JPWO2020149400A1 - Thermoplastic Elastomer Composition and Method for Producing Thermoplastic Elastomer Composition - Google Patents

Abstract

A polymer (A) having a side chain (a) containing a hydrogen-binding 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. Contains at least one polymer component selected from the group consisting of the polymer (B) containing a sex-crosslinking site and a covalently-binding crosslinking site and having a glass transition point of 25 ° C. or lower, and a fatty acid amide compound. A thermoplastic elastomer composition having a molecular weight of the fatty acid amide compound of 400 or more.

Description

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

In recent years, reuse of used materials has been desired from the standpoint of environmental protection and resource saving. Cross-linked rubber (vulcanized rubber) has a stable three-dimensional network structure in which a polymer substance and a cross-linking agent (vulcanizing agent) are covalently bonded, and exhibits extremely high strength, but due to cross-linking due to strong covalent bonds. Difficult to remold. On the other hand, the thermoplastic elastomer utilizes physical cross-linking, can be easily molded by heat melting without requiring a complicated vulcanization / molding step 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, and at room temperature, the resin component is crystallized to prevent plastic deformation, and the temperature rises to soften or melt the resin component to cause plastic deformation. Thermoplastic elastomers are known.

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

Japanese Unexamined Patent Publication No. 2006-131663 Japanese Unexamined Patent Publication No. 2016-193970

However, while such a thermoplastic elastomer has an excellent property that it can be easily molded while exhibiting excellent tensile strength, it has a high surface tacking force (stickiness) when it is made into a cured product, and when used, it has a high surface tacking force. A feeling of stickiness may occur. Further, at the time of molding, it is easy to stick to a heat roll, a pass roll, a mold or the like, and there is a possibility that the yield may be low 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 tacking force when made into a cured product, and a method for producing the thermoplastic elastomer composition. And.

As a result of diligent studies to solve the above problems, the present inventors have made a combination of a specific polymer component and a fatty acid amide compound having a molecular weight of 400 or more, and obtained a cured product in a thermoplastic elastomer composition containing these. We have found that the tack force on the surface of the time is remarkably reduced, and have completed the present invention.
That is, one aspect of the present invention is the following thermoplastic elastomer composition and a method for producing the thermoplastic elastomer composition.

(1) A polymer (A) having a side chain (a) containing a hydrogen-binding 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 side chain. At least one polymer component selected from the group consisting of the polymer (B) containing a hydrogen-binding cross-linking site and a co-binding cross-linking site and having a glass transition point of 25 ° C. or lower.
Contains fatty acid amide compounds,
A thermoplastic elastomer composition having a molecular weight of 400 or more of the fatty acid amide compound.
(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 heterocycle in the side chain.
(3) The thermoplastic elastomer composition according to (1) or (2) above, wherein the ratio of the content of the fatty acid amide compound to 100% by mass of the thermoplastic elastomer composition is 0.1% by mass or more.
(4) The thermoplastic elastomer composition according to any one of (1) to (3) above, further containing a process oil.
(5) The thermoplastic elastomer composition according to (4) above, wherein the ratio of the content of the process oil to 100% by mass of the thermoplastic elastomer composition is 30% by mass or more.
(6) The thermoplastic elastomer composition according to any one of (1) to (5) above, wherein the cured Shore A hardness according to JIS K6253 is 70 or less.
(7) The thermoplastic elastomer composition according to any one of (1) to (6) above, wherein the polymer (A) and the polymer (B) are polyolefin-based polymers.
(8) A dynamically crosslinked thermoplastic elastomer composition composed of a dispersed phase and a continuous phase, wherein the dispersed phase contains the polymer component and the continuous phase contains a thermoplastic resin. (1) to (7). The thermoplastic elastomer composition according to any one of the above.
(9) The polymer component contains the polymer (B).
The polymer (B) is a polymer having a cyclic acid anhydride group in the side chain, and the polymer (B).
Reacts with the mixed raw material of the compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-binding cross-linking site and the compound (II) that forms a covalently-bonding cross-linking site, or with the cyclic acid anhydride group. The thermoplastic elastomer composition according to any one of (1) to (8) above, which is a reaction product of a compound capable of forming both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site.
(10) The polymer component contains the polymer (B).
The polymer (B) is a polymer having a cyclic acid anhydride group in the side chain, and the polymer (B).
One of the above (1) to (9), which is a reaction product of a compound capable of reacting with the cyclic acid anhydride group to form both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site. The thermoplastic elastomer composition of the description.
(11) The polymer having the cyclic acid anhydride group in the side chain is a maleic anhydride-modified polymer.
The 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 contains a nitrogen-containing heterocycle-containing polyol, a nitrogen-containing heterocycle-containing polyamine, and a nitrogen-containing heterocycle-containing compound. The thermoplastic elastomer composition according to (9) or (10) above, which is at least one compound selected from the group consisting of polythiols.
(12) The 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 the following <1> to <3> is obtained, and the polymer and the raw material compound are used. To obtain a polymer component by reacting with
A thermoplastic elastomer composition comprising blending a fatty acid amide compound with the mixture before reacting the polymer with the raw material compound, or with the mixture after reacting the polymer with the raw material compound. How to make things.
<1> Compound (I), which 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 bonded site.
<3> A compound capable of reacting with the cyclic acid anhydride group to form both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a thermoplastic elastomer composition in which the tack force on the surface of a cured product is reduced, and a method for producing the thermoplastic elastomer composition.

Hereinafter, the thermoplastic elastomer composition of the present invention and embodiments of the thermoplastic elastomer composition will be described.

<< Thermoplastic Elastomer Composition >>
The thermoplastic elastomer composition of the embodiment is a polymer having a side chain (a) containing a hydrogen-binding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or lower. A) and at least one polymer selected from the group consisting of the polymer (B) having a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site in the side chain and having a glass transition point of 25 ° C. or lower. It contains a component and a fatty acid amide compound, and the molecular weight of the fatty acid amide compound is 400 or more.

The inventors have found that the combination of the above-mentioned specific polymer component and a fatty acid amide compound having a molecular weight of 400 or more significantly reduces the surface tacking force of a cured product in a thermoplastic elastomer composition containing the above-mentioned specific polymer component. I found that.

Hereinafter, each component contained in the thermoplastic elastomer composition of the embodiment will be described in detail.

<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 further 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 strong surface stickiness. The thermoplastic elastomer composition of the embodiment has a fatty acid amide compound having a molecular weight of 400 or more, so that the tack force on the surface of the cured product is significantly reduced.
The details of the mechanism by which the tack force on the surface of the cured product of the thermoplastic elastomer composition is significantly reduced are not clear at this time, but the molecular weight of the fatty acid amide compound is 400 or more, so that the thermoplastic elastomer composition is cured. It is presumed that the fatty acid amide compound is likely to be present on the surface of the cured product when it is made into a product, so that the reduction of the tack force is effectively exhibited. On the other hand, when 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, the fatty acid amide compound is largely distributed inside the cured product of the thermoplastic elastomer composition. Therefore, it is inferred that the effect of reducing the tack force is difficult to be exhibited.
Further, if the miscibility state of the additive and the polymer component is not good, the additive may be partially aggregated and whitening of the additive may occur. 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 in which the mixture is in a good state when the two are mixed, and the whitening of the additive or the like appears on the surface of the cured product. There are advantages such as 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 tack force.

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., and more preferably 100 ° C. or higher and lower than 160 ° C. preferable. By using a fatty acid amide compound whose melting point is within the above temperature range, it becomes easy to perform melt mixing in a state where the fatty acid amide compound is melted.

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

(In the general formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group. However, all of R ¹ , R ² and R ³ are hydrogen atoms. There is no such thing.)

In the compound represented by the general formula (I), when R ¹ is a monovalent organic group and is an R ² and R ³ hydrogen atom (primary amide); R ¹ is a monovalent organic group. , R ² and R ³ are monovalent organic groups, and ^{either R 2} or R ³ is a hydrogen atom (secondary amide); R ¹ is a monovalent organic group. Yes, the case where R ² and R ³ are monovalent organic groups (tertiary amide) can be exemplified.
The monovalent organic group of R ¹ is preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group is either a saturated aliphatic hydrocarbon group (alkyl group) which may have a substituent or an unsaturated aliphatic hydrocarbon group (alkenyl group) which may have a substituent. But it may be.
The ^{carbon number of the organic group in R 1} , R ² and R ³ may be appropriately determined within the range of the molecular weight defined by 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 the 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, an alkyl group 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, the bisamide compound represented by the following general formula (III) can be exemplified.

(In the general formula ^(III), R ^{11, R 12} and ^{R 5} represents the same meaning as ^{R 11, R 12} and ^{R 5} in the general formula (II).)

In the general formulas (II) and (III), ^{the monovalent organic group of R 11} and R ¹² is preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group (alkyl group) which may have a substituent or an unsaturated aliphatic hydrocarbon group (alkenyl group) which may have a substituent. good. The carbon number of the organic group in R ¹¹ and R ¹² may be appropriately determined within the range of the molecular weight defined by the fatty acid amide compound according to the embodiment, but the carbon number of 9 to 29 is preferable, and the carbon number of 13 to 25 is more. It is preferable, and the number of carbon atoms is more preferably 15 to 20.
In the general formula (II) and (III), the divalent organic group for ^{R 5} is an alkylene group is preferred. The number of carbon atoms of the alkylene group for R ⁵ is may be appropriately determined in a range of molecular weight defined by the fatty acid amide compounds according to embodiment, is preferably 1 to 10 carbon atoms from 1 to 20 carbon atoms It is more preferable, and it is further preferable that the number of carbon atoms is 1 to 3.
Examples of the substituent in the alkyl group and the alkenyl group include a hydroxyl group and the like.

As the bisamide compound represented by the general formula (III), R ¹¹ and R ¹² are independently alkyl groups or alkenyl groups having 15 to 20 carbon atoms, and R ⁵ is an alkylene group having 1 to 3 carbon atoms. The base is preferred.

Examples of the compound represented by the general formula (III) include an alkylene bis fatty acid amide obtained by reacting a diamine with a fatty acid.
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, pentadecylic acid, palmitic acid, stearic acid, oleic acid, linolenic acid, linolenic acid, behenic acid, montanic acid, and melissic acid.

Examples of the compound represented by the general formula (III) include N, N'-methylenebistearic acid amide, N, N'-methylenebisoleic acid amide, N, N'-ethylene bisstearic acid amide, N, N. '-Ethethylenebisoleic acid amide, N, N'-hexamethylene bisstearoamide, N, N'-methylenebisoctadecaneamide, N, N'-methylenebislauric acid amide, N, N'-methylenebismyristic acid Amide, N, N'-methylenebispalmitic acid amide, N, N'-methylenebisbechenic acid amide, N, N'-methylenebiserkaic acid amide, N, N'-ethylenebislauric acid amide, N, N' -Ethethylene bismilistic acid amide, N, N'-ethylene bispalmitic acid amide, N, N'-ethylene bisbechenic acid amide, N, N'-ethylene bis-erucate amide, N, N'-(1,6 hexane) Diyl) bis [12-hydroxyoctadecaneamide] and the like can be exemplified.

The fatty acid amide compound may be used alone 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 polymer component, the type of the fatty acid amide compound, etc., with respect to the total mass (100% by mass) of the thermoplastic elastomer composition of the embodiment. 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 to 100% by mass of the thermoplastic elastomer composition is equal to or higher than the above lower limit, the surface tacking force when the thermoplastic elastomer composition is a cured product is more effective. Can be reduced to. Further, when the ratio of the content of the fatty acid amide compound to 100% by mass of the thermoplastic elastomer composition is not more than the above upper limit value, the contamination of the molding processing equipment and the like due to the 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-binding 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 at least one selected from the group consisting of the polymer (B) containing a hydrogen-binding cross-linking site and a co-binding cross-linking site in the side chain and having a glass transition point of 25 ° C. or lower. ..

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 an elastomeric property and / or an elastomeric polymer (B) having an elastomeric property. There may be.

The thermoplastic elastomer composition of the embodiment has thermoplasticity and elastomeric properties (elasticity). However, as illustrated below, in the thermoplastic elastomer composition, the main chain portion of the polymer (and the polymer forming the main chain portion described later), which is one of the constituent elements, does not necessarily have elastomeric properties. It is also good. In such a case, it is considered that the elastomeric property of the thermoplastic elastomer composition of the embodiment is exhibited by the above-mentioned cross-linking site. Here, the "main chain of the polymer" is a side chain (side chain (a), side chain (a'), side chain (b) constituting the cross-linking site described later from the polymers (A) to (B). , And the part excluding the side chain (c)).

In the polymers (A)-(B), the "side chain" refers to the side chain and end of the polymer.
Further, the "side chain (a) containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle" is a hydrogen bond to an atom (usually a carbon atom) forming the main chain of the polymer. It means that the carbonyl-containing group and / or the nitrogen-containing heterocycle (more preferably, the carbonyl-containing group and the nitrogen-containing heterocycle) as the sex-crosslinking site have a chemically stable bond (covalent bond). Further, "the side chain contains a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site" is referred to as a side chain having a hydrogen-bonding cross-linking site (hereinafter, for convenience, in some cases, "side chain (a')". ) And a side chain having a covalently cross-linked site (hereinafter, for convenience, referred to as "side chain (b)" in some cases), thereby forming a hydrogen-bonded cross-linked site on the side chain of the polymer. And a side chain having both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site (a hydrogen-bonding cross-linking site and a covalent-bonding site in one side chain) Side chain containing both cross-linking sites: Hereinafter, such side chains are sometimes referred to as "side chains (c)"), whereby hydrogen-bonding cross-linking sites and covalent bonds are included in the side chains of the polymer. It is a concept including the case where both of the binding cross-linking sites are contained.

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

The polymers (A) to (B) have a main chain of a polymer having a glass transition point of room temperature (25 ° C.) or lower, such as a natural polymer or a synthetic polymer, and have a carbonyl-containing group and / or a nitrogen-containing heterocycle. A polymer containing a side chain (a) containing a hydrogen-binding cross-linking site having a , A side chain having a hydrogen-binding cross-linking site (a') and a side chain having a co-binding cross-linking site (b); the glass transition point of a natural polymer or synthetic polymer is at room temperature (25 ° C). The following polymer may be used as a main chain and may contain a side chain (c) containing both a hydrogen-binding cross-linking site and a co-binding cross-linking site; and the like.

The polymers forming the main chain portions of the polymers (A) to (B) include a diene-based rubber, a hydrogenated agent of the diene-based rubber, an olefin-based rubber, a polystyrene-based polymer which may be hydrogenated, and a polyolefin-based polymer, respectively. It is preferably composed of at least one selected from a polymer, a polyvinyl chloride polymer, a polyurethane polymer, a polyester polymer, and a polyamide polymer. The polyolefin-based polymer is a polymer having a structural unit derived from olefin, and is, for example, low-density polyethylene (LDPE, density 910 kg / m ³ or more and less than 930 kg / m ³ ), high-density polyethylene (HDPE, density 942 kg). / M ³ or more), linear polyethylene (LLDPE), polypropylene and the like. Further, as the polymer forming the main chain portion of such a polymer component (polymers (A) to (B)), a diene-based rubber hydrogenated product is used from the viewpoint that there is no aging-prone double bond. Olefin-based rubbers and polyolefin-based polymers are preferable, and diene-based rubbers are preferable from the viewpoint of low cost and high reactivity (having many double bonds capable of enreacting with compounds such as maleic anhydride). preferable. The polymer forming the main chain portion may be a polymer having an elastomeric property or a polymer having no elastomeric property.

Further, as the polymer forming the main chain portion of such a polymer component, polyethylene (more preferably high density polyethylene (HDPE)), ethylene-butene copolymer, among others, from the viewpoint of being able to reduce compression set. It is more preferably at least one selected from the group consisting of an ethylene-propylene copolymer and polypropylene, and more preferably composed of polyethylene (more preferably high density polyethylene (HDPE)) and an ethylene-butene copolymer. It is particularly preferable that it is at least one selected from the group.

The polymer forming the main chain portion of such a polymer component (the polymers (A) to (B)) may be a rubber-based polymer having an elastomeric property, for example, natural rubber (NR) or isoprene rubber ( IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM) ) And other diene rubbers and their hydrogen additives; ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), chlorosulfonated polyethylene, acrylic rubber, fluororubber, polyethylene rubber, etc. Examples thereof include olefin rubber such as polypropylene rubber; epichlorohydrin rubber; polysulfide rubber; silicone rubber; urethane rubber; and the like.

Further, the polymer forming the main chain portion of the polymer component (the polymers (A) to (B)) may be a polymer component having an elastomeric property, for example, a polystyrene-based elastomeric property which may be hydrogenated. Examples thereof include polymers (for example, 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, and the like, and polyolefin-based. Elastolic polymers are preferred. As the polyolefin-based elastomeric polymer, an ethylene-based copolymer can be exemplified, and an ethylene-α-olefin copolymer is preferable. Examples of the α-olefin include 1-butene and the like.

Further, as the polymer forming the main chain portion of the polymer having an elastomeric property (the elastomeric polymers (A) to (B)), from the viewpoint that there is no aging-prone double bond, a diene rubber is hydrogenated. Diene-based rubbers are preferable, and diene-based rubbers are preferable from the viewpoint of low cost and high reactivity (having many double bonds capable of enreacting with a compound such as maleic anhydride). Further, when an olefin rubber is used for forming the main chain portion of the elastomer component (the elastomeric polymers (A) to (B)) suitable as the polymer component, deterioration is further caused because no double bond is present. It tends to be sufficiently suppressed.

Further, the polymers (A) to (B) may be in a liquid or solid state, and the molecular weight thereof is not particularly limited, depending on the application in which the thermoplastic elastomer composition of the embodiment is used, the required physical properties, and the like. Can be selected as appropriate.

When the fluidity when the thermoplastic elastomer composition of the embodiment is heated (decrosslinking or the like) is emphasized, the polymers (A) to (B) are preferably liquid, for example, forming a main chain portion. When the polymer to be polymerized is a diene rubber such as isoprene rubber or butadiene rubber, the weight average molecular weight of the main chain portion is 1,000 to 100 in order to make the polymers (A) to (B) liquid. It is preferably 000, and particularly preferably about 1,000 to 50,000.

On the other hand, when the strength of the thermoplastic elastomer composition of the embodiment is emphasized, the polymers (A) to (B) are preferably in a solid state, and for example, the polymer forming the main chain portion is isoprene rubber. In the case of a diene-based rubber such as butadiene rubber, the weight average molecular weight of the main chain portion is preferably 100,000 or more in order to make the polymers (A) to (B) solid. It is particularly preferably about 500,000 to 1,500,000.

The weight average molecular weight of the main chain portion is determined by gel permeation chromatography (Gel).
It is a weight average molecular weight (in terms of 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, two or more of the polymers (A) to (B) can be mixed and used. In this case, the mixing ratio of the polymers can be any ratio depending on the application in which the thermoplastic elastomer composition of the embodiment is used, the required physical properties, and the like.

Further, the glass transition point of the polymers (A) to (B) is 25 ° C. or lower as described above. This is because the thermoplastic elastomer composition of the embodiment exhibits rubber-like elasticity at room temperature when the glass transition point of the polymer is in this range. Further, in the embodiment, the “glass transition point” is a glass transition point measured by differential scanning calorimetry. At the time of measurement, the rate of temperature rise is 10 ° C./min.

The polymer forming the main chain portion of the polymers (A) to (B) has a glass transition point of the polymers (A) to (B) of 25 ° C. or less, and is a molded product made of the obtained thermoplastic elastomer composition. Shows rubber-like elasticity at room temperature (25 ° C), so natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), ethylene- Diene-based rubbers such as propylene-diene rubber (EPDM) and butyl rubber (IIR); olefin-based rubbers such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM) and ethylene-butene rubber (EBM); .. Further, when an olefin-based rubber is used for forming the main chain portions of the polymers (A) to (B), the tensile strength of the obtained thermoplastic elastomer composition is improved and the double bond does not exist. Deterioration tends to be suppressed more sufficiently.

The amount of bonded styrene of the styrene-butadiene rubber (SBR) that can be used for the polymers (A) to (B), the watering ratio of the polystyrene-based elastomeric polymer that may be hydrogenated, and the like are particularly limited. However, it can be adjusted to an arbitrary ratio according to the application in which the thermoplastic elastomer composition of the embodiment is used, the physical properties required for the composition, and the like.

Further, ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), and ethylene-butene rubber (EBM) are used to form the main chain portions of the polymers (A) to (B). , The ethylene content is preferably 10 to 90 mol%, more preferably 30 to 90 mol%. When the ethylene content is in this range, it is preferable because it is excellent in compressive permanent strain and mechanical strength, particularly tensile strength, when it is used as a thermoplastic elastomer (composition).

Further, as described above, the polymers (A) to (B) have a side chain (a); a side chain containing a hydrogen-binding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle as a side chain; A side chain (a') containing a sex-linking site and a side chain (b) containing a covalent cross-linking site; and a side chain (c) containing a hydrogen-binding cross-linking site and a covalently-bonding site. It will have at least one of them. In the present specification, it can be said that the side chain (c) is a side chain that functions as a side chain (a') and also as a side chain (b). Each side chain will be 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 hydrogen-bonding cross-linking (for example, a hydroxyl group, a hydrogen-bonding cross-linking site contained in the side chain (a) described later, etc.). The structure 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 the polymers by hydrogen bonding. In addition, cross-linking by hydrogen bond includes a hydrogen acceptor (a group containing an atom containing an isolated electron pair, etc.) and a hydrogen donor (a group having a hydrogen atom covalently bonded to an atom having a large electric negative degree). Since it is formed for the first time, no hydrogen bond cross-linking is formed in the absence of both a hydrogen acceptor and a hydrogen donor between the side chains of the polymers. Therefore, hydrogen-bonding cross-linking sites are present in the system only when both the hydrogen acceptor and the hydrogen donor are present between the side chains of the polymers. In the present specification, there are 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) between the side chains of the polymers. Therefore, 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 a hydrogen-bonding cross-linking site.

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

<Side chain (a): Side chain containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and / or a 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 be any as long as it has a carbonyl-containing group and / or a nitrogen-containing heterocycle, and other configurations are particularly present. Not limited. As such a hydrogen-bonding cross-linking site, one having a carbonyl-containing group and a nitrogen-containing heterocycle is more preferable.

The carbonyl-containing group may be any one containing a carbonyl group, and is not particularly limited, and specific examples thereof include amides, esters, imides, carboxy groups, and carbonyl groups. Such a carbonyl-containing group may be a group introduced into the main chain (a polymer forming a main chain portion) by using a compound capable of introducing the carbonyl-containing group into the main chain. For example, the carbonyl-containing group is formed by introducing a carbonyl-containing group into the high-density polyethylene which is the main chain (polymer of the main chain portion) using a compound capable of introducing the carbonyl-containing group into the main chain. It may be a base. The compound capable of introducing such a carbonyl-containing group into the main chain is not particularly limited, and specific examples thereof include ketones, carboxylic acids and derivatives thereof.

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

Specific examples of the carboxylic acid and its derivatives include malonic acid, maleic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, and p-hydroxybenzoic acid. These carboxylic acids containing carboxylic acids such as acids, p-aminobenzoic acid, mercaptoacetic acid and substituents; such as succinic acid anhydride, maleic anhydride, glutaric acid anhydride, phthalic acid anhydride, propionic acid anhydride, benzoic acid anhydride, etc. Acid anhydrides; aliphatic esters such as maleic acid ester, malonic acid ester, succinic acid ester, glutarate 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 quinone, anthraquinone, naphthoquinone; glycine, tyrosine, bicin, alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N- ( Amino acids such as p-aminobenzoyl) -β-alanine; maleeamide, maleeamic acid (maleinmonoamide), succinic acid monoamide, 5-hydroxybarrelamide, N-acetylethanolamine, N, N'-hexamethylenebis (acetamide) ), Amids such as malonamide, cycloserine, 4-acetamidephenol, p-acetamide succinic acid; imides such as maleinimide and succinimide; and the like.

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

Further, when the side chain (a) has a nitrogen-containing heterocycle, the nitrogen-containing heterocycle may be introduced into the main chain directly or via an organic group, and its configuration and the like are particularly limited. It's not a thing. Such a nitrogen-containing heterocycle may be used even if the heterocycle contains a nitrogen atom and has a heteroatom other than the nitrogen atom, for example, a sulfur atom, an oxygen atom, a phosphorus atom, or the like. can. Here, when a nitrogen-containing heterocycle is used in the side chain (a), the hydrogen bond forming a crosslink becomes stronger when the heterocyclic structure is provided, and the thermoplastic elastomer composition of the obtained embodiment is obtained. It is preferable because it improves tensile strength and impact resistance.

Further, the nitrogen-containing heterocycle may have a substituent, and the substituent may be, for example, an alkyl group such as a methyl group, an ethyl group, a (iso) propyl group or a hexyl group; a methoxy group or an ethoxy group. , (Iso) alkoxy group such as propoxy group; group consisting of halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; cyano group; amino group; aromatic hydrocarbon group; ester group; ether group; acyl group Examples thereof include a thioether group; a hydroxyl group; a thiol group; a carboxy group; an isocyanate group; an epoxy group; an alkoxysilyl group, and these can be used in combination. The substitution position of these substituents is not particularly limited, and the number of substituents is also not limited.

Further, the nitrogen-containing heterocycle may or may not have aromaticity, but the thermoplastic elastomer composition of the embodiment obtained as having aromaticity is permanently compressed. It is preferable because the strain and mechanical strength are further improved.

Further, such a nitrogen-containing heterocycle is not particularly limited, but is a 5-membered ring or a 6-membered ring from the viewpoint that the hydrogen bond becomes stronger and the compression set and the mechanical strength are further improved. Is preferable. As such a nitrogen-containing heterocycle, a nitrogen-containing heterocycle condensed with a benzene ring or a nitrogen-containing heterocycle condensed with each other may be used. Examples of such nitrogen-containing heterocycles include pyrrolin, pyrrolidone, oxyindole (2-oxyindole), indoxyl (3-oxyindole), dioxyindole, isatin, indrill, phthalimidine, β-isoindigo, and monoporphyrin. , Diporphyrin, tripolphyllin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phylloerythrin, imidazole, pyrazole, triazole, tetrazole, benzoimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazoline Pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrol, pyrrolin, indole, indolin, oxylindole, carbazole, phenothiazine, indolenin, isoindole, oxazole, thiazole, isoxazole, isothiazole, oxaziazole, thiazazole. , Oxazole, Thiatriazole, Phenanthroline, Oxazine, Benzoxazine, Phthalazine, Pteridine, Pyrazine, Phenazine, Tetradine, Benzoxazole, Benzoisoxazole, Anthranil, Benzothazole, Benzofrazan, Ppyridine, Kinolin, Isoquinoline, Aclysine, Phenantridin, Examples thereof include anthrazolin, naphthylidine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxalin, triazine, histidine, triazolidine, melamine, adenine, guanine, timine, cytosine, hydroxyethyl isocyanurate and derivatives thereof. Among these, particularly for the nitrogen-containing 5-membered ring, the following compound (cyclic structure described by the chemical formula), the triazole derivative represented by the following general formula (10) and the imidazole derivative represented by the following general formula (11) Is preferably exemplified. Further, these may have the above-mentioned various substituents, or may be hydrogenated or desorbed.

The substituents X, Y, and Z in the formulas (10) and (11) are independently hydrogen atoms, alkyl groups having 1 to 30 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and 6 to 20 carbon atoms. It is an aryl group or an amino group. It should be noted that any one of X and Y in the above formula (10) is not a hydrogen atom, and similarly, at least one of X, Y and Z in the above formula (11) is not a hydrogen atom.

Examples of such substituents X, Y and Z include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a dodecyl group and a stearyl group in addition to the hydrogen atom and the amino group. 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 groups; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, trill group (o-, m-, p-), dimethylphenyl group and mesityl group; etc. Be done.

Among these, the thermoplastic elastomer composition of the embodiment obtained in which the substituents X, Y and Z are an alkyl group, particularly a butyl group, an octyl group, a dodecyl group, an isopropyl group and a 2-ethylhexyl group. It is preferable because the processability of the above is good.

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

Further, those obtained by condensing the nitrogen-containing heterocycle with a benzene ring or a nitrogen-containing heterocycle can also be used, and specifically, the following fused ring is preferably exemplified. These fused rings may also have the above-mentioned various substituents, or may have hydrogen atoms added or removed.

Examples of such a nitrogen-containing heterocycle include a triazole ring and an isocyanurate ring because they are excellent in recyclability, compression set, hardness and mechanical strength, particularly tensile strength, of the thermoplastic elastomer composition of the obtained embodiment. It is preferably at least one selected from a thiadiazole ring, a pyridine ring, an imidazole ring, a triazine ring and a hydantin ring, and at least one selected from a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring and a hydantin ring. It is preferably one kind.

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

[In formula (1), A is a nitrogen-containing heterocycle, 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. ; Alternatively, it is an organic group which may contain these atoms or groups. ]
It is more preferable that the side chain containing the structural portion represented by is introduced into the main chain as one side chain. As described above, the hydrogen-bonding cross-linking site of the side chain (a) preferably contains a structural portion represented by the general formula (1).

Here, as the nitrogen-containing heterocycle A in the above formula (1), specifically, the nitrogen-containing heterocycle exemplified above can be mentioned. The substituent B in the above formula (1) is 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, eg, an alkylene group or an aralkylene group having 1 to 20 carbon atoms; an alkylene ether group having these atoms or groups at the end and having 1 to 20 carbon atoms (alkylene). Oxy group, eg, -O-CH ₂ CH ₂ − group), alkylene amino group (eg, -NH-CH ₂ CH ₂ − group, etc.) or alkylene thioether group (alkylene thio group, eg, -SCH ₂ CH). ₂ -Group); aralkylene ether group (aralkyleneoxy group) having 1 to 20 carbon atoms, aralkyleneamino group or aralkylthioether 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 an isomer, such as 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. Groups, decyl groups and the like can be mentioned. Oxygen atom, sulfur atom and amino group NR'; Or, an oxygen atom such as an aralkylene ether group, an aralkylene amino group, an aralkylthioether group, an amino group NR'and a sulfur atom are combined with an adjacent carbonyl group to form a conjugated ester group, amide group, imide group, etc. It is preferable to form a thioester group or the like.

Of these, the substituent B is an oxygen atom, a sulfur atom or an amino group forming a conjugated system; an alkylene ether group having 1 to 20 carbon atoms, an alkylene amino group or an alkylene having these atoms or groups at the end. It is preferably a thioether group, preferably an amino group (NH), an alkylene amino group (-NH-CH ₂ -group, -NH-CH ₂ CH ₂ -group, -NH-CH ₂ CH ₂ CH ₂ -group), an alkylene group. Particularly preferably, it is an ether group (-O-CH _2- group, -O-CH ₂ CH _2- group, -O-CH ₂ CH ₂ CH _{2- group).}

When the side chain (a) is a side chain containing a hydrogen-binding cross-linking site having the carbonyl-containing group and the nitrogen-containing heterocycle, the hydrogen bond having the carbonyl-containing group and the nitrogen-containing heterocycle. The sex cross-linking site is more preferably a side chain introduced into the polymer main chain at its 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 heterocycle, and B and D are independently single bonds; an oxygen atom, an amino group NR'(R'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or. A sulfur atom; or an organic group which may contain these atoms or groups. ]
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 independently substituted groups exemplified in the above formula (1). It is basically the same as B. However, the substituent D in the above formula (3) is an alkylene having 1 to 20 carbon atoms which may contain a single bond; an oxygen atom, a nitrogen atom or a sulfur atom among those exemplified as the substituent B in the above formula (1). It preferably forms a conjugated system of a group or an aralkylene group, and is particularly preferably a single bond. That is, it is preferable to form an alkylene amino group or an aralkylene amino group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom together with the imide nitrogen of the above formula (3), and the above formula (3). It is particularly preferable that the nitrogen-containing heterocycle is directly bonded to the imide nitrogen of the above (single bond). Specifically, the substituent D is a single bond; an alkylene ether or an aralkylene ether group having 1 to 20 carbon atoms having an oxygen atom, a sulfur atom or an amino group at the end, and the like; methylene containing an isomer. Examples thereof include a group, an ethylene group, a propylene group, a butylene group, a hexylene group, a phenylene group, a xylylene group and the like.

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 heterocycle, the hydrogen-bonding cross-linking site of the side chain (a) is generally described below. Equation (101):

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

Those having a structure represented by are more preferable. Further, 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 to the nitrogen-containing heterocycle that the polymer component can have is not particularly limited, and a ratio of 2: 1 facilitates the formation of complementary interactions and can be easily produced. Therefore, it is preferable.

The side chain (a) containing a hydrogen-bonding cross-linking site having such a carbonyl-containing group and / or a nitrogen-containing heterocycle is at a ratio of 0.1 to 50 mol% with respect to 100 mol% of the main chain portion ( It is preferably introduced at a rate of introduction), and more preferably at a rate of 1 to 30 mol%. If the introduction rate of the side chain (a) is less than 0.1 mol%, the tensile strength at the time of crosslinking may not be sufficient, while if it exceeds 50 mol%, the crosslinking density becomes high and the rubber elasticity is lost. There is. That is, if the introduction rate is within the above range, cross-linking is efficiently formed between the molecules by the interaction between the side chains of the polymer components, so that the tensile strength at the time of cross-linking is high and the recyclability is excellent. preferable.

The introduction rate is the side chain (a) containing the side chain (ai) containing the hydrogen-binding cross-linking site having the carbonyl-containing group and the hydrogen-binding cross-linking site having the nitrogen-containing heterocycle. When the chain (a-ii) is introduced independently, the side chain (a-i) containing the carbonyl-containing group and the side chain (a-ii) containing the nitrogen-containing heterocycle are used. According to the ratio of, these are considered as one side chain (a) in a set and calculated. When either one of the side chains (a-i) and (a-ii) is excessive, the introduction rate may be considered with the larger side chain as a reference.

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

Further, as the side chain (a), a cyclic acid anhydride group (preferably a cyclic acid anhydride having a carbonyl group in the ring skeleton) as a functional group is added to the polymer (material for forming the polymer) that forms the main chain after the reaction. Using a polymer having a physical group, more preferably a maleic anhydride group (a polymer having a cyclic acid anhydride group in the side chain), the functional group (cyclic acid anhydride group) and the cyclic acid anhydride group A compound that reacts to form a hydrogen-binding cross-linking site (a compound that can introduce a nitrogen-containing heterocycle) is reacted to form a hydrogen-binding cross-linking site, and the side chain of the polymer is combined with the side chain (a). Is preferable. The compound into which such a nitrogen-containing heterocycle can be introduced may be the nitrogen-containing heterocycle itself exemplified above, and a substituent (for example, a hydroxyl group, a thiol) that reacts with a cyclic acid anhydride group such as maleic anhydride. It may be a nitrogen-containing heterocycle having a group (group, amino group, etc.).

Here, the "cyclic acid anhydride group" is subject to a change in the structure required for a cyclic acid anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride to bind 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 has a structure generated by dehydration condensation of a carboxylic acid (for example, -CO-O-CO-). It may have a 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. The cyclic acid anhydride-modified polymer can be formed by bonding the cyclic acid anhydride directly or via an organic group to the polymer.

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

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

In such a side chain (a), the bonding position of the nitrogen-containing n-membered ring compound to be bonded to the copolymer directly or via an organic group is not particularly limited, and any bonding position (position 1 to n) is not particularly limited. But it may be. It is preferably the 1st position or the 3rd to nth position.

When the nitrogen-containing n-membered ring compound contains one nitrogen atom (for example, a pyridine ring, etc.), a chelate is easily formed in the molecule and the composition is excellent in physical properties such as tensile strength. ~ (N-1) position is preferable. By selecting the bond position of the nitrogen-containing n-membered ring compound, the polymer is easy to form crosslinks between the molecules of the polymers by hydrogen bonds, ionic bonds, coordination bonds, etc., has excellent recyclability, and has mechanical properties. In particular, it tends to have excellent tensile strength.

<Side chain (b): Side chain containing covalently crosslinked sites>
In the present specification, the "side chain (b) containing a covalently bonded site" refers to an atom (usually a carbon atom) forming the main chain of the polymer as a covalently bonded site (an amino group-containing compound described later). By reacting with "a compound that forms a covalent bond" or the like, a functional group that can form at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers, etc.) It means that they have a chemically stable bond (covalent bond). The side chain (b) is a side chain containing a covalently crosslinked site, but has a covalently bonded site and further has a group capable of hydrogen bonding, and hydrogen bonds between the side chains. In the case of forming a crosslink due to the above, it will be used as a side chain (c) described later.
If both the hydrogen donor and the hydrogen acceptor, which can form hydrogen bonds between the side chains of the polymers, are not contained, for example, the system simply contains an ester group (-COO-). When only the contained side chains are present, hydrogen bonds are not particularly formed between the ester groups (-COO-), so that such groups do not function as hydrogen-bonding cross-linking sites.

On the other hand, when the side chains of the polymers include a structure having both a hydrogen-bonded hydrogen donor site and a hydrogen acceptor site, such as a carboxy group and a triazole ring, the polymers are used. Since hydrogen bonds are formed between the side chains of the above, hydrogen-bonding cross-linking sites are contained. Further, for example, when an ester group and a hydroxyl group coexist between the side chains of polymers and a hydrogen bond is formed between the side chains by these groups, the site where the hydrogen bond is formed is a hydrogen bond cross-linking site. Will be. Therefore, it may be used as the side chain (c) depending on the structure itself of the side chain (b), the type of the structure of the side chain (b) and the type of the substituent of the other side chain, and the like. Further, the "covalently cross-linking site" referred to here is a site that crosslinks polymers with each other by covalent bonding.

The side chain (b) containing such a covalently crosslinked site is not particularly limited, and for example, a polymer having a functional group in the side chain (a polymer for forming the main chain portion) and the functional group It preferably contains a covalently crosslinked site that is formed by reacting with a compound that reacts to form a covalently bonded site (a compound that produces a covalent bond). The cross-linking of the side chain (b) at the covalent cross-linking site is formed by at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers. Is preferable. Therefore, the functional group contained in the polymer constituting the main chain is a functional group capable of forming at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers. Is preferable.

As such a "compound that forms a covalent bridging site (a compound that forms a covalent bond)", for example, two or more amino groups and / or imino groups (both amino groups and imino groups) in one molecule. Polyamine compounds having two or more of these groups in total if they have; polyol compounds having two or more hydroxyl groups in one molecule; polyisocyanate compounds having two or more isocyanate (NCO) groups in one molecule; 1 Examples thereof include polythiol compounds having two or more thiol groups (mercapto groups) in the molecule; and the like.

Here, "a compound that forms a covalent bond (a compound that forms a covalent bond)" refers to the type of substituent that the compound has, the degree of progress of the reaction when the reaction is carried out using the compound, and the like. Depending on the case, the compound may be a compound capable of introducing both the hydrogen-binding 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-bonding 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 in the side chain, and the remaining one hydroxyl group may remain as a hydroxyl group. Can also be introduced at sites that form hydrogen-binding bridges). Therefore, the "compound that forms a covalent bond site (compound that forms a covalent bond)" exemplified here also includes "a compound that forms both a hydrogen bond bond site and a covalent bond site". obtain.

From this point of view, when forming the side chain (b), a compound is appropriately selected from "compounds that form covalently crosslinked sites (compounds that generate covalent bonds)" according to the desired design. The side chain (b) may be formed by appropriately controlling the degree of progress of the reaction. When the compound forming the covalently bonded cross-linking site has a heterocycle, it becomes possible to more efficiently produce the hydrogen-bonded cross-linked site at the same time, and the side chain (c) described later can be used. , It becomes possible to efficiently form a side chain having the covalently bonded site. Therefore, specific examples of the compound having such a heterocycle will be described as a suitable compound for producing the side chain (c), particularly together with the side chain (c). The side chain (c) can be said to be a suitable form of a side chain such as a side chain (a) or a side chain (b) because of its structure.

Examples of the polyamine compound that can be used as such a "compound that forms a covalent bond (compound that forms a covalent bond)" include the following alicyclic amines, aliphatic polyamines, and aromatic polyamines. Examples thereof include nitrogen-containing heterocyclic amines.

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

The aliphatic polyamine is not particularly limited, and for example, methylenediamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, 1,3-diaminopentane, hexamethylenediamine, diaminoheptane, diaminododecane, diethylenetriamine, and the like. 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'-diamine Examples thereof include -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, and are, for example, diaminotoluene, diaminoxylene, tetramethylxylene rangeamine, tris (dimethylaminomethyl) phenol, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenyl. Examples include sulfone, 3-amino-1,2,4-triazole and the like.

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

Further, the polyamine compound may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be adjusted to an arbitrary ratio according to the application in 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 preferable because they have a high effect of improving compressive permanent strain, mechanical strength, and particularly tensile strength. ..

The polyol compound that can be used as a "compound that forms a covalent bond (a compound that forms a covalent bond)" is not particularly limited as long as it is a compound having two or more hydroxyl groups, and its molecular weight, skeleton, and the like are not particularly limited. For example, the following polyether polyols, polyester polyols, other polyols, mixed polyols thereof and the like can be mentioned.

Specific examples of such polyether polyols include, for example, 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, as well as ethylene oxide and propylene. Polyols obtained by adding at least one selected from oxide, butylene oxide, styrene oxide and the like; polyoxytetramethylene oxide; etc. may be mentioned, and these may be used alone or in combination of two or more. good.

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

Specific examples of other polyols include polymer polyols, polycarbonate polyols; polybutadiene polyols; hydrogenated polybutadiene polyols; acrylic polyols; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, and pentanediol. Hexadiol, polyethylene glycol laurylamine (eg, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine) , Polyethylene glycol octylamine (eg, N, N-bis (2-hydroxyethyl) octylamine), Polyethylene glycol octylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) octylamine), Polyethylene Small molecules such as glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) stearylamine). Polyethylene; etc. may be mentioned, and these may be used alone or in combination of two or more.

Examples of the polyisocyanate compound that can be used as "a compound that forms a covalently bonded site (a compound that forms a covalent bond)" include 2,4-tolylene diisocyanate (2,4-TDI) and 2,6-tri. Ranged isocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylenediocyanate, xyl Aromatic polyisocyanates such as range isocyanate (XDI), tetramethylxylylene range isocyanate (TMXDI), trizine diisocyanate (TODI), 1,5-naphthalenedi isocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI). ), Lysine diisocyanate, aliphatic polyisocyanate such as norbornan diisocyanatomethyl (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; isocyanates of these isocyanate compounds Nurate-modified polyisocyanates; urethane prepolymers obtained by reacting these isocyanate compounds with the polyol compounds exemplified above; and the like; these may be used alone or in combination of two or more. ..

The polythiol compound is not particularly limited as long as it is a compound having two or more thiol groups, and its molecular weight, skeleton, and the like are not particularly limited. 2,3-Butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,10-decandithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1, , 9-Nonandithiol, 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-thiathiozole, 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, trimethylolpropanetris (β-thiopropionate), trimethylolpropanetris (thioglycolate) , Polythiol (thiochol or thiol-modified polymer (resin, rubber, etc.)) and the like, and these may be used alone or in combination of two or more.

The functional groups of the polymer constituting the main chain that reacts with such "compounds that form covalently bonded sites (compounds that generate covalent bonds)" include amides, esters, lactones, urethanes, and thiourethanes. A functional group capable of forming at least one bond selected from the group consisting of and thioether is preferable, and as such a functional group, a cyclic acid anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, a thiol group and the like are preferable. Illustrated in.

In addition, the polymer (B) having the side chain (b) has a cross-linking at the covalent cross-linking site in the portion of the side chain (b), that is, the functional group and the above-mentioned "covalent cross-linking site". It has at least one covalently bonded crosslink formed by reaction with a "forming compound (a compound that forms a covalent bond)" in one molecule, and is particularly composed of lactone, urethane, ether, thiourethane and thioether. When a crosslink is formed by at least one bond selected from the group, it is preferable to have two or more, more preferably 2 to 20, and 2 to 10. Is even more preferable.

Further, the thermoplastic elastomer composition obtained by the fact that 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 compressive permanent strain and mechanical strength (break elongation, breaking strength) of an object can be improved more easily. In this case, a polymer having a side chain containing a group capable of forming a hydrogen bond with respect to a tertiary amino bond (-N =) and an ester bond (-COO-) is included. In some cases (for example, when there is another polymer having a side chain containing a hydroxyl group or the like), the covalently bonded site can function as the side chain (c) described later.

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)). If the cross-linking at the covalent cross-linking site has the tertiary amino bond and / or the ester bond, those groups and the side chain (a) (carbonyl-containing group and / or side chain having a nitrogen-containing polymer ring). It is considered that the crosslink density can be further improved by hydrogen-bonding (interacting) with the group in). 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 covalently bonded site is formed. Examples of the "compound (compound that forms a covalent bond)" include polyethylene glycol laurylamine (for example, N, N-bis (2-hydroxyethyl) laurylamine) and polypropylene glycol laurylamine (for example,) among those exemplified above. N, N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (eg, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycolstearylamine (eg, N, N- Bis (2-methyl-2-hydroxyethyl) stearylamine) is preferred.

Even if a compound that forms a covalently crosslinked site (a compound that forms a covalent bond) as described above is used, it depends on the progress of the reaction, the type of substituent, the chemical quantity ratio of the raw material used, and the like. Since a hydrogen-binding cross-linking site may also be introduced, the suitable structure of the covalent-bonding cross-linking site should be combined with the suitable structure of the covalent-bonding cross-linking site in the side chain (c). I will explain.

<Side chain (c): Side chain containing both hydrogen-bonding cross-linking site and covalent-bonding cross-linking site>
Such a side chain (c) is a side chain containing both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site in one side chain. The hydrogen-bonding cross-linking site contained in such a side chain (c) may be the same as that exemplified as the hydrogen-bonding cross-linking site described in the side chain (a'), and may be in the side chain (a). The same as those exemplified as the hydrogen-bonding cross-linking site are preferable. Further, 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 (the suitable cross-linking thereof is also the same). Can be used.).

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-binding cross-linking site and a covalent-bonding cross-linking site. It is preferable that the side chain is formed by reacting with a compound that forms both of the above (a compound that introduces both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site). The compound that forms both the hydrogen-bonded cross-linking site and the covalent-bonding cross-linking site (a compound that introduces both the hydrogen-binding cross-linking site and the covalent-bonding cross-linking site) is a heterocycle (particularly preferably nitrogen-containing). Compounds having a covalent bond (compound ring) and capable of forming a covalent bond (a compound that produces a covalent bond) are preferable, and among them, a heterocycle-containing polyol, a heterocycle-containing polyamine, a heterocycle-containing polythiol, and the like are more preferable. preferable.

It should be noted that the polyol, polyamine and polythiol containing such a heterocycle may form the above-mentioned "covalently bonded site" except that the polyol, polyamine and polythiol have a heterocycle (particularly preferably a nitrogen-containing heterocycle). Examples of the polyols, polyamines and polythiols described in "Possible Compounds (Compounds Producing Covalent Bonds)" can be appropriately used. The heterocyclic-containing polyol is not particularly limited, and for example, bis (2-hydroxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate, kojic acid, dihydroxydithian, and trishydroxyethyltriazine. Can be mentioned. The heterocyclic-containing polyamine is not particularly limited, and examples thereof include acetguanamine, piperazine, bis (aminopropyl) piperazine, benzoguanamine, and melamine. Further, examples of such a heterocyclic-containing polythiol include dimercaptothiadiazole and tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate. As described above, 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, a polyamine, a polythiol or the like containing a heterocycle. , The resulting side chain is preferred.

It constitutes the main chain that reacts with "a compound that forms both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site (a compound that introduces both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site)". The functional group of 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, and the functional group is cyclic acid anhydride. 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 at the covalently bonded site in one molecule in the portion of the side chain (c), particularly lactone. When a crosslink is formed by at least one bond selected from the group consisting of urethane, ether, thiourethane and thioether, it is preferable to have two or more, preferably 2 to 20. It is more preferable to have 2 to 10 pieces. Further, the thermoplastic elastomer composition obtained by the fact that 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 the mechanical strength (break elongation, breaking strength) of the object are further improved.

(Regarding the structure suitable as a covalently bonded site in the side chains (b) to (c))
With respect to the side chains (b) and / or (c), the cross-linking at the covalent cross-linking site contains a tertiary amino bond (-N =), an ester bond (-COO-). When these bond sites also function as hydrogen-bondable cross-linking sites, it is preferable because the compression set and mechanical strength (break elongation, break strength) of the obtained thermoplastic elastomer composition are improved to a higher degree. .. Thus, a tertiary amino bond (-N =) or an ester bond (-COO-) in a side chain having a covalently crosslinked site forms a hydrogen bond with another side chain. In this case, the covalent cross-linking site containing such a tertiary amino bond (-N =) and an ester bond (-COO-) also includes a hydrogen-bonding cross-linking site, and serves as a side chain (c). Can work.

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, if 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 thought that

Here, a compound (hydrogen) capable of reacting with a functional group of the polymer constituting the main chain to form a covalently bonded site containing the tertiary amino bond and / or the ester bond. Examples of the compound capable of forming both the binding cross-linking site and the co-binding cross-linking site) include polyethylene glycol laurylamine (for example, N, N-bis (2-hydroxyethyl) laurylamine) and polypropylene glycol laurylamine. (For example, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (eg, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octylamine (eg). , N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycolstearylamine (eg, N) , N-bis (2-methyl-2-hydroxyethyl) stearylamine) can be mentioned as suitable.

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

In the above general formulas (4) to (6), E, J, K and L are independently single bonds; an oxygen atom and an amino group NR'(R'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ) Or a sulfur atom; or an organic group which may contain these atoms or groups, where 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 basically the same as the substituent B exemplified in the above general formula (1) independently of each other.

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 a substituent G include a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, a 1,6-hexylene group and a 1,7-heptylene. Group, alkylene group such as 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 1,11-undecylene group, 1,12-dodecylene group; N, N-diethyldodecylamine-2 , 2'-Diyl, N, N-dipropyldodecylamine-2,2'-diyl, N, N-diethyloctylamine-2,2'-diyl, N, N-dipropyloctylamine-2,2' -Diyl, N, N-diethylstearylamine-2,2'-diyl, N, N-dipropylstearylamine-2,2'-diyl ,; vinylene group; divalent such as 1,4-cyclohexylene group Alicyclic hydrocarbon group; a divalent aromatic hydrocarbon group such as 1,4-phenylene group, 1,2-phenylene group, 1,3-phenylene group, 1,3-phenylenebis (methylene) group; Trivalents such as propane-1,2,3-triyl, butane-1,3,4-triyl, trimethylamine-1,1', 1 "-triyl, triethylamine-2,2', 2" -triyl, etc. A hydrocarbon group; a trivalent cyclic hydrocarbon containing an oxygen atom such as an isocyanurate group or a triazine group, a sulfur atom or a nitrogen atom; a tetravalent hydrocarbon group represented by the following formulas (12) and (13); and Substituents formed by combining these; and the like can be mentioned.

Further, the cross-linking of the side chain (c) at the covalent cross-linking site is represented by any of the following formulas (7) to (9) that bind to the main chain of the polymer described above at the α-position or the β-position. It is preferable that at least one structure thereof is contained, and it is more preferable that G in the formula contains a tertiary amino group (the structures represented by the formulas (7) to (9) contain a hydroxyl group and a carbonyl group. It can be said that the structure includes both the hydrogen-binding cross-linking site and the 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 the formulas (7) to (9), the substituents E, J, K and L are basically the same as the substituents E, J, K and L exemplified in the above formulas (4) to (6) independently. The substituent G is basically the same as the substituent G exemplified in the above formula (4).

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

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

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

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

Further, in such side chains (b) and (c), the cross-linking at the covalent cross-linking site is at least one selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers. It is more preferably formed by bonding.

The side chains (a'), side chains (a), side chains (b), and side chains (c) have been described above. It can be confirmed by a commonly used analytical means such as an IR spectrum.

Further, the polymer (A) is a polymer having the side chain (a) and having a glass transition point of 25 ° C. or lower, and the polymer (B) has a hydrogen-binding cross-linking site and a co-binding cross-linking site on the side chain. A polymer having a glass transition point of 25 ° C. or less containing the above (a polymer having both a side chain (a') and a side chain (b) as a side chain, or at least one side chain (c) in the side chain. 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 mixed and used.

The polymer (B) may be a polymer having both a side chain (a') and a side chain (b), or a polymer having a side chain (c), and such a polymer ( As the hydrogen-binding cross-linking site contained in the side chain of B), a hydrogen-binding cross-linking site having a carbonyl-containing group and / or a nitrogen-containing polymer ring is more preferable from the viewpoint of forming a stronger hydrogen bond. Is a hydrogen-binding cross-linking site having a carbonyl-containing group and a nitrogen-containing polymer ring). Further, the cross-linking at the covalently cross-linked site contained in the side chain of the polymer (B) can also induce an intermolecular interaction such as a hydrogen bond between the side chains containing the cross-linked site. From the viewpoint, it is preferably formed by at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers.

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

Further, as a method for producing such polymers (A) to (B), for example, a polymer having a functional group (for example, a cyclic acid anhydride group) in the side chain is used, and the polymer is used as the functional group. A compound that reacts with the functional group to form a hydrogen-binding cross-linking site, a compound that reacts with the functional group to form a hydrogen-binding cross-linking site, and a compound that reacts with the functional group to form a covalent cross-linking site. The polymer having the side chain (a); the polymer having the side chain (a') and the side chain (b); and / or the side chain (c) by reacting with at least one raw material compound of the mixed raw materials. ) (The polymers (A) to (B)) may be produced. The conditions (temperature conditions, atmospheric conditions, etc.) adopted in such a reaction are not particularly limited, and a functional group or a compound that reacts with the functional group (a compound that forms a hydrogen-binding cross-linking site and / or is shared). It may be appropriately set according to the type of the compound) forming the binding cross-linking site). In the case of the polymer (A), a monomer having a hydrogen bond site may be polymerized to produce the polymer (A).

The polymer having such a functional group (for example, a cyclic acid anhydride group) in the side chain is a polymer capable of forming the main chain of the above-mentioned polymers (A) to (B), and the functional group can be used. Those having in the side chain are preferable. Here, the "polymer containing a functional group in the side chain" is a chemically stable bond (such as the above-mentioned functional group, for example, a cyclic acid anhydride group) to an atom forming the main chain. A polymer having a covalent bond), and a polymer 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, and above all, a cyclic group. An acid anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, a thiol group and the like are preferable, and when clay is contained in the composition, the cyclic acid can be dispersed more efficiently. An anhydride group is particularly preferred.
Further, such a cyclic acid anhydride group may be a cyclic acid anhydride group having a carbonyl group in the ring skeleton, and may be a succinic anhydride group, a maleic anhydride group, a glutaric anhydride group, or a phthalic anhydride group. Is preferable, and among them, the maleic anhydride group is more preferable from the viewpoint that it can be easily introduced into the polymer side chain and is easily available industrially. When the functional group is a cyclic acid anhydride group, for example, succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride and derivatives thereof may be used as compounds into which the functional group can be introduced. Cyclic acid anhydrides may be used to introduce functional groups into polymers (eg, known natural or synthetic polymers).

The compound that reacts with the functional group to form a hydrogen-bonding cross-linking site is not particularly limited, but the above-mentioned "compound that forms a hydrogen-bonding cross-linking site (a compound that can introduce a nitrogen-containing heterocycle)" is used. It is preferable to use it. The compound that reacts with the functional group to form a covalent bond site is not particularly limited, but the above-mentioned "compound that forms a covalent bond site (compound that produces a covalent bond)" can be used. Is preferable. Further, as a compound forming a hydrogen-bonding cross-linking site (a compound capable of introducing a nitrogen-containing heterocycle) and a compound forming a covalent-bonding cross-linking site (a compound forming a covalent bond), the compound reacts with the functional group. A compound that forms both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site (for example, a nitrogen-containing heterocyclic ring-containing polyol, a nitrogen-containing heterocyclic ring-containing polyamine, a nitrogen-containing heterocyclic ring-containing polythiol, etc.) is also preferably used. Can be done.

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 a polymer component (polymers (A) to (B)). The polymer is shared by reacting with the functional group to form a hydrogen-binding cross-linking site, a compound reacting with the functional group to form a hydrogen-binding cross-linking site, and reacting with the functional group. The polymer (A) having the side chain (a), the hydrogen-binding cross-linking site and the covalent bond to the side chain by reacting with at least one raw material compound of the mixed raw materials of the compounds forming the binding cross-linking site. When the method for producing the polymer (B) containing the sex cross-linking site is adopted, the polymer having a functional group in the side chain has clay and the functional group in the side chain before being reacted with the raw material compound. A method of mixing with a polymer, then adding the raw material compound and reacting the mixture to form a composition at the same time as preparing the polymer component (method of pre-adding clay) may be adopted.

When the thermoplastic elastomer composition of the embodiment is a thermoplastic elastomer composition containing the polymer (A) as a polymer component, the properties derived from the side chain (a) can be imparted to the composition, and thus the composition is particularly broken. It is possible to improve elongation, breaking strength, and fluidity. Further, in the thermoplastic elastomer composition containing the polymer (B) as a polymer component, since the property derived from the covalently bonded site in the side chain can be imparted to the composition, the compression set is particularly improved. Is possible. In the thermoplastic elastomer composition containing the polymer (B) as a polymer component, in the composition, in addition to the characteristics derived from the covalently bonded site, the hydrogen-bonded crosslinked site (side chain (a')). Since it is possible to impart properties derived from the hydrogen-bonding cross-linking site described in the above section, it is also possible to exhibit compression-resistant permanent strain resistance while maintaining fluidity (formability), and the side chains thereof. By appropriately changing the type, the type of the polymer (B), and the like, it is possible to more efficiently exhibit the desired characteristics according to the application.

Further, in the thermoplastic elastomer composition of the embodiment, the thermoplastic elastomer composition containing the polymer (A) as the polymer component and the thermoplastic elastomer composition containing the polymer (B) as the polymer component were separately produced. Later, this may be mixed to obtain a thermoplastic elastomer composition containing the polymers (A) and (B) as polymer components.

Further, in the present specification, the polymer component may contain at least the polymers (A) and (B), but the covalent cross-linking site is present in the composition to more efficiently covalently bond. From the viewpoint of utilizing the characteristics of the cross-linking 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 is used. Therefore, it is possible to impart substantially the same characteristics as the thermoplastic elastomer composition using the polymer (B) containing a hydrogen-binding cross-linking site and a co-binding cross-linking site in the side chain. Further, when a thermoplastic elastomer composition containing the polymers (A) and (B) is produced as a polymer component, or a polymer having the polymer (A) and the side chain (b) other than the polymer (B). In the case of producing a thermoplastic elastomer composition containing the above, the desired properties can be appropriately exhibited by appropriately changing the ratio of each component (for example, each component of the polymer (A) and the polymer (B)). It will be possible.

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

Further, the thermoplastic elastomer composition of the embodiment is a polymer having a polymer (A) and a side chain (b) as a polymer component other than the polymer (B) (hereinafter, “polymer (C)” in some cases”. When the polymer (A) and the polymer (C) are contained, the content ratio of the polymer (A) to the polymer (C) is 1: 9 to 9: 1 in terms of mass ratio ([polymer (A)]: [polymer (C)]). It is preferably 2: 8 to 8: 2, and more preferably. If the content ratio of the polymer (A) is less than the lower limit, the fluidity (formability) and mechanical strength tend to be insufficient, while if the content ratio exceeds the upper limit, the compression set tends to decrease. ..

Further, in the thermoplastic elastomer composition of the embodiment, when both the side chain (a') and the side chain (b) are present in the composition, the total amount of the side chain (a') and the side chain are present. The total amount of (b) is preferably 1: 9 to 9: 1 based on the mass ratio, and more preferably 2: 8 to 8: 2. If the total amount of such side chains (a') is less than the lower limit, the fluidity (formability) and mechanical strength tend to be insufficient, while if the total amount exceeds the upper limit, the compression set tends to decrease. be. It should be noted that such a side chain (a') is a concept including the side chain (a). Therefore, even when only the side chain (a) is contained as the side chain (a'), both the side chain (a) and the side chain (b) are present in the composition at the above mass ratio. Is preferable.

The thermoplastic elastomer composition of the embodiment is capable of exhibiting a sufficiently high tensile stress and a sufficiently high heat resistance. In such a thermoplastic elastomer composition, by appropriately changing the composition, the characteristics required depending on the application (for example, characteristics such as self-repairing property and / or compression permanent strain resistance) are appropriately exhibited. It is possible to make it. That is, the thermoplastic elastomer composition of the embodiment can exhibit a sufficiently high tensile stress and a sufficiently high heat resistance, and additionally, depending on the composition, has sufficient compression resistance and / or permanent strain resistance. It is also possible to exert sufficient self-healing properties. As described above, by appropriately changing the composition, it is possible to appropriately exhibit the required properties in a well-balanced manner according to the application of the thermoplastic elastomer composition. Therefore, when the thermoplastic elastomer composition is used for various applications as described above. It is preferable to appropriately change the type (composition) of the components in the composition in consideration of the properties required according to the intended use.

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) of the thermoplastic elastomer composition of the embodiment may be appropriately determined. The ratio of the content of the polymer component to%) 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. More preferably, it is 40% by mass or less. When the ratio of the content of the polymer component to 100% by mass of the thermoplastic elastomer composition is within the above range, the rubber elasticity of the thermoplastic elastomer composition can be made preferable.

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

[Manufacturing method of 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> Compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site, <2> Covalently-bonding site that reacts with the compound (I) and the cyclic acid anhydride group to form a hydrogen-bonding cross-linking site. A mixed raw material of compound (II) forming
<3> A compound capable of reacting with the cyclic acid anhydride group to form both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site.

Here, the "polymer having a cyclic acid anhydride group in the side chain" is a polymer in which the cyclic acid anhydride group has a chemically stable bond (covalent bond) to the atom forming the main chain of the polymer. That is, 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 preferable. Can be used for.

Examples of the polymer capable of forming such a main chain portion include those exemplified in the above <polymer component>.

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

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, and is preferably a succinic anhydride group, a maleic anhydride group, or anhydrous. A glutaric acid group and an phthalic anhydride group are preferable, and a maleic anhydride group is more preferable from the viewpoint of high reactivity of the raw material and easy industrial availability of the raw material.

The polymer having a cyclic acid anhydride group in the side chain is a polymer which is capable of forming the main chain portion of the polymers (A) to (B), for example, under the conditions usually used, for example, heating. It may be produced by a method of graft-polymerizing a cyclic acid anhydride by stirring below. Further, as the polymer having a cyclic acid anhydride group in the side chain, a commercially available product may be used.

Examples of commercially available products of polymers having such a cyclic acid anhydride group in the side chain include maleic anhydride-modified isoprene rubber such as LIR-403 (manufactured by Kuraray); modified such as LIR-410 (manufactured by Kuraray). Isoprene rubber; carboxy-modified nitrile rubber such as Clinac 110, 221 and 231 (manufactured by Polycer); carboxy-modified polybutene such as CPIB (manufactured by Nisseki Chemical Co., Ltd.); , M (eg, MP0610 (Mitsui Chemicals), MP0620 (Mitsui Chemicals)) and other maleic anhydride-modified ethylene-propylene rubber; Toughmer M (eg, MA8510, MH7010, MH7020 (Mitsui Chemicals)). ), MH5010, MH5020 (manufactured by Mitsui Chemicals), MH5040 (manufactured by Mitsui Chemicals)), maleic anhydride-modified ethylene-butene rubber; )), HPR series (maleic anhydride-modified EEA, maleic anhydride-modified EVA (manufactured by Mitsui / Jupon polyolefin)), Bondfast series (maleic anhydride-modified EMA (manufactured by Sumitomo Chemical Co., Ltd.)), Dumilan series (maleic anhydride) Acid-modified EVOH (manufactured by Takeda Yakuhin Kogyo Co., Ltd.)), Bondine (ethylene / acrylic acid ester / maleic anhydride ternary copolymer (manufactured by Atofina)), Tough Tech (maleic anhydride-modified SEBS, M1943 (manufactured by Asahi Kasei)) , Clayton (maleic anhydride-modified SEBS, FG1901, FG1924 (manufactured by Clayton Polymer)), tough prene (maleic anhydride-modified SBS, 912 (manufactured by Asahi Kasei)), Septon (maleic anhydride-modified SEPS (manufactured by Kuraray)), Maleic anhydride-modified such as Lexpearl (maleic anhydride-modified EVA, ET-182G, 224M, 234M (manufactured by Nippon polyolefin)) and aurolen (maleic anhydride-modified EVA, 200S, 250S (manufactured by Nippon Paper Chemical Co., Ltd.)). Polyethylene; maleic anhydride-modified polypropylene such as Admer (eg, QB550, LF128 (manufactured by Mitsui Chemicals, Inc.)); and the like.

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

As the compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-binding cross-linking site, a compound (nitrogen-containing heterocycle) that forms a hydrogen-binding cross-linking site described in the above polymer component can be introduced. Those exemplified as (Compound) can be preferably used, and for example, the nitrogen-containing heterocycle itself described in the thermoplastic elastomer composition of the above embodiment may be used, or the nitrogen-containing heterocycle may be anhydrous malein. It may be a compound (for example, a nitrogen-containing heterocycle having the substituent) to 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 a compound (I), a compound forming both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site (both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site can be introduced at the same time). (A compound) may be used (note that a side chain having both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site can be said to be a preferable form of a side chain having a hydrogen-binding cross-linking site).

The compound (I) is not particularly limited, and is a compound as described above, depending on the type of side chain (side chain (a) or side chain (a')) in the target polymer. A suitable compound can be appropriately selected and used from (I). From the viewpoint of obtaining higher reactivity, such compound (I) may have at least one substituent among a hydroxyl group, a thiol group and an amino group, such as triazole and pyridine. Thisiazol, imidazole, isocyanurate, triazine or hydantin is preferable, and triazole, pyridine, thiazyl, imidazole, isocyanurate, triazine or hydantin having the above-mentioned substituent is more preferable, and the above-mentioned substituent is used. It is more preferably triazole, isocyanurate or triazine which has, and particularly preferably triazole which has the above-mentioned substituent. Examples of triazole, pyridine, thiazylazole, imidazole or hydantoin which may have such a substituent include 4H-3-amino-1,2,4-triazole, aminopyridine, aminoimidazole and aminotriazine. , Aminoisocyanurate, hydroxypyridine, hydroxyethylisocyanurate and the like.

Further, as the compound (II) that reacts with the cyclic acid anhydride group to form a covalent bond site, the compound (II) that forms a covalent bond site described in the above-mentioned thermoplastic polymer component is described as a compound (covalent bond). The same compounds as those exemplified as "the compound to be produced)" can be preferably used (the same compounds are also suitable). Further, as such a compound (II), it is possible to simultaneously introduce both a compound forming both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site (both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site). (A compound) may be used (note that a side chain having both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site can be said to be a preferable form of a side chain having a covalent-bonding cross-linking site).

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

Further, as the compound (I) and / or (II), since both the hydrogen-binding cross-linking site and the covalent-bonding cross-linking site can be introduced into the composition more efficiently, the cyclic acid. A compound that reacts with an anhydride group to form both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site (a compound capable of simultaneously introducing both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site). It is preferable to use it. As the compound forming both the hydrogen-bonded cross-linking site and the covalently-bonded cross-linking site, the heterocyclic-containing polyol, the heterocycle-containing polyamine, and the heterocyclic-containing polythiol can be preferably used, and the heterocyclic ring-containing polyol is preferably used. A nitrogen heterocycle-containing polyol, a nitrogen-containing heterocycle-containing polyamine, and a nitrogen-containing heterocycle-containing polythiol can be more preferably used, and among them, trishydroxyethyl isocyanurate is particularly preferable.

The amount of the compound (I) and the compound (II) added (the total amount thereof: the amount of the one compound when only one compound is used) is not particularly limited, but is included in the compound. When active hydrogen such as amine and alcohol is contained in the compound, the amount of active hydrogen such as amine and alcohol in the compound is 20 to 250 mol% with respect to 100 mol% of the cyclic acid anhydride group. , More preferably 50 to 150 mol%, and even more preferably 80 to 120 mol%. If the amount of such addition is less than the above lower limit, the amount of side chains to be introduced becomes small, it becomes difficult to make the crosslink density sufficiently high, and the physical properties such as tensile strength tend to decrease. On the other hand, if the upper limit is exceeded, the proportion of the added compound (I) and compound (II) that do not form the cross-linking site increases, so that the cross-linking density tends to decrease.

Further, the amount of the compound (I) and the compound (II) added is such that the total amount thereof (when only one compound is used, the amount of the other compound is used), the polymer in the mixture ( A polymer having a cyclic acid anhydride group in the side chain) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass. It is more preferably 9.0 parts by mass. If the amount of the compound (I) and the compound (II) added (amount based on parts by mass) is less than the lower limit, the cross-linking density tends not to increase and the desired physical properties tend not to be exhibited, while if the amount exceeds the upper limit, the cross-linking tends to occur. The density tends to decrease.

When both the compound (I) and the compound (II) are used, the order in which the compound (I) and the compound (II) are added is not particularly limited, and either of them may be added first. Further, when both compound (I) and compound (II) are used, the compound (I) is reacted with a part of the cyclic acid anhydride group of the polymer having a cyclic acid anhydride group in the side chain. May be good. This also makes it possible to react compound (II) with an unreacted cyclic acid anhydride group (unreacted cyclic acid anhydride group) to form a covalently bonded site. The part referred to here is preferably 1 mol% or more and 50 mol% or less with respect to 100 mol% of the cyclic acid anhydride group.
Within this range, the effect of introducing a group derived from the compound (I) (for example, a nitrogen-containing heterocycle) is sufficiently expressed in the obtained polymer (B), and the recyclability tends to be further improved. The compound (II) is preferably reacted with the cyclic acid anhydride group so that the number of crosslinks by covalent bond is appropriate (for example, 1 to 3 in one molecule).

When the polymer is reacted with the raw material compound (compound (I) and / or compound (II)), the cyclic acid anhydride group contained in the polymer is opened, and the cyclic acid anhydride group and the raw material compound ( The compound (I) and / or the compound (II)) is chemically bonded. The temperature conditions for reacting the polymer with the raw material compound (the compound (I) and / or the compound (II)) (opening the ring of the cyclic acid anhydride group) are not particularly limited, and the compound and the compound are not particularly limited. Depending on the type of cyclic acid anhydride group, the temperature may be adjusted so that these can react, but from the viewpoint of softening and proceeding the reaction instantly, the temperature may be 100 to 280 ° C., or 160 to 230. The temperature may be 180 to 220 ° C.

By 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. Therefore, a hydrogen-bonding cross-linking site (carbonyl) is formed on the side chain of the polymer. It is possible to contain a moiety having a containing group and / or a nitrogen-containing heterocycle, more preferably a moiety having a carbonyl-containing group and a nitrogen-containing heterocycle). The side chain formed (introduced) by such a reaction can be made to contain the structure represented by the above formula (2) or (3).

Further, at least at the site where the compound (II) and the cyclic acid anhydride group have reacted by such a reaction, a covalently cross-linking site is formed, so that the side chain of the polymer is covalently crosslinked. It is possible to use a portion containing a portion (side chain (b) or side chain (c)). Then, the side chain formed by such a reaction may contain the structures represented by the above formulas (7) to (9).

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

By reacting in this manner, the polymer (A) having a side chain (a) containing a hydrogen-binding 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 at least one polymer component selected from the group consisting of the polymer (B) having a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site in the side chain and having a glass transition point of 25 ° C. or lower. Can be obtained.

<Process oil>
The thermoplastic elastomer composition of the embodiment can contain a process oil to improve its processability and the quality of the rubber processed product. The process oil is not particularly limited and may be any, but the process oil preferably contains a hydrocarbon oil derived from petroleum (Petroleum-Derived). The content ratio of the petroleum-derived hydrocarbon oil in the process oil may be 50% by mass or more, 80% by mass or more, 95% by mass or more, and substantially petroleum-derived hydrocarbon oil. It may consist of.

As the process oil, rosefin oil is preferable from the viewpoint of being well-adapted to the polymer component and having excellent fluidity, heat resistance, color stability, and stain resistance. As used herein, the term "paraffin oil" refers to the oil as a percentage of the total carbon number of the paraffin carbon number obtained by performing a correlation ring analysis (nd-M ring analysis) based on ATM D3238-85. Paraffin carbon when the percentage of total carbon number of naphthen carbon (naphthen part: CN) and the percentage of aromatic carbon number of total carbon number (aromatic part: CA) are determined. It means that the percentage (CP) with respect to the total carbon number of the number is 60% or more, preferably 60% or more and 90% or less, and more preferably 70% or more and 85% or less.

In the thermoplastic elastomer composition of embodiment, the process oil, is measured according to JIS K 2283 (published in 2000), kinematic viscosity at 40 ℃ of 50mm ² / s~700mm ² / s is preferably one, more preferably 150~600mm ² / s, and further preferably from 300 to 500 mm ² / s.
If the kinematic viscosity (ν) is less than the lower limit, oil bleeding tends to occur easily, while if the kinematic viscosity (ν) exceeds the upper limit, sufficient fluidity tends not to be imparted. The kinematic viscosity of such process oil adopts the value measured according to JIS K 2283 (issued in 2000) under the temperature condition of 40 ° C., for example, JIS K 2283 (issued in 2000). ) May be used, and the value automatically measured under the temperature condition of 40 ° C. may be adopted by using a Canon Fenceke type viscometer (for example, the trade name “SO series” manufactured by Shibata Scientific Technology Co., Ltd.).

Further, in the thermoplastic elastomer composition of the embodiment, it is preferable that the process oil has an aniline point of 80 ° C. to 145 ° C. as measured by a U-shaped tube method based on JIS K2256 (issued in 2013). It is more preferably 100 to 145 ° C, and even more preferably 105 to 145 ° C. For the aniline point of such a process oil, a value measured by the U-shaped tube method based on JIS K2256 (issued in 2013) is adopted. For example, the aniline point based on JIS K2256 (issued in 2013) is adopted. A value measured using a measuring device (for example, a trade name “ap-6” manufactured by Tanaka Scientific Instruments Co., Ltd.) may be adopted.

As such a process oil, commercially available ones can be used as appropriate. For example, the trade names "Super Oil M Series P200", "Super Oil M Series P400" and "Super Oil M Series P500S" manufactured by JXTG Energy Co., Ltd. can be used. "Diana Process Oil PW90", "Diana Process Oil PW150", "Diana Process Oil PW380" manufactured by Idemitsu Kosan Co., Ltd .; 150, 2100, 2280, etc.) ”; The trade name“ Gargoyle Arctic Series (1010, 1022, 1032, 1046, 1068, 1100, etc.) ”manufactured by Mobile Co., Ltd. may be appropriately used.

The content of the process oil in the thermoplastic elastomer composition may be appropriately determined according to the polymer component, the type of the process oil, etc., but is described above with respect to the total mass (100% by mass) of the thermoplastic elastomer composition of the embodiment. The content ratio 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 preferable, 35% by mass or more and 70% by mass or less is further preferable, and 50% by mass or more and 85% by mass or less is particularly preferable. When the ratio of the content of the process oil to 100% by mass of the thermoplastic elastomer composition is at least the above lower limit value (particularly, the above lower limit is 30% by mass or more), the hardness of the thermoplastic elastomer composition is lowered. , The molding processability can be made more excellent. Further, when the ratio of the content of the process oil to 100% by mass of the thermoplastic elastomer composition is not more than the above upper limit value, contamination of molding processing 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.

By blending the process oil, the thermoplastic elastomer composition is improved in processability, but there is a problem that the tack force (stickiness) of the surface when the thermoplastic elastomer composition is made into a 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, it has a very excellent tacking force (stickiness). Demonstrate the effect of reduction.

When the thermoplastic elastomer composition contains a process oil, the content of the fatty acid amide compound is preferably 0.01 part by mass or more, preferably 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 further preferable. As described above, when the content of the fatty acid amide compound is at least the above lower limit, the effect of reducing the tack force due to the process oil tends to be suitably exhibited. Further, even when the ratio of the content of the process oil to 100% by mass of the thermoplastic elastomer composition having a relatively high content of the process oil is 30% by mass or more, the tacking force (stickiness) is very excellent. Feeling) The effect of reduction can be demonstrated. On the other hand, when the content of the fatty acid amide compound is not more than the above upper limit, contamination of molding processing 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 one having a small hardness value is preferable from the viewpoint of excellent moldability. For example, the cured thermoplastic elastomer composition preferably has a shore A hardness of 70 or less, more preferably 60 or less, and even more preferably 50 or less, in accordance with JIS K6253. By setting the ratio of the content of the process oil to 100% by mass of the thermoplastic elastomer composition, for example, 80% by mass or more, the thermoplastic elastomer composition having a shore A hardness of 0 after curing can also be produced. It is possible.

The hardness of the thermoplastic elastomer composition can be appropriately adjusted depending on the type and blending amount of the raw material compound, but the hardness can be adjusted by blending the above-mentioned procel oil and the blending amount of the above-mentioned procel oil. As the amount of procell oil blended in the thermoplastic elastomer composition is increased, the hardness value of the thermoplastic elastomer composition can be reduced, 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 tack force (stickiness) of the surface when the thermoplastic elastomer composition is used as a 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, it has a very excellent tacking force (stickiness). Demonstrate the effect of reduction. Further, the thermoplastic elastomer composition of the embodiment is very excellent even when the blending amount of the process oil is relatively high and the shore A hardness according to JIS K6253 after curing is 30 or less. The effect of reducing tack force (stickiness) can be demonstrated.

<Thermoplastic resin>
The thermoplastic elastomer composition of the embodiment is preferably a dynamically crosslinked thermoplastic elastomer composition. Examples of the dynamically crosslinked thermoplastic elastomer composition include a dispersed phase and a continuous phase, the dispersed phase containing the polymer component, and the continuous phase containing a thermoplastic resin.
Dynamic cross-linking can be formed by performing a cross-linking reaction while melt-kneading a raw material containing a cross-linking agent and a polymer molecule that reacts 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 the polymer component forms a dispersed phase.
The dynamically crosslinked thermoplastic elastomer composition is very useful because it has 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 dynamically crosslinked thermoplastic elastomer containing the same as a constituent.

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, and examples thereof include polyolefin-based resins such as polyethylene-based resins and polypropylene-based resins. Specific examples of these resins include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene, high density polyethylene, polypropylene and the like.

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

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, and the total mass of the thermoplastic elastomer composition of the embodiment (100). The ratio of the content of the thermoplastic resin to (% by 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 and 40% by mass or less are more preferable. When the ratio of the content of the thermoplastic resin to 100% by mass of the thermoplastic elastomer composition is within the above range, the processability of the thermoplastic elastomer composition can be made preferable.

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 preferably, for example, 10% by mass or more, preferably 10% by mass. % Or more and 85% by mass or less is preferable, 30% by mass or more and 75% by mass or less is more preferable, and 50% by mass or more and 65% by mass or less is further preferable. When the ratio of the total content of the polymer component and the thermoplastic resin to 100% by mass of the thermoplastic elastomer composition is within the above range, the processability and rubber elasticity of the thermoplastic elastomer composition are preferable. Can be done.

The total content of the polymer component and the thermoplastic resin in the thermoplastic elastomer composition and the content ratio of the process oil (total of the polymer component and the thermoplastic resin) / (process oil) is a mass ratio. It is preferably 5/1 to 1/5, more preferably 3/1 to 1/3, and 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 support of the process oil in the thermoplastic elastomer composition becomes suitable, and both the processability and the rubber elasticity of the thermoplastic elastomer composition can be realized at a high level.

<Clay>
The thermoplastic elastomer composition of the embodiment can contain clay. The clay is not particularly limited, and known clays (clay minerals and the like) can be appropriately used. Examples of such clays include natural clays, synthetic clays, and organic clays.

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

Clay containing silicon and magnesium as main components refers to clay in which the main components of the metal of the metal oxide which is a constituent of clay are silicon (Si) and magnesium (Mg), and other metal oxides (clay). Aluminum (Al), iron (Fe), etc.) may be contained as an auxiliary component. The clay containing silicon and magnesium as main components is not particularly limited, and known clays can be appropriately used. By using clay containing silicon and magnesium as main components, it is possible to improve the reinforcing property because the particle size is small. Further, as the clay containing silicon and magnesium as main components, clay having a smectite structure is preferable from the viewpoint of easy availability.

Examples of such clays containing silicon and magnesium as main components include stepnsite, hectorite, saponite, talc and the like, but among them, from the viewpoint of dispersibility, stepnsite and hector. It is more preferable to use light and saponite.

Further, as the clay containing silicon and magnesium as main components, synthetic clay is preferable. As such synthetic clay, commercially available ones may be used. For example, the product names "Smecton SA" and "Smecton ST" manufactured by Kunimine Kogyo Co., Ltd., the product name "Ionite" manufactured by Mizusawa Industrial Chemicals Co., Ltd., and CO-OP The product name "Lucentite" manufactured by Chemical Co., Ltd. can be used as appropriate.

The organic clay is not particularly limited, but it is preferable that the clay is organicated by an organicizing agent. The clay before being organicized is not particularly limited, and may be a so-called clay mineral, for example, montmorillonite, saponite, hectorite, byderite, stepvensite, nontronite, vermiculite, halloysite, mica, etc. Examples include fluorinated mica, kaolinite, and pyrophyllite.
Moreover, such clay may be a natural product or a synthetic product.

The organic agent is not particularly limited, and a known organic agent capable of organicizing clay can be appropriately used. For example, hexylammonium ion, octylammonium ion, and 2-ethylhexylammonium ion can be used. , Dodecylammonium ion, laurylammonium ion, octadecylammonium ion, dioctyldimethylammonium ion, trioctylammonium ion, dioctadecyldimethylammonium ion, trioctylammonium ion, dioctadecyldimethylammonium ion, trioctadecylammonium ion and the like can be used. ..

Further, as such an organic clay, a quaternary ammonium salt of clay can be preferably used from the viewpoint of monolayer dispersibility. The quaternary ammonium salt of such an organic clay is not particularly limited, and is, for example, a trimethylstearylammonium salt, an oleylbis (2-hydroxylethyl) salt, a methylammonium salt, a dimethylstearylbenzylammonium salt, or a dimethyloctadecylammonium salt. , And a mixture of two or more of these can be preferably used. As the quaternary ammonium salt of such an organic clay, dimethylstearylbenzylammonium salt, dimethyloctadecylammonium salt, and a mixture thereof can be more preferably used from the viewpoint of improving tensile strength and heat resistance, and dimethyl. A mixture of stearylbenzylammonium salt and dimethyloctadecylammonium salt can be more preferably used.

Further, as such an organic clay, a commercially available one may be used, for example, other than the trade names "Kunifil-D36", "Kunifil-B1", "Kunifil-HY" manufactured by Kunimine Industry Co., Ltd. , Product name "ESBEN series (C, E, W, WX, N-400, NX, NX80, NZ, NZ70, NE, NEZ, NO12S, NO12", "Organite series (D, T)" manufactured by Hojun. Among such commercially available organic clays, the product name "Kunifil-D36" manufactured by Kunimine Industry Co., Ltd. and the product name "Esben Series WX" manufactured by Hojun Co., Ltd. can be preferably used. ..

As described above, as the clay, clay containing silicon and magnesium as main components and organic clay are preferable from the viewpoint of high dispersibility, and among them, organic clay can obtain a higher tensile stress (modulus). 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, and 0 by mass with respect to 100 parts by mass of the polymer component. It is more preferably .05 to 5 parts by mass. When the content of such clay is at least the above lower limit, the effect of improving tensile stress and heat resistance tends to be suitably exhibited, while when it is at least the above upper limit, the degree of crosslinking is preferable. Therefore, the 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 other components that do not fall under these, if necessary, to the extent that the object of the present invention is not impaired. May be good. As other components, polymers other than the above polymer components (hereinafter referred to as "polymers"), reinforcing agents (fillers), hydrogen-binding reinforcing agents (fillers), and fillers obtained by introducing an amino group (filler). Hereinafter, it is simply referred to as "amino group-introduced filler"), an amino group-containing compound other than the amino group-introduced filler, a compound containing a metal element (hereinafter, simply referred to as "metal salt"), an antioxidant, and an antioxidant. Agents, pigments (dye), plasticizers, rocking modifiers, UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrators, rust inhibitors, adhesion enhancers, antistatic agents Examples thereof include various additives such as agents and fillers. For example, as the antioxidant, the antioxidant, the pigment (dye), and the plasticizer, those described below can be appropriately used.

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

Further, as such a reinforcing agent (filler), carbon black, silica, calcium carbonate and the like can be mentioned. Wet silica is preferably used as silica, and calcium carbonate is preferably used.

As such an antiaging agent, for example, compounds such as hindered phenol-based compounds, aliphatic and aromatic hindered amine-based compounds can be appropriately used. Further, 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, red iron oxide, lithopon, lead, cadmium, iron, cobalt, aluminum, hydrochlorides and sulfates, and organic pigments such as azo pigments and copper phthalocyanine pigments. Pigments and the like can be appropriately used, and examples of the plasticizer include benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebatic acid, fumaric acid, maleic acid, itaconic acid and citrus. In addition to derivatives such as acids, polyesters, polyethers, epoxys and the like can be appropriately used. 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 a component other than the polymer component and the fatty acid amide compound (for example, the additive), the content of the other component is particularly limited. However, in the case of polymers and reinforcing materials (fillers), the amount is preferably 300 parts by mass or less with respect to 100 parts by mass of the polymer component, and more preferably 20 to 200 parts by mass. If the content of such other components is less than the lower limit, the effect of using the other components tends not to be sufficiently exhibited, while if the content exceeds the upper limit, it depends on the type of the component to be used. , The effect of the polymer component is diminished, and the physical properties tend to be deteriorated.

When the above-mentioned other component is another additive (other than polymers and reinforcing materials (filler)), the content of the other component is 100 parts by mass of the polymer component. On the other hand, it is preferably 20 parts by mass or less, and more preferably 0.1 to 10 parts by mass. If the content of such other components is less than the lower limit, the effect of using the other components tends not to be sufficiently exhibited, while if the content 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 embodiment is at least one selected from the group consisting of the polymer component and the fatty acid amide compound, and optionally process oil, a thermoplastic resin, clay, and other components not corresponding thereto. Ingredients and, including. The thermoplastic elastomer composition of the embodiment can contain the above-mentioned components so that the total content (% by mass) does not exceed 100% by mass.

<Use, etc.>
When the thermoplastic elastomer composition of the embodiment is heated (for example, heated to 100 to 280 ° C.), hydrogen bonds formed at the hydrogen-bonding cross-linking site of the polymer component and other cross-linking structures are dissociated. It can be softened and fluidized. It is considered that this is because the interaction between the side chains formed between molecules or within the molecule (mainly the interaction due to hydrogen bonds) is weakened by heating. In the thermoplastic elastomer composition of the embodiment, since the side chain contains at least a polymer component containing a hydrogen-bonding cross-linking site, it is dissociated when it is left to stand after being imparted with fluidity by heating. Since the hydrogen bonds formed are rebonded and cured, it is possible to more efficiently develop recyclability in the thermoplastic elastomer composition depending on the composition.

Moreover, as one embodiment of the present invention, a cured product of a thermoplastic elastomer composition can be obtained. As an example, the curing is performed when the thermoplastic elastomer composition is set to a temperature or lower at which the above-mentioned fluidity can be imparted.

Therefore, as one embodiment of the present invention, it is possible to provide a cured product of the thermoplastic elastomer composition of the embodiment.
The tack force on the surface of the cured product of the thermoplastic elastomer composition may be 4N or less, 0.1N or more and 4N or less, 1N or more and 3.5N or less, and 2N or more and 2.7N. It may be as follows. When the tack force is not more than the above upper limit value, a sticky feeling is less likely to occur during use, and sticking to the molding equipment is prevented.
The tack force shall be measured under the measurement conditions described in the examples described later.

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

Examples of the molding method include injection molding, extrusion molding, compression molding and the like.

The extrusion amount of extrusion molding is not particularly limited, but can be exemplified by 1 to 50 kg / h.

The heating referred to here may correspond to the heating at the time of melting and mixing in the << method for producing a thermoplastic elastomer composition >> described later, or once, a molded product of the thermoplastic elastomer composition is obtained. After that, it may be heated again to correspond to the heating when imparting fluidity.

The molded product of the thermoplastic elastomer composition is a cured product of the thermoplastic elastomer composition of the embodiment, and may be manufactured by using the thermoplastic elastomer composition of the embodiment, and the thermoplastic elastomer composition may be used. It may contain, and may consist of a thermoplastic elastomer composition.

The molded product of the thermoplastic elastomer composition of the embodiment includes those used as materials for various products such as pellets and sheets. By containing the fatty acid amide compound in the thermoplastic elastomer composition of the embodiment, it is possible to prevent blocking between pellets and sheets.

The thermoplastic elastomer composition of the embodiment can be used for various rubber applications by utilizing, for example, rubber elasticity. Further, it is preferable to use it as a hot melt adhesive or as an additive contained therein because heat resistance and recyclability can be improved. The thermoplastic elastomer composition of the embodiment is a rubber part for an automobile, a hose, a belt, a sheet, a vibration-proof rubber, a roller, a lining, a rubberized cloth, a sealing material, a glove, a fender, and a medical rubber (syringe gasket, a tube). , Catheter), 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 above-mentioned rubber parts for automobiles include tire treads, carcasses, sidewalls, inner liners, under treads, belt parts, and other tire parts; exterior radiator grilles, side moldings, and garnishes (pillars, rear). , Cowl top), Aero parts (Air dam, Spoiler), Wheel cover, Weather strip, Cow belt grill, Air outlet louver, Air scoop, Hood bulge, Ventilation port parts, Anti-proof parts (Over fender, Side seal panel, Malls (windows, hoods, door belts)), marks; parts for interior window frames such as doors, lights, weather strips of wipers, glass runs, glass run channels; air duct hoses, radiator hoses, brake hoses; crank shaft seals, valve stem seals Lubricating oil parts such as head cover gasket, A / T oil cooler hose, mission oil seal, P / S hose, P / S oil seal; fuel system parts such as fuel hose, emission control hose, inlet filler hose, diaphragms, etc. Anti-vibration parts such as engine mounts and in-tank pump mounts; Boots such as CVJ boots, racks & pinion boots; Air conditioning parts such as A / C hoses and A / C seals; Timing belts, auxiliary equipment Belt parts such as belts; sealers such as windshield sealers, vinyl plastic sealers, anaerobic sealers, body sealers, spot weld sealers; and the like.

Further, when the thermoplastic elastomer composition of the embodiment is contained in a resin or rubber that causes cold flow at room temperature as a rubber modifier (for example, a flow inhibitor), the flow and cold flow during extrusion are prevented. be able to.

<< Manufacturing method of thermoplastic elastomer composition >>
The thermoplastic elastomer composition is obtained by blending a fatty acid amide compound, a polymer component or a raw material thereof, and, if necessary, each other component constituting the thermoplastic elastomer composition.
More preferably, the thermoplastic elastomer composition is prepared by blending a fatty acid amide compound, a polymer component or a raw material thereof, and, if necessary, other components constituting the thermoplastic elastomer composition, and melt-mixing them. Obtained by doing. If the fatty acid amide compound and the polymer component or its raw material (and the thermoplastic resin if the thermoplastic elastomer composition contains the thermoplastic resin) are melted, all the components to be blended are melted. It does not have to be.

When the raw material of the polymer component is used, the polymer component can be synthesized from the raw material of the polymer component at the time of the above-mentioned melt mixing.

As a device for blending the above-mentioned components constituting the thermoplastic elastomer composition, a mixer, for example, a stirring blade type mixer can be used, and the blending time may be 5 to 40 minutes. .. Further, the order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.

The temperature of the melt mixing of each of the above-mentioned components constituting the thermoplastic elastomer composition may be appropriately determined according to the components constituting the thermoplastic elastomer composition or the raw materials thereof, but the fatty acid amide compound and the polymer component or It is preferable that the temperature is equal to or higher than the melting point of various substances including the raw material, and examples thereof include temperatures lower than the thermal decomposition temperature of various substances. As an example, the temperature of the melt mixing may be 100 to 280 ° C, 160 to 230 ° C, or 180 to 220 ° C.
Further, the apparatus for performing melt mixing may be either a batch type or a continuous type. Examples of such an apparatus include a melt-kneading apparatus, and examples thereof include a single-screw extruder, a twin-screw extruder, a kneader, and a Banbury mixer.
The time for melt-mixing may be appropriately determined depending on the components constituting the thermoplastic elastomer composition or the raw materials thereof, but may be 2 minutes to 30 minutes.

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

When the fatty acid amide compound is blended together with the raw material of the polymer component (in the case of the above-mentioned pre-addition), the polymer component is synthesized in a mixture thereof 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 the post-addition), the fatty acid amide compound may be added to the molded product containing the thermoplastic elastomer to obtain a thermoplastic elastomer composition. In this case, the application of the fatty acid amide compound to the surface of the molded product can be exemplified, and the application method includes mixing the molded product with the fatty acid amide compound, spraying the fatty acid amide compound onto the molded product, and fatty acid amide. Immersion of the molded product in a compound, impregnation of the molded product in a fatty acid amide compound, and the like can be exemplified.

That is, the following aspects are provided as a method for producing a thermoplastic elastomer composition according to the present invention, which comprises the above embodiment using a raw material of a 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 the following <1> to <3> is obtained, and the polymer and the raw material compound are used. To obtain a polymer component by reacting with
The heat according to the present invention, which comprises blending a fatty acid amide compound with the mixture before reacting the polymer with the raw material compound, or with the mixture after reacting the polymer with the raw material compound. A method for producing a plastic elastomer composition.
<1> Compound (I), which 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 bonded site.
<3> A compound capable of reacting with the cyclic acid anhydride group to form both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site.

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

When the thermoplastic elastomer composition of the embodiment is a dynamically crosslinked thermoplastic elastomer composition, the method for producing the dynamically crosslinked thermoplastic elastomer composition is as follows.
A mixture containing a polymer, a cross-linking agent for cross-linking the polymer, and a thermoplastic resin is obtained, and the polymer and the cross-linking agent are dynamically cross-linked under melting conditions to obtain a polymer component.
The present invention comprises blending a fatty acid amide compound into the mixture before the polymer and the cross-linking agent are dynamically cross-linked, or the mixture after the polymer and the cross-linking agent are dynamically cross-linked.

The following aspects are provided as a method for producing a dynamically crosslinked thermoplastic elastomer composition according to the present invention, which comprises the above embodiment.

A mixture containing a polymer having a cyclic acid anhydride group in a side chain, at least one raw material compound selected from the above group consisting of <2> to <3>, and a thermoplastic resin was obtained, and melt conditions were obtained. By dynamically cross-linking the polymer and the raw material compound underneath, a polymer component can be obtained.
The present invention comprises blending a fatty acid amide compound into the mixture before the polymer and the raw material compound are dynamically crosslinked, or the mixture after the polymer and the raw material compound are dynamically crosslinked. A method for producing a dynamically crosslinked thermoplastic elastomer composition according to the present invention.

Here, "dynamically cross-linking under melting conditions" in the present specification means that the polymer and the raw material compound are reacted while applying shear stress to the mixture in a melted state by kneading.

The device for performing dynamic cross-linking may be either a batch type or a continuous type. Examples of such an apparatus include a melt-kneading apparatus, and examples thereof include a single-screw extruder, a twin-screw extruder, a kneader, and a Banbury mixer.
The time for performing the dynamic cross-linking may be appropriately determined depending on the components constituting the thermoplastic elastomer composition or the raw materials thereof, but may be 2 minutes to 30 minutes.

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

Further, for example, a thermoplastic elastomer composition containing the polymer (A) as a polymer component and a thermoplastic elastomer composition containing the polymer (B) as a polymer component are separately produced, and then mixed to obtain a polymer. A thermoplastic elastomer composition containing the polymers (A) and (B) as components may be used. Further, in the case of producing a thermoplastic elastomer composition containing a combination of the polymers (A) and (B) as the polymer component, the ratio of the polymer (A) to the polymer (B) is appropriately changed in the composition. It is also possible to exhibit desired characteristics by appropriately changing the ratio of the hydrogen-binding cross-linking site and the covalent-bonding cross-linking site existing in the above.

According to the method for producing a thermoplastic elastomer composition of the embodiment, the thermoplastic elastomer composition of the embodiment can be produced. The thermoplastic elastomer composition of the present invention is not limited to that produced by the method.

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 (trade name "Toughmer MH5040" manufactured by Mitsui Chemicals, Inc.) 35 kg, Trishydroxyethyl isocyanurate (trade name "Tanac" manufactured by Nissei Sangyo Co., Ltd.) 0.78 kg, high-density polyethylene (Product name "HJ590N" manufactured by Nippon Polyethylene) 25 kg, styrene block copolymer (product name "G1633EU" manufactured by Clayton) 40 kg, process oil (product name "300HV-S (J)" manufactured by JXTG Energy), Percentage (CP) 78.6%) 62 kg, organic clay (trade name "Esben WX" manufactured by Hojun) 0.035 kg, anti-aging agent (trade name "Adecastab AO-50" manufactured by ADEKA) 0.49 kg , And 0.33 kg of ethylenebisoleic acid amide (trade name "Alflow AD-281F" manufactured by Nichiyu Co., Ltd.) as a surface modifier is weighed and mixed uniformly at a temperature of 50 ° C. or lower with a stirring blade type mixer. A raw material mixture was obtained. The content of ethylene bisoleic acid amide with respect to 100% by mass of the raw material mixture is about 0.2% by mass. The ethylene bisoleic 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. The composition was then pelletized to give pellets.

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

[Example 3]
Pellets were prepared in the same manner as in Example 1 except that the amount of ethylene bisoleic acid amide added was 8.2 kg in Example 1.
The content of ethylene bisoleic 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 bisstearic acid amide (trade name "Alflow H-50S" manufactured by NOF CORPORATION) was added instead of ethylene bisoleic acid amide in Example 1 above. To prepare pellets.
The content of ethylene bisstearic acid amide with respect to 100% by mass of the raw material mixture is about 3% by mass. Ethylene bisstearic acid amide has a molecular weight of 593 and a melting point of 145 ° C.

[Comparative Example 1]
In Example 1 above, 4.9 kg of oleic acid monoamide (trade name "Alflow E-10" manufactured by NOF CORPORATION) was added in place of ethylene bisoleic acid amide, but in the same manner as in Example 1. Pellets were made.
The content of oleic acid monoamide with respect to 100% by mass of the raw material mixture is about 3% by mass. The molecular weight of oleic acid monoamide is 281 and the melting point is 74 ° C.

[Comparative Example 2]
In Example 1 above, 4.9 kg of erucic acid monoamide (trade name "Alflow P-10" manufactured by NOF CORPORATION) was added in place of ethylene bisoleic acid amide, but in the same manner as in Example 1. Pellets were made.
The content of erucic acid monoamide with respect to 100% by mass of the raw material mixture is about 3% by mass. The erucic acid monoamide has a molecular weight of 338 and a melting point of 81 ° C.

[Comparative Example 3]
Pellets were prepared in the same manner as in Example 1 except that the fatty acid amide compound was not added.

<Evaluation>
-Removability from injection molding die From the pellets of Examples 1 to 4 and Comparative Examples 1 to 3 obtained above, a flat plate having a thickness of 100 mm × 100 mm × 2 mm was molded at 200 ° C. using an injection molding machine and molded. The peelability of the product from the injection molding die was evaluated. The temperature of the mold was 40 ° C. The evaluation criteria are as follows.
○… The molded product could be peeled off from the mold by pushing down the ejector.
×: There was adhesion to the mold, and the molded product could not be peeled off from the mold by pushing down the ejector.

-Removability from thermal rolls From the pellets of Examples 1 to 4 and Comparative Examples 1 to 3 obtained above, a sheet was formed by a mixing roll device equipped with two rolls having a diameter of 200 mm and a length of 610 mm. , The peelability of the molded product from the roll was evaluated. The temperature of each roll was 130 ° C., and the clearance between the two rolls was 0.3 mm. The evaluation criteria are as follows.
◯… The molded product could be easily peeled off from the heat roll.
X ... There was adhesion to the heat roll, and the molded product could not be peeled off from the heat roll, or the molded product was damaged although it could be peeled off.

-Feeling of stickiness of the molded product The presence or absence of the feeling of stickiness on the surface of the molded product (flat plate and sheet) obtained above was evaluated.

-Tacking force of the molded product The flat plate with a thickness of 2 mm obtained above is cut into a length of 50 mm and a width of 40 mm, and the main surface of the flat plate (50 mm) after cutting with a Picuma Tack Tester manufactured by Toyo Seiki Seisakusho Co., Ltd. The tack force was measured with respect to (× 40 mm) using a probe (diameter 50 mm, width 14 mm, wheel shape, the circumference of the wheel in contact with the flat plate sample) attached to the measuring device. The measurement conditions were an environment of 23 ° C., a pressing force of 5 N, a crimping time of 3 seconds, a holder descending speed of 1000 mm / min, and a holder ascending speed of 500 mm / min.

-Hardness of molded product A flat plate having a thickness of 100 mm x 100 mm x 2 mm is molded from the pellet of Example 1 in the same manner as above, and the shore A hardness conforming to JIS K6253 is measured with respect to the central portion of the main surface of the flat plate. When I did, it was 50.

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

The molded product of the thermoplastic elastomer composition of Comparative Examples 1 to 3 containing no fatty acid amide compound having a molecular weight of 400 or more has adhesion to the mold, and the molded product cannot be peeled off from the mold by pushing down the ejector. rice field. In addition, the molded product had adhesion to the roll, and the sheet could not be peeled off from the heat roll.

On the other hand, the molded articles of the thermoplastic elastomer compositions of Examples 1 to 4, which contain a fatty acid amide compound having a molecular weight of 400 or more, have a reduced tack force, and are resistant to peeling from an injection mold and from a thermal roll. There was no problem with the peelability of the molded product, and there was no sticky feeling on the surface of the molded product.

Further, according to the comparison between Comparative Examples 1 and 2 and Examples 1 and 4, in Comparative Examples 1 and 2 containing the fatty acid amide compound having a molecular weight of less than 400, the fatty acid amide compound having a molecular weight of 400 or more was contained. 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 when the molecular weight of the fatty acid amide compound is 400 or more, a very excellent tack force reducing effect is exhibited.

Further, in the molded product of the thermoplastic elastomer composition of Examples 1 to 4, the ratio of the content of the process oil to 100% by mass of the thermoplastic elastomer composition is 30% by mass or more, and such a process oil. It can be seen that the tack force reducing effect is very effectively exhibited by containing a small amount of the fatty acid amide compound having a molecular weight of 400 or more in spite of the composition containing a large amount of.

Each configuration and a combination thereof in each embodiment are examples, and the configurations can be added, omitted, replaced, and other changes without departing from the spirit of the present invention. Moreover, the present invention is not limited to each embodiment, but is limited only to the scope of the claims.

The present invention can provide a thermoplastic elastomer composition having a reduced surface tack force when made into a cured product, and a method for producing the thermoplastic elastomer composition.

Claims (12)

A polymer (A) having a side chain (a) containing a hydrogen-binding 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 the polymer (B) containing a sex-linking site and a covalently-binding cross-linking site and having a glass transition point of 25 ° C. or lower,
Contains fatty acid amide compounds,
A thermoplastic elastomer composition having a molecular weight of 400 or more of the fatty acid amide compound. 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 heterocycle in the side chain. The thermoplastic elastomer composition according to claim 1 or 2, wherein the ratio of the content of the fatty acid amide compound to 100% by mass of the thermoplastic elastomer composition is 0.1% by mass or more. The thermoplastic elastomer composition according to any one of claims 1 to 3, further comprising a process oil. The thermoplastic elastomer composition according to claim 4, wherein the ratio of the content of the process oil to 100% by mass of the thermoplastic elastomer composition is 30% by mass or more. The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the cured Shore A hardness according to JIS K6253 is 70 or less. The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the polymer (A) and the polymer (B) are polyolefin-based polymers. The dynamic 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 7. The thermoplastic elastomer composition of the description. The polymer component comprises the polymer (B).
The polymer (B) is a polymer having a cyclic acid anhydride group in the side chain, and the polymer (B).
Reacts with the mixed raw material of the compound (I) that reacts with the cyclic acid anhydride group to form a hydrogen-binding cross-linking site and the compound (II) that forms a covalently-bonding cross-linking site, or with the cyclic acid anhydride group. The thermoplastic elastomer composition according to any one of claims 1 to 8, which is a reaction product of a compound capable of forming both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site. The polymer component comprises the polymer (B).
The polymer (B) is a polymer having a cyclic acid anhydride group in the side chain, and the polymer (B).
The heat according to any one of claims 1 to 9, which is a reaction product of a compound capable of forming both a hydrogen-binding cross-linking site and a covalent-bonding cross-linking site by reacting with the cyclic acid anhydride group. Plastic elastomer composition. The polymer having the cyclic acid anhydride group in the side chain is a maleic anhydride-modified polymer.
The 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 contains a nitrogen-containing heterocycle-containing polyol, a nitrogen-containing heterocycle-containing polyamine, and a nitrogen-containing heterocycle-containing compound. The thermoplastic elastomer composition according to claim 9 or 10, which is at least one compound selected from the group consisting of polythiols. The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 11.
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 the following <1> to <3> is obtained, and the polymer and the raw material compound are used. To obtain the polymer component by reacting with
The fatty acid amide compound having a molecular weight of 400 or more is blended with the mixture before the reaction between the polymer and the raw material compound or the mixture after the reaction between the polymer and the raw material compound. A method for producing a thermoplastic elastomer composition, which comprises.
<1> Compound (I), which 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 bonded site.
<3> A compound capable of reacting with the cyclic acid anhydride group to form both a hydrogen-bonding cross-linking site and a covalent-bonding cross-linking site.