen bonding crosslinking site and a covalent crosslinking site) It is preferable to use it. 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.

  Further, the amount of compound (I) and compound (II) added (the total amount thereof: when only one compound is used, the amount of one compound is not particularly limited) is not particularly limited. When active hydrogen such as amine and alcohol is contained in the amount, the amount of active hydrogen such as amine and alcohol in the compound is 20 to 250 mol% with respect to 100 mol% of the cyclic acid anhydride group. The amount is preferably 50 to 150 mol%, more preferably 80 to 120 mol%. 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.

  Further, the amount of compound (I) and compound (II) added is such that the total amount thereof (when only one compound is used, is the amount of one compound), the polymer ( The elastomeric polymer having a cyclic acid anhydride group in the side chain) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, relative to 100 parts by mass, 0.5 More preferably, it is -5.0 mass parts. 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 will be too many, and there exists a tendency for a branch to increase and a crosslinking density to fall.

  In the case of using both compound (I) and compound (II), the order of adding compound (I) and compound (II) is not particularly limited, and either may be added first. In the case where both compound (I) and compound (II) are used, compound (I) is reacted with a part of the cyclic acid anhydride group of the elastomeric polymer having a cyclic acid anhydride group in the side chain. You may let them. Thereby, it is also possible to react the compound (II) with an unreacted cyclic acid anhydride group (a cyclic acid anhydride 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 cyclic acid anhydride group. Within this range, in the resulting 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. In addition, it is preferable to make compound (II) react with the said cyclic acid anhydride group so that the bridge | crosslinking by a covalent bond may become a suitable number (for example, 1-3 in 1 molecule).

  When the polymer and the raw material compound (compound (I) and / or compound (II)) are reacted, the cyclic acid anhydride group of the polymer is opened, and the cyclic acid anhydride group and the raw material compound ( The compound (I) and / or compound (II)) is chemically bonded. There are no particular restrictions on the temperature conditions for reacting such a polymer with the raw material compound (the compound (I) and / or compound (II)) (opening the cyclic acid anhydride group), and the compound and Depending on the kind of the cyclic acid anhydride group, it may be adjusted to a temperature at which they can react, but from the viewpoint of softening and allowing the reaction to proceed instantaneously, it is preferably 100 to 250 ° C., 120 to 230 More preferably, the temperature is set to ° 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. 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 can contain the 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. It becomes possible to set it as the thing containing a part (a side chain (b) or a side chain (c)). And the side chain formed by such reaction can also contain the structure represented by the said Formula (7)-(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.

By reacting in this manner, an elastomeric polymer having a side chain (a) containing a hydrogen-bonding cross-linking 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;
Clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
The styrene block copolymer;
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 addition, according to this invention, it becomes possible to manufacture efficiently the thermoplastic elastomer composition which can make heat resistance and breaking strength more advanced. The reason why such an effect is achieved by the present invention is not necessarily clear, but the present inventors infer as follows. That is, first, in the present invention, the thermoplastic elastomer composition modifies the elastomeric polymer having the cyclic acid anhydride group in the side chain (hereinafter sometimes referred to as “an acid anhydride-containing polymer”). Manufactured. In this way, by mixing the clay and the acid anhydride polymer and dispersing the clay in the acid anhydride polymer in advance, the acid anhydride group and the clay interact with each other, and the clay layer is easily peeled off. Become. In particular, when the clay is an organic clay that is preferably used in the present invention (organic clay), an organic substance such as an ammonium salt present between the layers interacts more efficiently with the acid anhydride. The layer tends to peel easily. Then, after the clay is dispersed, the raw material compound (functions as a cross-linking agent for forming a cross-link. Hereinafter, sometimes referred to as “cross-linking agent”) is reacted with the cross-linking agent and the acid anhydride group. Thus, at least hydrogen bonding cross-linking sites (for example, carboxylic acid groups) are generated in the system. Therefore, interaction by hydrogen bonding is caused between the clay and the clay is further dispersed in the elastomer. Therefore, in the thermoplastic elastomer composition obtained by the present invention, the clay is sufficiently dispersed, and the clay and the hydrogen bonding cross-linking site interact to form a uniform surface cross-linking site. Therefore, the present inventors speculate that sufficient heat resistance can be obtained. In the present invention, the resulting thermoplastic elastomer composition contains the styrene block copolymer together with the clay and the elastomer component. Since such a styrene block copolymer does not interfere with the crosslinking reaction of the elastomer component serving as a matrix, it can exhibit excellent mechanical properties without hindering the inherent properties of the elastomer structure serving as a crosslinked matrix. The present inventors speculate. For this reason, the inventors speculate that the thermoplastic elastomer composition of the present invention can achieve higher heat resistance and higher breaking strength.

In this way, the thermoplastic elastomer composition obtained by the present invention can contain a single layer of clay in the composition. Moreover, in the thermoplastic elastomer composition obtained in this way, a measurement point having a size of 5.63 μm ² above any three points on the surface of the thermoplastic elastomer composition is measured with a transmission electron microscope (TEM). In all measurement points, 50% or more (more preferably 70% or more, more preferably 80 to 100%, particularly preferably 85 to 100%) of the total clay is simply used at all measurement points based on the number. It can also be present as a layer of clay. When the abundance of such a single layer of clay is less than the lower limit, the elongation at break and the strength at break tend to decrease.

  In addition, in the manufacturing method (first manufacturing method) of the thermoplastic elastomer composition of the present invention, the proportion of clay in a single layer form (single layer clay) in the thermoplastic elastomer composition is more efficiently determined. It is possible to set it as the said suitable ratio. In this regard, in the first step described above, the clay interacts with the cyclic acid anhydride group, making it possible to more efficiently peel off the layers of the multilayered clay, and the clay is in a single layer state. It is possible to disperse (finely disperse) at a higher rate, so that a higher proportion of single-layered clay (single-layer clay) is present in the composition, and the above-mentioned preferred proportion of single-layered clay The present inventors infer that the clay can be contained. Note that the presence of such a single-layered clay can be confirmed by measuring the surface of the obtained composition with a transmission electron microscope (TEM).

  Further, according to the present invention, for example, after separately producing 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, respectively. These may be mixed to produce a thermoplastic elastomer composition containing the 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.

  The thermoplastic elastomer composition thus obtained can be suitably used, for example, for various rubber applications by utilizing its rubber elasticity, for example, a hot melt adhesive or an additive contained therein, an automobile, Rubber parts, hoses, belts, sheets, anti-vibration rubber, rollers, linings, rubberized cloth, sealing materials, gloves, fenders, medical rubber (syringe gaskets, tubes, catheters), gaskets (for home appliances, construction) ), Asphalt modifiers, hot melt adhesives, boots, grips, toys, shoes, sandals, keypads, gears, PET bottle cap liners, and the like.

[Method for producing thermoplastic elastomer composition (second production method)]
The method for producing the thermoplastic elastomer composition of the present invention (the method for producing the second thermoplastic elastomer composition of the present invention) includes:
An elastomeric polymer having a cyclic acid anhydride group in the side chain;
With clay,
A styrene block copolymer having no chemically-bonded crosslinking site;
Compound (I) which reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site, and compound which reacts with the compound (I) and the cyclic acid anhydride group to form a covalent-bonding cross-linking site At least one raw material compound of the mixed raw materials of (II);
And a process of obtaining a thermoplastic elastomer composition by reacting the elastomeric polymer having the cyclic acid anhydride group in the side chain with the raw material compound,
The thermoplastic elastomer composition has an elastomeric polymer (a) having a side chain (a) 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 ( A) and at least one selected from the group consisting of 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 An elastomer component of
The clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
The styrene block copolymer;
And a composition comprising
Using the clay in such a proportion that the content of the clay in the thermoplastic elastomer composition is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
It is the method characterized by this.

  An elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and a chemically bonding cross-linked site used in the second thermoplastic elastomer composition production method (second production method) of the present invention. The styrene block copolymer and raw material compound which are not present are the same as those described in the above-mentioned first production method (the production method of the first thermoplastic elastomer composition of the present invention). (Preferable conditions (conditions such as the type of each component and the amount used) are the same). Further, the thermoplastic elastomer composition obtained by the second thermoplastic elastomer composition production method (second production method) of the present invention is also the above-mentioned first production method (first thermoplastic elastomer of the present invention). (The manufacturing method of the composition) can be the same as that described in the method (the preferred one can also be the same).

  Further, in such a second method for producing a thermoplastic elastomer composition of the present invention (second production method), an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and chemically bonded cross-linking What is necessary is just to mix the styrene block copolymer which does not have a site | part, and a raw material compound, and the order in which these are added is not restrict | limited in particular, For example, reaction containers (For example, the heating cylinder (heating cylinder) of an extruder, etc.) These components may be added simultaneously (for example, by adding a mixture of components prepared in advance with a blender, etc.) and mixed, or each component may be added to the reaction vessel in sequence. And may be mixed. Moreover, when adding each component to a reaction container in order and mixing, the manufacturing method of the thermoplastic elastomer composition of this invention containing the said 1st process and said 2nd process (1st manufacturing method: It is preferable to employ the first method for producing a thermoplastic elastomer composition of the present invention and mix the respective components sequentially. Thus, as the method for producing the second thermoplastic elastomer composition of the present invention, the above-mentioned method for producing the first thermoplastic elastomer composition of the present invention (first production method) can be suitably employed. it can.

  Further, the elastomeric polymer having the cyclic acid anhydride group in the side chain, the clay, the styrene block copolymer having no chemically-bonded cross-linking site, and the raw material compound are mixed, A method for reacting the polymer and the raw material compound is not particularly limited, and a known method can be appropriately employed. For example, a mixture of these components is continuously mixed using an extruder (continuous kneading). ) Method can also be suitably employed. As such an extruder, from the viewpoint of adjusting the kneading time, a multi-screw extruder is preferably used, and a twin-screw extruder is particularly preferably used.

  In addition, when adopting a method of continuously mixing (continuous kneading) using the extruder when the elastomeric polymer and the raw material compound are reacted, the temperature condition is set from the viewpoint of allowing the reaction to proceed efficiently. The temperature at which the polymer and the raw material compound (the compound (I) and / or the compound (II)) can react (preferably 100 to 250 ° C., more preferably 120, described in the first production method above). ˜230 ° C.). Moreover, as temperature conditions in the case of adopting the method of continuous mixing (continuous kneading) in this way, 140 to 249 ° C is more preferable, and 160 to 220 ° C is still more preferable. If such a temperature condition is less than the lower limit, the fluidity tends to decrease. On the other hand, if it exceeds the upper limit, thermal degradation of the polymer component occurs and the breaking strength tends to decrease.

  In addition, when adopting a method of continuous mixing (continuous kneading) using the extruder when reacting the elastomeric polymer and the raw material compound, the characteristics (shape, etc.) of the screw to be used are not particularly limited, The design can be changed as appropriate. Moreover, as such a screw, what satisfy | fills the conditions that L / D is 30 or more is more preferable in the relationship between the length (L) of a screw, and the diameter (D) of a screw. When satisfying such a relationship, the fluidity is improved and the breaking strength tends to be improved.

Moreover, when employ | adopting the method of mixing continuously (continuous kneading | mixing) using the said extruder when making the said elastomeric polymer and the said raw material compound react, a maximum shear rate is 1-1599sec < ^-1 > ( ¹ ). more preferably 50~900sec ^-1, more preferably it is preferred to adjust the rotational speed of the screw so that 100~600sec ^-1). When the maximum shear rate is less than the lower limit, the fluidity tends to decrease, and when it exceeds the upper limit, the breaking strength tends to decrease.

In addition, when continuous mixing (continuous kneading) is performed using the extruder, each component (an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and a chemically bonding cross-linked site is included in the extruder. A plurality of supply ports corresponding to the styrene block copolymer and the raw material compound) are provided, and each component is sequentially added to the extruder, so that the order of addition of the components to be used is appropriately changed. Also good. Thus, the method for producing the thermoplastic elastomer composition of the present invention containing the first step and the second step while using the extruder (the first production method: the first thermoplastic elastomer composition of the present invention) In the second production method, in the thermoplastic elastomer composition finally obtained, it is possible to more efficiently carry out the step of sequentially mixing the components. The clay content is 20 parts by mass or less (more preferably 0.1 to 10 parts by mass, still more preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass with respect to 100 parts by mass of the elastomer component. ) Using the above-mentioned clay in such a proportion that the elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, a styrene block copolymer having no chemically-bonded crosslinking site, and And the raw material compounds are mixed. If the content of such clay exceeds the above upper limit, the crosslinking is too strong, and on the contrary, the elongation and strength are reduced. On the other hand, if it is less than the lower limit, the amount of clay is too small and the effect obtained by using clay. Will fall.

  In the second production method, a polymer other than the elastomer component, a reinforcing agent (filler), and a filler obtained by introducing an amino group (hereinafter simply referred to as “ An amino group-introduced filler ”), an amino group-containing compound other than the amino group-introduced filler, a compound containing a metal element (hereinafter simply referred to as“ metal salt ”), a maleic anhydride-modified polymer, an anti-aging agent, Antioxidants, pigments (dyes), plasticizers, thixotropic agents, UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, rust inhibitors, adhesion promoters, A step of further adding other components such as various additives such as an antistatic agent and a filler may be included. Such additives and the like are not particularly limited, and those commonly used can be appropriately used. Moreover, conditions, such as content of such another component, are the same as the conditions demonstrated in the above-mentioned 1st manufacturing method (The suitable range is also the same).

Thus, by mixing the elastomeric polymer, the clay, the styrene block copolymer, and the raw material compound, by reacting the elastomeric polymer and the raw material compound, carbonyl-containing An elastomeric polymer (A) having a side chain (a) containing a hydrogen-bonding cross-linked moiety having a 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), which contains a crosslinkable moiety and a covalently crosslinked moiety and has a glass transition point of 25 ° C. or lower;
Clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
The styrene block copolymer;
Can be obtained (can be the same as the composition obtained by the first production method). 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.

[Laminate]
The laminate of the present invention comprises a metal layer,
An elastomer layer comprising the thermoplastic elastomer composition of the present invention;
It is characterized by providing.

  As the metal forming the metal layer in such a laminate, various metals can be appropriately used and are not particularly limited, but from the viewpoint of being chemically stable and readily available, iron, steel plate, Selected from the group consisting of copper, aluminum, stainless steel, brass, galvanized steel, titanium, zirconium, cobalt, tin, palladium, manganese, indium, iridium, chromium, nickel, gold, silver, platinum, zinc and their oxides At least one of these can be suitably used. Among these metals, at least one selected from the group consisting of iron, steel plate, copper, aluminum, stainless steel, brass, galvanized steel, titanium, zirconium and oxides thereof from the viewpoint of safety and availability. More preferably, at least one selected from the group consisting of iron, steel plate, copper, aluminum, stainless steel, brass, galvanized steel and oxides thereof, iron, steel plate, copper, aluminum, stainless steel and the like Particularly preferred is at least one selected from the group consisting of these oxides.

  Furthermore, the form (shape, etc.) of the metal layer in such a laminated body is not particularly limited, and may be appropriately designed according to the use of the laminated body. For example, a plate-like body (a substrate made of metal) may be used. Other shapes (for example, a spherical shape, a block shape, a column shape, a disk shape, etc.) may be used. For example, when the metal layer is made of a substrate made of metal (plate-like body), the elastomer layer may be laminated on at least one surface of the substrate to form a laminate. In the case where the metal layer is spherical, a core-shell type laminate may be formed by arranging a sphere made of metal in the core portion and forming an elastomer layer on the outside thereof. Further, such a metal layer may be a layer formed on the surface of another substrate (such as a substrate made of resin).

  Moreover, when the metal layer in such a laminated body is a sheet-like or plate-like form, the thickness of the metal layer is not particularly limited, but is preferably 0.1 to 500 mm. It is more preferable that it is 5-300 mm, and it is still more preferable that it is 1.0-100 mm. If the thickness of such a metal layer is less than the lower limit, it tends to be too thin to hold the shape, whereas if it exceeds the upper limit, it tends to be too thick to function as a laminate.

  Moreover, the elastomer layer concerning this invention is a layer which consists of a thermoplastic elastomer composition of the said invention. Such an elastomer layer should just consist of the thermoplastic-elastomer composition of the said invention, The form in particular is not restrict | limited, What is necessary is just to design suitably according to the use. Such an elastomer layer may be laminated on the metal layer in the form of a sheet or a plate, for example, or may have a structure in which a part of the surface is laminated on a metal as various shapes (for example, an automobile It is preferable to use a shape suitable for the application, such as a shape suitable for engine mounts and bushing members).

  When the elastomer layer is in the form of a sheet or plate, the thickness of the elastomer layer is preferably 0.1 to 500 mm, more preferably 0.5 to 300 mm, 1.0 More preferably, it is -100 mm. If the thickness is less than the lower limit, it tends to be too thin to exhibit rubber properties, while if it exceeds the upper limit, it tends to be too thick to function as a laminate.

  In the present invention, it is preferable that an adhesive layer is further provided between the metal layer and the elastomer layer. That is, the laminate of the present invention preferably has a structure in which the metal layer and the elastomer layer are laminated (adhered) via an adhesive layer.

  The adhesive that forms such an adhesive layer is not particularly limited, and a known adhesive capable of adhering a metal and an elastomer can be appropriately used. As such an adhesive, a commercially available product may be used as appropriate. For example, a trade name “THIXON, MEGUM” manufactured by Rohm & Haas (Dowchemical); a trade name “METALOC” manufactured by Toyo Chemical Research Co., Ltd. Trade names "CHEMLOK", "IBM1000", "487A & B" manufactured by Road Corporation; trade names "CIL BOND" manufactured by Chemical Innovation Co., etc. can be used as appropriate. Among these adhesives, an adhesive for thermoplastic elastomers (for example, trade names “CHEMLOK”, “IBM1000”, etc., manufactured by Road Corporation), etc.) is preferable from the viewpoint of high affinity with the present elastomer. Among them, a thermoplastic adhesive can be particularly preferably used.

  The thickness of the adhesive layer is not particularly limited, but is preferably 0.001 to 10,000 μm, and more preferably 0.01 to 1000 μm. If the thickness of such an adhesive layer is less than the lower limit, the adhesive force tends to be insufficient, whereas if the upper limit is exceeded, the adhesive layer tends to be too thick to be easily broken by force. is there.

In addition, the structure of the laminate of the present invention is not particularly limited, and may further include other layers. As such another layer, for example, a layer made of an organic material (for example, resin) or a layer made of an inorganic material may be used. Further, the laminated structure of such a laminated body (hereinafter, “/” indicates that it is laminated in some cases) is not particularly limited.
Metal layer / elastomer layer (for example, a laminate in which a metal is vapor deposited on an elastomer)
Metal layer / Adhesive layer / Elastomer layer Metal layer / Adhesive layer / Elastomer layer / Adhesive layer / Metal layer Elastomer layer / Adhesive layer / Metal layer / Adhesive layer / Elastomer layer Metal layer / Adhesive layer / Elastomer layer / Resin layer other than elastomer A laminated structure such as a resin layer other than an elastomer / metal layer / adhesive layer / elastomer layer can be exemplified. In addition, the laminated structure here may be a structure in which, for example, an elastomer (string-like elastomer) is laminated so that only an outer edge portion of a metal plate is covered, or The structure may be such that a part of the massive elastomer (elastomer layer) is laminated on a part of the massive metal (metal layer), and the state is not particularly limited. Thus, in the laminated body of the present invention, the shape of each layer, the size of the laminated portion (size of the overlapping portion of each layer, etc.) and the like are not particularly limited.

  The method for producing such a laminate is not particularly limited, and a known method that can be used when a laminate is obtained by laminating a resin layer and a metal layer can be appropriately applied. A method of obtaining a laminate by adhering the thermoplastic elastomer composition of the present invention on a plate through an adhesive layer may be appropriately employed.

  Moreover, when laminating | stacking the said adhesive layer, the method in particular of forming this adhesive layer is not restrict | limited, For example, you may employ | adopt the method of apply | coating an adhesive agent on the surface of a metal layer or an elastomer layer. The method of application is not particularly limited, and a known method (for example, a method using a brush, a method using screen printing, a method using various coaters, or the like) can be appropriately used. Further, in the case of applying the adhesive in this way, depending on the type of adhesive, etc., from the viewpoint of more efficiently laminating an adhesive layer with a uniform thickness, the step of drying after applying the adhesive It is preferable to laminate the adhesive layer by applying. Such a drying step is preferably a step of drying for 0.1 to 168 hours at a temperature of 20 to 250 ° C. If such temperature condition or time is less than the lower limit, drying tends to be insufficient and adhesive force does not sufficiently develop.On the other hand, if the upper limit is exceeded, adhesive tends to deteriorate and adhesive force does not sufficiently develop. is there.

  Since such a laminate has a sufficiently high adhesion between the elastomer layer and the metal layer, for example, engine mounts, bushes (for example, suspension bushes), dampers (for example, dynamic dampers) , Hoses and tubes (for example, suction hoses, flexible duct hoses), boots (for example, dust boots), gaskets (for example, engine gaskets), belts, covers, and other parts (rubber buffers, rubber bumpers) Automotive parts such as shock absorbers, rubber wheels, gas caps, rubber stands, cab insulators / drive sprockets, step pedals, exhaust mounts, etc. (particularly metal parts and elastomer parts are laminated (partially bonded etc.)) Has a structure like Can be suitably used for such members).

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

First, the evaluation method of the characteristic of the thermoplastic elastomer composition obtained by each Example and each comparative example is demonstrated.
<Melt flow rate (MFR)>
Using the thermoplastic elastomer compositions obtained in each Example and each Comparative Example, the melt flow rate (MFR, unit: g / 10) in accordance with the method B described in JIS K6922-2 (issued in 2010) Minute). That is, using the thermoplastic elastomer compositions obtained in each Example and each Comparative Example, using the product name “Melt Indexer G-01” manufactured by Toyo Seiki Seisakusho as the melt flow rate measuring device, the furnace of the device After adding 3 g of the thermoplastic elastomer composition in the body, maintaining the temperature at 230 ° C. for 5 minutes, maintaining the temperature at 230 ° C. and loading 10 kg, the diameter 1 mm connected to the lower part of the furnace body Measure the mass (g) of the elastomer flowing out in 10 minutes from the opening of the cylindrical orifice member having a length of 8 mm (opening having a diameter of 1 mm) (with the temperature in the furnace set at 230 ° C. for 5 minutes) The load was started after being held, and then the measurement of the mass of the flowing out elastomer was started.).

<Compression set (C-Set)>
Using the thermoplastic elastomer compositions obtained in each Example and each Comparative Example, first, the thermoplastic elastomer composition was hot-pressed at 200 ° C. for 10 minutes to prepare a sheet having a thickness of about 2 mm. . The sheets thus obtained were punched into a disk shape having a diameter of 29 mm, and seven sheets were stacked, so that samples were prepared so that the height (thickness) was 12.5 ± 0.5 mm. Using the sample obtained in this manner, compression set (unit:%) after 25% compression with a dedicated jig and left at 70 ° C. for 22 hours was measured according to JIS K6262 (issued in 2013). did. In addition, the brand name "vulcanized rubber compression set tester SCM-1008L" made from a dumbbell company was used as a compression apparatus.

<5% weight loss temperature>
Using the thermoplastic elastomer compositions obtained in each Example and each Comparative Example, using a thermogravimetric measuring device (TGA) as a measuring device, measuring at a temperature rising rate of 10 ° C./min, 5% from the initial weight The temperature at which the weight decreased (unit: ° C.) was measured. In addition, about 10 mg was used for the measurement sample.

<Tensile properties>
Using the thermoplastic elastomer compositions obtained in each Example and each Comparative Example, first, the thermoplastic elastomer composition was hot-pressed at 200 ° C. for 10 minutes to prepare a sheet having a thickness of 2 mm. A No. 3 dumbbell-shaped test piece was punched from the sheet thus obtained, and a tensile test at a tensile speed of 500 mm / min was conducted in accordance with JIS K6251 (issued in 2010), and the breaking strength (T _B ) [units] : MPa] and elongation at break (E _B ) [unit:%] were measured at room temperature (25 ° C.).

<JIS-A hardness>
Using the thermoplastic elastomer compositions obtained in each Example and each Comparative Example, first, the thermoplastic elastomer composition was hot-pressed at 200 ° C. for 10 minutes to prepare a sheet having a thickness of about 2 mm. . Next, the sheet thus obtained was punched into a disk shape having a diameter of 29 mm, and seven sheets were overlapped to prepare a sample so that the height (thickness) was 12.5 ± 0.5 mm. Using the sample thus obtained, JIS-A hardness was measured according to JIS K6253 (issued in 2012).

Example 1
First, 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% by mass) 50 g Was added to a pressure kneader and 100 g of paraffin oil (trade name “Super Oil M Series P500S” manufactured by JX Nippon Oil & Energy Corporation) was dropped into the pressure kneader while kneading at 200 ° C. -Ethylene-butylene-styrene block copolymer and paraffin oil were mixed for 1 minute. Next, in the pressure kneader, maleic anhydride-modified ethylene-butene copolymer (maleinized EBM: trade name “Tuffmer MH5040” manufactured by Mitsui Chemicals, crystallinity: 4%) 100 g, ethylene-propylene copolymer The mixture (EPM: Mitsui Chemicals, trade name “Tafmer DF7350”, crystallinity: 10%) 75 g and anti-aging agent (trade name “AO-50”, manufactured by Adeka Co., Ltd.) 0.3 g were further added to the temperature. The mixture was masticated at 200 ° C. for 2 minutes to obtain a first mixture (a mixture containing SEBS and maleated EBM). In addition, the said 1st mixture was plasticized by this mastication process. Next, 1 g of organoclay (trade name “Kunifil D-36” manufactured by Kunimine Kogyo Co., Ltd.) is further added to the first mixture in the pressure kneader and kneaded at 200 ° C. for 4 minutes. A second mixture was obtained.

  Next, 2.62 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 200 ° C. for 8 minutes. A composition was prepared. Table 1 shows the evaluation results and the like of the properties of the obtained thermoplastic elastomer composition.

  In such a composition, the maleic anhydride group in the maleic anhydride-modified ethylene-butene copolymer reacts 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) was formed (note that the side chain (i) to (iii) are stoichiometrically determined from the raw materials used). If considered, the 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 the reaction based on the raw materials used. In some cases, the type of side chain that is considered to be mainly 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 ethylene and butene.

[In the formulas (26) to (28), the 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). . ]
(Examples 2 to 5)
A thermoplastic elastomer composition was obtained in the same manner as in Example 1 except that the type of styrene block copolymer was changed and each styrene block copolymer described below was used in each example. As is clear from the description of such a production method, the thermoplastic elastomer compositions obtained in Examples 1 to 5 have the same composition except for the type of styrene block copolymer. . Table 1 shows the evaluation results of the properties of the thermoplastic elastomer composition obtained in each Example.
<Styrene block copolymer used in Example 2>
SEBS: trade name “G1641” manufactured by Clayton Co., Ltd., molecular weight: 250,000-350,000, styrene content: 33% by mass
<Styrene block copolymer used in Example 3>
SEBS: trade name “G1651” manufactured by Clayton Co., Ltd., molecular weight: 250,000-350,000, styrene content: 33% by mass
<Styrene block copolymer used in Example 4>
SEEPS: Kuraray's trade name “4077”, molecular weight: 400,000 to 500,000, styrene content: 30% by mass
<Styrene block copolymer used in Example 5>
SEEPS: Product name “4099” manufactured by Kuraray Co., Ltd., molecular weight: 500,000 to 600,000, styrene content: 30% by mass.

(Comparative Example 1)
First, 50 g of 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% by mass) is charged into a pressure kneader. While being kneaded at 200 ° C., 100 g of paraffin oil (trade name “Super Oil M Series P500S” manufactured by JX Nippon Mining & Energy Corporation) was dropped into the pressure kneader, and the styrene-ethylene-butylene-styrene block was added. The copolymer and paraffin oil were mixed for 1 minute. Next, in the pressure kneader, 100 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM: trade name “Tuffmer MH5040” manufactured by Mitsui Chemicals), ethylene-propylene copolymer (EPM: Mitsui Chemicals) The product name “Tafmer DF7350”, crystallinity 10%) 75 g and anti-aging agent (Adeka product name “AO-50”) 0.3 g were further added, and the mixture was kneaded at 200 ° C. for 2 minutes. Thus, a mixture (a mixture containing SEBS and maleated EBM) was obtained. In addition, the said mixture was plasticized by this mastication process. Next, 2.62 g of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.) was added to the mixture and mixed at 200 ° C. for 8 minutes to prepare a thermoplastic elastomer composition. Table 1 shows the evaluation results and the like of the properties of the obtained thermoplastic elastomer composition.

[Evaluation of properties of thermoplastic elastomer compositions obtained in Examples 1 to 5 and Comparative Example 1]
As is clear from the description in Table 1, the thermoplastic elastomer compositions (Examples 1 to 5) of the present invention are based on a 5% weight loss temperature as compared with the thermoplastic elastomer composition obtained in Comparative Example 1. It was found that the heat resistance was higher. Furthermore, it was confirmed that the thermoplastic elastomer composition (Examples 1 to 5) of the present invention has a higher breaking strength than the thermoplastic elastomer composition obtained in Comparative Example 1. From such a result, when it contains an organized clay and a styrene block copolymer in a thermoplastic elastomer composition (Example 1), compared with the case where an organized clay is not used (Comparative Example 1), It has been found that higher heat resistance and breaking strength can be obtained.

  From the above results, in a thermoplastic elastomer composition containing an elastomeric polymer mainly having a side chain (iii), a composition obtained by using a combination of a styrene block copolymer and an organized clay. It was found that can have higher heat resistance, and the breaking strength of the composition can be higher. The thermoplastic elastomer compositions (Examples 1 to 5) of the present invention are confirmed to have fluidity upon heating from the MFR value and have processability, and have a value of elongation at break and JIS hardness. value. From the value of compression set, it was also found that the rubber product has sufficient elongation characteristics (tensile characteristics) and hardness, as well as resistance to compression set. Thus, it was also found that the thermoplastic elastomer compositions (Examples 1 to 5) of the present invention have sufficient heat processability and have characteristics that can be sufficiently used as rubber products.

(Example 6)
14.6 kg of a styrene-ethylene-butylene-styrene block copolymer (trade name “G1633” manufactured by Kraton Co., Ltd.) was placed in a blender (mixer). Next, 29.2 kg of paraffin oil (trade name “Super Oil M Series P500S” manufactured by JX Energy Co., Ltd.) was added dropwise to the blender (mixer), and then, maleic anhydride-modified ethylene-butene copolymer was further added. 7.3 kg of polymer (trade name “Tuffmer MH5040” manufactured by Mitsui Chemicals, Inc.), polyethylene (PE: product name “HJ590N” manufactured by Nippon Polyethylene, crystallinity: 74%, MFR: 40 g / 10 minutes (2. 16 kg, 190 ° C.), Mw: 70000) 3.6 kg, anti-aging agent (trade name “AO-50” manufactured by ADEKA), 0.055 kg, organic clay (trade name “Kunifil D-36” manufactured by Kunimine Industries, Ltd.) ) 7.3 g and 0.19 kg of trishydroxyethyl isocyanurate (trade name “Tanac” manufactured by Nissei Sangyo Co., Ltd.) The mixture was stirred at room temperature (25 ° C.) for 10 minutes to obtain a mixture of raw materials.

Next, the obtained mixture of raw materials is put into a biaxial extruder (biaxial kneading extruder) and continuously kneaded (continuous kneading) for 35 seconds at a temperature of 190 ° C. and a shear rate of 400 sec ^−1. Thus, the maleic acid-modified ethylene-butene copolymer and trishydroxyethyl isocyanurate were reacted to obtain a thermoplastic elastomer. Table 2 shows the measurement results of the 5% weight loss temperature, breaking strength, and MFR of the thermoplastic elastomer composition thus obtained.

(Example 7)
A thermoplastic elastomer was obtained in the same manner as in Example 6 except that the time for continuous kneading (continuous kneading) in a biaxial kneading extruder was changed from 35 seconds to 108 seconds. Table 2 shows the measurement results of the 5% weight loss temperature, breaking strength, and MFR of the thermoplastic elastomer composition thus obtained.

  As is clear from the results shown in Table 2, the thermoplastic elastomer compositions (Examples 6 to 7) of the present invention have sufficiently high heat resistance based on the 5% weight loss temperature. I understood that. Furthermore, it was confirmed that the thermoplastic elastomer composition (Examples 6 to 7) of the present invention has a sufficiently high breaking strength. In addition, from the results of Examples 6 to 7, it was also found that when the kneading time is longer, higher fluidity can be obtained based on MFR.

(Example 8)
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%) 9 .75 g was charged into a pressure kneader and kneaded at 180 ° C., while 19.5 g of paraffin oil (trade name “Super Oil M Series P500S” manufactured by JX Nippon Oil & Energy Corporation) was added to the pressure kneader. The styrene-ethylene-butylene-styrene block copolymer and paraffin oil were mixed for 1 minute. Next, 6.5 g of maleic anhydride-modified ethylene-butene copolymer (maleinized EBM: trade name “Toughmer MH5040”, crystallinity: 4%) manufactured by Mitsui Chemicals, Ltd., polyethylene (PE) : Trade name “HJ590N” manufactured by Nippon Polyethylene Co., Ltd., crystallinity: 74%, MFR: 40 g / 10 minutes (2.16 kg, 190 ° C., Mw: 70000) 13 g and anti-aging agent (trade name manufactured by Adeka) 0.0488 g of “AO-50”) was further added, and the mixture was masticated at a temperature of 180 ° C. for 2 minutes to obtain a first mixture (a mixture containing SEBS and maleated EBM). In addition, the said 1st mixture was plasticized by this mastication process. Next, 0.0065 g of organic clay (trade name “Esven WX” manufactured by Hojun Co., Ltd.) is further added to the first mixture in the pressure kneader and kneaded at 180 ° C. for 4 minutes. A second mixture was obtained.

  Next, 0.1703 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. Table 3 shows the evaluation results of the properties of the obtained thermoplastic elastomer composition.

  As is clear from the results shown in Table 3, the thermoplastic elastomer composition (Example 8) of the present invention has sufficiently high heat resistance based on a 5% weight loss temperature. I understood. Furthermore, it was confirmed that the thermoplastic elastomer composition (Example 8) of the present invention has a sufficiently high breaking strength.

Example 9
Using the thermoplastic elastomer composition obtained in Example 8, a laminate was produced as follows. That is, first, the surface of an aluminum plate (trade name “A1100” manufactured by Miyama Metal Co., Ltd., size: 20 mm long, 50 mm wide, 2 mm thick) was degreased with toluene and air-dried. Next, an adhesive (trade name “IMB1000” manufactured by Road Corporation) was applied to one surface of the aluminum plate using a brush and dried at room temperature (25 ° C.) for 3 hours. An adhesive layer (thickness: 100 μm) was formed on the substrate. Next, the aluminum plate on which the adhesive layer was formed was placed on the movable mold side of an injection molding machine (trade name “TS-50” manufactured by Meiki Seisakusho Co., Ltd.). In such a mold of an injection molding machine, the surface of the aluminum plate (the surface on the side on which the adhesive layer is formed) is a cavity part of the mold on the fixed side (length 10 mm, width 50 mm, thickness 2 mm). ) And a part of a rectangular area of 5 mm in length and 20 mm in width. And, using the injection molding machine (trade name “TS-50” manufactured by Meiki Seisakusho Co., Ltd.), the thermoplastic elastomer composition obtained in Example 8 has an injection pressure of 6 MPa, a mold clamping pressure of 50 tons, By injection molding under the conditions that the heating cylinder temperature (H3) is 200 ° C. and the mold temperature is 30 ° C., a plate-like body (elastomer of the thermoplastic elastomer composition having a size of 10 mm in length, 50 mm in width and 2 mm in thickness). A laminate was obtained in which a molded body was laminated on the surface of an aluminum plate so that a rectangular region of 5 mm in length and 20 mm in width overlapped on one surface of the plate-like body via an adhesive layer. Thus, the laminated body which consists of a plate-shaped body (elastomer layer) / adhesion layer / aluminum plate (metal layer) of a thermoplastic elastomer composition was formed. In such a laminate, the vertical portion of the surface of the elastomer layer and the vertical portion of the surface of the aluminum plate are parallel, and the horizontal portion of the surface of the elastomer layer and the horizontal portion of the surface of the aluminum plate are It was parallel. The size of the elastomer layer and the aluminum plate and the size of the overlapping area in the laminate obtained in this way are specified below.

Elastomer layer: 10 mm long, 50 mm wide, 2 mm thick
Aluminum plate: 20 mm long, 50 mm wide, 2 mm thick
Overlapping part (adhesive part): 5 mm long and 20 mm wide.

(Example 10)
When forming the adhesive layer, instead of drying at room temperature (25 ° C.) for 3 hours, it was dried at 65 ° C. for 10 minutes, and the heating cylinder temperature at the time of injection molding was changed from 200 ° C. to 180 ° C. In the same manner as in Example 9, a laminate (plate body of thermoplastic elastomer composition (elastomer layer) / adhesive layer / aluminum plate (metal layer)) was obtained.

[Evaluation of characteristics of laminates obtained in Examples 9 and 10]
After the laminates obtained in Examples 9 and 10 were allowed to stand for 24 hours (one day), a tensile test was performed as follows, and the maximum test force when the elastomer layer was peeled from the aluminum plate [unit: N] And the maximum point strength (MPa) which is a value obtained by dividing the maximum test force by the adhesion area, and the fractured surface fractured by the tensile test was evaluated.

  In the tensile test, first, the end of the aluminum plate and the end of the elastomer layer of the laminate were respectively attached to chucks of a tensile tester (trade name “Strograph” manufactured by Toyo Seiki Co., Ltd.) Both ends of the body were attached to the chuck of a tensile tester). When installing the laminate on the tensile tester in this way, the spacer is sandwiched so that the vertical part of the elastomer layer and the vertical part of the aluminum plate are perpendicular to the horizontal plane (ground). The laminate was placed in the machine so as to be straight (so as not to sag). Thereafter, a tensile test was performed under the condition of a tensile speed of 300 mm / min, and the maximum test force and the maximum point strength were measured. In addition, the evaluation of the fracture surface fractured by the tensile test was performed visually according to the following criteria. Table 4 shows the results of the maximum test force, the maximum point strength, and the peel evaluation thus measured.

<Evaluation criteria for fracture surface (peeling evaluation)>
CF: It is confirmed that the adhesive is in both the aluminum plate side and the elastomer layer side (in this state, it can be seen that the adhesive layer is broken and peeled).

  GF: The elastomer layer is broken and the laminated state is maintained at the bonded portion.

  AF: It is confirmed that the adhesive is only on the aluminum plate side and does not exist on the elastomer layer side (the state where the interface between the elastomer layer and the adhesive layer is peeled) (in this state, the elastomer layer breaks). It can be seen that they have peeled

  As a result of such measurement, in the laminate obtained in Example 9, the part peeled off at the adhesive layer (the part in the CF state: the adhesive is on both the aluminum plate side and the elastomer layer side) Where the adhesive layer is broken and peeled off), and where the elastomer layer itself is destroyed and the laminated structure is maintained (location in the GF state: some elastomer is bonded (laminated)) It was confirmed that the aluminum plate and the elastomer layer were laminated with very high adhesive strength. In the laminate obtained in Example 10, the entire surface was peeled off at the adhesive layer (CF state: the adhesive was on both the aluminum plate side and the elastomer layer side) It was confirmed that the adhesive layer was broken and peeled), and the aluminum plate and the elastomer layer were laminated with very high adhesive strength.

  From such a result, since the laminated bodies (Examples 9 to 10) of the present invention have sufficiently high adhesive strength between the metal layer and the elastomer layer, the shape of the metal layer and the shape of the elastomer layer are the same. It has been found that it can be suitably used for components such as engine mounts and bushes for automobiles, which are made of a combination of metal and elastomer.

  As described above, according to the present invention, it is possible to provide a thermoplastic elastomer composition capable of making heat resistance and breaking strength higher, and a method for producing the same. Moreover, according to this invention, it becomes possible to provide the laminated body which can make the adhesive strength between a metal layer and an elastomer layer sufficient.

  Therefore, since the thermoplastic elastomer composition of the present invention can exhibit the above-mentioned various properties in a balanced manner, for example, products around automobiles, hoses, belts, sheets, anti-vibration rubber, rollers, linings, etc. , Rubberized cloth, sealing materials, gloves, fenders, medical rubber (syringe gaskets, tubes, catheters), gaskets (for home appliances, construction), asphalt modifiers, hot melt adhesives, boots, grips It is useful as a material for producing products used for applications such as toys, shoes, sandals, keypads, gears, and plastic bottle cap liners.

Claims (20)

An elastomeric polymer (A) having a side chain (a) containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle, and having a glass transition point of 25 ° C. or lower; At least one elastomer component selected from the group consisting of an elastomeric polymer (B) containing a hydrogen-bonding cross-linking site and a covalent bond cross-linking site and having a glass transition point of 25 ° C. or lower;
Clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
A styrene block copolymer having no chemically-bonded crosslinking site;
A thermoplastic elastomer composition comprising:   The thermoplastic elastomer composition according to claim 1, wherein a content ratio of the styrene block copolymer is 10 to 400 parts by mass with respect to 100 parts by mass of the elastomer component.   The styrene block copolymer is a styrene-isoprene-styrene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, a styrene-ethylene-ethylene-propylene-styrene block copolymer, or a styrene-butadiene-styrene block. It is at least one selected from the group consisting of copolymers, styrene-ethylene-butylene-styrene block copolymers, styrene-isoprene-butadiene-styrene block copolymers, and hydrogenated products thereof. The thermoplastic elastomer composition according to claim 1 or 2.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the styrene block copolymer is a styrene block copolymer having a styrene content of 20 to 40% by mass. .   The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the styrene block copolymer has a weight average molecular weight of 200,000 or more and 700,000 or less.   6. The hydrogen-bonding crosslinking site contained in the side chain of the elastomeric polymer (B) is a hydrogen-bonding crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring. The thermoplastic elastomer composition according to any one of the above.   The said clay is at least 1 sort (s) selected from the group which consists of the clay which has silicon and magnesium as a main component, and an organized clay, It is any one of Claims 1-6 characterized by the above-mentioned. A thermoplastic elastomer composition.   The thermoplastic elastomer composition according to any one of claims 1 to 7, wherein the clay is an organized clay.   The crosslinking at the covalent crosslinking site contained in the side chain of the elastomeric polymer (B) is at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. The thermoplastic elastomer composition according to any one of claims 1 to 8, wherein the composition is a thermoplastic elastomer composition. The hydrogen-bonding cross-linked site of the side chain (a) is represented by 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. ]
The thermoplastic elastomer composition as described in any one of Claims 1-9 characterized by containing the structural part represented by these.   The thermoplastic elastomer composition according to any one of claims 1 to 10, wherein the nitrogen-containing heterocycle is a 5-membered ring and / or a 6-membered ring.   The nitrogen-containing heterocycle is at least one selected from a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring, a triazine ring, an isocyanurate ring, and a hydantoin ring. The thermoplastic elastomer composition according to any one of the above.   The main chains of the elastomeric polymers (A) to (B) are a diene rubber, a hydrogenated diene rubber, an olefin rubber, an optionally hydrogenated polystyrene elastomer polymer, and a polyolefin elastomer. It consists of at least 1 sort (s) selected from a polymer, a polyvinyl chloride type elastomeric polymer, a polyurethane type elastomeric polymer, a polyester type elastomeric polymer, and a polyamide type elastomeric polymer. The thermoplastic elastomer composition according to any one of the above. A first step of mixing an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and a styrene block copolymer having no chemically-bonded crosslinking site 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 second step of obtaining a thermoplastic elastomer composition by adding at least one raw material compound among the mixed raw materials of the compound (II) that forms the compound, and reacting the polymer and the raw material compound;
Including,
The thermoplastic elastomer composition obtained in the second step has a side chain (a) containing a hydrogen-bonded crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle, and has a glass transition point of 25 ° C. A group consisting of the following elastomeric polymer (A) and 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. At least one elastomer component selected from:
The clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
The styrene block copolymer;
And a composition comprising
In the first step, the cyclic acid anhydride is used by using the clay in such a proportion that the content of the clay in the thermoplastic elastomer composition is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component. Mixing the elastomeric polymer having a group in the side chain, the clay, and the styrene block copolymer;
A process for producing a thermoplastic elastomer composition characterized by the above.   The method for producing a thermoplastic elastomer composition according to claim 14, wherein the elastomeric polymer having a cyclic acid anhydride group in a side chain is a maleic anhydride-modified elastomeric polymer.   The compound (I) and / or (II) is a compound that reacts with the cyclic acid anhydride group to form both a hydrogen bonding crosslinking site and a covalent bonding site. A method for producing the thermoplastic elastomer composition according to 14 or 15.   Among the compounds (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 is used. The manufacturing method of the thermoplastic-elastomer composition as described in any one of these. An elastomeric polymer having a cyclic acid anhydride group in the side chain;
With clay,
A styrene block copolymer having no chemically-bonded crosslinking site;
Compound (I) which reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site, and compound which reacts with the compound (I) and the cyclic acid anhydride group to form a covalent-bonding cross-linking site At least one raw material compound of the mixed raw materials of (II);
And a process of obtaining a thermoplastic elastomer composition by reacting the elastomeric polymer having the cyclic acid anhydride group in the side chain with the raw material compound,
The thermoplastic elastomer composition has an elastomeric polymer (a) having a side chain (a) 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 ( A) and at least one selected from the group consisting of 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 An elastomer component of
The clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
The styrene block copolymer;
And a composition comprising
Using the clay in such a proportion that the content of the clay in the thermoplastic elastomer composition is 20 parts by mass or less with respect to 100 parts by mass of the elastomer component;
A process for producing a thermoplastic elastomer composition characterized by the above. A metal layer,
An elastomer layer comprising the thermoplastic elastomer composition according to any one of claims 1 to 13;
A laminate comprising:   The laminate according to claim 19, further comprising an adhesive layer between the metal layer and the elastomer layer.