JP7320005B2 - Thermoplastic elastomer composition and method for producing thermoplastic elastomer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition and a method for producing a thermoplastic elastomer composition.
This application claims priority based on Japanese Patent Application No. 2019-006378 filed in Japan on January 17, 2019, the content of which is incorporated herein.

In recent years, from the standpoint of environmental protection, resource saving, etc., reuse of used materials has been desired. Crosslinked rubber (vulcanized rubber) has a stable three-dimensional network structure in which a polymer substance and a crosslinking agent (vulcanizing agent) are covalently bonded, and exhibits extremely high strength. Difficult to reshape. Thermoplastic elastomers, on the other hand, utilize physical cross-linking, and can be easily molded by heating and melting without the need for complicated vulcanization and molding processes, including preforming, and can be reused. is also possible.

A typical example of such a thermoplastic elastomer includes a resin component and a crosslinked rubber component. At room temperature, plastic deformation is prevented by crystallization of the resin component, and plastic deformation occurs due to softening or melting of the resin component at elevated temperatures. Thermoplastic elastomers are known.

As thermoplastic elastomers, development of materials having excellent physical properties such as mechanical strength, particularly tensile strength, has been promoted. For example, in JP-A-2006-131663 (Patent Document 1), a side chain containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and a nitrogen-containing heterocycle, and the other side containing a covalent cross-linking site A thermoplastic elastomer comprising a polymer having a glass transition temperature of 25° C. or less is disclosed. Further, Japanese Patent Application Laid-Open No. 2016-193970 (Patent Document 2) discloses a thermoplastic elastomer in which tensile stress and heat resistance are improved by containing clay.

JP 2006-131663 A JP 2016-193970 A

However, while such thermoplastic elastomers exhibit excellent tensile strength and can be easily molded, they have a high surface tackiness (tackiness) when cured, making them difficult to handle during use. In some cases, a sticky feeling occurred. In addition, during molding, it tends to stick to hot rolls, pass rolls, molds, etc., and there is a risk of a low yield in the molding process.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a thermoplastic elastomer composition having a reduced surface tackiness when cured, and a method for producing the thermoplastic elastomer composition. and

In order to solve the above problems, the present inventors conducted intensive studies and found that a thermoplastic elastomer composition containing a specific polymer component in combination with a fatty acid amide compound having a molecular weight of 400 or more was obtained as a cured product. The present inventors have found that the tack force of the surface is remarkably reduced, leading to the completion of the present invention.
That is, one aspect of the present invention is the following thermoplastic elastomer composition and method for producing the thermoplastic elastomer composition.

(1) A 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 less, and a side chain at least one polymer component selected from the group consisting of polymers (B) containing a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site and having a glass transition point of 25° C. or lower;
containing a fatty acid amide compound,
A thermoplastic elastomer composition, wherein the fatty acid amide compound has a molecular weight of 400 or more.
(2) The thermoplastic elastomer composition according to (1) above, wherein the hydrogen-bonding cross-linking site of the polymer (B) has a carbonyl-containing group and/or a nitrogen-containing heterocyclic ring in its side chain.
(3) The thermoplastic elastomer composition according to (1) or (2) above, wherein the content of the fatty acid amide compound is 0.1% by mass or more relative to 100% by mass of the thermoplastic elastomer composition.
(4) The thermoplastic elastomer composition according to any one of (1) to (3) above, which further contains process oil.
(5) The thermoplastic elastomer composition according to (4) above, wherein the content of the process oil is 30% by mass or more with respect to 100% by mass of the thermoplastic elastomer composition.
(6) The thermoplastic elastomer composition according to any one of (1) to (5) above, which has a Shore A hardness of 70 or less according to JIS K6253 after curing.
(7) The thermoplastic elastomer composition according to any one of (1) to (6) above, wherein the polymer (A) and the polymer (B) are polyolefin polymers.
(8) A dynamically crosslinkable thermoplastic elastomer composition comprising a dispersed phase and a continuous phase, wherein the dispersed phase contains the polymer component and the continuous phase contains a thermoplastic resin, wherein (1) to (7) The thermoplastic elastomer composition according to any one of .
(9) the polymer component comprises the polymer (B),
The polymer (B) is a polymer having a cyclic acid anhydride group in a side chain,
A mixed raw material of compound (I) that forms a hydrogen-bonding cross-linking site by reacting with the cyclic acid anhydride group and compound (II) that forms a covalent cross-linking site, or reacting with the cyclic acid anhydride group The thermoplastic elastomer composition according to any one of (1) to (8) above, which is a reactant with a compound capable of forming both hydrogen-bonding cross-linking sites and covalent-bonding cross-linking sites.
(10) the polymer component comprises the polymer (B),
The polymer (B) is a polymer having a cyclic acid anhydride group in a side chain,
any one of (1) to (9) above, which is a reaction product of a compound capable of forming both a hydrogen-bonded cross-linked site and a covalently-bonded cross-linked site by reacting with the cyclic acid anhydride group; The thermoplastic elastomer composition described.
(11) the polymer having a cyclic acid anhydride group in a side chain is a maleic anhydride-modified polymer;
The compound capable of reacting with the cyclic acid anhydride group to form both a hydrogen-bonding cross-linking site and a covalently-bonding cross-linking site is a nitrogen-containing heterocycle-containing polyol, a nitrogen-containing heterocycle-containing polyamine, and a nitrogen-containing heterocycle-containing The thermoplastic elastomer composition according to (9) or (10), which is at least one compound selected from the group consisting of polythiols.
(12) A method for producing a thermoplastic elastomer composition according to any one of (1) to (11) above,
A mixture containing a polymer having a cyclic acid anhydride group in a side chain and at least one raw material compound selected from the group consisting of <1> to <3> below is obtained, and the polymer and the raw material compound are combined. obtaining a polymer component by reacting
blending a fatty acid amide compound into the mixture before reacting the polymer with the raw material compound or into the mixture after reacting the polymer with the raw material compound. A method of making things.
<1> Compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site,
<2> A mixed raw material of the compound (I) and the compound (II) that reacts with the cyclic acid anhydride group to form a covalently crosslinked site,
<3> A compound capable of forming both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site by reacting with the cyclic acid anhydride group

According to the present invention, it is possible to provide a thermoplastic elastomer composition having a reduced surface tackiness when cured, and a method for producing the thermoplastic elastomer composition.

The thermoplastic elastomer composition of the present invention and embodiments of the thermoplastic elastomer composition are described below.

<<Thermoplastic elastomer composition>>
The thermoplastic elastomer composition of the embodiment is a polymer ( A), and at least one polymer selected from the group consisting of a polymer (B) containing a hydrogen-bonding cross-linking site and a covalently-bonding cross-linking site in the side chain and having a glass transition point of 25°C or less. and a fatty acid amide compound, wherein the fatty acid amide compound has a molecular weight of 400 or more.

The inventors have found that the combination of the above specific polymer component and a fatty acid amide compound having a molecular weight of 400 or more can significantly reduce the tackiness of the surface of a cured product of a thermoplastic elastomer composition containing these components. I found out.

Each component included in the thermoplastic elastomer composition of the embodiment will be described in detail below.

<Fatty acid amide compound>
The molecular weight of the fatty acid amide compound according to the embodiment is 400 or more, preferably 400 or more and 1000 or less, more preferably 500 or more and 700 or less, and even more preferably 550 or more and 650 or less.
Conventionally, a cured product of a thermoplastic elastomer composition containing a fatty acid amide compound may have a strongly sticky surface. Since the thermoplastic elastomer composition of the embodiment contains a fatty acid amide compound having a molecular weight of 400 or more, the tackiness of the surface of the cured product is remarkably reduced.
Although the details of the mechanism by which the tackiness of the surface of the cured product of the thermoplastic elastomer composition is remarkably reduced are not clear at the present time, the thermoplastic elastomer composition can be cured by curing the thermoplastic elastomer composition when the molecular weight of the fatty acid amide compound is 400 or more. It is presumed that the fatty acid amide compound tends to exist on the surface of the cured product when it is made into a product, thereby effectively reducing the tackiness. On the other hand, if the molecular weight of the fatty acid amide compound is less than 400, even if the thermoplastic elastomer composition contains the fatty acid amide compound, a large amount of the fatty acid amide compound is distributed inside the cured product of the thermoplastic elastomer composition. Therefore, it is presumed that the effect of reducing the tack force is difficult to be exhibited.
Moreover, if the mixing state of the additive and the polymer component is not good, the additive may partially agglomerate to cause whitening of the additive. The combination of the specific polymer component and the fatty acid amide compound as an additive according to the embodiment is considered to be a combination that has a good mixing state when both are mixed, and whitening of the additive or the like appears on the surface of the cured product. It has the advantage of being less likely to occur.
By setting the molecular weight of the fatty acid amide compound contained in the thermoplastic elastomer composition of the embodiment to 400 or more, it is possible to achieve both prevention of whitening and reduction of tackiness.

The melting point of the fatty acid amide compound according to the embodiment is determined in relation to the value of the molecular weight, and is not particularly limited, but is preferably 90°C or higher and lower than 180°C, more preferably 100°C or higher and lower than 160°C. preferable. By using a fatty acid amide compound having a melting point within the above temperature range, melt-mixing can be easily performed while the fatty acid amide compound is molten.

The fatty acid amide compound according to the embodiment is a concept including carboxylic acid amides including fatty acid amides, and is a compound represented by the following general formula (I) having a molecular weight of 400 or more.

(In general formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, provided that all of R ¹ , R ² and R ³ are hydrogen atoms never.)

In the compound represented by the general formula (I), when R ^{1 is} a monovalent organic group and R ² and R ³ are hydrogen atoms (primary amide); , when either one of R ² and R ³ is a monovalent organic group and either one of R ² and R ³ is a hydrogen atom (secondary amide); when R ¹ is a monovalent organic group and R ² and R ³ are monovalent organic groups (tertiary amide).
The monovalent organic group for R ¹ is preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group is either a saturated aliphatic hydrocarbon group (alkyl group) optionally having a substituent or an unsaturated aliphatic hydrocarbon group (alkenyl group) optionally having a substituent. It's okay.
The number of carbon atoms of the organic groups in R ¹ , R ² and R ³ may be appropriately determined within the molecular weight range defined for the fatty acid amide compound according to the embodiment.

The compound represented by the general formula (I) is preferably a bisamide compound represented by the following general formula (II).

(In general formula (II), R ¹¹ and R ¹² each independently represent a monovalent organic group; R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group; R ⁵ is 2; represents a valent organic group.)

When R ¹⁴ and R ¹⁵ are monovalent organic groups, alkyl groups having 1 to 5 carbon atoms can be exemplified.

In the compound represented by the general formula (II), when R ¹⁴ and R ¹⁵ are hydrogen atoms, bisamide compounds represented by the following general formula (III) can be exemplified.

(R ¹¹ , R ¹² and R ⁵ in general formula (III) have the same meanings as R ¹¹ , R ¹² and R ⁵ in general formula (II).)

In the general formulas (II) and (III), the monovalent organic groups of R ¹¹ and R ¹² are preferably aliphatic hydrocarbon groups. The aliphatic hydrocarbon group is either a saturated aliphatic hydrocarbon group (alkyl group) optionally having a substituent or an unsaturated aliphatic hydrocarbon group (alkenyl group) optionally having a substituent good. The number of carbon atoms in the organic groups in R ¹¹ and R ¹² may be appropriately determined within the range of the molecular weight specified for the fatty acid amide compound according to the embodiment, preferably 9 to 29 carbon atoms, more preferably 13 to 25 carbon atoms. Preferably, it has 15 to 20 carbon atoms.
In general formulas (II) and (III), the divalent organic group for R ⁵ is preferably an alkylene group. The number of carbon atoms in the alkylene group of R ⁵ may be appropriately determined within the range of the molecular weight defined for the fatty acid amide compound according to the embodiment, but it preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. is more preferred, and it is even more preferred that it has 1 to 3 carbon atoms.
A hydroxyl group etc. can be illustrated as a substituent in the said alkyl group and alkenyl group.

In the bisamide compound represented by the general formula (III), R ¹¹ and R ¹² are each independently an alkyl or alkenyl group having 15 to 20 carbon atoms, and R ⁵ is an alkylene having 1 to 3 carbon atoms. Those which are radicals are preferred.

Examples of the compound represented by the general formula (III) include alkylenebis fatty acid amides obtained by reacting diamines with fatty acids.
Examples of the diamine include alkylenediamines such as methylenediamine, ethylenediamine, propylenediamine, butylenediamine, octamethylenediamine, dodecamethylenediamine, and undecamethylenediamine.
Examples of the fatty acid include decanoic acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, montanic acid, and melissic acid.

Examples of the compound represented by the general formula (III) include N,N'-methylenebisstearic acid amide, N,N'-methylenebisstearic acid amide, N,N'-ethylenebisstearic acid amide, N,N '-ethylenebisoleic acid amide, N,N'-hexamethylenebisstearamide, N,N'-methylenebisoctadecaneamide, N,N'-methylenebislauric acid amide, N,N'-methylenebismyristate amide, N,N'-methylenebispalmitamide, N,N'-methylenebisbehenamide, N,N'-methylenebiserucamide, N,N'-ethylenebislaurateamide, N,N' - ethylenebismyristate amide, N,N'-ethylenebispalmitamide, N,N'-ethylenebisbehenamide, N,N'-ethylenebiserucamide, N,N'-(1,6 hexane diyl)bis[12-hydroxyoctadecanamide] and the like.

Fatty acid amide compounds may be used singly or in combination of two or more.

The content of the fatty acid amide compound in the thermoplastic elastomer composition may be appropriately determined according to the type of the polymer component, the fatty acid amide compound, etc. , The content ratio of the fatty acid amide compound is preferably 0.1% by mass or more, preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 7% by mass or less, and 3% by mass or more. 6% by mass or less is more preferable. When the ratio of the content of the fatty acid amide compound with respect to 100% by mass of the thermoplastic elastomer composition is equal to or higher than the above lower limit, the tack force of the surface when the thermoplastic elastomer composition is used as a cured product is further effectively improved. can be reduced to Further, when the ratio of the content of the fatty acid amide compound with respect to 100% by mass of the thermoplastic elastomer composition is equal to or less than the above upper limit, contamination of molding processing equipment due to adhesion of the fatty acid amide compound is effectively prevented. .

<Polymer component>
The polymer component according to the embodiment is a polymer (A) having a side chain (a) containing a hydrogen-bonding crosslinked site having a carbonyl-containing group and/or a nitrogen-containing heterocycle and having a glass transition point of 25°C or less. and at least one selected from the group consisting of a polymer (B) having a side chain containing a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site and having a glass transition point of 25°C or less. .

The polymer component according to the embodiment is an elastomer component in which the polymer (A) and/or the polymer (B) is an elastomeric polymer (A) having elastomeric properties and/or an elastomeric polymer (B) having elastomeric properties. There may be.

The thermoplastic elastomer compositions of embodiments have thermoplastic and elastomeric properties (elasticity). However, as exemplified below, in the thermoplastic elastomer composition, the main chain portion of the polymer (and the polymer forming the main chain portion described below), which is one of the constituent elements thereof, does not necessarily have elastomeric properties. It's good. In such a case, it is considered that the elastomeric properties of the thermoplastic elastomer composition of the embodiment are exhibited by the above crosslinked sites. Here, the "main chain of the polymer" refers to the side chains (side chain (a), side chain (a'), side chain (b), which constitute the cross-linking site described later from the polymers (A) to (B) , and the side chain (c)).

In polymers (A) to (B), "side chain" refers to the side chain and end of the polymer.
In addition, the "side chain (a) containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and/or a nitrogen-containing heterocyclic ring" means that an atom (usually a carbon atom) forming the main chain of the polymer has a hydrogen bond carbonyl-containing group and/or nitrogen-containing heterocyclic ring (more preferably carbonyl-containing group and nitrogen-containing heterocyclic ring) forming a chemically stable bond (covalent bond). Further, "the side chain contains a hydrogen-bonding cross-linking site and a covalent cross-linking site" means a side chain having a hydrogen-bonding cross-linking site (hereinafter, for convenience, sometimes referred to as "side chain (a')" ) and a side chain having a covalent cross-linking site (hereinafter, for convenience, sometimes referred to as “side chain (b)”), so that a hydrogen-bonding cross-linking site is added to the side chain of the polymer. and covalent cross-linking sites, and side chains containing both hydrogen-bonding cross-linking sites and covalent cross-linking sites (hydrogen-bonding cross-linking sites and covalent cross-linking sites in one side chain). Side chains containing both cross-linking sites: hereinafter for convenience such side chains are sometimes referred to as "side chains (c)"), so that the side chains of the polymer have both hydrogen-bonding cross-linking sites and covalent This concept includes the case where both binding cross-linking sites are contained.

From the viewpoint of improving stretchability, such a polymer component contains a hydrogen-bonding cross-linking site and a covalent cross-linking site in the side chain and has a glass transition point of 25 ° C. or less from the polymer (B) At least one selected from the group consisting of is more preferable.

Polymers (A) to (B) have, for example, a polymer having a glass transition point of room temperature (25° C.) or lower such as a natural polymer or a synthetic polymer as a main chain, and a carbonyl-containing group and/or a nitrogen-containing heterocyclic ring. A side chain (a) containing a hydrogen-bonding cross-linking site having , containing a side chain (a′) having a hydrogen-bonding cross-linking site and a side chain (b) having a covalent cross-linking site; a natural polymer or synthetic polymer having a glass transition point of room temperature (25° C.) A polymer having the following polymer as a main chain and containing a side chain (c) containing both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site;

Polymers forming the main chain portions of polymers (A) to (B) include, respectively, diene rubbers, hydrogenated diene rubbers, olefin rubbers, optionally hydrogenated polystyrene polymers, and polyolefin rubbers. It is preferably made of at least one selected from polymers, polyvinyl chloride-based polymers, polyurethane-based polymers, polyester-based polymers, and polyamide-based polymers. ^The polyolefin-based polymer is a polymer ^having structural units derived from olefins. /m ³ or more), linear polyethylene (LLDPE), polypropylene, and the like. In addition, from the viewpoint that there is no double bond that is easily aged, hydrogenated diene rubber, Olefin-based rubbers and polyolefin-based polymers are preferred, and diene-based rubbers are preferred from the viewpoints of low cost and high reactivity (having many double bonds capable of en-reaction with compounds such as maleic anhydride). preferable. The polymer forming the main chain portion may be either an elastomeric polymer or a non-elastomeric polymer.

In addition, as the polymer forming the main chain portion of such a polymer component, polyethylene (more preferably high density polyethylene (HDPE)), ethylene-butene copolymer, Ethylene-propylene copolymer and more preferably at least one selected from the group consisting of polypropylene, polyethylene (more preferably high density polyethylene (HDPE)) and ethylene-butene copolymer At least one selected from the group is particularly preferred.

The polymer forming the main chain portion of such a polymer component (the polymers (A) to (B)) may be a rubber-based polymer having elastomeric properties, such as natural rubber (NR), isoprene rubber ( IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM ) and hydrogenated products thereof; ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), chlorosulfonated polyethylene, acrylic rubber, fluororubber, polyethylene rubber, olefin rubber such as polypropylene rubber; epichlorohydrin rubber; polysulfide rubber; silicone rubber;

In addition, the polymer forming the main chain portion of the polymer component (the polymers (A) to (B)) may be a polymer component having elastomeric properties, for example, a polystyrene-based elastomeric polymer that may be hydrogenated. Polymers (e.g., SBS, SIS, SEBS, etc.), polyolefin-based elastomeric polymers, polyvinyl chloride-based elastomeric polymers, polyurethane-based elastomeric polymers, polyester-based elastomeric polymers, polyamide-based elastomeric polymers, etc., and polyolefin-based Elastomeric polymers are preferred. Examples of polyolefin-based elastomeric polymers include ethylene-based copolymers, and ethylene-α-olefin copolymers are preferred. Examples of α-olefin include 1-butene.

In addition, as the polymer forming the main chain portion of the polymer having elastomeric properties (the elastomeric polymers (A) to (B)), from the viewpoint that there is no double bond that is susceptible to aging, hydrogenation of diene rubber is preferred. In view of low cost and high reactivity (having many double bonds capable of en-reaction with compounds such as maleic anhydride), diene rubbers are preferred. Further, if olefinic rubber is used to form the main chain portion of each of the elastomer components (the elastomeric polymers (A) to (B)) suitable as the polymer component, deterioration is more likely to occur due to the absence of double bonds. It tends to be well suppressed.

Furthermore, the polymers (A) to (B) may be liquid or solid, and their molecular weights are not particularly limited. can be selected as appropriate.

When emphasis is placed on fluidity when the thermoplastic elastomer composition of the embodiment is heated (decrosslinking, etc.), the polymers (A) and (B) are preferably liquid, and for example, form the main chain portion. When the polymer to be used is a diene rubber such as isoprene rubber or butadiene rubber, the main chain portion should have a weight average molecular weight of 1,000 to 100 in order to make the polymers (A) to (B) liquid. ,000, and particularly preferably about 1,000 to 50,000.

On the other hand, when emphasizing the strength of the thermoplastic elastomer composition of the embodiment, the polymers (A) and (B) are preferably solid. In the case of a diene rubber such as butadiene rubber, the main chain portion preferably has a weight average molecular weight of 100,000 or more in order to make the polymers (A) to (B) solid. It is particularly preferable to be about 500,000 to 1,500,000.

The weight average molecular weight of the main chain portion is determined by gel permeation chromatography (Gel
weight-average molecular weight (converted to polystyrene) measured by permeation chromatography (GPC). Tetrahydrofuran (THF) is preferably used as a solvent for the measurement.

In the thermoplastic elastomer composition of the embodiment, the polymers (A) to (B) can be used in combination of two or more. In this case, the mixing ratio of the respective polymers can be any ratio depending on the application for which the thermoplastic elastomer composition of the embodiment is used, the required physical properties, and the like.

Further, the glass transition points of the polymers (A) and (B) are 25° C. or less as described above. This is because if the glass transition point of the polymer is within this range, the thermoplastic elastomer composition of the embodiment exhibits rubber-like elasticity at room temperature. Further, in the embodiment, the "glass transition point" is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry). In the measurement, the heating rate is 10° C./min.

The polymer forming the main chain portion of the polymers (A) to (B) has a glass transition point of 25° C. or lower, and the resulting molded article made of the thermoplastic elastomer composition. 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- Diene rubber such as propylene-diene rubber (EPDM) and butyl rubber (IIR); Olefin rubber such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM) and ethylene-butene rubber (EBM); . Further, when an olefinic rubber is used to form the main chain portion of each of the polymers (A) to (B), the tensile strength of the resulting thermoplastic elastomer composition is improved, and double bonds are not present. deterioration tends to be more sufficiently suppressed.

The bound styrene content of the styrene-butadiene rubber (SBR) that can be used for the polymers (A) to (B), the hydrogenation rate of the optionally hydrogenated polystyrene-based elastomeric polymer, and the like are not particularly limited. However, the ratio can be adjusted to an arbitrary ratio depending on the application for which the thermoplastic elastomer composition of the embodiment is used, the physical properties required for the composition, and the like.

In addition, ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM) are used to form the main chain portions of the polymers (A) to (B). is used, its ethylene content is preferably 10 to 90 mol %, more preferably 30 to 90 mol %. When the ethylene content is within this range, the compression set, mechanical strength, and particularly tensile strength of the thermoplastic elastomer (composition) are excellent, which is preferable.

In addition, as described above, the polymers (A) to (B) have, as side chains, side chains (a) containing hydrogen-bonding cross-linking sites having a carbonyl-containing group and/or a nitrogen-containing heterocyclic ring; a side chain (a′) containing a sexual cross-linking site and a side chain (b) containing a covalent cross-linking site; and a side chain (c) containing a hydrogen-bonding cross-linking site and a covalent cross-linking site; It has at least one of them. In this specification, the side chain (c) can also be said to be a side chain that functions both as the side chain (a') and as the side chain (b). Each side chain is described below.

<Side chain (a′): side chain containing hydrogen-bonding cross-linking site>
The side chain (a′) containing a hydrogen-bonding cross-linking site has a group capable of forming a cross-linking by hydrogen bonding (e.g., a hydroxyl group, a hydrogen-bonding cross-linking site contained in the side chain (a) described later, etc.). , is not particularly limited as long as it is a side chain that forms a hydrogen bond based on the group. Here, the hydrogen-bonding cross-linking site is a site that cross-links polymers by hydrogen bonding. Cross-linking by hydrogen bonding consists of a hydrogen acceptor (group containing an atom containing a lone pair of electrons, etc.) and a hydrogen donor (group containing a hydrogen atom covalently bonded to an atom with high electronegativity, etc.). Therefore, if both the hydrogen acceptor and the hydrogen donor are not present between the side chains of the polymers, the cross-linking due to the hydrogen bond is not formed. Therefore, a hydrogen-bonding cross-linking site exists in the system only when both a hydrogen acceptor and a hydrogen donor are present between the side chains of the polymers. In the present specification, between the side chains of the polymers, both a portion that can function as a hydrogen acceptor (for example, a carbonyl group) and a portion that can function as a hydrogen donor (for example, a hydroxyl group) are present. Thus, the portion of the side chain that can function as a hydrogen acceptor and the portion that can function as a donor can be determined as hydrogen-bonding cross-linking sites.

From the viewpoint of forming a stronger hydrogen bond, the hydrogen-bonding cross-linking site in the side chain (a′) may be a hydrogen bond having a carbonyl-containing group and/or a nitrogen-containing heterocyclic ring, as described below. It is preferably a functional cross-linking site (a hydrogen-bonding cross-linking site contained in the side chain (a)). That is, the side chain (a') described below is more preferable as the side chain (a'). From the same point of view, 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 heterocyclic ring.

<Side Chain (a): Side Chain Containing Hydrogen Bonding Crosslinking Site Having Carbonyl-Containing Group and/or Nitrogen-Containing Heterocycle>
The side chain (a) containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and/or a nitrogen-containing heterocycle may have a carbonyl-containing group and/or a nitrogen-containing heterocycle, and other configurations are particularly Not limited. As such a hydrogen-bonding cross-linking site, one having a carbonyl-containing group and a nitrogen-containing heterocyclic ring is more preferable.

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 forming the main chain portion) using a compound capable of introducing a carbonyl-containing group into the main chain. For example, the carbonyl-containing group is formed by introducing a carbonyl-containing group into the main chain (polymer of the main chain portion) of high-density polyethylene using a compound capable of introducing the carbonyl-containing group into the main chain. may be a base. A 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 saturated or unsaturated hydrocarbon groups, and the hydrocarbon groups may be aliphatic, alicyclic, or aromatic. Specific examples of carboxylic acid derivatives include carboxylic anhydrides, amino acids, thiocarboxylic acids (mercapto group-containing carboxylic acids), esters, ketones, amides, imides, dicarboxylic acids and monoesters thereof. mentioned.

Specific examples of the carboxylic acid and derivatives thereof include malonic acid, maleic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, and p-hydroxybenzoic acid. carboxylic acids such as acids, p-aminobenzoic acid, mercaptoacetic acid and those containing substituents; succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, propionic anhydride, Acid 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 hydroxybenzoates; ketones such as quinones, anthraquinones, naphthoquinones; Amino acids such as p-aminobenzoyl)-β-alanine; maleamide, maleamic acid (malein monoamide), succinic acid monoamide, 5-hydroxyvaleramide, N-acetylethanolamine, N,N'-hexamethylenebis(acetamide) ), amides such as malonamide, cycloserine, 4-acetamidophenol and p-acetamidobenzoic acid; imides such as maleimide and succinimide;

Among these, compounds into which a carbonyl group (carbonyl-containing group) can be introduced are cyclic acid anhydrides having a carbonyl group in the ring skeleton, such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride. is preferred, and maleic anhydride is particularly preferred.

Further, when the side chain (a) has a nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring may be introduced into the main chain directly or via an organic group, and its configuration and the like are particularly limited. not a thing Such a nitrogen-containing heterocyclic ring may be one having a heteroatom other than a nitrogen atom in the heterocyclic ring, such as a sulfur atom, an oxygen atom, a phosphorus atom, etc., as long as the heterocyclic ring contains a nitrogen atom. can. Here, when a nitrogen-containing heterocyclic ring is used in the side chain (a), the presence of the heterocyclic ring structure strengthens the hydrogen bonds forming the crosslinks, and the resulting thermoplastic elastomer composition of the embodiment. It is preferable because it improves tensile strength and impact resistance.

In addition, 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 (isopropyl group) and a hexyl group; a methoxy group and an ethoxy group; , (iso) alkoxy group such as propoxy group; group consisting of halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; amino group; aromatic hydrocarbon group; ester group; thioether group; hydroxyl group; thiol group; carboxy group; isocyanate group; epoxy group; The substitution position of these substituents is not particularly limited, and the number of substituents is also not limited.

Furthermore, the nitrogen-containing heterocyclic ring may or may not have aromaticity, but if it has aromaticity, the compression permanent property of the thermoplastic elastomer composition of the embodiment is obtained. It is preferable because strain and mechanical strength are further improved.

In addition, such a nitrogen-containing heterocyclic ring is not particularly limited, but from the viewpoint that the hydrogen bond becomes stronger and the compression set and mechanical strength are further improved, a 5-membered ring and a 6-membered ring is preferably Such a nitrogen-containing heterocycle may be a nitrogen-containing heterocycle condensed with a benzene ring or a condensed nitrogen-containing heterocycle. Examples of such nitrogen-containing heterocycles include pyrroline, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl, phthalimidine, β-isoindigo, and monoporphyrin. , diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phylloerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone, hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, indole, indoline, oxyindole, carbazole, phenothiazine, indolenine, isoindole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole , oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine, pyrazine, phenazine, tetrazine, benzoxazole, benzisoxazole, anthranyl, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, Anthrazoline, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline, triazine, histidine, triazolidine, melamine, adenine, guanine, thymine, cytosine, hydroxyethyl isocyanurate and derivatives thereof. Among these, the nitrogen-containing 5-membered ring is particularly suitable for the following compounds (cyclic structures described by the chemical formula), triazole derivatives represented by the following general formula (10), and imidazole derivatives represented by the following general formula (11). are preferably exemplified. In addition, these may have the various substituents described above, and may be hydrogenated or eliminated.

The substituents X, Y, and Z in 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 a It is an aryl group or an amino group. Either one of X and Y in formula (10) above is not a hydrogen atom, and similarly, at least one of X, Y and Z in formula (11) above is not a hydrogen atom.

Examples of such substituents X, Y, and Z include, in addition to hydrogen atoms and amino groups, specific examples include methyl, ethyl, propyl, butyl, pentyl, octyl, dodecyl, and stearyl groups. Linear alkyl groups such as groups; 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; be done.

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

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

In addition, condensed nitrogen-containing heterocycles and benzene rings or nitrogen-containing heterocycles can also be used. Specifically, the following condensed rings are preferably exemplified. These condensed rings may also have the various substituents described above, or may have hydrogen atoms added or removed.

As such a nitrogen-containing heterocyclic ring, triazole ring, isocyanurate ring, It is preferably at least one selected from a thiadiazole ring, a pyridine ring, an imidazole ring, a triazine ring and a hydantoin ring, and at least one selected from a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring and a hydantoin ring. One type is preferred.

When both the carbonyl-containing group and the nitrogen-containing heterocycle are contained in the side chain (a), the carbonyl-containing group and the nitrogen-containing heterocycle are introduced into the main chain as independent side chains. However, it is preferable that the carbonyl-containing group and the nitrogen-containing heterocyclic ring are introduced into the main chain as one side chain bonded via different groups. Thus, as the side chain (a), it is preferable that a side chain containing a hydrogen-bonding cross-linking site having the carbonyl-containing group and the nitrogen-containing heterocyclic ring is introduced as one side chain into the main chain. , the following general formula (1):

[In the formula (1), A is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR'(R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) or a sulfur atom or an organic group that may contain these atoms or groups. ]
More preferably, the side chain containing the structural moiety represented by is introduced into the main chain as one side chain. Thus, the hydrogen-bonding cross-linking site of the side chain (a) preferably contains the structural moiety represented by the general formula (1).

Here, the nitrogen-containing heterocycle A in the above formula (1) specifically includes the nitrogen-containing heterocycles exemplified above. Further, as the substituent B in the above formula (1), specifically, for example, a single bond; an oxygen atom, a sulfur atom or an amino group NR'(R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) an organic group that may contain these atoms or groups, for example, an alkylene group or an aralkylene group having 1 to 20 carbon atoms; an alkylene ether group having 1 to 20 carbon atoms (alkylene an oxy group (eg, —O—CH ₂ CH ₂ — group), an alkyleneamino group (eg, —NH—CH ₂ CH ₂ — group) or an alkylenethioether group (eg, an alkylenethio group, —S—CH ₂ CH ₂ -group); an aralkylene ether group (aralkyleneoxy group) having 1 to 20 carbon atoms, an aralkylene amino group or an aralkylene lentioether group having these at the end; and the like.

Here, the alkyl group having 1 to 10 carbon atoms of the amino group NR' includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group, including isomers. group, decyl group, and the like. an oxygen atom, a sulfur atom and an amino group NR' of the substituent B in the above formula (1); Alternatively, an oxygen atom such as an aralkylene ether group, an aralkylene amino group, an aralkylene lentithioether group, an amino group NR' and a sulfur atom are combined with adjacent carbonyl groups to form a conjugated ester group, an amide group, an 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 that forms a conjugated system; It is preferably a thioether group, an amino group (NH), an alkyleneamino group (-NH-CH ₂ - group, -NH-CH ₂ CH ₂ - group, -NH-CH ₂ CH ₂ CH ₂ - group), alkylene An ether group (--O--CH ₂ --- group, --O--CH ₂ CH ₂ --- group, --O--CH ₂ CH ₂ CH ₂ --- group) is particularly preferred.

Further, when the side chain (a) is a side chain containing a hydrogen-bonding crosslinking 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 functional cross-linking 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).

[In the formula, 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 sulfur atoms; or organic groups that may contain these atoms or groups. ]
Here, the nitrogen-containing heterocycle A is basically the same as the nitrogen-containing heterocycle A exemplified in the above formula (1), and the substituents B and D are each independently the substituents exemplified in the above formula (1). It is basically the same as B. However, the substituent D in the above formula (3) is, among those exemplified as the substituent B in the above formula (1), a single bond; It preferably forms a conjugated system of groups or aralkylene groups, and particularly preferably a single bond. That is, together with the imide nitrogen of the above formula (3), 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, and the above formula (3) It is particularly preferred that the nitrogen-containing heterocyclic ring is directly bonded to the imide nitrogen of (single bond). Specifically, the substituent D includes 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 described above, or the like; methylene, including isomers group, ethylene group, propylene group, butylene group, hexylene group, phenylene group, xylylene group and the like.

Further, when the side chain (a) is a side chain containing a hydrogen-bonding cross-linking site having the carbonyl-containing group and the nitrogen-containing heterocyclic ring, the hydrogen-bonding cross-linking site of the side chain (a) is the following general Formula (101):

[In formula (101), A is a nitrogen-containing heterocycle. ]
It is preferable to contain the structural portion represented by. Such a nitrogen-containing heterocycle A in formula (101) is basically the same as the nitrogen-containing heterocycle A exemplified in formula (1) above. Further, from the viewpoint of high modulus and high breaking strength, the hydrogen-bonding cross-linking site of the side chain (a) may be the following general formula (102):

Those having a structure represented by are more preferable. Furthermore, it is particularly preferable that the side chain (a) is a group represented by the general formula (102).

The ratio of the carbonyl-containing group and the nitrogen-containing heterocyclic ring that the polymer component can have is not particularly limited, and when the ratio is 2:1, complementary interactions are likely to be formed, and production is easy. Therefore, it is preferable.

The side chain (a) containing a hydrogen-bonding cross-linking site having such a carbonyl-containing group and/or nitrogen-containing heterocyclic ring accounts for 0.1 to 50 mol% of the main chain portion 100 mol% ( introduction rate), and more preferably at a rate of 1 to 30 mol %. If the introduction ratio of the side chain (a) is less than 0.1 mol%, the tensile strength at the time of cross-linking may not be sufficient. There is That is, if the introduction rate is within the above range, cross-linking is efficiently formed between molecules due to the interaction between the side chains of the polymer component, so that the tensile strength at the time of cross-linking is high and the recyclability is excellent. preferable.

The introduction rate is based on the side chain (a) containing the hydrogen-bonding cross-linking site having the carbonyl-containing group and the side chain (ai) containing the hydrogen-bonding cross-linking site having the nitrogen-containing heterocyclic ring. When the chains (a-ii) are introduced independently, the side chain (a-i) containing the carbonyl-containing group and the side chain (a-ii) containing the nitrogen-containing heterocycle , these are considered as one side chain (a) for calculation. If any one of the side chains (ai) and (a-ii) is in excess, the introduction rate can be considered based on the side chain with the greater amount.

Further, the introduction ratio is, for example, when the polymer forming the main chain portion is ethylene-propylene rubber (EPM), the monomer into which the side chain portion is introduced is 0 per 100 units of ethylene and propylene monomer units. .1 to 50 units.

As the side chain (a), a cyclic acid anhydride group (preferably a cyclic acid anhydride having a group, more preferably a maleic anhydride group) (a polymer having a cyclic acid anhydride group in a side chain), the functional group (cyclic acid anhydride group) and the cyclic acid anhydride group A compound that reacts to form a hydrogen-bonding cross-linking site (a compound capable of introducing a nitrogen-containing heterocycle) is reacted to form a hydrogen-bonding cross-linking site, and the side chain of the polymer is combined with the side chain (a). preferably. A compound capable of introducing such a nitrogen-containing heterocycle may be the above-exemplified nitrogen-containing heterocycle itself, and a substituent reacting with a cyclic acid anhydride group such as maleic anhydride (e.g., hydroxyl group, thiol group, amino group, etc.).

Here, the “cyclic acid anhydride group” means a cyclic acid anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride undergoing a structural change necessary for binding to a polymer. means the resulting group. When the cyclic acid anhydride group is a cyclic acid anhydride group having a carbonyl group in the ring skeleton, the cyclic acid anhydride group is a structure generated by dehydration condensation of a carboxylic acid (e.g., -CO-O-CO- structure represented).
Here, the polymer having the cyclic acid anhydride group in the side chain can also be referred to as a cyclic acid anhydride-modified polymer. Cyclic anhydride-modified polymers can be formed by attaching a cyclic anhydride directly or through an organic group to the polymer.

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

The binding positions (“1-n positions”) described below are based on the IUPAC nomenclature.
For example, in the case of a compound having three nitrogen atoms each having a lone pair of electrons, the bonding positions are determined according to the order based on the IUPAC nomenclature. Specifically, the bonding positions are described for 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 that bonds to the copolymer directly or via an organic group is not particularly limited, and any bonding position (1-position to n-position) It's okay. Preferably, it is at the 1- or 3-n-position.

When the nitrogen atom contained in the nitrogen-containing n-membered ring compound is one (e.g., pyridine ring, etc.), chelates are easily formed in the molecule, and physical properties such as tensile strength when used as a composition are excellent. ~ (n-1) position is preferred. By selecting the bonding position of the nitrogen-containing n-membered ring compound, the polymer can easily form cross-links between polymer molecules by hydrogen bonding, ionic bonding, coordination bonding, etc., and has excellent recyclability and mechanical properties. In particular, it tends to be excellent in tensile strength.

<Side chain (b): Side chain containing covalent cross-linking site>
As used herein, the term "side chain (b) containing a covalent cross-linking site" refers to an atom (usually a carbon atom) forming the main chain of a polymer, and a covalent cross-linking site (such as an amino group-containing compound described later). A functional group capable of generating at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers, etc.) It means that a chemically stable bond (covalent bond) is formed. In addition, the side chain (b) is a side chain containing a covalent cross-linking site, and while having a covalent bonding site, it further has a group capable of hydrogen bonding, and hydrogen bonding is performed between the side chains. is used as a side chain (c), which will be described later.
In the case where both the hydrogen donor and the hydrogen acceptor that are capable of forming hydrogen bonds between the side chains of the polymers are not included, for example, there is simply an ester group (-COO-) in the system. When only side chains are present, hydrogen bonds are not particularly formed between ester groups (-COO-), and such groups do not function as hydrogen-bonding cross-linking sites.

On the other hand, for example, when the side chains of the polymers each contain a structure having both a site serving as a hydrogen donor for a hydrogen bond and a site serving as a hydrogen acceptor, such as a carboxy group or a triazole ring, the polymers Since a hydrogen bond is formed between the side chains of , a hydrogen-bonding cross-linking site is contained. Further, for example, when an ester group and a hydroxyl group coexist between the side chains of polymers and these groups form a hydrogen bond between the side chains, the site forming the hydrogen bond is a hydrogen-bonding cross-linking site. becomes. Therefore, it may be used as the side chain (c) depending on the structure of the side chain (b) itself and the type of substituents of the structure of the side chain (b) and other side chains. In addition, the "covalent cross-linking site" referred to herein is a site where polymers are cross-linked by covalent bonding.

The side chain (b) containing such a covalent cross-linking site is not particularly limited. It preferably contains a covalent cross-linking site formed by reacting with a compound that reacts to form a covalent cross-linking site (a compound that generates a covalent bond). The crosslink at the covalent crosslink site of the side chain (b) is formed by at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers. is preferred. Therefore, the functional group possessed by the polymer constituting the main chain is a functional group capable of forming at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. is preferred.

Examples of such a "compound that forms a covalent cross-linking site (compound that generates a covalent bond)" include, for example, two or more amino groups and/or imino groups in one molecule (both amino groups and imino groups a polyamine compound having two or more of these groups in total, if any); 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; polythiol compounds having two or more thiol groups (mercapto groups) in the molecule; and the like.

Here, the "compound that forms a covalent cross-linking site (compound that generates a covalent bond)" refers to the type of substituents possessed by such a compound, the progress of the reaction when such a compound is used for the reaction, etc. Depending on the situation, it becomes a compound capable of introducing both the hydrogen-bonding cross-linking site and the covalent-bonding cross-linking site (for example, when a compound having three or more hydroxyl groups is used to form a covalent cross-linking site, Depending on the degree of progress of the reaction, two hydroxyl groups may react with the functional group of the polymer having a functional group on its side chain, leaving the remaining one hydroxyl group as a hydroxyl group. can also introduce sites that form hydrogen-bonding crosslinks.). Therefore, the "compound that forms a covalent cross-linking site (compound that generates a covalent bond)" exemplified herein includes "a compound that forms both a hydrogen-bonding cross-linking site and a covalent cross-linking site". obtain.

From this point of view, when forming the side chain (b), a compound is appropriately selected from among "compounds that form covalent cross-linking sites (compounds that generate covalent bonds)" according to the desired design. Alternatively, the side chain (b) may be formed by appropriately controlling the degree of progress of the reaction. In addition, when the compound forming the covalent cross-linking site has a heterocyclic ring, it becomes possible to more efficiently produce a hydrogen-bonding cross-linking site at the same time. , it becomes possible to efficiently form a side chain having the covalent cross-linking site. Therefore, specific examples of compounds having such a heterocyclic ring will be described together with the side chain (c) as suitable compounds for producing the side chain (c). Note that the side chain (c) can be said to be a suitable form of the side chain such as the side chain (a) or the side chain (b) because of its structure.

Examples of the polyamine compound that can be used as such a "compound that forms a covalently crosslinked site (compound that generates a covalent bond)" include the following alicyclic amines, aliphatic polyamines, aromatic polyamines, Nitrogen-containing heterocyclic amines and the like can be mentioned.

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

The aliphatic polyamine is not particularly limited, but examples include 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, but examples include diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tris(dimethylaminomethyl)phenol, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, 3-amino-1,2,4-triazole and the like.

In addition, one or more hydrogen atoms of the polyamine compound 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. A heteroatom such as a sulfur atom may be included.

Moreover, the said polyamine compound may be used individually by 1 type, or may use 2 or more types together. When two or more types are used in combination, the mixing ratio can be adjusted to an arbitrary ratio depending on the application for which the thermoplastic elastomer composition of the embodiment is used, the physical properties required for the thermoplastic elastomer composition of the embodiment, and the like. can.

Among the polyamine compounds exemplified above, hexamethylenediamine, N,N'-dimethyl-1,6-hexanediamine, diaminodiphenylsulfone and the like are preferred because of their high effect of improving compression set, mechanical strength, particularly tensile strength. .

The polyol compound that can be used as a "compound that forms a covalent cross-linking site (compound that generates a covalent bond)" is not particularly limited in molecular weight, skeleton, etc., as long as it is a compound having two or more hydroxyl groups. Examples thereof include the following polyether polyols, polyester polyols, other polyols, mixed polyols thereof, and the like.

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, pentaerythritol and other polyhydric alcohols, ethylene oxide, propylene Polyol obtained by adding at least one selected from oxide, butylene oxide, styrene oxide, etc.; polyoxytetramethylene oxide; 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-weight polyols. Condensation polymerization of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid and other low-molecular-weight carboxylic acids and oligomeric acids with one or more species or two or more of them coalescence; ring-opening polymers such as propionlactone and valerolactone; and the like, and these may be used alone or in combination of two or more.

Specific examples of other polyols include polymer polyol, polycarbonate polyol; polybutadiene polyol; hydrogenated polybutadiene polyol; acrylic polyol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, Hexanediol, polyethylene glycol laurylamine (eg N,N-bis(2-hydroxyethyl)laurylamine), polypropylene glycol laurylamine (eg N,N-bis(2-methyl-2-hydroxyethyl)laurylamine) , polyethylene glycol octylamine (e.g. N,N-bis(2-hydroxyethyl)octylamine), polypropylene glycol octylamine (e.g. N,N-bis(2-methyl-2-hydroxyethyl)octylamine), polyethylene low-molecular-weight compounds such as glycol stearylamine (eg, N,N-bis(2-hydroxyethyl)stearylamine), polypropylene glycol stearylamine (eg, N,N-bis(2-methyl-2-hydroxyethyl)stearylamine); and the like, and these may be used singly or in combination of two or more.

Examples of the polyisocyanate compound that can be used as the "compound that forms a covalent cross-linking site (compound that generates a covalent bond)" include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tri diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xyl Aromatic polyisocyanates such as diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalenediisocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI) ), aliphatic polyisocyanates such as lysine diisocyanate and norbornane diisocyanate methyl (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (hydrogenated Diisocyanate compounds such as alicyclic polyisocyanates such as MDI) and H ₆ TDI (hydrogenated TDI); Polyisocyanate compounds such as polymethylene polyphenylene polyisocyanate; Carbodiimide-modified polyisocyanates of these isocyanate compounds; Nurate-modified polyisocyanate; urethane prepolymers obtained by reacting these isocyanate compounds with the polyol compounds exemplified above; .

The polythiol compound is not particularly limited in molecular weight, skeleton, etc., as long as it is a compound having two or more thiol groups. 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, 1 ,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.)), etc., and these may be used alone or in combination of two or more.

Examples of functional groups possessed by the polymer constituting the main chain that react with such a "compound that forms a covalent cross-linking site (compound that generates a covalent bond)" include amide, ester, lactone, urethane, and thiourethane. and a functional group capable of forming at least one bond selected from the group consisting of thioether, and such a functional group is preferably a cyclic acid anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, a thiol group, or the like. is exemplified.

In addition, the polymer (B) having the side chain (b) is crosslinked at the covalent crosslink site in the side chain (b) portion, that is, the functional group and the above-described "covalent crosslink site. Forming compound (compound that generates a covalent bond)" has at least one covalent bond crosslink in one molecule, especially lactones, urethanes, ethers, thiourethanes and thioethers When a crosslink is formed by at least one bond selected from the group, it preferably has 2 or more, more preferably 2 to 20, and 2 to 10. is more preferred.

Further, the thermoplastic elastomer composition to be obtained, wherein the cross-linking at the covalent cross-linking site of the side chain (b) contains a tertiary amino bond (-N=) and an ester bond (-COO-). It is preferable because the compression set and mechanical strength (elongation at break, strength at break) of the product can be improved more easily. In this case, polymers having side chains containing groups capable of forming hydrogen bonds with respect to tertiary amino bonds (-N=) and ester bonds (-COO-) are included. In some cases (for example, when there is another polymer having a side chain containing a hydroxyl group or the like), the covalent cross-linking site can function as a side chain (c) described below.

For example, in the case of the polymer (B) having the side chain (a) as the side chain (a′) (that is, when the polymer (B) is a polymer having both the side chains (a) and (b)) , when the bridge at the covalent cross-linking site has the tertiary amino bond and/or the ester bond, those groups and the side chain (a) (a side chain having a carbonyl-containing group and/or a nitrogen-containing heterocycle ), the crosslink density can be further improved by hydrogen bonding (interacting) with the groups in ). In addition, from the viewpoint of forming a side chain (b) having a structure containing such a tertiary amino bond (-N=) and an ester bond (-COO-), "a covalent cross-linking site is formed As the compound (compound that generates a covalent bond)", among those exemplified above, polyethylene glycol laurylamine (e.g., N,N-bis(2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (e.g., N,N-bis(2-methyl-2-hydroxyethyl)laurylamine), polyethylene glycol octylamine (e.g. N,N-bis(2-hydroxyethyl)octylamine), polypropylene glycol octylamine (e.g. N, N-bis(2-methyl-2-hydroxyethyl)octylamine), polyethylene glycol stearylamine (e.g. N,N-bis(2-hydroxyethyl)stearylamine), polypropylene glycol stearylamine (e.g. N,N- bis(2-methyl-2-hydroxyethyl)stearylamine).

Even if a compound that forms a covalent cross-linking site (a compound that generates a covalent bond) as described above is used, depending on the progress of the reaction, the type of substituent, the stoichiometric ratio of the raw materials used, etc., Since a hydrogen-bonding cross-linking site may also be introduced together, the preferred structure of the covalent cross-linking site is described in conjunction with the preferred structure of the covalent cross-linking site in the side chain (c). to explain.

<Side Chain (c): Side Chain Containing Both Hydrogen Bonding Crosslinking Site and Covalent Bonding Crosslinking Site>
Such side chains (c) are side chains that contain both hydrogen-bonding and covalent cross-linking sites in one side chain. The hydrogen-bonding cross-linking site contained in such a side chain (c) may be the same as those exemplified as the hydrogen-bonding cross-linking sites described in the side chain (a′). The same as those exemplified as the hydrogen-bonding cross-linking site are preferred. In addition, as the covalent cross-linking site contained in the side chain (c), the same one as exemplified as the covalent cross-linking site in the side chain (b) can be used (preferred cross-linking is also the same. available.).

Such a side chain (c) is a polymer having a functional group in the side chain (a polymer for forming the main chain portion), and reacts with the functional group to form a hydrogen-bonding cross-linking site and a covalent cross-linking site. is preferably a side chain formed by reacting with a compound that forms both (a compound that introduces both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site). Compounds that form both hydrogen-bonding cross-linking sites and covalent cross-linking sites (compounds that introduce both hydrogen-bonding cross-linking sites and covalent cross-linking sites) include heterocyclic rings (particularly preferably nitrogen-containing Heterocyclic ring) and capable of forming a covalent cross-linking site (compound that generates a covalent bond) are preferred, and among them, heterocyclic ring-containing polyols, heterocyclic ring-containing polyamines, heterocyclic ring-containing polythiols, etc. are more preferred. preferable.

In addition, polyols, polyamines and polythiols containing such a heterocyclic ring, except those having a heterocyclic ring (particularly preferably a nitrogen-containing heterocyclic ring), are capable of forming a covalent cross-linking site as described above. Those exemplified as polyols, polyamines and polythiols described in "Possible compounds (compounds that generate covalent bonds)" can be used as appropriate. In addition, such heterocycle-containing polyols are not particularly limited, but examples include bis(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)isocyanurate, kojic acid, dihydroxydithiane, and trishydroxyethyltriazine. is mentioned. The heterocycle-containing polyamine is not particularly limited, and examples thereof include acetoguanamine, piperazine, bis(aminopropyl)piperazine, benzoguanamine, and melamine. Further such heterocycle-containing polythiols include dimercaptothiadiazole, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate. Thus, as the side chain (c), a polymer having a functional group in the side chain (a polymer for forming the main chain portion) is reacted with a polyol containing a heterocycle, a polyamine, a polythiol, or the like. , is preferably the resulting side chain.

In addition, it constitutes the main chain that reacts with "a compound that forms both a hydrogen-bonding cross-linking site and a covalent cross-linking site (a compound that introduces both a hydrogen-bonding cross-linking site and a covalent cross-linking site)". The functional group possessed by the polymer is preferably a functional group capable of forming at least one bond selected from the group consisting of amide, ester, lactone, urethane, thiourethane and thioether. Groups, hydroxyl groups, amino groups, carboxy groups, isocyanate groups, thiol groups and the like are preferably exemplified.

Further, the polymer (B) having the side chain (c) has at least one crosslink in one molecule at the covalent crosslink site in the portion of the side chain (c). , urethane, ether, thiourethane and thioether. More preferably, it is more preferable to have 2 to 10. Further, the thermoplastic elastomer composition to be obtained, wherein the cross-linking at the covalent cross-linking site of the side chain (c) contains a tertiary amino bond (-N=) and an ester bond (-COO-). It is preferable because the compression set and mechanical strength (elongation at break, strength at break) of the product are further improved.

(Structures Suitable as Covalent Crosslinking Sites in Side Chains (b) to (c))
With respect to side chains (b) and/or (c), when the crosslink at the covalent crosslink site contains a tertiary amino bond (-N=), an ester bond (-COO-), When these bonding sites also function as hydrogen-bonding cross-linking sites, the compression set and mechanical strength (elongation at break, strength at break) of the resulting thermoplastic elastomer composition are preferably improved. . Thus, a tertiary amino bond (-N=) or an ester bond (-COO-) in a side chain having a covalent cross-linking site forms a hydrogen bond with another side chain. In this case, the covalent cross-linking site containing the tertiary amino bond (-N=) and the ester bond (-COO-) is also provided with a hydrogen-bonding cross-linking site, and the side chain (c) is can function.

In addition, for example, in the case of the polymer (B) having the side chain (a) as the side chain (a′), the covalent bond containing the tertiary amino bond and/or the ester bond In the case of having a cross-linking site, when the tertiary amino bond and/or the ester bond forms a hydrogen bond (interaction) with the group in the side chain (a), the cross-linking density can be further improved. It is considered that

Here, a compound (hydrogen Compounds capable of forming both binding cross-linking sites and covalent cross-linking sites) include polyethylene glycol laurylamine (eg, N,N-bis(2-hydroxyethyl)laurylamine), polypropylene glycol laurylamine. (e.g. N,N-bis(2-methyl-2-hydroxyethyl)laurylamine), polyethylene glycol octylamine (e.g. N,N-bis(2-hydroxyethyl)octylamine), polypropylene glycol octylamine (e.g. , N,N-bis(2-methyl-2-hydroxyethyl)octylamine), polyethylene glycol stearylamine (e.g. N,N-bis(2-hydroxyethyl)stearylamine), polypropylene glycol stearylamine (e.g. N , N-bis(2-methyl-2-hydroxyethyl)stearylamine) are suitable.

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

In the above 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 has a linear, branched or cyclic carbon number 1 to 20 hydrocarbon groups.

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

Further, the substituent G is a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms and may contain an oxygen atom, a sulfur atom or a nitrogen atom. Examples of such substituent G include methylene group, ethylene group, 1,3-propylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group and 1,7-heptylene group. alkylene groups such as 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 1,11-undecylene group and 1,12-dodecylene group; N,N-diethyldodecylamine-2 ,2′-diyl, N,N-dipropyldodecylamine-2,2′-diyl, N,N-diethyloctylamine-2,2′-diyl, N,N-dipropyloctylamine-2,2′ -diyl, N,N-diethylstearylamine-2,2'-diyl, N,N-dipropylstearylamine-2,2'-diyl,; vinylene group; divalent such as 1,4-cyclohexylene group alicyclic hydrocarbon group; 1,4-phenylene group, 1,2-phenylene group, 1,3-phenylene group, divalent aromatic hydrocarbon group such as 1,3-phenylenebis (methylene) group; Trivalent compounds such as propane-1,2,3-triyl, butane-1,3,4-triyl, trimethylamine-1,1′,1″-triyl and triethylamine-2,2′,2″-triyl a hydrocarbon group; a trivalent cyclic hydrocarbon containing an oxygen atom, a sulfur atom or a nitrogen atom such as an isocyanurate group and a triazine group; a tetravalent hydrocarbon group represented by the following formulas (12) and (13); and Substituents formed by combining these; and the like.

Furthermore, the cross-linking at the covalent cross-linking site of the side chain (c) is represented by any one of the following formulas (7) to (9), which binds to the main chain of the polymer at the α-position or the β-position. and more preferably G in the formula contains a tertiary amino group (structures shown in formulas (7) to (9) contain a hydroxyl group and a carbonyl group and can be said to be a structure containing both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site, and the side chain having such a structure can function as the side chain (c)). Further, G in the formula is preferably an isocyanurate group (isocyanurate ring) from the viewpoint of high heat resistance and high strength due to hydrogen bonding.

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

Further, as the structure represented by any one of formulas (7) to (9), specifically, compounds represented by the following formulas (14) to (25) are preferably exemplified.

(Wherein, l represents an integer of 1 or more.)

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

In the side chains (b) and (c), the crosslinks at the covalent crosslink sites are preferably formed by 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 (e.g., maleic anhydride group) as a functional group, the cyclic acid anhydride group of the polymer, a hydroxyl group or an amino group and / Or by reacting with a compound that forms the covalent cross-linking site having an imino group (a compound that generates a covalent bond) to form a covalent cross-linking site and cross-linking between polymers. It is good also as a bridge|crosslinking.

In addition, in such side chains (b) and (c), the crosslinks at the covalent crosslink sites are at least one selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers. 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. It can be confirmed by commonly used analysis means such as IR spectrum.

Further, the polymer (A) is a polymer having the side chain (a) and a glass transition point of 25° C. or less, and the polymer (B) includes a hydrogen-bonding cross-linking site and a covalent cross-linking site in the side chain. A polymer with a glass transition point of 25 ° C. or less containing including polymers, etc.). As such a polymer component, one of the polymers (A) to (B) may be used alone, or two or more of them may be used in combination.

The polymer (B) may be a polymer having both the side chain (a') and the side chain (b) or a polymer having the side chain (c). The hydrogen-bonding cross-linking site contained in the side chain of B) is a hydrogen-bonding cross-linking site having a carbonyl-containing group and/or a nitrogen-containing heterocyclic ring (more preferably is preferably a hydrogen-bonding bridging moiety having a carbonyl-containing group and a nitrogen-containing heterocyclic ring. In addition, the cross-linking at the covalent cross-linking sites contained in the side chains of the polymer (B) can also cause intermolecular interactions such as hydrogen bonding between the side chains containing the cross-linking sites. From a viewpoint, it is preferably formed by at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether.

The method for producing such polymers (A) to (B) is not particularly limited, and includes side chains (a); side chains (a′) and side chains (b); and side chains as described above. (c); A known method capable of introducing at least one selected from the group consisting of; For example, as a method for producing the polymer (B), the method described in JP-A-2006-131663 may be employed. Further, in order to obtain the polymer (B) having the side chains (a′) and side chains (b) as described above, for example, a cyclic acid anhydride group (for example, a maleic anhydride group) as a functional group is added to the side chain. A compound that reacts with the cyclic acid anhydride group to form a covalent cross-linking site (a compound that generates a covalent bond) and a hydrogen-bonding cross-linking site that reacts with the cyclic acid anhydride group in the polymer having Each side chain may be introduced at the same time by using a mixture (mixed raw material) with a forming compound (a compound capable of introducing a nitrogen-containing heterocycle).

Further, as a method for producing such polymers (A) to (B), for example, using a polymer having a functional group (eg, a cyclic acid anhydride group, etc.) in a side chain, the polymer is a compound that reacts with 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 compound that reacts with the functional group to form a covalent cross-linking site. A polymer having the side chain (a); a polymer having the side chain (a′) and the side chain (b); and/or the side chain (c ) (polymers (A) to (B)) may be employed. The conditions (temperature conditions, atmospheric conditions, etc.) employed for such reactions are not particularly limited, and functional groups and compounds to be reacted with the functional groups (compounds forming hydrogen-bonding cross-linking sites and/or covalent It may be appropriately set according to the type of compound forming a binding cross-linking site). The polymer (A) may be produced by polymerizing a monomer having a hydrogen bonding site.

As the polymer having such a functional group (for example, a cyclic acid anhydride group) in the side chain, a polymer capable of forming the main chain of the above-described polymers (A) to (B), wherein the functional group is Those having side chains are preferred. Here, the term "polymer containing a functional group in a side chain" refers to a chemically stable bond ( covalent bond), and those obtained by reacting a polymer (for example, a known natural polymer or synthetic polymer) with a compound capable of introducing a functional group can be preferably used.

Further, such a functional group is preferably a functional group capable of forming at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. An acid anhydride group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, a thiol group, and the like are preferable, and from the viewpoint of being able to disperse the clay more efficiently when the composition contains clay, a cyclic acid group is preferred. Anhydride groups are particularly preferred.
Further, such a cyclic acid anhydride group may be a cyclic acid anhydride group having a carbonyl group in the ring skeleton, such as a succinic anhydride group, a maleic anhydride group, a glutaric anhydride group and a phthalic anhydride group. is preferred, and maleic anhydride groups are more preferred from the viewpoint of being easily introduced into the polymer side chain and being industrially readily available. Further, when the functional group is a cyclic acid anhydride group, for example, compounds into which the functional group can be introduced include succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride and derivatives thereof. Cyclic anhydrides may be used to introduce functional groups into polymers, such as known natural or synthetic polymers.

The compound that forms a hydrogen-bonding cross-linking site by reacting with the functional group is not particularly limited. It is preferable to use The compound that forms a covalent cross-linking site by reacting with the functional group is not particularly limited, but the above-mentioned "compound that forms a covalent cross-linking site (compound that generates a covalent bond)" may be used. is preferred. In addition, as a compound that forms a hydrogen-bonding cross-linking site (a compound capable of introducing a nitrogen-containing heterocycle) and a compound that forms a covalent cross-linking site (a compound that generates a covalent bond), Compounds that form both hydrogen-bonding cross-linking sites and covalent cross-linking sites (e.g., nitrogen-containing heterocycle-containing polyols, nitrogen-containing heterocycle-containing polyamines, nitrogen-containing heterocycle-containing polythiols, etc.) can also be suitably used. can be done.

Further, when clay is contained in the composition, a polymer having a functional group (for example, a cyclic acid anhydride group) in the side chain is used in the method for producing such polymer components (polymers (A) to (B)). a compound that reacts with the functional group to form a hydrogen-bonding cross-linking site, and a compound that reacts with the functional group to form a hydrogen-bonding cross-linking site, and a compound that reacts with the functional group to form a covalent The polymer (A) having the side chain (a), hydrogen-bonding cross-linking sites and covalent bonds on the side chains are reacted with at least one raw material compound among the mixed raw materials of compounds that form bonding cross-linking sites. When adopting the method of producing the polymer (B) containing a functional cross-linking site, before reacting the polymer having a functional group on the side chain with the raw material compound, the clay and the functional group on the side chain are mixed. A method of mixing with a polymer and then adding and reacting the raw material compound to form a composition simultaneously with the preparation of the polymer component (method of adding clay first) may be employed.

When the thermoplastic elastomer composition of the embodiment is a thermoplastic elastomer composition containing the polymer (A) as a polymer component, it is possible to impart properties derived from the side chain (a) to the composition. It becomes possible to improve elongation, breaking strength, and fluidity. In addition, in the thermoplastic elastomer composition containing the polymer (B) as a polymer component, it is possible to impart properties derived from the covalently crosslinked sites in the side chains to the composition. becomes possible. In addition, in the thermoplastic elastomer composition containing the polymer (B) as a polymer component, in addition to the properties derived from the covalently crosslinked sites, the hydrogen-bonded crosslinked sites (side chains (a') Since properties derived from the hydrogen-bonding cross-linking site described in ) can also be imparted, it is possible to exhibit compression set resistance at the same time while maintaining fluidity (moldability). By appropriately changing the type, the type of the polymer (B), and the like, it is possible to more efficiently exhibit the desired properties according to the application.

In the thermoplastic elastomer composition of the embodiment, a thermoplastic elastomer composition containing the polymer (A) as the polymer component and a thermoplastic elastomer composition containing the polymer (B) as the polymer component were separately produced. Afterwards, these may be mixed to form a thermoplastic elastomer composition containing polymers (A) and (B) as polymer components.

In the present specification, the polymer component may contain at least the polymers (A) and (B). From the viewpoint of utilizing the characteristics of the crosslinked site, a polymer having a side chain (b) other than the polymer (B) may be mixed and used. For example, when the polymer (A) is used as the polymer component, when a polymer having a side chain (b) other than the polymer (B) is used in combination, the side chain contained in the composition Therefore, it is possible to impart substantially the same properties as those of a thermoplastic elastomer composition using a polymer (B) containing a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site in the side chain. Further, in the case of producing a thermoplastic elastomer composition containing polymers (A) and (B) as polymer components, or a polymer having polymer (A) and side chains (b) other than polymer (B) When producing a thermoplastic elastomer composition containing It becomes possible.

When the thermoplastic elastomer composition of the embodiment contains the polymers (A) and (B) as polymer components, the content ratio of the polymer (A) to the polymer (B) is the mass ratio ([polymer (A )]:[Polymer (B)]) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. If the content of the polymer (A) is less than the lower limit, fluidity (moldability) and mechanical strength tend to be insufficient, while if it exceeds the upper limit, compression set tends to decrease. .

Further, the thermoplastic elastomer composition of the embodiment comprises, as polymer components, a polymer (A) and a polymer having a side chain (b) other than the polymer (B) (hereinafter sometimes referred to as "polymer (C)"). ), the content ratio of the polymer (A) and the polymer (C) is a mass ratio ([polymer (A)]:[polymer (C)]) of 1: 9 to 9: 1 It is preferable that the ratio is 2:8 to 8:2. If the content of the polymer (A) is less than the lower limit, fluidity (moldability) and mechanical strength tend to be insufficient, while if it exceeds the upper limit, compression set tends to decrease. .

In addition, in the thermoplastic elastomer composition of the embodiment, when both side chains (a′) and side chains (b) are present in the composition, the total amount of the side chains (a′) and the side chains The total amount of (b) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, based on mass ratio. If the total amount of such side chains (a') is less than the lower limit, fluidity (moldability) and mechanical strength tend to be insufficient, while if the total amount exceeds the upper limit, compression set tends to decrease. be. Incidentally, such a side chain (a') is a concept including the side chain (a). Therefore, even when only the side chain (a) is included as the side chain (a'), both the side chain (a) and the side chain (b) must be present in the composition at the above mass ratio. is preferred.

The thermoplastic elastomer compositions of embodiments are capable of exhibiting sufficiently high tensile stress and sufficiently high heat resistance. In addition, in such a thermoplastic elastomer composition, by appropriately changing the composition, properties required according to the application (for example, properties such as self-healing property and/or compression set resistance) can be exhibited as appropriate. It is possible to That is, the thermoplastic elastomer compositions of the embodiments can exhibit sufficiently high tensile stress and sufficiently high heat resistance, and additionally, depending on the composition, have sufficient compression set resistance and/or It is also possible to exhibit sufficient self-healing properties. In this way, by appropriately changing the composition, it is possible to appropriately exhibit the necessary properties in a well-balanced manner according to the application of the thermoplastic elastomer composition. It is preferable to appropriately change the types (composition) of the components in the composition in consideration of the properties required according to the application.

The content of the polymer component in the thermoplastic elastomer composition may be appropriately determined according to the type of the polymer component and the fatty acid amide compound according to the embodiment, but the total mass (100 mass %) is, for example, preferably 5% by mass or more, preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 50% by mass or less, and 20% by mass or more. 40% by mass or less is more preferable. When the proportion of the content of the polymer component with respect to 100% by mass of the thermoplastic elastomer composition is within the above range, the thermoplastic elastomer composition can have favorable rubber elasticity.

The thermoplastic elastomer composition of the embodiment has been described above, and the thermoplastic elastomer composition of the embodiment that can be suitably used as a method for producing the thermoplastic elastomer composition of such an embodiment will be described below. A method for producing an elastomer composition will be described.

[Method for producing polymer component]
The polymer component according to the embodiment is obtained by obtaining a mixture of a polymer having a cyclic acid anhydride group in a side chain and at least one raw material compound selected from the group consisting of the following <1> to <3>, It can be obtained by reacting the polymer with the raw material compound.
<1> The compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bonded cross-linking site, <2> The compound (I) and the cyclic acid anhydride group that reacts with the covalently-bonded cross-linking site A mixed raw material of compound (II) to form
<3> A compound capable of forming both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site by reacting with the cyclic acid anhydride group.

Here, "a polymer having a cyclic acid anhydride group in a side chain" refers to a polymer in which a cyclic acid anhydride group is chemically stable bonded (covalently bonded) to an atom forming the main chain of the polymer. For example, those obtained by reacting a polymer capable of forming the main chain portion of the polymers (A) to (B) with a compound capable of introducing a cyclic acid anhydride group are preferred. can be used for

In addition, as a polymer capable of forming such a main chain portion, those exemplified in the above <polymer component> can be mentioned.

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.

Further, the cyclic acid anhydride group of the polymer having a cyclic acid anhydride group in the side chain is preferably a cyclic acid anhydride group having a carbonyl group in the ring skeleton, a succinic anhydride group, a maleic anhydride group, an anhydride A glutaric acid group and a phthalic anhydride group are preferred, and among these, a maleic anhydride group is more preferred from the viewpoint of high reactivity of the raw material and industrial availability of the raw material.

A polymer having a cyclic acid anhydride group in a side chain can be prepared by a commonly used method, for example, a polymer capable of forming the main chain portion of the polymers (A) to (B) under conditions normally performed, such as heating. You may manufacture by the method of graft-polymerizing a cyclic acid anhydride by stirring etc. below. Moreover, as the polymer having a cyclic acid anhydride group in a side chain, a commercially available product may be used.

Examples of commercially available polymers having such cyclic acid anhydride groups in side chains include maleic anhydride-modified isoprene rubbers such as LIR-403 (manufactured by Kuraray Co., Ltd.); Isoprene rubber; carboxy-modified nitrile rubber such as Krynac 110, 221, 231 (manufactured by Polycer); carboxy-modified polybutene such as CPIB (manufactured by Nisseki Chemical Co., Ltd.); Toughmer M (e.g., MP0610 (manufactured by Mitsui Chemicals), MP0620 (manufactured by Mitsui Chemicals)), maleic anhydride-modified ethylene-propylene rubber; Toughmer M (e.g., MA8510, MH7010, MH7020 (manufactured by Mitsui Chemicals) ), MH5010, MH5020 (manufactured by Mitsui Chemicals), MH5040 (manufactured by Mitsui Chemicals)) and other maleic anhydride-modified ethylene-butene rubbers; Adtex series (maleic anhydride-modified EVA, maleic anhydride-modified EMA (manufactured by Japan Polyolefin )), HPR series (maleic anhydride-modified EEA, maleic anhydride-modified EVA (manufactured by Mitsui Dupont Polyolefin Co., Ltd.)), Bondfast series (maleic anhydride-modified EMA (manufactured by Sumitomo Chemical Co., Ltd.)), Dumilan series (maleic anhydride Acid-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 Corporation)) , Kraton (maleic anhydride-modified SEBS, FG1901, FG1924 (manufactured by Kraton Polymer)), Tufprene (maleic anhydride-modified SBS, 912 (manufactured by Asahi Kasei)), Septon (maleic anhydride-modified SEPS (manufactured by Kuraray)), Maleic anhydride-modified such as Rexpearl (maleic anhydride-modified EVA, ET-182G, 224M, 234M (manufactured by Nippon Polyolefin Co., Ltd.)), Aurorene (maleic anhydride-modified EVA, 200S, 250S (manufactured by Nippon Paper Chemicals Co., Ltd.)) polyethylene; maleic anhydride-modified polypropylene such as ADMER (for example, QB550, LF128 (manufactured by Mitsui Chemicals, Inc.));

In addition, as the polymer having a cyclic acid anhydride group in a side chain, maleic anhydride-modified polymers are preferable from the viewpoint of high molecular weight and high strength, such as maleic anhydride-modified ethylene-propylene rubber and maleic anhydride-modified ethylene. - Butene rubber is more preferred.

As the compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site, the compound that forms a hydrogen-bonding cross-linking site described in the polymer component (a nitrogen-containing heterocyclic ring can be introduced) compound) can be suitably used, for example, the nitrogen-containing heterocycle itself described in the thermoplastic elastomer composition of the above embodiment may be used, or maleic anhydride may be added to the nitrogen-containing heterocycle. It may be a compound (nitrogen-containing heterocyclic ring having the aforementioned 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 an acid is bonded. As such compound (I), a compound that forms both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site (both of the hydrogen-bonding cross-linking site and the covalent-bonding cross-linking site can be introduced at the same time). compound) may be used (a side chain having both a hydrogen-bonding cross-linking site and a covalent cross-linking site can be said to be a preferred form of a side chain having a hydrogen-bonding cross-linking site).

In addition, such compound (I) is not particularly limited, and depending on the type of side chain (side chain (a) or side chain (a')) in the target polymer, the above-mentioned compounds A suitable compound can be appropriately selected and used from among (I). Such compound (I) may have at least one substituent selected from a hydroxyl group, a thiol group and an amino group, triazole, pyridine, It is preferably thiadiazole, imidazole, isocyanurate, triazine or hydantoin, more preferably triazole, pyridine, thiadiazole, imidazole, isocyanurate, triazine or hydantoin having the substituent, and the substituent is more preferably triazole, isocyanurate or triazine, and particularly preferably triazole having the above-mentioned substituents. Examples of triazole, pyridine, thiadiazole, imidazole or hydantoin which may have such substituents include 4H-3-amino-1,2,4-triazole, aminopyridine, aminoimidazole and aminotriazine. , aminoisocyanurate, hydroxypyridine, hydroxyethylisocyanurate and the like.

As the compound (II) that reacts with the cyclic acid anhydride group to form a covalent cross-linking site, the "compound that forms a covalent cross-linking site (covalent bond The same compounds as those exemplified as "produced compounds)" can be preferably used (preferred compounds may also be the same). In addition, as such compound (II), a compound that forms both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site (both of the hydrogen-bonding cross-linking site and the covalent-bonding cross-linking site can be introduced at the same time). compound) may be used (a side chain having both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site can be said to be a preferred form of a side chain having a covalent-bonding cross-linking site).

From the viewpoint of compression set resistance, such compound (II) is preferably tris-hydroxyethyl isocyanurate, sulfamide or polyether polyol, more preferably tris-hydroxyethyl isocyanurate or sulfamide, and tris-hydroxyethyl isocyanurate. More preferred.

In addition, as the compounds (I) and / or (II), it is possible to introduce both a hydrogen-bonding cross-linking site and a covalent cross-linking site into the composition more efficiently. A compound that reacts with an anhydride group to form both hydrogen-bonding and covalent cross-linking sites (a compound capable of simultaneously introducing both hydrogen-bonding and covalent cross-linking sites) It is preferable to use As the compound that forms both the hydrogen-bonding cross-linking site and the covalent-bonding cross-linking site, the heterocyclic ring-containing polyol, the heterocyclic ring-containing polyamine, and the heterocyclic ring-containing polythiol can be preferably used. Nitrogen-containing heterocycle-containing polyols, nitrogen-containing heterocycle-containing polyamines, and nitrogen-containing heterocycle-containing polythiols can be more preferably used, and among them, trishydroxyethyl isocyanurate is particularly preferable.

In addition, the amount of compound (I) and compound (II) to be added (total amount of these: when only one of the compounds is used, the amount of one of the compounds is used) is not particularly limited, but in the compound When the compound contains active hydrogen such as amine, alcohol, etc., the amount of active hydrogen such as amine, alcohol, etc. in the compound is 20 to 250 mol% with respect to 100 mol% of the cyclic acid anhydride group. is preferred, the amount of 50 to 150 mol % is more preferred, and the amount of 80 to 120 mol % is even more preferred. If the amount added is less than the above lower limit, the amount of side chains to be introduced is reduced, making it difficult to achieve a sufficiently high crosslink density, and physical properties such as tensile strength tend to decrease. On the other hand, when the above upper limit is exceeded, the percentage of the compound (I) and the compound (II) added that do not form the cross-linking site increases, so that the cross-linking density tends to decrease.

In addition, the amount of compound (I) and compound (II) added is such that the total amount of these (when only one of the compounds is used, the amount of one of the compounds is used), the polymer in the mixture ( It is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, more preferably 0.5 to 5 0 parts by mass is more preferable. If the amount of compound (I) and compound (II) added (amount based on parts by mass) is less than the above lower limit, the crosslink density tends not to increase and the desired physical properties tend not to be exhibited. Density tends to decrease.

When using both compound (I) and compound (II), the order of addition of compound (I) and compound (II) is not particularly limited, and either may be added first. Further, when using both the compound (I) and the compound (II), the compound (I) is reacted with a part of the cyclic acid anhydride groups of the polymer having the cyclic acid anhydride group in the side chain. good too. As a result, it is also possible to react unreacted cyclic acid anhydride groups (unreacted cyclic acid anhydride groups) with compound (II) to form covalently crosslinked sites. The term "a part" as used herein is preferably 1 mol % or more and 50 mol % or less with respect to 100 mol % of the cyclic acid anhydride groups.
Within this range, in the obtained polymer (B), the effect of introducing a group derived from the compound (I) (for example, a nitrogen-containing heterocyclic ring, etc.) tends to be sufficiently exhibited, and the recyclability tends to be further improved. Compound (II) is preferably reacted with the cyclic acid anhydride group so that an appropriate number of covalent crosslinks (eg, 1 to 3 per molecule) is obtained.

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 compounds (I) and/or compounds (II)) are chemically bonded. The temperature conditions for the reaction (opening of the cyclic acid anhydride group) between the polymer and the raw material compound (the compound (I) and/or the compound (II)) are not particularly limited. Depending on the type of the cyclic acid anhydride group, the temperature may be adjusted so that they can react. ℃, or 180 to 220 ℃.

As a result of such a reaction, at least a hydrogen-bonding cross-linking site is formed at the site where the compound (I) reacts with the cyclic acid anhydride group, so that a hydrogen-bonding cross-linking site (carbonyl moieties containing groups and/or nitrogen-containing heterocycles, more preferably moieties having carbonyl-containing groups and nitrogen-containing heterocycles). The side chain formed (introduced) by such a reaction can contain the structure represented by the above formula (2) or (3).

In addition, since such a reaction forms at least a covalently crosslinked site at the site where the compound (II) reacts with the cyclic acid anhydride group, the side chains of the polymer are covalently crosslinked. (side chain (b) or side chain (c)). The side chains formed by such reactions can also contain structures represented by the above formulas (7) to (9).

In addition, each group (structure) of the side chain in such a polymer, that is, the unreacted cyclic acid anhydride group, the structures 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 way, a polymer (A ), and at least one polymer component selected from the group consisting of a polymer (B) containing a hydrogen-bonding cross-linking site and a covalently-bonding cross-linking site in the side chain and having a glass transition point of 25°C or less. can be obtained.

<Process oil>
The thermoplastic elastomer composition of embodiments may contain processing oil to improve its processability and quality of processed rubber products. Such process oil is not particularly limited, and any process oil may be used, but the process oil preferably contains a petroleum-derived hydrocarbon oil. The content of the petroleum-derived hydrocarbon oil in the process oil may be 50% by mass or more, may be 80% by mass or more, or may be 95% by mass or more, and is substantially petroleum-derived hydrocarbon oil It may consist of

As the process oil, paraffin oil is preferable from the viewpoint of good affinity with the polymer component and excellent fluidity, heat resistance, color stability, and stain resistance. As used herein, the term “paraffin oil” means that the oil is subjected to correlation ring analysis (ndM ring analysis) in accordance with ASTM D3238-85, and the number of paraffin carbon atoms is the percentage of the total number of carbon atoms ( Paraffin part: CP), percentage of naphthene carbon number to total carbon number (naphthene part: CN), and percentage of aromatic carbon number to total carbon number (aromatic part: CA) When calculating each, paraffin carbon The percentage (CP) of the total number of carbon atoms is 60% or more, preferably 60% or more and 90% or less, and more preferably 70% or more and 85% or less.

Further, in the thermoplastic elastomer composition of the embodiment, the process oil has a kinematic viscosity at 40° C. of 50 mm ² /s to 700 mm ² /s, measured according to JIS K 2283 (published in 2000). , more preferably 150 to 600 mm ² /s, even more preferably 300 to 500 mm ² /s.
If the kinematic viscosity (ν) is less than the lower limit, the oil tends to bleed, while if it exceeds the upper limit, it tends to be impossible to impart sufficient fluidity. The kinematic viscosity of such process oil adopts a value measured in accordance with JIS K 2283 (published in 2000) under a temperature condition of 40 ° C. ) using a Canon Fenske viscometer (for example, the product name “SO series” manufactured by Shibata Kagaku Co., Ltd.), and a value automatically measured at a temperature of 40° C. may be employed.

Furthermore, in the thermoplastic elastomer composition of the embodiment, the process oil preferably has an aniline point of 80° C. to 145° C. measured by the U-tube method according to JIS K2256 (published in 2013). It is more preferably 100 to 145°C, even more preferably 105 to 145°C. The aniline point of such process oil adopts the value measured by the U-tube method in accordance with JIS K2256 (issued in 2013). A value measured using a measuring device (for example, trade name “aap-6” manufactured by Tanaka Scientific Instruments Co., Ltd.) may be employed.

As such a process oil, commercially available ones can be used as appropriate. "; trade names "Diana Process Oil PW90", "Diana Process Oil PW150", "Diana Process Oil PW380" manufactured by Idemitsu Kosan; trade names "SUNPAR Series (110, 115, 120, 130, 150, 2100, 2280, etc.)"; Mobil's trade name "Gargoyle Arctic Series (1010, 1022, 1032, 1046, 1068, 1100, etc.)" may be used as appropriate.

The content of the process oil in the thermoplastic elastomer composition may be appropriately determined according to the type of the polymer component, the process oil, etc. The content of the process oil is preferably 0.1% by mass or more, preferably 0.1% by mass or more and 95% by mass or less, preferably 1% by mass or more and 90% by mass or less, and 30% by mass or more and 85% by mass or less. is more preferably 35% by mass or more and 70% by mass or less, and particularly preferably 50% by mass or more and 85% by mass or less. By setting the content of the process oil to 100% by mass of the thermoplastic elastomer composition to be equal to or higher than the lower limit (particularly, the lower limit is equal to or higher than 30% by mass), the hardness of the thermoplastic elastomer composition is reduced. , the moldability can be further improved. Further, when the content of the process oil is equal to or less than the above upper limit with respect to 100% by mass of the thermoplastic elastomer composition, contamination of molding equipment and the like can be more effectively prevented.

One type of process oil may be used alone, or two or more types may be used in combination.

Although the processability of the thermoplastic elastomer composition is improved by blending the process oil, there is a problem that the tackiness (tackiness) of the surface of the cured product is also improved.
On the other hand, the thermoplastic elastomer composition of the embodiment contains a fatty acid amide compound having a molecular weight of 400 or more, so that even when a process oil is blended, excellent tackiness (stickiness) can be obtained. The effect of reduction is exhibited.

Further, when the thermoplastic elastomer composition contains a process oil, the content of the fatty acid amide compound is preferably 0.01 parts by mass or more, and 0.01 to 30 parts by mass with respect to 100 parts by mass of the process oil. is more preferable, and 0.05 to 20 parts by mass is even more preferable. When the content of the fatty acid amide compound is at least the above lower limit, the effect of reducing the tack force caused by the process oil tends to be exhibited favorably. In addition, even when the content of the process oil is 30% by mass or more with respect to 100% by mass of the thermoplastic elastomer composition, which has a relatively high blending amount of the process oil, the tackiness (stickiness) is very good. feeling) can be effectively reduced. On the other hand, when the content of the fatty acid amide compound is equal to or less than the above upper limit, contamination of molding equipment and the like due to adhesion of process oil tends to be more effectively prevented.

The hardness of the thermoplastic elastomer composition is not particularly limited, but from the viewpoint of being excellent in moldability, one having a low hardness value is preferred. For example, the cured thermoplastic elastomer composition preferably has a Shore A hardness according to JIS K6253 of 70 or less, more preferably 60 or less, and even more preferably 50 or less. A thermoplastic elastomer composition having a Shore A hardness of 0 after curing can also be produced by setting the content of the process oil to, for example, 80% by mass or more with respect to 100% by mass of the thermoplastic elastomer composition. It is possible.

The hardness of the thermoplastic elastomer composition can be appropriately adjusted by the type and blending amount of the raw material compound, and the hardness can be adjusted by blending the above procell oil and adjusting the blending amount of the above procell oil. As the blending amount of the procell oil in the thermoplastic elastomer composition is increased, the hardness value of the thermoplastic elastomer composition can be decreased, and the processability of the thermoplastic elastomer composition can be improved.
However, although the processability of the thermoplastic elastomer composition is improved by blending the process oil, there is a problem that the tackiness (tackiness) of the surface of the cured product is also increased.

On the other hand, the thermoplastic elastomer composition of the embodiment contains a fatty acid amide compound having a molecular weight of 400 or more, so that even when a process oil is blended, excellent tackiness (stickiness) can be obtained. The effect of reduction is exhibited. In addition, the thermoplastic elastomer composition of the embodiment has a relatively high blending amount of process oil, and even when the Shore A hardness according to JIS K6253 after curing is 30 or less, it is extremely excellent. The effect of reducing tackiness (stickiness) can be exhibited.

<Thermoplastic resin>
The thermoplastic elastomer composition of the embodiment is preferably a dynamically crosslinked thermoplastic elastomer composition. Examples of the dynamically crosslinkable thermoplastic elastomer composition include those composed of a dispersed phase and a continuous phase, the dispersed phase containing the polymer component, and the continuous phase containing the thermoplastic resin.
Dynamic cross-linking can be formed by carrying out a cross-linking reaction while melt-kneading raw materials containing a cross-linking agent and polymer molecules that react with the cross-linking agent. It is said that this cross-linking reaction increases the melt viscosity of the polymer component, increases the viscosity ratio with the thermoplastic resin, and causes the polymer component to form a dispersed phase.
Dynamic cross-linking type thermoplastic elastomer compositions are very useful because they have both excellent rubber elasticity as an elastomer and excellent processability as a thermoplastic resin. According to the thermoplastic elastomer composition of the embodiment, it is possible to provide a dynamic cross-linking thermoplastic elastomer having it as a constituent component.

The thermoplastic resin is not particularly limited as long as it is a thermoplastic resin that does not correspond to the polymer component according to the embodiment, but examples thereof include polyolefin resins such as polyethylene resins and polypropylene resins. Specific examples of these resins include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene, high-density polyethylene, and polypropylene.

Further, the thermoplastic resin may be a thermoplastic elastomer, preferably a styrene-based elastomer. As the styrene-based elastomer, among the above, a styrene-conjugated diene block copolymer is preferable. The styrenic elastomer may be hydrogenated. Specific examples of styrene elastomers include styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and the like.

The content of the thermoplastic resin in the thermoplastic elastomer composition may be appropriately determined according to the type of the polymer component and the fatty acid amide compound according to the embodiment, but the total mass (100 %), for example, the content ratio of the thermoplastic resin is preferably 5% by mass or more, preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 50% by mass or less, 20% by mass % or more and 40 mass % or less is more preferable. When the content of the thermoplastic resin is within the above range with respect to 100% by mass of the thermoplastic elastomer composition, the thermoplastic elastomer composition can have favorable processability.

When the thermoplastic elastomer composition contains a thermoplastic resin, the ratio of the total content of the polymer component and the thermoplastic resin to 100% by mass of the thermoplastic elastomer composition is, for example, preferably 10% by mass or more, and 10% by mass. % or more and 85 mass % or less are preferable, 30 mass % or more and 75 mass % or less are more preferable, and 50 mass % or more and 65 mass % or less are still more preferable. The proportion of the total content of the polymer component and the thermoplastic resin relative to 100% by mass of the thermoplastic elastomer composition is within the above range, so that the thermoplastic elastomer composition has favorable processability and rubber elasticity. can be done.

In the thermoplastic elastomer composition, the content ratio of the total content of the polymer component and the thermoplastic resin to the process oil (the total content of the polymer component and the thermoplastic resin)/(process oil) is the mass ratio. It is preferably 5/1 to 1/5, more preferably 3/1 to 1/3, even more preferably 2/1 to 1. When the thermoplastic elastomer composition does not contain a thermoplastic resin, the total content of the polymer component and the thermoplastic resin is the content of only the polymer component. When the mass ratio is within the above range, the process oil is favorably carried in the thermoplastic elastomer composition, and both processability and rubber elasticity of the thermoplastic elastomer composition can be achieved at a high level.

<Clay>
The thermoplastic elastomer composition of embodiments can contain clay. Such clay is not particularly limited, and known clays (clay minerals, etc.) can be used as appropriate. Further, examples of such clays include natural clays, synthetic clays, and organized clays.

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

In addition, the clay mainly composed of silicon and magnesium refers to clay in which the main metal components of the metal oxides that are the constituents of the clay are silicon (Si) and magnesium (Mg), and other metal oxides ( Aluminum (Al), iron (Fe), etc.) may be included as an accessory component. The clay containing silicon and magnesium as main components is not particularly limited, and known clays can be used as appropriate. By using clay containing silicon and magnesium as main components, it is possible to increase the reinforcing properties due to the small particle size. From the standpoint of availability, clay having a smectite structure is preferable as the clay containing silicon and magnesium as main components.

Examples of clays containing silicon and magnesium as main components include stevensite, hectorite, saponite, and talc. It is more preferable to use light and saponite.

Synthetic clay is preferable as the clay containing silicon and magnesium as main components. As such synthetic clays, commercially available ones may be used. The product name "Lucentite" manufactured by Chemical Co., Ltd. can be used as appropriate.

The organized clay is not particularly limited, but it is preferable that the clay is made organic by an organizing agent. The clay before being organized is not particularly limited, and may be a so-called clay mineral, such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, mica, Examples include fluorinated mica, kaolinite, pyrophyllolite, and the like.
Also, such clays may be natural or synthetic.

The organic agent is not particularly limited, and known organic agents capable of organicizing clay can be appropriately used. , dodecyl ammonium ion, lauryl ammonium ion, octadecyl ammonium ion, dioctyldimethyl ammonium ion, trioctyl ammonium ion, dioctadecyl dimethyl ammonium ion, trioctyl ammonium ion, dioctadecyl dimethyl ammonium ion, trioctadecyl ammonium ion, etc. can be used. .

As such an organized clay, a quaternary ammonium salt of clay can be preferably used from the viewpoint of monolayer dispersibility. Such quaternary ammonium salts of organized clays are not particularly limited, but examples include trimethylstearylammonium salts, oleylbis(2-hydroxylethyl) salts, methylammonium salts, dimethylstearylbenzylammonium salts, and dimethyloctadecylammonium salts. , and mixtures of two or more of these can be suitably used. As the quaternary ammonium salt of such organized clay, dimethylstearylbenzylammonium salt, dimethyloctadecylammonium salt, and mixtures thereof can be more preferably used from the viewpoint of improving tensile strength and heat resistance. A mixture of stearylbenzylammonium salt and dimethyloctadecylammonium salt can more preferably be used.

In addition, as such an organized clay, a commercially available one may be used. , Hojun's product names "Esben series (C, E, W, WX, N-400, NX, NX80, NZ, NZ70, NE, NEZ, NO12S, NO12", "Organite series (D, T) Among such commercially available organic clays, the trade name "Kunifil-D36" manufactured by Kunimine Industries Co., Ltd. and the trade name "Esben Series WX" manufactured by Hojun Co., Ltd. can be suitably used. .

As described above, from the viewpoint of high dispersibility, clays containing silicon and magnesium as main components and organized clays are preferable. is particularly preferred.

When the thermoplastic elastomer composition contains clay, the content of the clay is preferably 20 parts by mass or less, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the polymer component. It is more preferably 0.05 to 5 parts by mass. When the clay content is at least the above lower limit, the effect of improving the tensile stress and heat resistance tends to be favorably exhibited. Therefore, elongation and strength tend to be good.

<Other ingredients>
In addition to the polymer component and the fatty acid amide compound, the thermoplastic elastomer composition of the embodiment further contains, if necessary, other components that do not fall under these within a range that does not impair the object of the present invention. good too. Other components include polymers other than the polymer components (hereinafter referred to as "polymers"), reinforcing agents (fillers), hydrogen-bonding reinforcing agents (fillers), fillers containing amino groups ( 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"), anti-aging agents, antioxidants agents, pigments (dyes), plasticizers, thixotropic agents, UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, rust inhibitors, adhesion agents, antistatic agents various additives such as agents and fillers. For example, anti-aging agents, anti-oxidants, pigments (dyes), and plasticizers can be appropriately used as described below.

As the polymer other than the polymer component, a polymer having a side chain (b) and other than the polymer (B) can be preferably used.

Examples of such a reinforcing agent (filler) include carbon black, silica, calcium carbonate, and the like. As silica, wet silica and calcium carbonate are preferably used.

As such an anti-aging agent, for example, compounds such as hindered phenols, aliphatic and aromatic hindered amines can be used as appropriate. Moreover, as the antioxidant, for example, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), and the like can be appropriately used. Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides and sulfates, and 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, and citric acid. In addition to acid derivatives, polyesters, polyethers, epoxies, and the like can be used as appropriate. Incidentally, as such additives and the like, those exemplified in JP-A-2006-131663 may be appropriately used.

When the thermoplastic elastomer composition of the embodiment contains components other than the polymer component and the fatty acid amide compound (for example, the additives, etc.), the content of the other components is not particularly limited. However, in the case of polymers and reinforcing materials (fillers), the amount is preferably 300 parts by mass or less, more preferably 20 to 200 parts by mass, based on 100 parts by mass of the polymer component. If the content of such other components is less than the lower limit, there is a tendency that the effect of using other components will not be sufficiently exhibited. , the effect of the polymer component is weakened, and the physical properties tend to deteriorate.

In addition, when the above-mentioned other components are other additives (other than polymers and reinforcing materials (fillers)), the content of the other components is 100 parts by mass of the polymer component. On the other hand, it is preferably 20 parts by mass or less, more preferably 0.1 to 10 parts by mass. If the content of such other components is less than the lower limit, the effect of using the other components tends to be insufficient, while if it exceeds the upper limit, the reaction of the polymer component is adversely affected. , on the contrary, the physical properties tend to deteriorate.

The thermoplastic elastomer composition of the embodiments comprises the polymer component, the fatty acid amide compound, and optionally at least one selected from the group consisting of process oils, thermoplastic resins, clays, and other components not included therein. including ingredients; The thermoplastic elastomer composition of the embodiment can contain the above components so that the total content (% by mass) does not exceed 100% by mass.

<Application etc.>
When the thermoplastic elastomer composition of the embodiment is heated (for example, heated to 100 to 280° C.), the hydrogen bonds formed at the hydrogen-bonding crosslinked sites of the polymer components and other crosslinked structures are dissociated. can be softened and given fluidity. This is presumably because the heating weakens the interaction between side chains formed between molecules or within molecules (mainly due to hydrogen bonding). In addition, in the thermoplastic elastomer composition of the embodiment, since the side chain contains a polymer component containing at least a hydrogen-bonding cross-linking site, the fluidity is imparted by heating, and when left to stand, dissociation occurs. Since the formed hydrogen bonds are rebonded and cured, depending on the composition, it is possible to make the thermoplastic elastomer composition exhibit more efficient recyclability.

Moreover, as one embodiment of the present invention, a cured product of the thermoplastic elastomer composition can be obtained. For curing, for example, the thermoplastic elastomer composition is cured at a temperature equal to or lower than the temperature at which the fluidity can be imparted.

Therefore, as one embodiment of the present invention, a cured product of the thermoplastic elastomer composition of the embodiment can be provided.
The surface tack force of the cured product of the thermoplastic elastomer composition may be 4 N or less, may be 0.1 N or more and 4 N or less, may be 1 N or more and 3.5 N or less, or may be 2 N or more and 2.7 N. It may be below. When the tack force is equal to or less than the upper limit, stickiness is less likely to occur during use, and sticking to molding materials is prevented.
The tack force is measured under the measurement conditions described in Examples below.

As described above, the thermoplastic elastomer composition of the embodiment can be heated to impart fluidity, molded, and cured to obtain a molded article of the thermoplastic elastomer composition.

Molding methods include injection molding, extrusion molding, compression molding, and the like.

The extrusion rate for extrusion molding is not particularly limited, but can be exemplified from 1 to 50 kg/h.

The term "heating" as used herein may correspond to heating at the time of melt-mixing in <<method for producing thermoplastic elastomer composition>> described below, or once a molded product of the thermoplastic elastomer composition is obtained, After that, it may be heated again to correspond to the heating at the time of imparting fluidity.

A molded article of the thermoplastic elastomer composition is a cured product of the thermoplastic elastomer composition of the embodiment, and may be produced using the thermoplastic elastomer composition of the embodiment. It may comprise a thermoplastic elastomer composition.

Molded articles of the thermoplastic elastomer composition of the embodiments include those used as materials for various products, such as pellets and sheets. By containing a fatty acid amide compound, the thermoplastic elastomer composition of the embodiment can prevent blocking between pellets or between sheets.

The thermoplastic elastomer compositions of the embodiments can be used in various rubber applications, for example, by exploiting rubber elasticity. Moreover, it is preferable to use it as a hot-melt adhesive or as an additive to be contained therein, because it can improve heat resistance and recyclability. The thermoplastic elastomer composition of the embodiment can be used for automotive rubber parts, hoses, belts, sheets, anti-vibration rubber, rollers, linings, rubber-coated fabrics, 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 capliners, etc. Used.

Specific examples of the rubber parts for automobiles include tire parts such as tire tread, carcass, sidewall, inner liner, undertread, and belt; exterior radiator grille, side molding, garnish (pillar, rear , 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, Molds (windows, hoods, door belts)), marks; interior window frame parts such as doors, lights, wiper weather strips, glass runs, glass run channels; air duct hoses, radiator hoses, brake hoses; crankshaft seals, valve stem seals , head cover gaskets, A/T oil cooler hoses, mission oil seals, P/S hoses, P/S oil seals; fuel hoses, emission control hoses, inlet filler hoses, diaphragms, etc. Anti-vibration parts such as engine mounts and in-tank pump mounts; Boots such as CVJ boots and rack & pinion boots; Air conditioning parts such as A/C hoses and A/C seals; Timing belts and accessories belt parts such as belts; sealers such as windshield sealers, vinyl plastisol sealers, anaerobic sealers, body sealers and spot weld sealers;

Further, when the thermoplastic elastomer composition of the embodiment is incorporated as a rubber modifier (for example, an anti-flow agent) into a resin or rubber that causes cold flow at room temperature, flow and cold flow during extrusion can be prevented. be able to.

<<Method for producing thermoplastic elastomer composition>>
A thermoplastic elastomer composition is obtained by blending a fatty acid amide compound, a polymer component or raw materials thereof, and, if necessary, other components constituting the thermoplastic elastomer composition.
More preferably, the thermoplastic elastomer composition is prepared by blending a fatty acid amide compound, a polymer component or raw materials thereof, and, if necessary, other components constituting the thermoplastic elastomer composition, followed by melt-mixing. obtained by doing If the fatty acid amide compound, the polymer component or its raw material (and the thermoplastic resin if the thermoplastic elastomer composition contains a thermoplastic resin) are melted, then all of the blended components are melted. It doesn't have to be.

When raw materials for the polymer component are used, the polymer component can be synthesized from the raw materials for the polymer component during the above-described melt-mixing.

A mixer such as a stirring blade mixer can be used as a device for blending the above-described components constituting the thermoplastic elastomer composition, and the time for blending may be 5 to 40 minutes. . Moreover, the order of addition of each component at the time of blending is not particularly limited, and two or more components may be added at the same time.

The temperature for melt-mixing the components constituting the thermoplastic elastomer composition may be appropriately determined according to the components constituting the thermoplastic elastomer composition or their raw materials. It is preferably at a temperature equal to or higher than the melting point of various substances including the raw material, and examples include temperatures lower than the thermal decomposition temperature of the various substances. As an example, the temperature of melt mixing may be 100-280°C, 160-230°C, or 180-220°C.
Moreover, the device for melt-mixing may be either a batch type or a continuous type. Examples of such devices include melt-kneading devices such as single-screw extruders, twin-screw extruders, kneaders, and Banbury mixers.
The time for melt-mixing may be appropriately determined depending on the components constituting the thermoplastic elastomer composition or the raw materials thereof, and may be 2 to 30 minutes.

The fatty acid amide compound may be blended together with the raw materials of the polymer component (added before synthesis of the polymer component), or the fatty acid amide compound may be blended together with the synthesized polymer component (added after synthesis of the polymer component).

When the fatty acid amide compound is blended together with the raw materials of the polymer component (in the case of pre-addition), the polymer component is synthesized in the mixture to obtain a thermoplastic elastomer composition containing the fatty acid amide compound and the polymer component. be able to.
When the fatty acid amide compound is blended together with the polymer component (in the case of post-addition described above), the fatty acid amide compound may be added to the molded article containing the thermoplastic elastomer to obtain the thermoplastic elastomer composition. In this case, it can be exemplified by coating the surface of the molded article with a fatty acid amide compound. Examples include immersion of the molded article in a compound, impregnation of the molded article in a fatty acid amide compound, and the like.

That is, the following aspects are provided as a method for producing a thermoplastic elastomer composition according to the present invention, including the above-described embodiment using raw materials for the polymer component.

A mixture containing a polymer having a cyclic acid anhydride group in a side chain and at least one raw material compound selected from the group consisting of <1> to <3> below is obtained, and the polymer and the raw material compound are combined. obtaining a polymer component by reacting
adding a fatty acid amide compound to the mixture before reacting the polymer and the raw material compound or to the mixture after reacting the polymer and the raw material compound. A method for producing a plastic elastomer composition.
<1> Compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site,
<2> A mixed raw material of the compound (I) and the compound (II) that reacts with the cyclic acid anhydride group to form a covalently crosslinked site,
<3> A compound capable of forming both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site by reacting with the cyclic acid anhydride group

As the polymer component, the compound (I), the compound (II), the compound capable of forming both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site, and the fatty acid amide compound, the above <<thermoplastic elastomer composition>> , can be exemplified.

When the thermoplastic elastomer composition of the embodiment is a dynamically crosslinkable thermoplastic elastomer composition, the method for producing the dynamically crosslinkable thermoplastic elastomer composition comprises:
obtaining a polymer component by obtaining a mixture comprising a polymer, a cross-linking agent for cross-linking the polymer, and a thermoplastic resin, and dynamically cross-linking the polymer and the cross-linking agent under melt conditions;
and blending a fatty acid amide compound into the mixture before dynamically cross-linking the polymer and the cross-linking agent or into the mixture after dynamically cross-linking the polymer and the cross-linking agent.

The following aspects are provided as a method for producing a dynamically crosslinkable thermoplastic elastomer composition according to the present invention, including the above embodiments.

Obtaining a mixture containing a polymer having a cyclic acid anhydride group in a side chain, at least one raw material compound selected from the group consisting of the above <2> to <3>, and a thermoplastic resin, melting conditions obtaining a polymer component by dynamically cross-linking the polymer and a raw material compound below;
blending a fatty acid amide compound into the mixture before dynamic crosslinking of the polymer and the raw material compound or into the mixture after dynamic crosslinking of the polymer and the raw material compound. A method for producing a dynamically crosslinkable thermoplastic elastomer composition according to the invention.

Here, the term "dynamically cross-linking under melting conditions" as used herein means reacting the polymer and the raw material compound while applying shear stress to the mixture in the molten state by kneading.

An apparatus for dynamic cross-linking may be either a batch type or a continuous type. Examples of such devices include melt-kneading devices such as single-screw extruders, twin-screw extruders, kneaders, and Banbury mixers.
The time for dynamic cross-linking may be appropriately determined according to the components constituting the thermoplastic elastomer composition or the raw materials thereof, and may be from 2 minutes to 30 minutes.

The temperature at the time of dynamic crosslinking may be appropriately determined according to the components constituting the thermoplastic elastomer composition or the raw materials thereof, but the above-mentioned melt-mixing temperature can be exemplified, and includes fatty acid amide compounds and raw materials of polymer components. It is preferably at a temperature equal to or higher than the melting point of various raw materials, and a temperature below the thermal decomposition temperature of various raw materials can be exemplified. As an example, the temperature of melt mixing may be 100-280°C, 160-230°C, or 180-220°C.

Alternatively, for example, a thermoplastic elastomer composition containing the polymer (A) as the polymer component and a thermoplastic elastomer composition containing the polymer (B) as the polymer component are separately produced and then mixed to form a polymer A thermoplastic elastomer composition containing polymers (A) and (B) as components may also be used. Further, in the case of producing a thermoplastic elastomer composition containing a combination of polymers (A) and (B) as polymer components, the ratio of polymer (A) and polymer (B) may be changed as appropriate in the composition. By appropriately changing the ratio of the hydrogen-bonding cross-linking site and the covalent-bonding cross-linking site, etc., it is possible to exhibit the desired properties.

According to the method for producing the thermoplastic elastomer composition of the embodiment, the thermoplastic elastomer composition of the embodiment can be produced. In addition, the thermoplastic elastomer composition of the present invention is not limited to one produced by this method.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[Example 1]
Maleic anhydride-modified ethylene-butene copolymer (manufactured by Mitsui Chemicals, trade name "Tafmer MH5040") 35 kg, trishydroxyethyl isocyanurate (manufactured by Nissei Sangyo Co., Ltd., trade name "Tanac") 0.78 kg, high-density polyethylene (trade name “HJ590N” manufactured by Japan Polyethylene Co., Ltd.) 25 kg, styrene block copolymer (trade name “G1633EU” manufactured by Kraton) 40 kg, process oil (trade name “300HV-S (J)” manufactured by JXTG Energy), Percentage (CP) 78.6%) 62 kg, organic clay (trade name “Esben WX” manufactured by Hojun Co.) 0.035 kg, anti-aging agent (trade name “ADEKA STAB AO-50” manufactured by ADEKA) 0.49 kg , And as a surface modifier, 0.33 kg of ethylene bis oleic acid amide (manufactured by NOF Corporation, trade name "ALFLOW AD-281F") is weighed and mixed uniformly at a temperature of 50 ° C. or less in a stirring blade mixer. A raw material mixture was obtained. The content of ethylenebisoleamide is about 0.2% by mass with respect to 100% by mass of the raw material mixture. Ethylenebisoleic acid amide has a molecular weight of 589 and a melting point of 115°C.
The obtained raw material mixture was put into a twin-screw extruder and kneaded at an extrusion rate of 20 kg/h at 200° C. to obtain a thermoplastic elastomer composition. Next, this composition was pelletized to obtain pellets.

[Example 2]
Pellets were produced in the same manner as in Example 1 above, except that the amount of ethylenebisoleic acid amide added was 4.9 kg.
The content of ethylenebisoleic acid amide with respect to 100% by mass of the raw material mixture is about 3% by mass.

[Example 3]
Pellets were produced in the same manner as in Example 1 above, except that the amount of ethylenebisoleic acid amide added was changed to 8.2 kg.
The content of ethylenebisoleic acid amide with respect to 100% by mass of the raw material mixture is about 5% by mass.

[Example 4]
Same as Example 1 except that 4.9 kg of ethylene bis-stearic acid amide (trade name "ALFLOW H-50S" manufactured by NOF Corporation) was added instead of ethylene bis-oleic acid amide in Example 1 above. to produce pellets.
The content of ethylenebisstearic acid amide with respect to 100% by mass of the raw material mixture is about 3% by mass. Ethylene bis stearamide has a molecular weight of 593 and a melting point of 145°C.

[Comparative Example 1]
In Example 1 above, in the same manner as in Example 1, except that 4.9 kg of oleic acid monoamide (trade name "ALFLOW E-10" manufactured by NOF Corporation) was added instead of ethylenebisoleic acid amide. A pellet was made.
The content of oleic acid monoamide with respect to 100% by mass of the raw material mixture is about 3% by mass. Oleic acid monoamide has a molecular weight of 281 and a melting point of 74°C.

[Comparative Example 2]
In the above Example 1, in the same manner as in Example 1, except that 4.9 kg of erucic acid monoamide (trade name "ALFLOW P-10" manufactured by NOF Corporation) was added instead of ethylenebisoleic acid amide. A pellet was made.
The content of erucic acid monoamide with respect to 100% by mass of the raw material mixture is about 3% by mass. Erucic acid monoamide has a molecular weight of 338 and a melting point of 81°C.

[Comparative Example 3]
Pellets were produced in the same manner as in Example 1 above, except that no fatty acid amide compound was added.

<Evaluation>
・Peelability from injection molding mold From the pellets of Examples 1 to 4 and Comparative Examples 1 to 3 obtained above, a flat plate with a thickness of 100 mm × 100 mm × 2 mm is molded at 200 ° C. with an injection molding machine. The peelability of the product from the injection mold was evaluated. The temperature of the mold was 40°C. Evaluation criteria are as follows.
Good: The molded product was able to be peeled off from the mold by pushing down the ejector.
x: There was adhesion to the mold, and the molded product could not be peeled off from the mold when pushed down by an ejector.

・Peelability from hot rolls Sheets were formed from the pellets of Examples 1 to 4 and Comparative Examples 1 to 3 obtained above with a mixing roll device equipped with two rolls with a diameter of 200 mm and a length of 610 mm. , to evaluate the releasability of the molded product from the roll. The temperature of each roll was 130° C., and the clearance between the two rolls was 0.3 mm. Evaluation criteria are as follows.
Good: The molded product was easily peeled off from the hot roll.
x: Adhesion to the hot roll was observed, and the molded article could not be peeled off from the hot roll, or the molded article was damaged although it was peeled off.

• Stickiness of Molded Article The presence or absence of stickiness on the surface of the molded article (flat plate and sheet) obtained above was evaluated.

・ Tack force of molded product The flat plate with a thickness of 2 mm obtained above is cut into a length of 50 mm × width of 40 mm, and the main surface of the flat plate after cutting (50 mm × 40 mm), the tack force was measured using a probe attached to the measuring device (wheel-shaped with a diameter of 50 mm and a width of 14 mm, the circumference of the wheel comes into contact with the flat plate sample). The measurement conditions were an environment of 23° C., an applied pressure of 5 N, a crimping time of 3 seconds, a descending speed of the holder of 1000 mm/min, and an ascending speed of the holder of 500 mm/min.

- Hardness of molded product From the pellets of Example 1, in the same manner as described above, a flat plate with a thickness of 100 mm × 100 mm × 2 mm is formed, and the center of the main surface of the flat plate is measured for Shore A hardness according to JIS K6253. It turned out to be 50.

Table 1 shows the types and physical properties of the fatty acid amide compounds used as raw materials, and the above evaluation results.

Molded articles of the thermoplastic elastomer compositions of Comparative Examples 1 to 3, which did not contain a fatty acid amide compound having a molecular weight of 400 or more, adhered to the mold and could not be removed from the mold by pushing down the ejector. rice field. In addition, the molded article had adhesion to the roll, and the sheet could not be peeled off from the hot roll.

On the other hand, the molded articles of the thermoplastic elastomer compositions of Examples 1 to 4, which contained the fatty acid amide compound having a molecular weight of 400 or more, had a reduced tack force, and exhibited excellent releasability from the injection mold and from the hot roll. There was no problem with the releasability of the resin, and there was no feeling of stickiness on the surface of the molded product.

Further, according to a comparison between Comparative Examples 1 and 2 and Examples 1 to 4, in Comparative Examples 1 and 2 containing fatty acid amide compounds having a molecular weight of less than 400, the implementations containing fatty acid amide compounds having a molecular weight of 400 or more Compared with Examples 1 to 4, the effect of reducing the tack force of the molded product was inferior. That is, it can be seen that by setting the molecular weight of the fatty acid amide compound to 400 or more, a very excellent tack force reducing effect is exhibited.

In the molded articles of the thermoplastic elastomer compositions of Examples 1 to 4, the content of the process oil was 30% by mass or more with respect to 100% by mass of the thermoplastic elastomer composition. In spite of the composition containing a large amount of the fatty acid amide compound having a molecular weight of 400 or more, it can be seen that the effect of reducing the tack force is exhibited very effectively.

Each configuration and combination thereof in each embodiment is an example, and addition, omission, replacement, and other modifications of the configuration are possible without departing from the scope of the present invention. Moreover, the present invention is not limited by each embodiment, but only by the scope of the claims.

INDUSTRIAL APPLICABILITY The present invention can provide a thermoplastic elastomer composition having a reduced surface tackiness when cured, and a method for producing the thermoplastic elastomer composition.

Claims (11)

A 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, and a hydrogen bond to the side chain at least one polymer component selected from the group consisting of polymers (B) containing a sexual cross-linking site and a covalent cross-linking site and having a glass transition point of 25° C. or lower;
containing a fatty acid amide compound,
The fatty acid amide compound has a molecular weight of 400 or more,
The fatty acid amide compound is a bisamide compound represented by the following general formula (II),
A thermoplastic elastomer composition , wherein the polymer (A) and the polymer (B) are polyolefin polymers .

(In general formula (II), R ¹¹ and R ¹² each independently represent a monovalent organic group; R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group; R ⁵ is 2; represents a valent organic group.) 2. The thermoplastic elastomer composition according to claim 1, wherein the hydrogen-bonding cross-linking site of the polymer (B) has a carbonyl-containing group and/or a nitrogen-containing heterocyclic ring in its side chain. 3. The thermoplastic elastomer composition according to claim 1, wherein the content of said fatty acid amide compound is 0.1% by mass or more with respect to 100% by mass of said thermoplastic elastomer composition. The thermoplastic elastomer composition according to any one of claims 1 to 3, further comprising process oil. 5. The thermoplastic elastomer composition according to claim 4, wherein the content of said process oil is 30% by mass or more with respect to 100% by mass of said thermoplastic elastomer composition. 6. The thermoplastic elastomer composition according to any one of claims 1 to 5, having a Shore A hardness of 70 or less according to JIS K6253 after curing. A dynamically crosslinked thermoplastic elastomer composition comprising a dispersed phase and a continuous phase, wherein the dispersed phase contains the polymer component and the continuous phase contains a thermoplastic resin, according to any one of claims 1 to 6 . The thermoplastic elastomer composition described. The polymer component contains the polymer (B),
The polymer (B) is a polymer having a cyclic acid anhydride group in a side chain,
A mixed raw material of compound (I) that forms a hydrogen-bonding cross-linking site by reacting with the cyclic acid anhydride group and compound (II) that forms a covalent cross-linking site, or reacting with the cyclic acid anhydride group The thermoplastic elastomer composition according to any one of claims 1 to 7 , which is a reaction product of a compound capable of forming both hydrogen-bonding cross-linking sites and covalent-bonding cross-linking sites. The polymer component contains the polymer (B),
The polymer (B) is a polymer having a cyclic acid anhydride group in a side chain,
The heat according to any one of claims 1 to 8 , which is a reaction product of a compound capable of forming both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site by reacting with the cyclic acid anhydride group. A plastic elastomer composition. The polymer having a cyclic acid anhydride group in a side chain is a maleic anhydride-modified polymer,
The compound capable of reacting with the cyclic acid anhydride group to form both a hydrogen-bonding cross-linking site and a covalently-bonding cross-linking site is a nitrogen-containing heterocycle-containing polyol, a nitrogen-containing heterocycle-containing polyamine, and a nitrogen-containing heterocycle-containing 10. The thermoplastic elastomer composition according to claim 8 or 9 , which is at least one compound selected from the group consisting of polythiols. A method for producing the thermoplastic elastomer composition according to any one of claims 1 to 10 ,
A mixture containing a polymer having a cyclic acid anhydride group in a side chain and at least one raw material compound selected from the group consisting of <1> to <3> below is obtained, and the polymer and the raw material compound are combined. obtaining the polymer component by reacting
adding the fatty acid amide compound having a molecular weight of 400 or more to the mixture before reacting the polymer with the raw material compound or to the mixture after reacting the polymer with the raw material compound; A method for producing a thermoplastic elastomer composition, comprising:
<1> Compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site,
<2> A mixed raw material of the compound (I) and the compound (II) that reacts with the cyclic acid anhydride group to form a covalently crosslinked site,
<3> A compound capable of forming both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site by reacting with the cyclic acid anhydride group