JP2017057322A - Thermoplastic elastomer composition and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition capable of having breaking strength, compressive permanent set resistance and heat resistance at sufficiently high levels and with a good balance while having improved hardness.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 surface treated calcium carbonate which is surface treated by organic acid.SELECTED DRAWING: None

Description

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

  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. And in such patent document 1, as a reinforcing material of the composition containing a thermoplastic elastomer, in addition to carbon black and silica, iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, carbonic acid Examples include calcium, magnesium carbonate, zinc carbonate, wax stone clay, kaolin clay, and calcined clay.

  However, with respect to such a composition containing the thermoplastic elastomer described in Patent Document 1, even if the reinforcing material is simply used, the strength of the composition is increased while breaking strength and elongation at break are increased. However, it was not always sufficient in terms of having a well-balanced compression set and heat resistance at a sufficiently high level.

JP 2006-131663 A

  The present invention has been made in view of the problems of the prior art, and has a sufficiently high level of fracture strength, compression set resistance, and heat resistance while maintaining a higher hardness. It is an object of the present invention to provide a thermoplastic elastomer composition that can be produced, and a method for producing the same.

  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 And 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 surface-treated calcium carbonate surface-treated with an organic acid. By containing, the thermoplastic elastomer composition obtained has a higher hardness, while having a breaking strength, compression set resistance and heat resistance. It found that Tsu characteristics with sufficiently high levels it is possible that can be assumed to have good balance, 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;
Surface-treated calcium carbonate surface-treated with an organic acid,
It is characterized by containing.

  In the thermoplastic elastomer composition of the present invention, the content of the surface-treated calcium carbonate is preferably 50 parts by mass or less with respect to 100 parts by mass of the elastomer component.

  Moreover, in the thermoplastic elastomer composition of the present invention, the organic acid is preferably at least one of fatty acid and rosin acid. As described above, the surface-treated calcium carbonate is calcium carbonate that is surface-treated with at least one organic acid of fatty acid and rosin acid (by at least one organic acid of fatty acid and rosin acid). It is preferably a surface treated product of calcium carbonate.

  In the thermoplastic elastomer composition of the present invention, the surface-treated calcium carbonate is preferably composed of particles having an average particle size of 0.5 μm or less (more preferably 0.01 to 0.5 μm).

  Furthermore, in the thermoplastic elastomer composition of the present invention described above, the hydrogen bondable crosslinkable site contained in the side chain of the elastomeric polymer (B) has hydrogen bondability having a carbonyl-containing group and / or a nitrogen-containing heterocycle. 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.

  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.

  Furthermore, 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.

  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, in the thermoplastic elastomer composition of the present invention, paraffin oil, styrene block copolymer having no chemical bonding crosslinking site, and α-olefin resin having no chemical bonding crosslinking site. It is preferable to contain further.

The method for producing a thermoplastic elastomer composition of the present invention comprises mixing an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and surface-treated calcium carbonate surface-treated with an organic acid. A first step to obtain,
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 surface-treated calcium carbonate;
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 surface-treated calcium carbonate;
It is the method characterized by this.

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

  In the method for producing the thermoplastic elastomer composition of the present invention, the compound (I) and / or (II) reacts with the cyclic acid anhydride group to react with a hydrogen-bonding cross-linked site and a covalent bond. It is preferable to use a compound that forms both sites.

  Furthermore, in the method for producing a thermoplastic elastomer composition of the present invention, the compound (I) and / or (II) has at least one substituent selected from a hydroxyl group, a thiol group, an amino group, and an imino group. It is preferable to use the compound which has.

  According to the present invention, a thermoplastic elastomer composition capable of having a sufficiently high balance in terms of breaking strength, compression set resistance and heat resistance while having a higher hardness, and The manufacturing method can be provided.

  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;
Surface-treated calcium carbonate surface-treated with an organic acid,
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 using an X-ray diffractometer (for example, trade name “MiniFlex300” manufactured by Rigaku Corporation) as a measuring device, measuring a diffraction peak, and measuring a scattering peak derived from crystalline / amorphous. It can be obtained by calculating the integration 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.

(Surface treatment calcium carbonate surface-treated with organic acid)
The surface-treated calcium carbonate surface-treated with an organic acid according to the present invention is calcium carbonate that has been surface-treated with an organic acid, and is a surface-treated product of calcium carbonate with an organic acid. The term “surface treatment” as used herein refers to a treatment for generating a chemical bond between an organic acid and calcium carbonate, whereby the surface of the calcium carbonate has at least an organic acid bonded (coated state) and Become. Therefore, it can be said that the surface-treated calcium carbonate is calcium carbonate in which an organic acid is bonded to the surface (calcium carbonate in which an organic acid is coated on at least a part or all of the surface).

  In such surface-treated calcium carbonate, the organic acid is not particularly limited, but fatty acid and rosin acid are preferable from the viewpoint of reactivity with the carbonyl group of calcium carbonate. Such organic acids can be used singly or in combination of two or more.

  Examples of such fatty acids include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearin Examples include acids, isostearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, behenic acid, arachidonic acid, and arachidic acid.

  Furthermore, examples of the rosin acid include resin acids such as abietic acid, parastrinic acid, isopimaric acid, neoabietic acid, pimaric acid, dehydroabietic acid, and salts thereof.

  The surface-treated calcium carbonate is more preferably in the form of particles (made of particles) from the viewpoint of dispersibility in the elastomer. The surface-treated calcium carbonate particles preferably have an average particle size of 0.5 μm or less, more preferably 0.01 to 0.5 μm, and 0.01 to 0.3 μm. Is particularly preferred. When the average particle diameter of such surface-treated calcium carbonate particles exceeds the upper limit, aggregation tends to occur and the dispersibility to the elastomer tends to decrease. On the other hand, if the average particle diameter is less than the lower limit, the particle diameter becomes finer and tends to rise. Therefore, there is a tendency that the workability in the experiment and manufacturing of the elastomer mixing is lowered.

Further, such a surface-treated calcium carbonate preferably has a BET specific surface area of 1 to ²⁰⁰ cm ² / g, more preferably ^{2 to} 150 cm ² / g, and 2.5 to 100 cm ² / g. More preferably. When such a BET specific surface area is less than the lower limit, the particle size becomes finer and tends to rise, so that it is difficult to mix in the elastomer component, and the workability in production tends to be lowered, while the upper limit is exceeded. Aggregation tends to occur and the dispersibility in the elastomer tends to be reduced. In addition, as a value of such a BET specific surface area, you may employ | adopt the value measured using the brand name "ASAP 2020 series" by Shimadzu Corporation as a measuring apparatus, for example.

  Such surface-treated calcium carbonate is not particularly limited as long as it is a surface-treated product obtained by subjecting conventionally known calcium carbonate to surface treatment. For example, the surface-treated calcium carbonate is surface-treated with calcium carbonate synthesized by a known method. And the like, and surface treated products of heavy calcium carbonate.

  Such surface-treated calcium carbonate can be obtained by a known production method. Further, such surface-treated calcium carbonate may be commercially available, for example, trade names “Vigot-10”, “Vigot-15”, “CC”, “CC-R” manufactured by Shiroishi Kogyo Co., Ltd. , “Viscolite-SV”, “Viscoexcel-30”, “Carmos”, “U”, “Homocal D”, “Homocal DM”, “Gelton 50”, “O”, “DD”, “TDD”, “IGV” "Product names" Whiteon 305 "," Whiteon 306 "," Whiteon 310 "," RS-10 "," PLUS ONE "manufactured by Toyo Fine Chemical; product names" FSK-3 "manufactured by Calfine , "ASK-5", "SST-40", "UST-50", "BSR-5", "Suncut-160", etc. can be used as appropriate.

(Composition)
The thermoplastic elastomer composition of the present invention contains the elastomer component, the clay, and surface-treated calcium carbonate that has been surface-treated with the organic acid.

  The reason why the thermoplastic elastomer composition of the present invention makes it possible to have a sufficiently high balance between fracture strength, compression set resistance and heat resistance while making the hardness higher. Although not necessarily clear, the present inventors infer 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)). In this way, when an elastomeric polymer and clay are combined, an interaction between the clay and the hydrogen-bonding cross-linking site (formation of a new hydrogen bond, etc.) causes the elastomer component to utilize the surface of the clay. 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 only other elastomer components are used, Even if it is 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 (breaking strength, etc.) of the composition is lowered. From this point of view, when the elastomeric polymers (A) and (B) are not used as a base elastomer component, an interaction with the clay cannot be formed. The present inventors infer that the mechanical strength is lowered due to the presence, 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 infer that this is because a sufficiently high tensile stress (particularly, breaking strength) and sufficiently high heat resistance can be exhibited.

  Moreover, in the thermoplastic elastomer composition of this invention, the surface treatment calcium carbonate surface-treated with the said organic acid is contained with the said thermoplastic elastomer composition and clay. By using such surface-treated calcium carbonate, it becomes possible to disperse in the elastomer molecule without agglomeration due to the functional group derived from the organic acid present on the surface and the polarity reduction of the calcium carbonate fine powder due to the surface treatment. Since the effect of calcium can be made uniform throughout the elastomer, the mechanical strength and the like of the composition are not lowered while the hardness is increased. Therefore, by using a combination of the elastomer component, the surface-treated calcium carbonate, and the clay, it is possible to have higher hardness, and furthermore, breaking strength, breaking elongation, compression set resistance It is possible to have a sufficiently high level of heat resistance and heat resistance and to have these properties in a well-balanced manner. For example, when calcium carbonate that has not been surface-treated is simply used, the hardness can be improved, but the calcium carbonate cannot be sufficiently dispersed in the composition. , Because non-uniform micro-aggregation occurs (because calcium carbonate is non-uniformly dispersed in the elastomer), it is difficult to maintain sufficient mechanical strength of the composition, and the hardness is made higher. However, various characteristics such as breaking strength, compression set resistance and heat resistance cannot be maintained at a sufficiently high level.

  Thus, in the thermoplastic elastomer composition of the present invention, higher mechanical strength and the like due to the interaction between the elastomer component and clay, while having a higher hardness derived from the surface-treated calcium carbonate. As a result, the present inventors are able to have a sufficiently high balance in terms of fracture strength, compression set resistance and heat resistance while maintaining a higher hardness. I guess.

  In the present invention, depending on the overall structure of the elastomer component, etc., depending on the type of the elastomer component, hydrogen bonds formed by hydrogen-bonding cross-linked sites in the side chain contained in the elastomer component, It is also possible to impart fluidity (moldability) while maintaining sufficient heat resistance and the like. Depending on the structure, even if the hydrogen bond disappears once during heat processing, the hydrogen bond is formed again during curing, and fluidity (formability) is obtained during heating while maintaining sufficient heat resistance and the like. Because.

  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 ratio conditions and the like will be further described.

  The thermoplastic elastomer composition of the present invention contains the elastomer component, the clay, and surface-treated calcium carbonate surface-treated with the organic acid, and the content of the clay is the elastomer component. It is 20 mass parts or less with respect to 100 mass parts. 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 (content ratio) of the surface-treated calcium carbonate surface-treated with the organic acid is 50 parts by mass or less with respect to 100 parts by mass of the elastomer component. Is preferred, 1 to 45 parts by mass is more preferred, 3 to 40 parts by mass is still more preferred, 5 to 35 parts by mass is particularly preferred, and 10 to 30 parts by mass is most preferred. . When the content of such surface-treated calcium carbonate is less than the lower limit, the absolute amount of calcium carbonate is small, and it tends to be difficult to make the effect of improving the hardness sufficient, and on the other hand, exceeds the upper limit. And rubber elasticity falls, and it exists in the tendency for the fall of mechanical strength to occur easily.

  In the thermoplastic elastomer composition of the present invention, the content of the surface-treated calcium carbonate surface-treated with the organic acid is 0.1 to 5% by mass with respect to the total amount of the thermoplastic elastomer composition. Is preferable, it is more preferable that it is 0.3-7.5 mass%, and it is still more preferable that it is 0.5-5 mass%. When the content of such surface-treated calcium carbonate is less than the lower limit, the absolute amount of calcium carbonate is small, and it tends to be difficult to make the effect of improving the hardness sufficient, and on the other hand, exceeds the upper limit. And rubber elasticity falls, and it exists in the tendency for the fall of mechanical strength to occur easily.

  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.

  In addition, in the thermoplastic elastomer composition of the present invention, in addition to the surface-treated calcium carbonate surface-treated with the elastomer component, the clay and the organic acid, the effects of the present invention are not impaired. Further additional components (other components: additives) may be contained.

  As such an additive component (other component: additive), paraffin oil is preferable from the viewpoint that the fluidity can be further improved without reducing various physical properties. In addition, when such a paraffin oil is used in combination with a styrenic block polymer, which will be described later, the oil component can be absorbed into the block polymer, improving the workability by adding oil (improving fluidity), and styrene. It is possible to achieve a sufficiently high level of improvement in mechanical properties due to the addition of block polymers, so that production processing such as extrusion processability and injection moldability can be achieved while maintaining sufficient mechanical properties and heat resistance. Sex can be made more advanced. Such paraffin oil is not particularly limited, and known paraffin oil can be appropriately used.

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

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

  Further, such a paraffin oil preferably has an aniline point measured by a U-tube method according to JIS K2256 (issued in 2013) of 80 ° C to 145 ° C, more preferably 100 to 145 ° C. Preferably, it is 105-145 degreeC. In addition, the aniline point of such paraffin oil employs a value measured by the U-tube method in accordance with JIS K2256 (issued in 2013). For example, an aniline point in accordance with JIS K2256 (issued in 2013) You may employ | adopt the value measured using the measuring apparatus (For example, brand name "aap-6" by Tanaka Scientific Instruments company).

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

  Moreover, when the said paraffin oil is further contained in the thermoplastic elastomer composition of this invention, it is preferable that content of the said paraffin oil is 10-600 mass parts with respect to 100 mass parts of said elastomer components, 50- The amount is more preferably 550 parts by mass, still more preferably 75 to 500 parts by mass, and particularly preferably 100 to 400 parts by mass. If the content of such paraffin oil is less than the lower limit, the content of paraffin oil is too small, and the effect obtained by further adding paraffin oil (especially the effect of improving fluidity and workability) is not always sufficient. On the other hand, if the upper limit is exceeded, bleeding of paraffin oil tends to be induced.

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

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

  The styrene block copolymer, which is a component suitably used for the thermoplastic elastomer composition of the present invention, does not have a chemically bonding cross-linked 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” referred to here may be a polymer having a styrene block structure at any site. 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 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”; product names “S4055” “S4077” “S4099” “S8006” “S4044” “S8006” “S4033” “S8004” “S8007” “Kuraray” "S8076"; trade names "Tuff Tech H1041" "Tuff Tech N504" "Tuff Tech H1272" "Tuff Tech M1911" "Tuff Tech M1913" "Tuftech MP10" manufactured by Asahi Kasei Corporation; trade names "AR-710" and "AR-720" manufactured by Aron Kasei. "AR-731" "A -741 "" AR-750 "," AR-760 "," AR-770 "," AR-781 "," AR-791 "; and the like may be appropriately used.

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

  Further, when the thermoplastic elastomer composition of the present invention further contains a styrene block copolymer having no chemically-bonded crosslinking site, the styrene block copolymer having no chemically-bonded crosslinking site is used. The content is preferably 5 to 60% by mass, more preferably 7 to 45% by mass, and still more preferably 10 to 30% by mass with respect to the total amount of the thermoplastic elastomer composition. If the content of the styrene block copolymer having no such chemical bonding cross-linking site is less than the lower limit, the content of the styrene block copolymer is too small, and the styrene block copolymer is further added. However, when the above upper limit is exceeded, the characteristics of the matrix structure (characteristics derived from the elastomer component) due to the crosslinked elastomer are dilute. Tend to be.

  Further, as the additive component (other components: additive), from the viewpoint of further improving physical properties such as fluidity and mechanical properties without interfering with the crosslinking reaction of the base elastomer, the chemical bonding crosslinking An α-olefin resin having no site is preferred. Here, “having no chemically-bonded crosslinking site” has the same meaning as described in the above-described styrene block copolymer. Therefore, as an α-olefin resin that does not have such a chemical bond crosslinking site, for example, a functional group (for example, a hydroxyl group, a carbonyl group, a carboxyl group, a thiol) that forms a crosslinking point by a chemical bond. (Group, amide group, amino group) are not included, and those that do not include a binding site (such as a cross-linking site by a covalent bond) that directly cross-links the polymer chains are preferably used. In addition, the α-olefin resin not having such a chemical bonding cross-linking site is at least the side chain (a), the side chain (a ′), the side chain (b), the side chain ( c) The polymer does not have.

  Further, the “α-olefin resin” referred to here means an α-olefin homopolymer and an α-olefin copolymer. The “α-olefin” as used herein refers to an alkene having a carbon-carbon double bond at the α-position (an alkene having a carbon-carbon double bond at the terminal: the alkene may be linear. It may be branched, and preferably has 2 to 20 carbon atoms (more preferably 2 to 10). For example, ethylene, propylene, 1-butene, 1-pentene, 1 -Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like can be mentioned.

  As the α-olefin-based resin having no such chemically bondable crosslinking site, an α-olefin polymer (poly α-olefin: a homopolymer or a copolymer may be used). Although it does not restrict | limit in particular, For example, polyethylene, a polypropylene, an ethylene-propylene copolymer, an ethylene-butene copolymer, a propylene-ethylene-butene copolymer etc. are mentioned. Among the α-olefin resins not having such a chemical bonding crosslinking site, polypropylene, polyethylene, and ethylene-propylene copolymer are preferable from the viewpoint of compatibility with the base elastomer. In addition, the alpha olefin resin which does not have such a chemical bond bridge | crosslinking site | part may be used individually by 1 type, or may be used in combination of 2 or more type.

  As such an α-olefin resin having no chemically bonding cross-linked site, those having a crystallinity of 10% or more are preferable, those having 10 to 80% are more preferable, and those having 10 to 75% are preferable. Further preferred. If such crystallinity is less than the lower limit, the resin-like properties become dilute, and even if this is utilized, it tends to be difficult to make mechanical properties and fluidity more advanced, If the upper limit is exceeded, resin-like properties become strong, and it tends to be difficult to exhibit mechanical properties at a higher level in a well-balanced manner. Such crystallinity is measured using an X-ray diffractometer (for example, trade name “MiniFlex300” manufactured by Rigaku Corporation) as a measuring device, measuring a diffraction peak, and measuring a scattering peak derived from crystalline / amorphous. It can be obtained by calculating the integration ratio.

  In addition, as an α-olefin resin not having such a chemical bonding cross-linking site, a melt flow at 190 ° C. under a load of 2.16 kg, measured in accordance with JIS K6922-2 (issued in 2010). The rate (MFR) is preferably 40 g / 10 min or more. When such a melt flow rate (MFR) is less than the lower limit, it is difficult to improve fluidity even when blended in an elastomer composition, and the effect obtained by adding an α-olefin resin tends to decrease. It is in. 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 α-olefin resin was added into the furnace of the apparatus, and the temperature was maintained at 190 ° C. for 5 minutes, and then maintained at 190 ° C. Measure the mass (g) of the elastomer flowing out in 10 minutes from the opening of a cylindrical orifice member with a diameter of 1 mm and a length of 8 mm connected to the lower part of the furnace body under the condition of loading 16 kg ( The temperature is set at 190 ° C. in the furnace body and held for 5 minutes, and then the load is started, and then the measurement of the mass of the elastomer flowing out is started. Kill.

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

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

  Moreover, it is preferable that the dispersion degree (Mw / Mn) of the molecular weight distribution of the α-olefin-based resin having no chemical bonding crosslinking site is 100 or less, and more preferably 1.5 to 50. If the degree of dispersion (Mw / Mn) of the molecular weight distribution is less than the lower limit, the fluidity tends to decrease, and if it exceeds the upper limit, the compatibility with the elastomer tends to decrease.

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

  Moreover, it is preferable that it is -150-5 degreeC, and, as for the glass transition point of the alpha olefin resin which does not have the said chemical bond cross-linking site | part, it is more preferable that it is -125-0. If such a glass transition point is less than the lower limit, the melting point becomes low and the heat resistance tends to be lowered. On the other hand, if the upper limit is exceeded, rubber elasticity after blending the elastomer 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 such an α-olefin-based resin having no chemical bonding crosslinking site is not particularly limited, and a known method can be appropriately employed. In addition, as such an α-olefin-based resin, commercially available products may be used. For example, trade names “Tafmer” manufactured by Mitsui Chemicals, Inc .; Novatec LL, “Kernel”; Prime Polymer's trade names “Hinex” “Neozex” “Ultzex” “Evolue” “Prime Polypro” “Polyfine” “Mostron L”; May be.

  Further, in the present invention, when the α-olefin resin not having the chemical bond crosslinking site is contained, the content (content ratio) of the α-olefin resin not having the chemical bond crosslinking site. However, it is preferably 250 parts by mass or less, more preferably 5 to 250 parts by mass, still more preferably 10 to 225 parts by mass, with respect to 100 parts by mass of the elastomer component. Part is particularly preferred, and most preferred is 35 to 175 parts by mass. If the content of the α-olefin-based resin having no such chemical bonding cross-linking site is less than the lower limit, the fluidity tends to decrease. On the other hand, if the upper limit is exceeded, mechanical properties (breaking strength, Compression set) tends to decrease.

  In the thermoplastic elastomer composition of the present invention, the content of the α-olefin-based resin having no chemically-bonded crosslinking site is 1 to 50% by mass with respect to the total amount of the thermoplastic elastomer composition. It is preferably 3 to 45% by mass, more preferably 5 to 40% by mass. If the content of the α-olefin-based resin having no such chemical bonding cross-linking site is less than the lower limit, the fluidity tends to decrease. On the other hand, if the upper limit is exceeded, mechanical properties (breaking strength, Compression set) tends to decrease.

  Further, in the thermoplastic elastomer composition of the present invention, from the viewpoint of improving the balance of physical properties such as mechanical properties and fluidity, the paraffin oil, the styrene block copolymer having no crosslinkable site of chemical bonding, And what further contains (alpha) -olefin type resin which does not have the said chemical bond cross-linking site | part (what contains these in combination) is more preferable. That is, the thermoplastic elastomer composition of the present invention includes the elastomer component, the clay, the surface-treated calcium carbonate surface-treated with the organic acid, the paraffin oil, and the styrene having no chemically-bonded cross-linking site. It is more preferable to use a block copolymer and an α-olefin-based resin that does not have the chemical bonding cross-linking site.

  Thus, the elastomer component, the clay, the surface-treated calcium carbonate surface-treated with the organic acid, the paraffin oil, the styrene block copolymer having no chemically-bonded cross-linking site, and the chemical In the case of containing a combination of α-olefin resins having no binding cross-linking sites, it is possible to make the breaking strength, breaking elongation, compression set resistance and heat resistance higher. The reason why such an effect is achieved is not necessarily clear, but the present inventors speculate as follows. That is, first, in the case of using in combination the paraffin oil, the styrene block copolymer having no chemically-bonded crosslinking site, and the α-olefin resin not having the chemically-bonded crosslinking site. The paraffin oil is highly compatible with the styrene block copolymer. And since a styrene block copolymer has high compatibility with the said elastomer component, it can disperse | distribute sufficiently uniformly in the elastomer component used as a base material. When the styrene block copolymer is dispersed in this way, paraffin oil having high compatibility with the styrene block copolymer is also uniformly dispersed throughout the composition, thereby achieving both mechanical properties and fluidity. be able to. Therefore, while maintaining the characteristics derived from the elastomer component (especially heat resistance, breaking strength, breaking elongation) sufficiently, production processability such as extrusion processability and injection moldability can be enhanced. . Further, since the styrene block copolymer does not interfere with the crosslinked structure of the elastomer component serving as a matrix and the crosslinking reaction during production, the inherent properties of the elastomer structure serving as the crosslinked matrix are not inhibited, and are derived from the elastomer component. It is possible to impart excellent mechanical properties (especially tensile properties, compression set, etc.) derived from the styrene block copolymer while maintaining sufficient properties, and a thermoplastic elastomer composition having higher performance. The present inventors speculate that a product is obtained. Moreover, since the styrene block copolymer and the α-olefin resin are highly compatible, they are uniformly dispersed in the system. Further, in such a system containing an α-olefin resin, the elastomer component has high compatibility with the α-olefin resin, and therefore the α-olefin resin is sufficiently uniform in the composition. Will be dispersed. As described above, since the elastomer component and the clay interact to form surface cross-linking, the clay is also present in a sufficiently dispersed state as the elastomer component is dispersed. As described above, when these components are contained in combination, each component is contained in a state in which each component is sufficiently uniformly dispersed with each other without inhibiting dispersion or the like. And, the state of the elastomer component (component that becomes a base material) that strongly affects the properties of the thermoplastic elastomer composition is sufficiently dispersed in a state of interacting with the clay (a state in which a strong bond is formed by surface cross-linking). Therefore, higher mechanical strength and heat resistance can be exhibited in a balanced manner. Therefore, the present inventors speculate that when the above components are contained in combination, the breaking strength, breaking elongation, compression set resistance and heat resistance can be further enhanced.

  As described above, the paraffin oil, the styrene block copolymer, and the α-olefin resin have been described as additive components that can be suitably used in the thermoplastic elastomer composition of the present invention. In addition to the component, if necessary, the polymer other than the elastomer component, the α-olefin-based resin and the styrene block copolymer, a reinforcing agent (filler), as long as the object of the present invention is not impaired. Hydrogen bonding reinforcing agent (filler), filler obtained by introducing an amino group (hereinafter simply referred to as “amino group-introduced filler”), amino group-containing compound other than the amino group-introduced filler, metal element Containing compounds (hereinafter simply referred to as “metal salts”), maleic anhydride-modified polymers, antioxidants, antioxidants, pigments (dyes), plastics other than the above paraffin oil Agents (including so-called softeners), thixotropic agents, UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, rust inhibitors, adhesion promoters, antistatic agents Various additives such as an agent and a filler can be appropriately contained. Such additives are not particularly limited, and commonly used ones (known ones) can be appropriately used. For example, the following can be appropriately used as an anti-aging agent, an antioxidant, a pigment (dye), and a plasticizer.

  As the polymer other than the elastomer component, in the thermoplastic elastomer field, a known polymer that can be appropriately used from the viewpoint of adjusting the hardness and maintaining the mechanical properties can be appropriately used, and is not particularly limited. Other elastomeric polymers having side chains (b) other than the elastomeric polymer (B) 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, and for example, oils can also be used. In addition, as such an additive etc., you may utilize suitably what is illustrated by Unexamined-Japanese-Patent No. 2006-131663.

  The thermoplastic elastomer composition of the present invention includes the elastomer component, the clay, the surface-treated calcium carbonate that has been surface-treated with the organic acid, the paraffin oil, the styrene that does not have the chemically-bonded crosslinking site. In the case of containing a block copolymer and other components (for example, the additive etc.) other than the α-olefin resin not having the chemically bonding cross-linked site, the content of the other components is Although not particularly limited, when the other component (for example, the additive or the like) is a polymer or a reinforcing material (filler), the total amount thereof is 400 with respect to 100 parts by mass of the elastomer component. The amount is preferably equal to or less than part by mass, and more preferably 20 to 300 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.

  In addition, when the above-mentioned other components are other additives (in the case of other than polymers and reinforcing materials (fillers)), the content of the other components is the total amount of the elastomer. It is preferable that it is 20 mass parts or less with respect to 100 mass parts of components, and it is more preferable that it is 0.1-10 mass parts. 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 softened by heating (for example, heating to 100 to 250 ° C.), so that the hydrogen bond formed at the hydrogen bond cross-linking site is dissociated and softened, thereby providing fluidity. You can also This is presumably because the interaction between the side chains formed between the molecules or within the molecule due to heating (mainly the interaction due to hydrogen bonding) is weakened. In the present invention, since the side chain contains an elastomer component containing at least a hydrogen-bonding cross-linked site, etc., when the fluidity is imparted by heating and left to stand, the dissociated hydrogen bond Since they are bonded and cured again, depending on the composition, the thermoplastic elastomer composition can be made to exhibit recyclability more efficiently.

  Further, the thermoplastic elastomer composition of the present invention has a melt flow rate (MFR) at 230 ° C. 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 a sufficiently high balance in terms of breaking strength, compression set resistance and heat resistance while making the hardness higher. In addition, in such a thermoplastic elastomer composition, it is possible to appropriately exhibit characteristics (for example, characteristics such as self-healing properties) required according to applications by appropriately changing the composition. In this way, by appropriately changing the composition, it is possible to appropriately exhibit the necessary characteristics in a balanced manner according to the use of the thermoplastic elastomer composition. In 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. A method for producing the elastomer composition will be described.

[Method for producing thermoplastic elastomer composition]
The method for producing a thermoplastic elastomer composition of the present invention comprises mixing an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and surface-treated calcium carbonate surface-treated with an organic acid. A first step to obtain,
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 surface-treated calcium carbonate;
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 surface-treated calcium carbonate;
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 surface-treated calcium carbonate surface-treated with an organic acid.

  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 surface-treated calcium carbonate surface-treated with the organic acid used in the first step is the same as the surface-treated calcium carbonate surface-treated with the organic acid described in the thermoplastic elastomer composition of the present invention. (And the preferred ones are also the same).

  In the first step, an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and surface-treated calcium carbonate surface-treated with an organic acid are mixed to obtain a mixture. In the preparation process of such a mixture, the addition order of the elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and the surface-treated calcium carbonate is not particularly limited, but the dispersibility of the clay is not limited. From the standpoint of further improving the surface treatment, after preparing a precursor of a mixture containing the surface-treated calcium carbonate and an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay is added to the precursor Is preferred.

  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 surface-treated calcium carbonate surface-treated with the organic acid. 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 step of such a mixture, the content of the surface-treated calcium carbonate in the finally obtained thermoplastic elastomer composition is 50 parts by mass or less (more preferably, 100 parts by mass of the elastomer component). 1 to 45 parts by mass, more preferably 3 to 40 parts by mass, particularly preferably 5 to 35 parts by mass, and most preferably 10 to 30 parts by mass). It is preferable to mix the elastomeric polymer having an acid anhydride group in the side chain, the clay, and the surface-treated calcium carbonate. If the content of such surface-treated calcium carbonate exceeds the upper limit, the rubber elasticity tends to decrease and the mechanical strength tends to decrease. On the other hand, if the content is less than the lower limit, the absolute amount of calcium carbonate is small and the hardness is low. It tends to be difficult to make the effect of improving the sufficient.

  Moreover, as content of the said surface treatment calcium carbonate in such a mixture, it is 50 mass parts or less (preferably 1-45 mass with respect to 100 mass parts of elastomeric polymers which have a cyclic acid anhydride group in a side chain. Part, more preferably 3 to 40 parts by weight, particularly preferably 5 to 35 parts by weight). When such content exceeds the upper limit, rubber elasticity tends to decrease and mechanical strength tends to decrease. On the other hand, when the content is less than the lower limit, the absolute amount of calcium carbonate is small and the effect of improving hardness is achieved. Tends to be difficult to achieve.

  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 addition, such a mixture further includes paraffin oil and / or a styrene block copolymer having no chemically-bonded crosslinking site and / or an α-olefin resin having no chemically-bonded crosslinking site. You may make it contain. Such a paraffin oil, a styrene block copolymer having no chemical bonding cross-linking site, and an α-olefin resin not having a chemical bonding cross-linking site are respectively the thermoplastic elastomer of the present invention. The same as those described in the composition (the preferred ones are also the same).

  In this way, in the case of further containing the paraffin oil and / or the styrene block copolymer and / or the α-olefin resin, an elastomeric polymer having the cyclic acid anhydride group in the side chain; Addition of the clay, the surface-treated calcium carbonate, the α-olefin resin, the paraffin oil and / or the styrene block copolymer having no chemically-bonded cross-linking site and / or the α-olefin resin The order is not particularly limited, but from the viewpoint of further improving the dispersibility of the clay, the elastomeric polymer having the cyclic acid anhydride group in the side chain, the surface-treated calcium carbonate, and the α-olefin system Resin, paraffin oil and / or styrene block that does not have chemical bond cross-linking site After preparing the precursor copolymer and / or a mixture comprising said α- olefin resin, it is preferable to add a clay in the precursor.

  When the paraffin oil is contained in the mixture, the paraffin oil content is preferably 600 parts by mass or less, more preferably 10 to 600 parts by mass with respect to 100 parts by mass of the elastomer component. 50 to 550 parts by mass, still more preferably 75 to 500 parts by mass, and most preferably 100 to 400 parts by mass. Moreover, when the said styrene block copolymer is contained in the said mixture, it is preferable that it is 400 mass parts or less with respect to 100 mass parts of said elastomer components, It is more preferable that it is 10-400 mass parts, 15- The amount is more preferably 350 parts by mass, particularly preferably 20 to 300 parts by mass, and most preferably 30 to 250 parts by mass. Furthermore, when the α-olefin-based resin is contained in the compound, the amount is preferably 250 parts by mass or less, more preferably 5 to 250 parts by mass with respect to 100 parts by mass of the elastomer component, It is further preferably 225 parts by mass, particularly preferably 25 to 200 parts by mass, and most preferably 35 to 175 parts by mass.

  Moreover, according to the use etc. of the thermoplastic elastomer composition finally obtained, you may contain another additive etc. with respect to the said mixture in the range which does not impair the objective of this invention. Examples of such other additives include a polymer other than the elastomer component, the α-olefin resin and the styrene block copolymer, a reinforcing agent (filler), and a filler obtained by introducing an amino group. (Hereinafter simply referred to as “amino group-introduced filler”), amino group-containing compounds other than the amino group-introduced filler, compounds containing metal elements (hereinafter simply referred to as “metal salts”), maleic anhydride-modified polymer , Anti-aging agent, antioxidant, pigment (dye), plasticizer, thixotropic agent, UV absorber, flame retardant, solvent, surfactant (including leveling agent), dispersant, dehydrating agent, rust inhibitor In addition, other components such as various additives such as an adhesion-imparting agent, an antistatic agent and a filler can be further contained. Thus, by including other components in the mixture, it is possible to appropriately include such components in the finally obtained thermoplastic elastomer composition. Such additives and the like are not particularly limited, and those commonly used can be appropriately used. In addition, as such other additives, those described in the thermoplastic elastomer composition of the present invention can be used as appropriate.

  The content of such other components (other additives) is such that the other components are polymers other than the elastomer component, the α-olefin resin and the styrene block copolymer, and reinforcing materials (filling). In the case of an agent), it is preferably 500 parts by mass or less, more preferably 20 to 400 parts by mass with respect to 100 parts by mass of the elastomer component. If the content of such other components is less than the lower limit, the effect of using the other components tends to be insufficiently expressed. On the other hand, if the content exceeds the upper limit, it depends on the type of the component used. The effect of the substrate elastomer is diminished and the physical properties tend to decrease.

  In addition, when the other component is other additive (in the case of other than the polymers and the reinforcing material (filler)), the content of the other component is based on 100 parts by mass of the elastomer component. 20 parts by mass or less is preferable, and 0.1 to 10 parts by mass is more preferable. 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 surface-treated calcium carbonate;
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 the present invention, it is possible to efficiently produce a thermoplastic elastomer composition having a sufficiently high level of fracture strength, compression set resistance, and heat resistance while maintaining a higher hardness. It becomes. 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 surface-treated calcium carbonate is contained together with the clay and the elastomer component in the obtained thermoplastic elastomer composition. Since such surface-treated calcium carbonate is coated with molecules having low polar atomic groups such as fatty acids and rosin acid, it can be uniformly dispersed without aggregation in a low polar elastomer molecular structure. Therefore, the present inventors speculate that the effect of adding calcium carbonate can be made uniform throughout the elastomer. Therefore, in the present invention, the obtained thermoplastic elastomer composition has a sufficiently high breaking strength, compression set resistance and heat resistance, and has a higher hardness. Et al.

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 the method for producing the thermoplastic elastomer composition of the present invention, the proportion of clay in the form of a single layer (single-layer clay) in the thermoplastic elastomer composition is more efficiently set to the above-mentioned suitable proportion. Is possible. 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.

  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.

<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).

<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.

<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.).

<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.

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., paraffin oil (trade name “Super Oil M Series P500S” manufactured by JX Nippon Mining & Energy Co., Ltd., kinematic viscosity: 472 mm ² / s, Cp value: 68, in the pressure kneader. 0.7%, aniline point: 123 ° C.) was dropped, and a styrene-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 MH5020” manufactured by Mitsui Chemicals, crystallinity: 4%) 100 g, surface treated calcium carbonate ( Surface-treated calcium carbonate surface-treated with fatty acid: trade name “Vigot-15” manufactured by Shiroishi Kogyo Co., Ltd., 25 g, average particle diameter: 0.20 μm, ethylene-propylene copolymer (EPM: trade name “Mitsui Chemicals, Inc.” TAFMER DF7350 ”, crystallinity: 10%, MFR: 35 g / 10 min (2.16 kg, 190 ° C.), Mw: 100,000) 75 g and anti-aging agent (trade name“ AO-50 ”manufactured by Adeka Corporation) 0 Further, 3 g was added, and the temperature was set to 200 ° C. and masticated for 2 minutes to prepare the first mixture (mixture containing surface-treated calcium carbonate and maleated EBM). Things) was obtained. In addition, the said 1st mixture was plasticized by this mastication process. Next, 1 g of organoclay (trade name “Kunifil-D36” 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 mixture of the two was obtained.

  Next, 1.31 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 the surface-treated calcium carbonate was changed, and the surface-treated calcium carbonate described later was used instead of the calcium carbonate surface-treated with a fatty acid. . 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 the surface-treated calcium carbonate. Table 1 shows the evaluation results of the properties of the thermoplastic elastomer composition obtained in each Example.
<Surface-treated calcium carbonate used in Example 2>
Surface-treated calcium carbonate surface-treated with a fatty acid (trade name “CC-R” manufactured by Shiroishi Kogyo Co., Ltd., average particle size: 0.12 μm)
<Surface-treated calcium carbonate used in Example 3>
Surface-treated calcium carbonate surface-treated with a fatty acid (trade name “Viscoexcel-30” manufactured by Shiroishi Kogyo Co., Ltd., average particle size: 0.08 μm)
<Surface treatment calcium carbonate used in Example 4>
Surface-treated calcium carbonate surface-treated with rosin acid (trade name “O” manufactured by Shiroishi Kogyo Co., Ltd., average particle size: 0.04 μm)
<Surface-treated calcium carbonate used in Example 5>
Surface-treated calcium carbonate surface-treated with rosin acid (trade name “TDD” manufactured by Shiroishi Kogyo Co., Ltd., average particle size: 0.14 μm).

(Comparative Example 1)
A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the surface-treated calcium carbonate was not used. Table 1 shows the evaluation results and the like of the properties of the obtained thermoplastic elastomer composition.

(Comparative Example 2)
In the same manner as in Example 1 except that calcium carbonate not subjected to surface treatment (trade name “Nesper” manufactured by Toyo Fine Chemical Co., Ltd., average particle size: 0.50 μm) was used instead of the surface-treated calcium carbonate. A thermoplastic elastomer composition was prepared. Table 1 shows the evaluation results and the like of the properties of the obtained thermoplastic elastomer composition.

(Comparative Example 3)
Trishydroxyethyl isocyanurate (commercial product made by Nissei Sangyo Co., Ltd.) was added to the first mixture without adding organoclay (trade name “Esven WX” manufactured by Hojun Co., Ltd.) to the first mixture. A thermoplastic elastomer composition was obtained in the same manner as in Example 5 except that 1.31 g of the name “Tanac”) was added and mixed at 200 ° C. for 8 minutes (except that the organic clay was not used). Table 1 shows the evaluation results and the like of the properties of the obtained thermoplastic elastomer composition.

(Comparative Example 4)
A thermoplastic elastomer composition was prepared in the same manner as in Comparative Example 3 except that the surface-treated calcium carbonate was not used. Table 1 shows the evaluation results and the like of the properties of the obtained thermoplastic elastomer composition.

(Comparative Example 5)
Example 1 except that magnesium oxide not subjected to surface treatment (trade name “Starmag PSF-150” manufactured by Kamishima Chemical Industry Co., Ltd., average particle size: 0.5 μm) was used in place of the surface-treated calcium carbonate. In the same manner, a thermoplastic elastomer composition was prepared. Table 1 shows the evaluation results and the like of the properties of the obtained thermoplastic elastomer composition.

(Comparative Example 6)
Instead of the surface-treated calcium carbonate, magnesium oxide surface-treated with a fatty acid (trade name “Magsarat 30” manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.5 μm) was used in the same manner as in Example 1. A thermoplastic elastomer composition was prepared. Table 1 shows the evaluation results and the like of the properties of the obtained thermoplastic elastomer composition.

[Characteristic evaluation of thermoplastic elastomer composition shown in Table 1]
As is clear from the results shown in Table 1, in the thermoplastic elastomer compositions (Examples 1 to 5) of the present invention containing the surface-treated calcium carbonate, the hardness is a value of 37 or more, and a comparative example It was confirmed that the hardness value was higher than that of the thermoplastic elastomer composition obtained in 1-6. In particular, when calcium carbonate is not used (Comparative Examples 1 and 4) and when magnesium oxide is used instead of calcium carbonate (Comparative Examples 5 and 6), when calcium carbonate is used (Examples 1 to 5). In Comparative Examples 2-3), it has been found that the hardness of the thermoplastic elastomer composition can be made higher. From these results, it was found that the hardness of the thermoplastic elastomer composition can be made higher by containing the surface-treated calcium carbonate.

  Moreover, in the thermoplastic elastomer composition of the present invention (Examples 1 to 5) containing surface-treated calcium carbonate, the value of compression set is 19% or less, whereas surface-treated carbonic acid In the system using calcium carbonate without surface treatment without using calcium (Comparative Example 2), the compression set value of the thermoplastic elastomer composition is 24%, and the surface treated calcium carbonate is used. In the system (Comparative Examples 5 to 6) using magnesium oxide or surface-treated magnesium oxide instead of, the value of compression set of the thermoplastic elastomer composition was 25% or more.

  From such a result, it was confirmed that the value of compression set can be made lower while the hardness of the thermoplastic elastomer composition is made higher by containing the surface-treated calcium carbonate. That is, from the results shown in Table 1, it was found that by using the surface-treated calcium carbonate, the hardness can be increased and a higher level of compression set resistance can be obtained.

  Furthermore, in the thermoplastic elastomer composition of the present invention (Examples 1 to 5), the 5% weight loss temperature is a value of 339 ° C. or more, and the thermoplastic elastomer composition containing no organoclay (comparison) It was found that a higher level of heat resistance was obtained compared to Examples 3-4).

  Moreover, in the thermoplastic elastomer composition (Examples 1-5) of this invention, the breaking strength is 5.1 Mpa or more, The thermoplastic elastomer composition (Comparative Examples 3-4) which does not contain organoclay ), A higher level of breaking strength was confirmed, and it was also found that sufficiently high breaking strength was obtained by the thermoplastic elastomer compositions of the present invention (Examples 1 to 5). It was. It was also found that the thermoplastic elastomer compositions (Examples 1 to 5) of the present invention all have sufficient tensile properties (elongation properties) as rubber from the value of elongation at break.

  Note that the thermoplastic elastomer composition obtained in Example 5 and the thermoplastic elastomer composition obtained in Comparative Example 3 differ only in the presence or absence of organic clay. Therefore, when comparing the thermoplastic elastomer composition obtained in Example 5 and the difference in composition of the thermoplastic elastomer composition obtained in Comparative Example 3 and the evaluation results of the properties, in addition to heat resistance, It was confirmed that the performances such as hardness, compression set resistance, and breaking strength were further improved by containing the organized clay.

  From these results, in the thermoplastic elastomer compositions (Examples 1 to 5) of the present invention, it is possible to make the hardness higher based on the composition, and at a sufficiently high level. It has been found that it is possible to have breaking strength, compression set resistance and heat resistance.

(Example 6)
First, 200 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) was charged into a pressure kneader. While being kneaded at 200 ° C., paraffin oil (trade name “Super Oil M Series P500S” manufactured by JX Nippon Mining & Energy Co., Ltd., kinematic viscosity: 472 mm ² / s, Cp value: 68, in the pressure kneader. (7%, aniline point: 123 ° C.) was added dropwise, and styrene-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 MH5020” manufactured by Mitsui Chemicals, crystallinity: 4%) 100 g, surface treated calcium carbonate ( Surface treated calcium carbonate surface treated with rosin acid; trade name “TDD” manufactured by Shiraishi Kogyo Co., Ltd., 5 g, average particle size: 0.14 μm, ethylene-propylene copolymer (EPM: trade name “Tafmer, manufactured by Mitsui Chemicals, Inc.) DF7350 ”, crystallinity: 10%, MFR: 35 g / 10 min (2.16 kg, 190 ° C.), Mw: 100,000) 75 g and anti-aging agent (trade name“ AO-50 ”manufactured by ADEKA CORPORATION) 3 g was further added, and the temperature was set to 200 ° C. for 2 minutes to obtain a first mixture (a mixture containing surface-treated calcium carbonate and maleated EBM). . In addition, the said 1st mixture was plasticized by this mastication process. Next, 0.1 g of organoclay (trade name “Esven WX” manufactured by Hojun Co., Ltd.) is further added to the first mixture in the pressure kneader, and kneaded at 200 ° C. for 4 minutes. A mixture of the two was obtained.

  Next, 1.31 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 2 shows the evaluation results 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. It can be seen that an elastomeric polymer mainly having the side chain (iii) was formed as described above. 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.

(Examples 7 to 8)
A thermoplastic elastomer composition was prepared in the same manner as in Example 6 except that the amount of calcium carbonate used was changed from 5 g to 10 g (Example 7) and 25 g (Example 8), respectively. As is clear from the description of such a production method, the thermoplastic elastomer compositions obtained in Examples 6 to 8 have the same composition except for the content of surface-treated calcium carbonate (TDD). Is. Table 2 shows the evaluation results of the properties of the obtained thermoplastic elastomer composition.

(Comparative Example 7)
A thermoplastic elastomer composition was prepared in the same manner as in Example 6 except that the surface-treated calcium carbonate was not used. Table 2 shows the evaluation results of the properties of the obtained thermoplastic elastomer composition.

[Characteristic evaluation of thermoplastic elastomer composition shown in Table 2]
As is clear from the results shown in Table 2, all of the thermoplastic elastomer compositions (Examples 6 to 8) of the present invention containing the surface-treated calcium carbonate were obtained in Comparative Example 7. It was found that the hardness could be higher than that of the product.

  Moreover, in the thermoplastic elastomer composition (Examples 6-8) of this invention, since the value of compression set is 17% or less, it is compression-resistant permanent of the level high enough as a rubber product. It was found to have distortion. Furthermore, in the thermoplastic elastomer composition of the present invention (Examples 6 to 8), the breaking strength was 5.0 MPa or more, and it was also found that the rubber product had a sufficiently high breaking strength. Furthermore, in the thermoplastic elastomer compositions (Examples 6 to 8) of the present invention, the 5% weight loss temperature is a value of 335 ° C. or more, and it is confirmed that sufficiently high heat resistance can be obtained. It was. It was also found that the thermoplastic elastomer compositions (Examples 6 to 8) of the present invention all have sufficient tensile properties (elongation properties) as rubber from the value of elongation at break.

  Thus, in the thermoplastic elastomer composition of the present invention (Examples 6 to 8), the hardness can be set to a higher value based on the composition, and a sufficiently high level of breaking strength can be obtained. It has been found that it is possible to have compression set resistance and heat resistance.

  As described above, according to the present invention, thermoplasticity capable of having a sufficiently high balance in terms of breaking strength, compression set resistance and heat resistance while achieving higher hardness. It becomes possible to provide an elastomer composition and a method for producing the same.

  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 (17)

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;
Surface-treated calcium carbonate surface-treated with an organic acid,
A thermoplastic elastomer composition comprising:   2. The thermoplastic elastomer composition according to claim 1, wherein the content of the surface-treated calcium carbonate is 50 parts by mass or less with respect to 100 parts by mass of the elastomer component.   The thermoplastic elastomer composition according to claim 1 or 2, wherein the organic acid is at least one of fatty acid and rosin acid.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the surface-treated calcium carbonate comprises particles having an average particle size of 0.5 µm or less.   The hydrogen-bonding cross-linking site contained in the side chain of the elastomeric polymer (B) is a hydrogen-bonding cross-linking 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 a clay which has silicon and magnesium as a main component, and an organized clay, The clay as described in any one of Claims 1-5 characterized by the above-mentioned. A thermoplastic elastomer composition.   The thermoplastic elastomer composition according to any one of claims 1 to 6, 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 7, 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 according to any one of claims 1 to 8, wherein the thermoplastic elastomer composition contains a structural portion represented by formula (1).   The thermoplastic elastomer composition according to any one of claims 1 to 9, 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 elastomer polymer, a polyurethane-type elastomer polymer, a polyester-type elastomer polymer, and a polyamide-type elastomer polymer. The thermoplastic elastomer composition according to any one of the above.   2. A paraffin oil, a styrene block copolymer having no chemically-bonded crosslinking site, and an α-olefin resin not having a chemically-bonded crosslinking site. The thermoplastic elastomer composition as described in any one of -12. A first step of obtaining a mixture by mixing an elastomeric polymer having a cyclic acid anhydride group in the side chain, clay, and surface-treated calcium carbonate surface-treated with an organic acid;
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 surface-treated calcium carbonate;
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 surface-treated calcium carbonate;
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.