WO2018235961A1

WO2018235961A1 - Elastomer composition containing rubber particles and production method therefor

Info

Publication number: WO2018235961A1
Application number: PCT/JP2018/023904
Authority: WO
Inventors: 知野　圭介; 由浩森永; 俊幸堤; 雄介松尾
Original assignee: Ｊｘｔｇエネルギー株式会社
Priority date: 2017-06-23
Filing date: 2018-06-22
Publication date: 2018-12-27

Abstract

An elastomer composition containing rubber particles which is characterized by comprising a matrix and the rubber particles dispersed in the matrix, the matrix comprising: a thermoplastic resin having no crosslinking moiety capable of undergoing chemical bonding; a polymer component, e.g., a polymer (A) which has a side chain (a) comprising a crosslinking moiety capable of undergoing hydrogen bonding and including a carbonyl-containing group and/or a nitrogenous heterocycle and has a glass transition temperature of 25°C or lower; and clay contained in an amount of 20 parts by mass or less per 100 parts by mass of the polymer component.

Description

Rubber particle-containing elastomer composition and method for producing the same

The present invention relates to a rubber particle-containing elastomer composition and a method for producing the same.

A thermoplastic elastomer composition is an industrially very useful material because it melts at its processing temperature during its molding process and can be molded by a known resin molding method. Therefore, in recent years, research on various types of thermoplastic elastomer compositions has been advanced.

For example, JP-A-8-291239 (Patent Document 1) discloses a thermoplastic elastomer composition containing a crystalline polyolefin resin, an olefin rubber, a styrene block copolymer, and a softener. It is done. Further, in JP-A-2016-193970 (Patent Document 2), it has a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring, and has a glass transition point From an elastomeric polymer (A) having a temperature of 25 ° C. or less and an elastomeric polymer (B) having a hydrogen bondable crosslinking site and a covalent crosslinking site in the side chain and having a glass transition temperature of 25 ° C. or less There is disclosed a thermoplastic elastomer composition comprising at least one elastomer component selected from the group consisting of: and a clay having a content ratio of 20 parts by mass or less based on 100 parts by mass of the elastomer component. However, even such conventional thermoplastic elastomer compositions as described in Patent Document 1 and Patent Document 2 are not necessarily sufficient from the viewpoint of reducing the compression set at a higher level.

JP-A-8-291239 JP, 2016-193970, A

The present invention has been made in view of the problems of the prior art, and provides a rubber particle-containing elastomer composition capable of reducing compression set at a higher level, and such a rubber particle-containing elastomer An object of the present invention is to provide a method for producing a rubber particle-containing elastomer composition capable of efficiently producing the composition.

As a result of intensive studies to achieve the above object, the present inventors have found that a thermoplastic resin having no chemically bondable crosslinking site and a hydrogen bondable bridge having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring. (A) having a side chain (a) containing a site and having a glass transition temperature of 25 ° C. or less, and a side chain containing a hydrogen bondable crosslinking site and a covalent crosslinking site and a glass Containing at least one polymer component selected from the group consisting of polymer (B) having a transition point of 25 ° C. or less; and clay having a content ratio of 20 parts by mass or less based on 100 parts by mass of the polymer component A rubber particle-containing elastomer composition containing a matrix which is obtained by the above method and rubber particles dispersed in the matrix, it is possible to reduce the compression set at a higher level. Found that, it has led to the completion of the present invention.

That is, the rubber particle-containing elastomer composition of the present invention contains a matrix and rubber particles dispersed in the matrix, and
A thermoplastic resin wherein the matrix does not have a chemically bondable crosslinking site;
Polymer (A) having a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or less, and hydrogen bond to the side chain At least one polymer component selected from the group consisting of a polymer (B) containing an anionic crosslinking site and a covalent crosslinking site and having a glass transition temperature of 25 ° C. or less
Clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component,
Containing
It is characterized by

The method for producing a first rubber particle-containing elastomer composition of the present invention (first method) comprises
A rubber particle-containing thermoplastic elastomer (I) containing a thermoplastic resin having no chemically bondable crosslinking site and rubber particles;
Polymer (A) having a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or less, and hydrogen bond to the side chain At least one polymer component selected from the group consisting of a polymer (B) containing an anionic crosslinking site and a covalent crosslinking site and having a glass transition temperature of 25 ° C. or less, and 100 parts by mass of the polymer component And a thermoplastic polymer composition (II) comprising a clay having a content ratio of 20 parts by mass or less;
By mixing
Rubber particles containing: thermoplastic resin having no chemically bondable crosslinking site, the polymer component, clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component, and rubber particles It is a method characterized by obtaining an elastomer composition.

The method for producing a second rubber particle-containing elastomer composition of the present invention (second production method) is
A polymer having a cyclic anhydride group in the side chain;
Compound (i) which reacts with the cyclic acid anhydride group to form a hydrogen bondable crosslinking site, and compound which reacts with the compound (i) and the cyclic acid anhydride group to form a covalent crosslinking site (Ii) at least one starting compound of the mixed starting materials;
Clay having a content of 20 parts by mass or less based on 100 parts by mass of the total amount of the polymer and the raw material compound;
A rubber particle-containing thermoplastic elastomer (I) containing a thermoplastic resin having no chemically bondable crosslinking site and rubber particles;
By mixing
The polymer having the cyclic acid anhydride group in the side chain is reacted with the raw material compound to have a side chain (a) having a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring. And a polymer (A) having a glass transition temperature of 25 ° C. or less, and a polymer having a hydrogen bonding crosslinking site and a covalent crosslinking site in the side chain and having a glass transition temperature of 25 ° C. or less (B) Form at least one polymer component selected from the group consisting of
Rubber particles containing: thermoplastic resin having no chemically bondable crosslinking site, the polymer component, clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component, and rubber particles It is a method characterized by obtaining an elastomer composition.

The third method for producing a rubber particle-containing elastomer composition of the present invention (third method) is
A polymer having a cyclic anhydride group in the side chain;
Compound (i) which reacts with the cyclic acid anhydride group to form a hydrogen bondable crosslinking site, and compound which reacts with the compound (i) and the cyclic acid anhydride group to form a covalent crosslinking site (Ii) at least one starting compound of the mixed starting materials;
Clay having a content of 20 parts by mass or less based on 100 parts by mass of the total amount of the polymer and the raw material compound;
A thermoplastic resin having no chemically bondable crosslinking site;
A diene rubber having no hydrogen bondable crosslinking site;
At least one crosslinker selected from the group consisting of peroxide crosslinkers, phenolic resin crosslinkers, sulfur crosslinkers and silane crosslinkers;
By mixing
The polymer having the cyclic acid anhydride group in the side chain is reacted with the raw material compound to have a side chain (a) having a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring. And a polymer (A) having a glass transition temperature of 25 ° C. or less, and a polymer having a hydrogen bonding crosslinking site and a covalent crosslinking site in the side chain and having a glass transition temperature of 25 ° C. or less (B) And at least one polymer component selected from the group consisting of: a rubber comprising a crosslinked product of a diene rubber by reacting the diene rubber not having the hydrogen bondable crosslinking site with the crosslinking agent. Form particles,
Rubber particles containing: thermoplastic resin having no chemically bondable crosslinking site, the polymer component, clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component, and rubber particles It is a method characterized by obtaining an elastomer composition.

The fourth method for producing a rubber particle-containing elastomer composition of the present invention (fourth production method) is
A thermoplastic resin having no chemically bondable crosslinking site;
A diene rubber having no hydrogen bondable crosslinking site;
At least one crosslinker selected from the group consisting of peroxide crosslinkers, phenolic resin crosslinkers, sulfur crosslinkers and silane crosslinkers;
Polymer (A) having a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or less, and hydrogen bond to the side chain At least one polymer component selected from the group consisting of a polymer (B) containing an anionic crosslinking site and a covalent crosslinking site and having a glass transition temperature of 25 ° C. or less, and 100 parts by mass of the polymer component And a thermoplastic polymer composition (II) comprising a clay having a content ratio of 20 parts by mass or less;
By mixing
The diene rubber having no hydrogen bondable crosslinking site is reacted with the crosslinking agent to form a rubber particle comprising a crosslinked product of diene rubber,
Rubber particles containing: thermoplastic resin having no chemically bondable crosslinking site, the polymer component, clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component, and rubber particles It is a method characterized by obtaining an elastomer composition.

According to the present invention, a rubber particle-containing elastomer composition capable of reducing compression set at a higher level, and a rubber particle capable of efficiently producing such a rubber particle-containing elastomer composition It becomes possible to provide a method for producing a containing elastomeric composition.

3 is a transmission electron micrograph (TEM photograph: 3000 × magnification) of a cross section of the rubber particle-containing elastomer composition obtained in Example 1. It is a transmission electron micrograph (TEM photograph: 10000 times of magnification) which expands and shows a part of cross section of the rubber particle containing elastomer composition shown in FIG.

Hereinafter, the present invention will be described in detail in line with its preferred embodiments.

[Rubber particle-containing elastomer composition]
The rubber particle-containing elastomer composition of the present invention contains a matrix and rubber particles dispersed in the matrix, and the matrix does not have a chemically bondable crosslinking site; Polymer (A) having a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or less, and hydrogen bond to the side chain At least one polymer component (more preferably a carbonyl-containing group and selected from the group consisting of polymers (B) containing a reactive crosslinking site and a covalent crosslinking site and having a glass transition temperature of 25 ° C. or less) And / or an elastomeric polymer (A) having a side chain (a) containing a hydrogen bonding crosslinking site having a nitrogen-containing heterocycle and having a glass transition temperature of 25 ° C. or less And at least one elastomer selected from the group consisting of an elastomeric polymer (B) having a hydrogen bonding crosslinking site and a covalent crosslinking site in the side chain and having a glass transition temperature of 25 ° C. or less Component) and clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component (when the polymer component is the elastomer component, 100 parts by mass of the elastomer component); It is characterized by a certain thing.

(Thermoplastic resin which does not have a chemically bondable crosslinking site)
Such a thermoplastic resin is a component contained in the matrix and has no chemically bondable crosslinking site. Here, “chemically linked crosslinking site” refers to hydrogen bond, covalent bond, chelation between metal ion and polar functional group, σ-π interaction between metal-unsaturated bond (double bond, triple bond) It refers to a site where a crosslink is formed by a chemical bond such as a bond formed. Therefore, in the present specification, "having no chemically bondable crosslinking site" means hydrogen bond, covalent bond, chelation between metal ion and polar functional group, metal-unsaturated bond (double bond, triple bond) It means that it does not have a chemical bond formed by the bond etc. formed by the σ-π interaction between them.

As a thermoplastic resin which does not have such a chemically bondable crosslinking site, a functional group (for example, a hydroxyl group, a carbonyl group, a carboxyl group, a thiol group, an amide group, an amino group, or the like) which forms a crosslinking point by chemical bonding Those which do not contain a group) and do not contain a binding site (such as a crosslinking site by covalent bond) which directly crosslinks polymer chains are preferably used. In addition, the thermoplastic resin which does not have such a chemically bondable crosslinking site is at least a side chain (a), a side chain (a '), a side chain (b), a side chain (c) etc. It can be said that it is a thermoplastic resin not possessed.

As such a thermoplastic resin, it is preferable that it is polyolefin which does not have a chemically bondable crosslinking site. Such a polyolefin is not particularly limited, but is preferably an α-olefin resin (homopolymer of α-olefin, copolymer of α-olefin). The term "alpha-olefin" as used herein refers to an alkene having a carbon-carbon double bond at the alpha position (alkenes having a carbon-carbon double bond at the end: such alkenes may be linear It may be branched, and preferably has 2 to 20 (more preferably 2 to 10) carbon atoms), for example, ethylene, propylene, 1-butene, 1-pentene, 1 -Hexene, 1-Heptene, 1-octene, 1-nonene, 1-decene and the like.

Such a thermoplastic resin is not particularly limited, and a known thermoplastic resin can be appropriately used (for example, a thermoplastic resin used for a so-called dynamic cross-linked thermoplastic elastomer (TPV: Thermo Plastic Vulcanizate) is appropriately used. Available). As such a thermoplastic resin, polyethylene and polypropylene are preferable and polypropylene is particularly preferable from the viewpoint of flowability, heat resistance and availability.

Moreover, it does not restrict | limit especially as such a polypropylene, Well-known polypropylene can be utilized suitably. The preparation method of such a polypropylene is not particularly limited, and a method of polymerizing by a known polymerization method can be appropriately adopted. Such polypropylene may be a copolymer of propylene with an α-olefin such as ethylene, butene-1, pentene-1, 4-methylpentene-1.

Moreover, as a thermoplastic resin in such a matrix, from the viewpoints of fluidity, heat resistance, availability, and compatibility, polypropylene and polypropylene; from among polyethylene, ethylene-propylene copolymer and ethylene-butene copolymer More preferably, at least one selected from: and is contained in combination.

Furthermore, as a thermoplastic resin which does not have such a chemically bondable crosslinking site, a commercial item may be suitably used. As such commercial products, for example, trade name "Sun Aroma" manufactured by Sun Aroma, trade name "Novatec PP" manufactured by Japan Polypropylene, trade name "Prime Polypro" manufactured by Prime Polymer, etc. may be mentioned. In addition, a rubber particle-containing thermoplastic elastomer (I) (which will be described later) containing a rubber particle and a thermoplastic resin having no chemically bondable crosslinking site at the time of production is used as a result. In the rubber particle-containing elastomer composition of the present invention, “a thermoplastic resin having no chemically bondable crosslinking site” may be contained. In addition, the thermoplastic resin which does not have such a chemically bondable crosslinking site (however, except for the later-mentioned "styrene block copolymer which does not have a chemical bondable crosslinking site") is one kind alone. You may use or you may use it in combination of 2 or more types.

(Polymer component)
The polymer component is a component contained in a matrix, and is at least one selected from the group consisting of the polymers (A) to (B) described above. In such polymers (A) to (B), the “side chain” refers to the side chain and the end of the polymer (when the polymers (A) to (B) are elastomeric polymers, elastomeric polymers). . In addition, “a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle” means that the polymer (when the polymers (A) to (B) are elastomeric polymers) A carbonyl-containing group as a hydrogen-bondable crosslinking site and / or a nitrogen-containing heterocycle (more preferably a carbonyl-containing group and a nitrogen-containing heterocycle) at an atom (usually a carbon atom) forming the main chain of the elastomeric polymer) Means a chemically stable bond (covalent bond). In addition, “a side chain containing a hydrogen bonding crosslinking site and a covalent bonding crosslinking site” means a side chain having a hydrogen bonding crosslinking site (hereinafter, for convenience, sometimes referred to as “side chain (a ′)” And a hydrogen bonding crosslinking site to the side chain of the polymer by including both side chains having a covalent crosslinking site (hereinafter, for convenience, sometimes referred to as “side chain (b)”). And a side chain having both a hydrogen bonding crosslinking site and a covalent crosslinking site (in one side chain a hydrogen bonding crosslinking site and a covalent bonding site, as well as when both a covalent crosslinking site are contained) Side chain containing both crosslinking sites: Hereinafter, by including such a side chain for convenience, sometimes referred to as “side chain (c)”, a hydrogen bondable crosslinking site and a covalent bond can be formed on the side chain of the polymer In the concept including the case where both of the binding crosslinking sites are contained is there. Here, as such a polymer component, an elastomer having a side chain (a) containing a hydrogen bonding crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring, and having a glass transition point of 25 ° C. or less Polymer (A), and an elastomeric polymer (B) having a hydrogen bondable crosslinking site and a covalent crosslinking site in the side chain and having a glass transition temperature of 25 ° C. or less It is preferred to be at least one elastomer component. That is, in such a polymer component, it is preferable that the polymer (A) is the elastomeric polymer (A), and the polymer (B) is the elastomeric polymer (B). An elastomer component suitable as such a polymer component is the same as the elastomer component described in Japanese Patent No. 5918878, and those described in paragraph [0032] to paragraph [0145] of the same publication can be suitably used. .

Moreover, the main chain (polymer forming the main chain portion) of such a polymer component (the polymers (A) to (B)) is a generally known natural polymer or synthetic polymer, and its glass It is not particularly limited as long as it has a transition point of a polymer at room temperature (25 ° C.) or less. As main chains of such polymers (A) to (B), diene rubbers, hydrogenated products of diene rubbers, olefin rubbers, polystyrene polymers which may be hydrogenated (preferably polystyrene polymers) are preferable. Elastomeric polymer), polyolefin-based polymer (preferably high density polyethylene (HDPE), polyolefin-based elastomeric polymer), polyvinyl chloride-based polymer (preferably polyvinyl chloride-based elastomeric polymer), polyurethane-based polymer (preferably polyurethane) Based on at least one selected from an elastomeric polymer (based on elastomeric polymer), a polyester based polymer (preferably based on polyester based elastomeric polymer), and a polyamide based polymer (preferably based on a polyamide based elastomeric polymer) Preferred. Examples of such polyolefin polymers include low density polyethylene (LDPE), high density polyethylene (HDPE), linear polyethylene (LLDPE), and polypropylene. Also, from the viewpoint that there is no aging-prone double bond as the main chain of such polymer components (the polymers (A) to (B)), hydrogenated products of diene-based rubbers, olefin-based rubbers, polyolefins From the viewpoint of low cost and high reactivity (having many double bonds capable of reacting with a compound such as maleic anhydride), diene based rubbers are preferred.

Furthermore, when the polymer component is the elastomeric polymers (A) to (B), the main chain (polymer forming the main chain portion) of such elastomeric polymers (A) to (B) is generally Known natural polymers or synthetic polymers which are elastomeric polymers having a glass transition temperature of room temperature (25 ° C.) or less (as long as they consist of so-called elastomers), It is not particularly limited. As the main chain (polymer forming the main chain portion) of such elastomeric polymers (A) to (B), known elastomeric polymers having a glass transition temperature of room temperature (25.degree. C.) or less (e.g. No. 5,918,878) can be appropriately used.

Furthermore, as main chains of the elastomeric polymers (A) to (B) suitable as such polymer components, diene rubbers, hydrogenated products of diene rubbers, olefin rubbers, optionally hydrogenated polystyrenes At least one selected from an elastomeric polymer, a polyolefin-based elastomeric polymer, a polyvinyl chloride-based elastomeric polymer, a polyurethane-based elastomeric polymer, a polyester-based elastomeric polymer, and a polyamide-based elastomeric polymer is preferred. Moreover, as the main chain of the above-mentioned elastomeric polymers (A) to (B) suitable as such a polymer component, from the viewpoint that there is no aging-prone double bond, hydrogenated products of diene rubbers, olefins A rubber is preferred, and a diene rubber is preferred from the viewpoint of low cost and high reactivity (having a large number of double bonds capable of reacting with a compound such as maleic anhydride). When an olefin rubber is used in the main chains of the elastomeric polymers (A) and (B), the deterioration of the composition tends to be sufficiently suppressed since no double bond is present.

Among these, polyethylene (more preferably high density polyethylene (HDPE)), ethylene-butene copolyester, as the main chain of such a polymer component, from the viewpoint that compression set can be reduced without reducing fluidity. It is more preferable that it is at least one selected from the group consisting of a polymer, an ethylene-propylene copolymer, an ethylene-octene copolymer, and polypropylene, polyethylene (more preferably high density polyethylene (HDPE)), Particularly preferred is at least one selected from the group consisting of ethylene-butene copolymers. In addition, the high density polyethylene said here means polyethylene with a density of 0.93 g / cm ³ or more.

Moreover, as such a polymer component (more preferably, an elastomer component), one of the polymers (A) to (B) (more preferably, elastomeric polymers (A) to (B)) is used alone Or a mixture of two or more. Further, the glass transition point of such polymers (A) to (B) (more preferably, the above-mentioned elastomeric polymers (A) to (B)) is 25 ° C. or less as described above. When the polymers (A) to (B) are elastomeric polymers, they exhibit rubbery elasticity at room temperature. Further, in the present invention, the “glass transition point” is a glass transition point measured by differential scanning calorimetry (DSC-differential scanning calorimetry). In the measurement, the temperature rising rate is preferably 10 ° C./min.

Further, the polymers (A) to (B) (more preferably, the above-mentioned elastomeric polymers (A) to (B)) have a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring as a side chain as described above. A side chain (a) containing a hydrogen bonding crosslinking site; a side chain (a ') containing a hydrogen bonding crosslinking site; and a side chain (b) containing a covalent crosslinking site; and a hydrogen bonding crosslinking site And at least one of side chains (c) containing a covalent crosslinking site. In the present invention, it can be said that the side chain (c) is a side chain which functions as the side chain (a ') and also functions as the side chain (b). Each side chain is described below.

<Side chain (a ′): side chain containing a hydrogen bondable crosslinking site>
The side chain (a ′) containing a hydrogen bondable crosslinking site has a group capable of forming a crosslink by a hydrogen bond (eg, a hydroxyl group, a hydrogen bondable crosslinking site contained in the side chain (a) described later, etc.) The side chain may be any side chain that forms a hydrogen bond based on the group, and the structure is not particularly limited. Here, the hydrogen bonding crosslinking site is a site that crosslinks polymers (more preferably, elastomers) by hydrogen bonding. Note that crosslinking by hydrogen bonding includes a hydrogen acceptor (a group containing an atom containing a lone electron pair, etc.) and a hydrogen donor (a group with a hydrogen atom covalently bonded to an atom having a high electronegativity etc.) As it is formed for the first time, no crosslinking by hydrogen bonding is formed if both a hydrogen acceptor and a hydrogen donor are not present between side chains of polymers (more preferably, elastomers). Therefore, a hydrogen bonding crosslinking site is present in the system only when both a hydrogen acceptor and a hydrogen donor are present between side chains of polymers (more preferably, elastomers). In the present invention, between the side chains of polymers (more preferably, elastomers), a portion that can function as a hydrogen acceptor (such as a carbonyl group) and a portion that can function as a hydrogen donor (such as a hydroxyl group) It is possible to judge that the moiety capable of functioning as a hydrogen acceptor of the side chain and the functionality capable of functioning as a donor are hydrogen-bondable crosslinking sites by the presence of both of).

From the viewpoint of forming a stronger hydrogen bond, a side chain (a) described later is more preferable as the hydrogen bonding crosslinking site in such side chain (a ′). From the same point of view, the hydrogen bonding crosslinking site in the side chain (a ′) is more preferably a hydrogen bonding crosslinking site having a carbonyl-containing group and a nitrogen-containing heterocyclic ring.

<Side chain (a): side chain containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle
The side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring may be any one having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring, and other structures are particularly preferred It is not limited. As such a hydrogen bondable crosslinking site, one having a carbonyl-containing group and a nitrogen-containing heterocyclic ring is more preferable.

Such a carbonyl-containing group is not particularly limited as long as it contains a carbonyl group, and specific examples thereof include an amide, an ester, an imide, a carboxy group, a carbonyl group and the like. Such a carbonyl-containing group may be a group introduced into the main chain (polymer of main chain portion) using a compound capable of introducing a carbonyl-containing group into the main chain. The compound which can introduce such a carbonyl-containing group into the main chain is not particularly limited, and specific examples thereof include ketones, carboxylic acids and derivatives thereof. In addition, as a compound which can introduce carbonyl containing groups, such as such carboxylic acid and its derivative (s) into the said principal chain, it is a well-known thing (For example, the thing as described in stage-of patent 5918878-[0053] Etc. can be used as appropriate. Moreover, as a compound which can introduce such a carbonyl group (carbonyl-containing group), cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride and the like are preferable, and maleic anhydride is particularly preferable. .

When the side chain (a) has a nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring may be introduced into the main chain directly or through an organic group, and the configuration thereof is particularly limited. It is not a thing. As such a nitrogen-containing heterocyclic ring, as long as it contains a nitrogen atom in the heterocyclic ring, one having a hetero atom other than a nitrogen atom in the heterocyclic ring, for example, a sulfur atom, an oxygen atom, or a phosphorus atom may be used it can. Here, when a nitrogen-containing heterocyclic ring is used in the side chain (a), a hydrogen bond forming a crosslink becomes stronger when having a heterocyclic structure, and thus the thermoplastic elastomer composition of the present invention obtained. It is preferable because tensile strength is further improved. As such a nitrogen-containing heterocyclic ring, known ones (for example, those described in paragraphs [0054] to [0067] of Japanese Patent No. 5918878) can be appropriately used.

Such nitrogen-containing heterocycles are excellent in recyclability, compression set, hardness and mechanical strength, particularly tensile strength, and thus triazole ring, isocyanurate ring, thiadiazole ring, pyridine ring, imidazole ring, triazine ring and hydantoin It is preferably at least one selected from among rings, and is preferably at least one selected from among a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring and a hydantoin ring.

When both the carbonyl-containing group and the nitrogen-containing heterocycle are included in the side chain (a), the carbonyl-containing group and the nitrogen-containing heterocycle are introduced into the main chain as mutually independent side chains. Although it may be preferable, it is preferable that the carbonyl-containing group and the nitrogen-containing heterocyclic ring be introduced into the main chain as one side chain linked via different groups. Such a side chain (a) may have a structure as described in, for example, paragraphs [0068] to [0081] of Japanese Patent No. 5918878.

Further, as the side chain (a), a cyclic acid anhydride group (more than a functional group) in the polymer (the material for forming the polymer (more preferably the material for forming the elastomeric polymer)) which forms the main chain after the reaction Preferably, the functional group (cyclic group) is formed using a polymer having a maleic anhydride group (a polymer having a cyclic acid anhydride group in a side chain (more preferably, an elastomeric polymer having a cyclic acid anhydride group in a side chain)). An acid anhydride group) is reacted with the cyclic acid anhydride group to form a hydrogen bondable crosslinking site (a compound capable of introducing a nitrogen-containing heterocycle) to form a hydrogen bondable crosslinking site. It is preferable that the side chain of the polymer be a side chain (a). The compound forming such a hydrogen bondable crosslinking site (compound capable of introducing a nitrogen-containing heterocycle) may be the above-mentioned nitrogen-containing heterocycle itself, and reacts with a cyclic acid anhydride group such as maleic anhydride It may be a nitrogen-containing heterocyclic ring having a substituent (eg, a hydroxyl group, a thiol group, an amino group, etc.).

<Side chain (b): side chain containing a covalent crosslinking site>
In the present specification, the “side chain (b) containing a covalent crosslinking site” is a covalent crosslinking site at an atom (usually a carbon atom) forming the main chain of a polymer (more preferably an elastomeric polymer). (By reacting with a “compound forming a covalent bond” such as an amino group-containing compound described later, at least one bond selected from the group consisting of an amide, an ester, a lactone, a urethane, an ether, a thiourethane and a thioether It means that a functional group etc. which can occur has a chemically stable bond (covalent bond). In addition, although the side chain (b) is a side chain containing a covalent bond crosslinking site, it has a group capable of hydrogen bonding while having a covalent bond site, and a hydrogen bond between the side chains In the case of forming a crosslink by the above, it will be used as a side chain (c) described later (note that hydrogen bonds can be formed between side chains of polymers (preferably elastomers)) In the case where both hydrogen donor and hydrogen acceptor are not contained, for example, in the case where only a side chain containing only an ester group (-COO-) is present in the system, an ester group Such groups do not function as hydrogen bondable crosslinking sites because (—COO—) does not form hydrogen bonds in particular, and on the other hand, sites that serve as hydrogen donors for hydrogen bonds, such as carboxy groups and triazole rings. And the water In the case where each side chain of polymers (preferably elastomers) contains a structure having both of the sites to be acceptors, hydrogen bonds are formed between the side chains of polymers (preferably elastomers), For example, an ester group and a hydroxyl group coexist between side chains of polymers (preferably, elastomers), and hydrogen is generated between the side chains by these groups. When a bond is formed, the site forming the hydrogen bond is a hydrogen bondable crosslink site, so the structure of the side chain (b) itself or the structure of the side chain (b) and other side chains It may be used as a side chain (c) depending on the kind of substituent group etc.). In addition, the “covalently crosslinking site” referred to here is a site that crosslinks polymers (preferably, elastomers) by covalent bonding.

The side chain (b) containing such a covalent crosslinking site is not particularly limited, but, for example, a polymer having a functional group in the side chain (a polymer for forming the main chain portion (also, such a functional) As the polymer having a group in the side chain, an elastomeric polymer having a functional group in the side chain is preferable) and a compound that reacts with the functional group to form a covalent crosslinking site (compound that forms a covalent bond) It is preferable to contain the covalent bond crosslinking site formed by reacting with The crosslinking at the covalent crosslinking site of the side chain (b) is formed by at least one bond selected from the group consisting of an amide, an ester, a lactone, a urethane, an ether, a thiourethane and a thioether. Is preferred. Therefore, the functional group contained in the polymer constituting the main chain is a functional group capable of generating at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. Is preferred.

Examples of such a “compound forming a covalent bond crosslinking site (compound forming a covalent bond)” include, for example, two or more amino groups and / or imino groups (both amino and imino groups in one molecule). When it has these, a polyamine compound having a total of two or more of these groups; a polyol compound having two or more hydroxyl groups in one molecule; a polyisocyanate compound having two or more isocyanate (NCO) groups in one molecule; And polythiol compounds having two or more thiol groups (mercapto groups) in the molecule. Here, the “compound forming a covalent bond crosslinking site (compound forming a covalent bond)” is a kind of a substituent that such a compound has, and the degree of progress of the reaction when reacted using such a compound, In some cases, the compound is a compound capable of introducing both the hydrogen bondable crosslinking site and the covalent bond crosslinking site (for example, in the case of forming a covalent bond crosslinking site using a compound having three or more hydroxyl groups). Depending on the degree of progress of the reaction, the two hydroxyl groups react with the functional group of the polymer having a functional group in the side chain (more preferably, the elastomeric polymer having the functional group in the side chain). It also occurs in the case where individual hydroxyl groups remain as hydroxyl groups, in which case a site that forms a hydrogen bondable crosslink can also be introduced. Therefore, the “compound that forms a covalent crosslinking site (compound that forms a covalent bond)” exemplified here also includes “a compound that forms both a hydrogen bonding crosslinking site and a covalent crosslinking site”. obtain. From such a point of view, when the side chain (b) is to be formed, the compound is appropriately selected from the “compound forming the covalent bond crosslinking site (compound forming the covalent bond)” in accordance with the intended design. The side chain (b) may be formed by appropriately controlling the degree of progress of the reaction or the like. In addition, when the compound which forms a covalent bond bridge | crosslinking site has a heterocyclic ring, it becomes possible to manufacture a hydrogen bondable bridge | crosslinking site simultaneously more efficiently, and it becomes as below-mentioned side chain (c), It becomes possible to efficiently form the side chain having the covalent bond crosslink site. Therefore, specific examples of the compound having such a heterocyclic ring 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 also be said to be a suitable form of side chain such as side chain (a) or side chain (b) from the structure.

Examples of the polyamine compound, the polyol compound, the polyisocyanate compound, and the polythiol compound which can be used as such a “compound forming a covalent bond crosslinking site (compound forming a covalent bond)” (for example, for example, Those described in paragraphs [0094] to [0106] of Japanese Patent No. 5918878 can be appropriately used.

In addition, as such “compound forming a covalent bond crosslinking site (compound forming a covalent bond)”, polyethylene glycol lauryl amine (eg, N, N-bis (2-hydroxyethyl) lauryl amine), polypropylene Glycol laurylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (eg, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octyl Amines (eg, N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine For example, N, is preferably N- bis (2-methyl-2-hydroxyethyl) stearylamine).

Examples of the functional group possessed by the polymer constituting the main chain which reacts with such a “compound forming a covalent bond crosslinking site (compound forming a covalent bond)” include amide, ester, lactone, urethane, thiourethane And functional groups capable of generating (forming: forming) at least one bond selected from the group consisting of A thiol group etc. are illustrated suitably.

<Side chain (c): side chain containing both a hydrogen bonding crosslinking site and a covalent crosslinking site>
Such side chain (c) is a side chain containing both a hydrogen bonding crosslinking site and a covalent crosslinking site in one side chain. The hydrogen bonding crosslinking site contained in such a side chain (c) is the same as the hydrogen bonding crosslinking site described in the side chain (a ′), and the hydrogen bonding crosslinking in the side chain (a) The same as the site is preferred. In addition, as the covalent crosslinking site contained in the side chain (c), the same one as the covalent crosslinking site in the side chain (b) can be used (the same suitable crosslinking can also be used. ).

Such a side chain (c) is a polymer having a functional group in a side chain (a polymer for forming the main chain portion: more preferably an elastomeric polymer having a functional group in a side chain), and the functional group The side formed by reacting with a compound that reacts to form both a hydrogen bondable crosslinking site and a covalent bond crosslinking site (a compound that introduces both a hydrogen bondable crosslinking site and a covalent bond crosslinking site) It is preferably a chain.

As a compound which forms both such a hydrogen bondable crosslinking site and a covalent bond crosslinking site (a compound which introduces both a hydrogen bondable crosslinking site and a covalent bond crosslinking site), a heterocycle (particularly preferably a nitrogen-containing compound) is particularly preferable. Compounds having a heterocycle) and capable of forming a covalent crosslinking site (compounds which form 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. In addition, polyols, polyamines and polythiols containing such a heterocycle may form the above-mentioned “covalent bond crosslinking site” except that they have a heterocycle (particularly preferably a nitrogen-containing heterocycle). The same polyol compounds, polyamine compounds and polythiol compounds as described in the section “Compatible Compounds (Compounds that Form a Covalent Bond)” can be appropriately used. In addition, as polyols, polyamines and polythiols containing a heterocycle, known ones (for example, those described in paragraph [0113] of Japanese Patent No. 5918878) can be appropriately used. The above-mentioned main chain is made to react with “a compound that forms both a hydrogen bondable crosslinking site and a covalent bond crosslinking site (a compound that introduces both a hydrogen bondable crosslinking site and a covalent bond crosslinking site)”. The functional group possessed by the polymer is preferably a functional group capable of generating (forming: forming) at least one bond selected from the group consisting of an amide, an ester, a lactone, a urethane, a thiourethane and a thioether. Preferred examples include cyclic acid anhydride group, hydroxyl group, amino group, carboxy group, isocyanate group, thiol group and the like.

(About a structure suitable as a covalent bond crosslinking site in side chains (b) to (c))
In the case of the side chains (b) and / or (c), the crosslink at the covalent bond crosslink contains a tertiary amino bond (-N =), an ester bond (-COO-), When these bonding sites also function as hydrogen bonding crosslinking sites, the reason for the higher compression set and mechanical strength (breaking elongation, breaking strength) of the resulting thermoplastic elastomer (composition) is improved It is preferable from Thus, a tertiary amino bond (-N =) or an ester bond (-COO-) in the side chain having a covalent crosslink site forms a hydrogen bond with the other side chain. In such a case, the covalent bond crosslinking site containing such a tertiary amino bond (-N =) or ester bond (-COO-) is also provided with a hydrogen bondable crosslinking site, and as a side chain (c) It can work.

A compound capable of reacting with a functional group of a polymer constituting the main chain to form a covalent bond crosslinking site containing the tertiary amino bond and / or the ester bond (hydrogen bondable crosslink Examples of compounds capable of forming both a moiety and a covalent crosslinking site include polyethylene glycol lauryl amine (eg, N, N-bis (2-hydroxyethyl) lauryl amine), polypropylene glycol lauryl amine (eg, 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) octyl Min), polyethylene glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine (eg, N, N-bis (2-methyl-2-hydroxyethyl) stearylamine) Can be mentioned as suitable.

The crosslinking at the covalent bond crosslinking site of the side chain (b) and / or the side chain (c) contains at least one structure represented by any one of the following general formulas (4) to (6) Are preferable, and those in which G in the formula contains a tertiary amino bond or an ester bond are more preferable. The chains are those utilized as side chains (c)).

In the above general formulas (4) to (6), E, J, K and L are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) Or a sulfur atom; or an organic group which may contain these atoms or groups, G may contain an oxygen atom, a sulfur atom or a nitrogen atom, and the number of linear, branched or cyclic carbon atoms It is a hydrocarbon group of 1 to 20.

As such substituent G, groups represented by the following general formulas (111) to (114) are preferable, and from the viewpoint of high heat resistance and high strength due to hydrogen bonding, the following general formula (111) And the group represented by the following general formula (112) is more preferable.

Furthermore, in the side chains (b) and (c), the crosslinking at the covalent bond crosslinking site is preferably formed by the reaction of a 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 after reaction has a cyclic acid anhydride group (eg, maleic anhydride group) as a functional group, the cyclic acid anhydride group of the polymer, a hydroxyl group or an amino group, and And / or a compound which forms the covalent bond-forming site having an imino group (compound which forms a covalent bond) is reacted to form a site to be crosslinked by covalent bond to form crosslinks between polymers. It is good also as a bridge.

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

The side chain (a ′), side chain (a), side chain (b) and side chain (c) have been described above, but each group (structure) of the side chain in such a polymer is NMR, It can confirm by the analysis means used normally, such as IR spectrum.

Further, the polymer (A) (preferably, the elastomeric polymer (A)) is a polymer having a glass transition temperature of 25 ° C. or less having the side chain (a) (more preferably, has the side chain (a)) The polymer (B) (preferably the elastomeric polymer (B)) has a hydrogen bondable crosslinking site and a covalent crosslinking site in its side chain. Polymers having a glass transition temperature of 25 ° C. or less (more preferably, an elastomeric polymer having a glass transition temperature of 25 ° C. or less containing a hydrogen bonding crosslinking site and a covalent crosslinking site in the side chain (as a side chain A polymer having both of a side chain (a ′) and a side chain (b), a polymer containing at least one side chain (c) in a side chain, etc.)). As such a polymer component (more preferably, an elastomer component), one of the polymers (A) to (B) (more preferably, the elastomeric polymers (A) to (B)) is used alone. Alternatively, two or more of them may be mixed and used.

The polymer (B) (more preferably, the elastomeric polymer (B)) is a polymer having a side chain (c) even if it is a polymer having both a side chain (a ') and a side chain (b) The hydrogen bond may be formed as a hydrogen bondable crosslinking site contained in the side chain of such polymer (B) (more preferably, the elastomeric polymer (B)). From the viewpoint of the above, a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring (more preferably, a hydrogen-bondable crosslinking site having a carbonyl-containing group and a nitrogen-containing heterocyclic ring) is preferred.

The method for producing such polymers (A) to (B) (more preferably elastomeric polymers (A) to (B)) is not particularly limited, and known methods (for example, described in Japanese Patent No. 5918878). A method (the method described in paragraphs [0139] to [0140], etc.) can be adopted as appropriate. Moreover, as a method for producing such polymers (A) to (B) (more preferably, elastomeric polymers (A) to (B)), for example, functional groups (eg, cyclic acid anhydride group etc.) Using a polymer having a chain (more preferably, an elastomeric polymer having a functional group (such as a cyclic acid anhydride group) in the side chain), the polymer (more preferably the elastomeric polymer) is reacted with the functional group Mixed with the compound forming the hydrogen bondable crosslinking site, the compound reacting with the functional group to form the hydrogen bondable crosslinking site, and the mixed raw material of the compound reacting with the functional group to form the covalent bond crosslinking site A polymer having the side chain (a) (more preferably, an elastomeric polymer having the side chain (a)); ') And a polymer having a side chain (b) (more preferably, an elastomeric polymer having a side chain (a') and a side chain (b)); and / or a polymer having the side chain (c) (more preferably The method may be a method of producing an elastomeric polymer having the side chain (c) (more preferably, a method of producing the elastomeric polymers (A) to (B)). The conditions (temperature conditions, atmosphere conditions, etc.) employed in such a reaction are not particularly limited, and a functional group or a compound to be reacted with the functional group (a compound forming a hydrogen bondable crosslinking site and / or a covalent bond It may be appropriately set according to the type of the compound forming the binding crosslinking site. In the case of the polymer (A) (more preferably, the elastomeric polymer (A)), it may be manufactured by polymerizing a monomer having a hydrogen bonding site.

As a polymer having such a functional group (for example, a cyclic acid anhydride group) in the side chain (more preferably, an elastomeric polymer having a functional group on the side chain), the main chains of the aforementioned polymers (A) to (B) Polymers capable of forming (more preferably, polymers capable of forming the main chain of the above-mentioned elastomeric polymers (A) to (B)), which preferably have a functional group in a side chain . Here, “a polymer having a functional group in a side chain” means a bond in which a functional group (such as the above-mentioned functional group, for example, a cyclic acid anhydride group) is chemically stable at an atom forming the main chain A polymer having a covalent bond) is preferably used, and one obtained by reacting a polymer (for example, known natural polymer or synthetic polymer) with a compound capable of introducing a functional group can be suitably used. In addition, “an elastomeric polymer containing a functional group in a side chain” suitable as a polymer containing such a functional group in a side chain means a functional group (an above-mentioned functional group, etc. (A cyclic acid anhydride group etc.) means a chemically stable bond (covalent bond), and an elastomeric polymer (eg, a known natural polymer or synthetic polymer) and a functional group are introduced. What is obtained by making it react with a compound to be obtained can be used suitably.

In addition, such a functional group is preferably a functional group capable of generating at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether, among which cyclic An acid anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, a thiol group and the like are preferable, and from the viewpoint of being able to disperse the clay more efficiently in the composition, the cyclic acid anhydride group is particularly preferable. preferable. Moreover, as such a cyclic acid anhydride group, a succinic anhydride group, a maleic anhydride group, a glutaric anhydride group, and a phthalic anhydride group are preferable, and among them, they can be easily introduced into polymer side chains and are industrially available Maleic anhydride group is more preferable from the viewpoint that is easy. When the functional group is a cyclic acid anhydride group, for example, compounds capable of introducing the functional group include succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride and derivatives thereof, etc. Cyclic acid anhydrides may be used to introduce functional groups into the polymer (eg, known natural or synthetic polymers, elastomeric polymers being preferred as such polymers).

Also, at least one polymer component selected from the group consisting of such polymers (A) and (B) (more preferably at least one selected from the group consisting of elastomeric polymers (A) and (B) As the kind of elastomer component), it is industrially easy to obtain, and from the viewpoint of being able to have mechanical strength and resistance to compression set in a highly balanced manner,
A polymer having a cyclic acid anhydride group in a side chain (more preferably an elastomeric polymer having a cyclic acid anhydride group in a side chain, still more preferably a maleic anhydride modified elastomeric polymer);
Triazole which may have at least one substituent of hydroxyl group, thiol group and amino group, pyridine which may have at least one substituent of hydroxyl group, thiol group and amino group, Thiadiazole which may have at least one substituent of hydroxyl group, thiol group and amino group, imidazole which may have at least one substituent of hydroxyl group, thiol group and amino group, Isocyanurate which may have at least one substituent of hydroxyl group, thiol group and amino group, triazine which may have at least one substituent of hydroxyl group, thiol group and amino group , Hydantoin optionally having substituent of at least one of hydroxyl group, thiol group and amino group, trishydroxyethyl At least one compound selected from the group consisting of socyanurate, 2,4-diamino-6-phenyl-1,3,5-triazine, pentaerythritol, sulfamide, and polyether polyol (hereinafter referred to simply as “compound ( X) ") and
It is preferable that it is at least one selected from the group consisting of the following: Thus, as the polymers (A) and (B) (more preferably elastomeric polymers (A) and (B)), polymers having the cyclic acid anhydride group in the side chain (more preferably the cyclic acid anhydride) The reaction product of the above-mentioned compound (X) with an elastomeric polymer having a substance group in a side chain, more preferably the above-mentioned maleic anhydride-modified elastomeric polymer) is preferred.

In addition, when a polymer component containing a covalent crosslinking site in a side chain (more preferably, an elastomer component containing a covalent crosslinking site in a side chain) is contained (for example, polymer (B) (more preferably elastomeric polymer (more preferably The present inventors speculate that, in the case where B) is included, the side chain containing the covalent crosslinking site also makes it possible to express a higher level of compression set resistance. Also, when a hydrogen bondable crosslinking site and a covalent bond crosslinking site are present in the polymer component (more preferably the elastomer component) (polymer (B) (more preferably elastomeric polymer (B))) When containing a mixture of polymer (B) (more preferably elastomeric polymer (B)) and another polymer (preferably elastomeric polymer), polymer (A) (more preferably elastomeric polymer (A)) And a mixture of polymer (B) (more preferably elastomeric polymer (B)), side chains other than polymer (A) (more preferably elastomeric polymer (A)) and polymer (B) Polymer having b) (more preferably elastomeric having side chains (b) other than elastomeric polymer (B) When using a mixture with a lymer), etc.), due to the presence of the hydrogen bondable crosslinking site and the covalent bond crosslink site, higher mechanical strength by covalent bond, hydrogen bond by use at the time of use It is also possible to simultaneously develop higher fluidity (moldability) by cleavage at the time of heating. Therefore, the present inventors speculate that the composition can be appropriately changed in accordance with the type of side chain to appropriately exhibit the characteristics according to the application. The polymer having a side chain (b) other than the polymer (B) as described above (more preferably, the elastomeric polymer having a side chain (b) other than the elastomeric polymer (B)) has a functional group (eg cyclic) Using a polymer having an acid anhydride group in a side chain (more preferably, an elastomeric polymer having a functional group (eg, a cyclic acid anhydride group) in a side chain), the polymer (more preferably, the elastomeric polymer) ) Is reacted with the functional group to form a covalent crosslinking site (compound forming a covalent bond), and the polymer having the side chain (b) (more preferably, the side chain (more preferably, the side chain (b)) It is possible to obtain by the method of producing the above-mentioned elastomeric polymer having b). Also in this case, as the compound forming the covalent bond crosslinking site (compound forming the covalent bond), the aforementioned “compound forming the covalent bond crosslinking site (compound forming the covalent bond)” is used can do.

Thus, depending on the type of the polymer component (more preferably, the elastomer component), it is also possible to appropriately impart properties to the composition obtained according to the application. For example, in the case where the polymer (A) is a polymer component (more preferably, when the elastomeric polymer (A) is a polymer component suitable as an elastomer component), the side chain (a) is derived from the composition. In particular, the breaking elongation, the breaking strength and the flowability can be improved. In addition, in the case where the polymer (B) is a polymer component (more preferably, when the elastomeric polymer (B) is a polymer component suitable as an elastomer component), covalent bonds in side chains are included in the composition. In particular, it is possible to improve the resistance to compression set (compression set resistance) because it is possible to impart more properties derived from the crosslinkable sites. In addition, in the case where the polymer (B) is contained as a polymer component (more preferably, when the elastomeric polymer (B) is contained as a suitable elastomer component as a polymer component), covalent crosslinking is caused in the composition. Since the characteristics derived from the hydrogen bondable crosslinking site (the hydrogen bondable crosslinking site described in the side chain (a ')) can also be imparted in addition to the properties derived from the site, the flowability (moldability) is maintained It is also possible to further improve the compression set resistance, and by appropriately changing the type of side chain, the type of polymer (B), etc., it is possible to exhibit desired properties according to the application more efficiently. It also becomes possible.

When the polymer component contains the polymers (A) and (B) (when the polymer component is the elastomer component, it contains the elastomeric polymers (A) and (B) as the elastomer component. In the case where the content ratio of the polymer (A) to the polymer (B) (when the polymer component is the elastomer component, the content ratio of the elastomeric polymer (A) to the elastomeric polymer (B)) is (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 such polymer (A) is less than the above lower limit, the flowability (moldability) and mechanical strength tend to be insufficient, while if it exceeds the above upper limit, the resistance to compression set tends to be reduced. It is in.

When both side chains (a ') and side chains (b) are present in the matrix derived from a polymer component (preferably an elastomer component), the total amount and side of the side chains (a') The total amount of the chain (b) is preferably 1: 9 to 9: 1, and more preferably 2: 8 to 8: 2, based on the mass ratio. If the total amount of such side chains (a ′) is less than the above lower limit, the flowability (formability) and mechanical strength tend to be insufficient, while if it exceeds the above upper limit, the resistance to compression set is lowered. There is a tendency. In addition, such a side chain (a ') is a concept including a 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 preferred.

(Clay)
The clay is not particularly limited, and known clays (for example, those described in paragraph [0146] to paragraph [0156] of Patent No. 5918878) can be appropriately used. Among such clays, at least one selected from the group consisting of clays containing silicon and magnesium as main components, and organized clays is preferable from the viewpoint of high dispersibility. As such a clay, it is particularly preferable to use an organically modified clay because a higher tensile stress (modulus) can be obtained.

The organic clay is not particularly limited, but it is preferable that the clay be organicized by an organic agent. Further, the organic agent is not particularly limited, and a known organic agent capable of organicizing clay (for example, the one described in paragraph [0152] of Japanese Patent No. 5918878) may be appropriately used. Can. Moreover, as such organically modified clay, a quaternary ammonium salt of clay can be suitably used from the viewpoint of single layer dispersibility. The quaternary ammonium salt of such organically modified clay is not particularly limited, and, for example, trimethylstearyl ammonium salt, salt of oleylbis (2-hydroxyethyl), methyl ammonium salt, dimethyl stearyl benzyl ammonium salt, dimethyl octadecyl ammonium salt And mixtures of two or more of these can be suitably used. From the viewpoint of improving tensile strength and heat resistance, dimethyl stearyl benzyl ammonium salt, dimethyl octadecyl ammonium salt, and a mixture thereof can be more suitably used as the quaternary ammonium salt of such organically modified clay, and dimethyl dimethyl is more preferable. A mixture of stearyl benzyl ammonium salt and dimethyl octadecyl ammonium salt can be further suitably used.

(matrix)
The matrix according to the present invention comprises the thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), and the clay.

In addition, the content (content ratio) of the clay in such a matrix is 20 parts by mass with respect to 100 parts by mass of the polymer component (when the polymer component is the elastomer component, 100 parts by mass of the elastomer component) It is below. When the content of such clay exceeds the above upper limit, the tensile properties are degraded. The content of such clay is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component) The amount is more preferably 0.05 to 5 parts by mass, and particularly preferably 0.08 to 3 parts by mass. If the content of such a clay is less than the above lower limit, the content of the clay is too small to obtain sufficient effects, while if it exceeds the above upper limit, the crosslink becomes too strong and the elongation or strength is rather Tend to be difficult to use for various applications (the practicability decreases).

The present inventors speculate that in the matrix, the polymer component (more preferably, the elastomer component) and the clay are in the following state. That is, first, as described above, the polymer component (more preferably, the elastomer component) contains a polymer having a side chain having at least a hydrogen bondable crosslinking site (a side chain (a side chain (a); a side chain (a)) ') And side chain (b); and a polymer containing at least one of side chains (c): as the polymer containing the side chain having the hydrogen bonding crosslinking site, the polymer having the hydrogen bonding crosslinking site Preferred are elastomeric polymers containing side chains). Therefore, when such a polymer (more preferably, an elastomeric polymer) and a clay are combined, first, interaction (for example, formation of a new hydrogen bond) between the clay and a hydrogen bondable crosslinking site is obtained. It is surmised that the surface of the polymer component (more preferably, the elastomer component) is surface-crosslinked using a surface. And if such surface crosslinks are formed, it is guessed that the crosslink point by a covalent bond and a hydrogen bond will be equalized. Thus, the polymer component (more preferably, the elastomer component) and the clay are in a state in which the polymer component (more preferably, the elastomer component) is surface-crosslinked using the surface of the clay, and the matrix The present inventors infer that it exists as a component of

In such a matrix, the content of the thermoplastic resin is 1 to 10000 parts by mass with respect to 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component) Is preferred. If the content of such a thermoplastic resin is less than the above lower limit, the flowability tends to decrease, while if it exceeds the above upper limit, the hardness tends to be too high. From the viewpoint of further improving the 100% modulus and the 300% modulus, the content of the thermoplastic resin is 100 parts by mass of the polymer component (when the polymer component is the elastomer component, 100 mass parts of the elastomer component The amount is more preferably 1 to 900 parts by mass, and further preferably 10 to 800 parts by mass. On the other hand, from the viewpoint that mechanical strength such as breaking strength and breaking elongation is further improved, the content of the thermoplastic resin is 100 parts by mass of the polymer component (when the polymer component is the elastomer component, the elastomer The amount is more preferably 400 to 8000 parts by mass, and still more preferably 500 to 7,000 parts by mass with respect to 100 parts by mass of the component.

In addition, the matrix may contain additives other than the thermoplastic resin, the polymer component (more preferably the elastomer component), and the clay, as needed, as long as the object of the present invention is not impaired. . Such additives are not particularly limited as long as they can be used for a thermoplastic elastomer composition, and can be appropriately used with known additives, for example, the thermoplastic resin And polymers other than the above polymer component (more preferably, the above elastomer component) (for example, styrene block copolymer having no chemically bondable crosslinking site), reinforcing agent (filler), hydrogen bonding reinforcing agent (filled) Agent, a filler obtained by introducing an amino group (hereinafter referred to simply as "amino group introduced filler"), an amino group-containing compound other than the amino group introduced filler, a compound containing a metal element (hereinafter referred to simply as " Metal salt)), maleic anhydride modified polymer, anti-aging agent, antioxidant, pigment (dye), plasticizer (softener), thixotropic agent, UV absorber, flame retardant, solvent, surfactant Agents (including leveling agents), various oils (for example, paraffin oil etc.), dispersants, dehydrating agents, antirust agents, adhesion inhibitors, antistatic agents, fillers, various additives such as fillers, etc. It may be Thus, the additive is not particularly limited, and, for example, slip agents, antioxidants, ultraviolet absorbers, light stabilizers, conductivity imparting agents, antistatic agents, dispersants, flame retardants, antibacterial agents, and the like You may make it contain suitably the well-known additive normally added to rubber | gum, such as a softener, a softener, a filler, a coloring agent, a thermally conductive filler. Such additives and the like are not particularly limited, and those generally used (known ones: for example, those described in paragraphs [0169] to [0174] of Japanese Patent No. 5918878, JP-A-2006-131663, And the like) may be used as appropriate.

When such an additive is included, the total amount of the thermoplastic resin and the polymer component (more preferably, the elastomer component) in the matrix is preferably 1 to 99% by mass, and 10 to 98% by mass. It is more preferable that If the total amount (total amount) of the thermoplastic resin and the polymer component (more preferably, the elastomer component (the polymer (A) and / or the polymer (B))) is less than the lower limit, the polymerizability tends to decrease. On the other hand, if the above upper limit is exceeded, the effect of the additive tends to be insufficient.

Further, the method for incorporating the additive and the like in the matrix is not particularly limited, but, for example, in the case of using the one containing the additive as the "rubber particle-containing thermoplastic elastomer (I)" in the production method described later; In the production process of the present invention, when using those containing the above-mentioned additives as the “thermoplastic polymer composition (II)”; “rubber particle-containing thermoplastic elastomer (I)” and “thermoplastic polymer composition (II)” In the case of using the additives containing the additive and the like in both of the above); the above-mentioned addition when mixing the respective raw materials of “rubber particle-containing thermoplastic elastomer (I)” and “thermoplastic polymer composition (II)” And the like (wherein the thermoplastic polymer composition (II) is a thermoplastic elastomer). Is preferably Narubutsu (II)).

Furthermore, it is preferable that such a matrix further contains a styrene block copolymer having no chemically bondable crosslinking site. As the styrene block copolymer having no such chemically bondable crosslinking site, those described in paragraph [0156] to paragraph [0163] of JP-A 2017-57393 can be suitably used. The "styrene block copolymer" may be a polymer having a styrene block structure at any site.

The styrene block copolymer having no such chemically bondable crosslinking site has a styrene content of 20 to 40% by mass (more preferably 25 to 37% by mass) from the viewpoint of mechanical strength and oil absorption. It is preferable that it is a styrene block copolymer of. Further, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (Mw / Mn) of molecular weight distribution of such a styrene block copolymer are each from the viewpoint of mechanical strength and oil absorbability. Mw is preferably 200,000 or more and 700,000 or less, more preferably 300,000 or more and 600,000 or less, still more preferably 350,000 or more and 550,000 or less, and Mn is preferably 100,000 or more and 600,000 or less. Or less, more preferably 150,000 or more and 550,000 or less, still more preferably 200,000 or more and 500,000 or less, and further preferably Mw / Mn is 5 or less, 1 to More preferably, it is 3. The glass transition temperature of such a styrene block copolymer is preferably −80 to −40 ° C., and more preferably −70 to −50 ° C., from the viewpoint of the elastomeric property. The measuring methods (Mw, Mn, etc.) of such various characteristics adopt the methods described in paragraph [0156] to paragraph [0163] of JP-A-2017-57393.

As a styrene block copolymer having no such chemically bondable crosslinking site, from the viewpoint of coexistence of rubber elasticity and thermoplasticity, styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-propylene- Styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-butadiene-styrene block copolymer (SIBS), and hydrogenated products thereof (so-called hydrogenated products) are preferable, and SEBS and SEEPS are more preferable. Such a styrene block copolymer may be used individually by 1 type, or may be used in combination of 2 or more type. As such a styrene block copolymer, a commercially available thing can be utilized suitably.

The content ratio of such a styrene block copolymer is 1 to 1000 parts by mass with respect to 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component) Is preferable, and 5 to 800 parts by mass is more preferable. If the content ratio is less than the lower limit, oil bleeding tends to occur easily. If the content ratio exceeds the upper limit, moldability tends to decrease.

Moreover, as such a matrix, it is more preferable to further contain paraffin oil. Such paraffin oil is not particularly limited, and any known paraffin oil can be appropriately used. For example, those described in paragraph [0153] to paragraph [0157] of JP-A-2017-57323 are preferably used. Available. In addition, as such paraffin oil, the correlation ring analysis (ndM ring analysis) based on ASTM D3238-85 is performed on the oil, and the percentage of paraffin carbon number to total carbon number (paraffin) Part: CP), naphthene carbon number to total carbon number (naphthene part: CN), and aromatic carbon number to total carbon number (aromatic part: CA), respectively, paraffin carbon number It is preferable that the percentage (CP) to the total carbon number of is 60% or more. In addition, the paraffin oil is flowable, from the viewpoint of safety, is measured according to JIS K 2283 (published in 2000), the kinematic viscosity of ^{^{10mm 2 / s ~ 700mm 2 /}} s at 40 ° C. It is preferably 20 to 600 mm ² / s, more preferably 30 to 500 mm ² / s. Furthermore, the paraffin oil preferably has an aniline point of 80 ° C. to 145 ° C. measured by the U-shaped tube method according to JIS K 2 256 (issued in 2013) from the viewpoint of fluidity and safety. The temperature is more preferably 145 ° C., further preferably 105 to 145 ° C. The kinematic viscosity and the aniline point can be measured by the methods described in paragraph [0153] to paragraph [0157] of JP-A-2017-57323, respectively. As such paraffin oil, a commercially available one can be appropriately used.

The content ratio of such paraffin oil is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component), The amount is more preferably 30 to 900 parts by mass, still more preferably 50 to 800 parts by mass, and particularly preferably 75 to 700 parts by mass. If the content of such paraffin oil is less than the above lower limit, the content of paraffin oil is too small, and in particular, there tends to be no sufficient effect in terms of flowability and processability, and on the other hand, the above upper limit is exceeded And, it tends to be easy to induce the bleeding of paraffin oil.

(Rubber particles)
Such rubber particles are not particularly limited as long as they can be used as so-called thermoplastic elastomers, and known rubber particles can be appropriately used. As such rubber particles, for example, those similar to rubber particles contained as a so-called soft segment in a known dynamic cross-linked thermoplastic elastomer (TPV: Thermo Plastic Vulcanizate) can be appropriately used. As such rubber particles, rubber particles described in, for example, JP-A-8-291239, Patent No. 5661439, etc. may be appropriately used.

The average particle diameter of such rubber particles is preferably 20 μm or less (more preferably 10 μm or less, still more preferably 8 μm or less, particularly preferably 5 μm or less, most preferably 4 μm or less). The average particle diameter of such rubber particles is preferably 0.01 to 20.0 μm (Note that the lower limit of the numerical range of such average particle diameter is preferably 0.1 μm, The upper limit of the numerical range of the average particle diameter is preferably 10.0 μm, more preferably 8.0 μm, and further preferably 0.2 μm, more preferably 0.3 μm, particularly preferably 0.5 μm. Preferably it is 5.0 μm, particularly preferably 4.0 μm, most preferably 3.0 μm). Furthermore, the average particle diameter of such rubber particles is more preferably 0.1 to 10.0 μm, still more preferably 0.3 to 8.0 μm, and further preferably 0.5 to 5.0 μm. Being particularly preferred. If the average particle size is less than the lower limit, the particle size is too small and mixing tends to be difficult, while if it exceeds the upper limit, it tends to be too large to become foreign matter and to deteriorate physical properties such as tensile strength. is there. When the cross section of the composition is observed using an electron microscope (SEM or TEM) as a measuring device, the average particle diameter of such rubber particles is any 30 or more (more preferably 50 or more) in the cross section. It can measure by calculating | requiring the average of the diameter of the rubber particle of. When measuring such an average particle diameter, the diameter of the largest circumscribed circle of the outer shape of the cross section of the particle which can be measured by the cross section observation is adopted as the diameter of the rubber particle (if the cross section is circular, the circle You can measure the diameter). Also, as a specific method of measuring the diameter of each particle, for example, by dragging the portion of the maximum diameter of each particle on the screen from the start point to the end point using the length measuring function of the measuring device According to the method, the diameter may be determined for each particle. Further, the magnification of the electron microscope (SEM or TEM) at the time of measurement of the diameter of each rubber particle may be appropriately changed within a suitable range depending on the size of the rubber particle etc., and it is not particularly limited. However, it is preferable to make it 3000 times or more. In addition, when performing such cross-sectional observation, a sheet is formed using a rubber particle containing elastomer composition (for example, a sheet is formed by a hot press etc.), and a sample piece (finally thickness 10) from the sheet After cutting out an extremely thin section (approximately ultrathin section) of about 300 nm, an ultrathin section is prepared from such a sample piece by a microtome or the like, and the obtained ultrathin section is used as a measurement sample Then, the cut surface (cut surface) at the time of preparation of the section may be measured as a cross section (observation surface) of the composition.

Further, such rubber particles are selected from the group consisting of a diene rubber having no hydrogen bondable crosslinking site, a peroxide crosslinking agent, a phenol resin crosslinking agent, a sulfur crosslinking agent and a silane crosslinking agent. It is preferable to be a crosslinked product of a diene rubber which is a reaction product with at least one crosslinking agent. The dispersion tends to be high by using rubber particles composed of such a diene rubber crosslinked product. Further, such a crosslinked product of a diene rubber is more preferably a reactant (dynamic crosslinked product) by so-called dynamic crosslinking because preparation is easier. In the diene rubber referred to herein, "having no hydrogen bondable crosslinking site" means that there is no site to be crosslinked by hydrogen bonding between diene rubbers and other components. .

The diene-based rubber having no such hydrogen bondable crosslinking site is not particularly limited, and known diene-based rubbers (eg, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1 Known rubbers such as 2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR) and ethylene-propylene-diene rubber (EPDM) It can be used appropriately. As such a diene rubber, ethylene-propylene-diene rubber, natural rubber, butadiene rubber, styrene-butadiene rubber, nitrile butadiene rubber are preferable from the viewpoint of compatibility (dispersibility), ethylene-propylene-diene rubber, natural rubber Styrene-butadiene rubber is more preferred, and ethylene-propylene-diene rubber is even more preferred.

The peroxide-based crosslinking agent used as such a crosslinking agent is not particularly limited, and a crosslinking agent composed of a known peroxide used for a diene rubber crosslinking agent can be appropriately used. As such a peroxide based crosslinking agent, organic peroxides are preferable, and as such organic peroxides, for example, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2 , 5-Dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-bis (t-butyl) Dialkyl peroxides such as peroxyisopropyl) benzene and 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane; t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, n-Butyl-4,4-bis (t-butylperoxy) valerate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexene Peroxy esters such as 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexin-3; diacetyl peroxide, lauroyl peroxide, dibenzoyl peroxide, p-chlorobenzoyl peroxide, And diacyl peroxides such as 4-dichlorobenzoyl peroxide. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 1,3-bis (t-butylperoxyisopropyl) benzene can be suitably used.

When an organic peroxide is used as such a peroxide-based crosslinking agent, the organic peroxide preferably has a half-life temperature of 140 ° C. to 230 ° C. for 1 minute. Examples of organic peroxides that satisfy such conditions include di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl). Peroxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-di (t-) Dialkylperoxides such as hexylperoxy) -3,3,5-trimethylcyclohexane; t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, n-butyl-4,4-bis (t-butylperoxy) ) Valerate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di Peroxy) hexyne-3, and the like.

When using an organic peroxide (a type of peroxide based crosslinking agent) as such a crosslinking agent, a crosslinking assistant may be further blended and used. As such a crosslinking assistant, for example, divinyl compounds such as divinylbenzene; oxime compounds such as p-quinone dioxime, p, p'-dibenzoylquinone dioxime; N-methyl-N-4-dinitrosoaniline , Nitroso compounds such as nitrosobenzene; malereimide compounds such as trimethylolpropane-N, N'-m-phenylenedimaleimide; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate etc. And polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate; and other sulfur, diphenyl guanidine, triallyl cyanurate and the like.

Moreover, as such a peroxide based crosslinking agent, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 3M, P, 25P are preferable from the viewpoint of crosslinking, and dicumyl peroxide is more preferable preferable.

Further, such a phenol resin-based crosslinking agent is not particularly limited, and a crosslinking agent composed of a known phenol resin used for a diene rubber crosslinking agent can be appropriately used. For example, Japanese Patent No. 6000714, US The phenolic resin described in Patent No. 3287440, U.S. Patent No. 3,709,840 and U.S. Patent No. 4,311,628 can be suitably used.

As such a phenol resin based crosslinking agent, for example, a phenol based resin obtained by condensation of a substituted phenol or unsubstituted phenol with an aldehyde (preferably formaldehyde), a substituted phenol or unsubstituted phenol and a difunctional phenol dialcohol And phenolic resins obtained by condensation with these. Further, such substituted phenol is preferably an alkyl group substituted with 1 to 10 carbon atoms. Furthermore, as such a phenol resin-based crosslinking agent, a halogenated phenol resin can also be suitably used.

As such a phenol resin crosslinking agent, a commercially available phenol resin can be appropriately selected and used. As a commercial item which can be used as such a phenol resin type crosslinking agent, for example, tackilol 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), tackilol 250-I (bromine ratio 4% bromine) Alkylphenol formaldehyde resin, made by Taoka Chemical Industry Co., Ltd., Takiroll 250-III (brominated alkylphenol formaldehyde resin, made by Taoka Chemical Industry Co., Ltd.), PR-4507 (made by Gunei Chemical Industry Co., Ltd.) Vulkaresat 510E (Hoechst), Vulkaresat 532E (Hoechst), Vulkaresen E (Hoechst), Vulkaresen 105E (Hoechst), Vulkaresen 130E (Hoech) t), Vulkaresol 315E (Hoechst), Amberol ST 137X (Rohm & Haas), Sumilite resin PR-22193 (Sumitomo Durez Co., Ltd.), Symphorm-C-100 (Anchor Chem.) Symphorm-C-1001 (Anchor Chem.), Tamanol 531 (Arakawa Chemical Co., Ltd.), Schenectady SP 1059 (Schenectady Chem.), Schenectady SP 1045 (Schenectady Chem.), CRR-0803 (U) .C.C), Schenectady SP-1055 (Schenectady Chem.), Schenectady SP-1056 (S) henectady Chem. companies made), CRM-0803 (Showa Union Synthesis Co., Ltd.), Vulkadur A (Bayer Co., Ltd.) and the like. Among these, those which are brominated alkylphenol formaldehyde resins can be preferably used.

Moreover, when using a phenol resin type crosslinking agent as such a crosslinking agent, it is preferable to use this crosslinking agent with an activator. As such an activator, known ones can be appropriately used. For example, stannous chloride, ferric chloride, chlorinated paraffin, halogenated polyethylene such as chlorinated polyethylene, chlorosulfonated polyethylene, and iron oxide Acid acceptors such as titanium oxide, magnesium oxide, silicon dioxide and zinc oxide are used. When the phenolic resin is halogenated, the halogen donor may not be used. When such a halogen donor is used, the addition amount of the halogen donor is preferably 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the diene rubber. It is more preferable that it is a part. When the acid acceptor is used, the addition amount of the acid acceptor is preferably 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, per 100 parts by mass of the diene rubber. Is more preferred.

Furthermore, it does not restrict | limit especially as said sulfur type crosslinking agent, The well-known sulfur type crosslinking agent utilized for the crosslinking agent of diene rubber can be utilized suitably. As such a sulfur-based crosslinking agent, powdered sulfur and oil-treated sulfur are preferable, and oil-treated sulfur is more preferable, from the viewpoint of reactivity.

Further, such a silane crosslinking agent is not particularly limited, and a known silane crosslinking agent used for a diene rubber crosslinking agent can be appropriately used. The silane type crosslinking agent described can be suitably used.

When such a silane-based crosslinking agent is used, a silane compound may be graft-copolymerized to crosslink the diene rubber. As such a silane compound, a compound having both a group capable of reacting with a diene rubber and an alkoxy group forming a crosslink by silanol condensation is preferable. As such a silane compound, for example, vinylsilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N Aminosilane compounds such as -β- (aminoethyl) γ-aminopropyltrimethoxysilane, β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, β- (3, Epoxysilane compounds such as 4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and acrylic silane compounds such as γ-methacryloxypropyltrimethoxysilane And polysulfide silane compounds such as bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and the like Mercaptosilane compounds and the like can be mentioned.

When a silane compound is graft-copolymerized to the diene rubber, a known general method, that is, mixing a predetermined amount of the silane compound and a free radical generator into the diene rubber, A method of melt kneading at temperature may be used. Moreover, as such a silane type crosslinking agent, a polysilane is more preferable from a crosslinkable viewpoint.

Further, among the crosslinking agents such as peroxide type crosslinking agent, phenol resin type crosslinking agent, sulfur type crosslinking agent and silane type crosslinking agent, from the viewpoint of high reactivity, high crosslinking density and high physical properties, Peroxide crosslinking agents and phenol resin crosslinking agents are preferred.

In addition, as a crosslinked product of such diene rubber, the ratio of 0.1 to 10 parts by mass (more preferably 0.1 to 5 parts by mass) of the crosslinking agent is based on 100 parts by mass of the diene rubber. It is preferable that it is used and made to react. If the content (use amount) of such a crosslinking agent is less than the above lower limit, the crosslink density tends to be low and the physical properties tend to be low. There is a tendency.

(Rubber particle-containing elastomer composition)
The rubber particle-containing elastomer composition of the present invention comprises the matrix and rubber particles dispersed in the matrix.

Thus, in the rubber particle-containing elastomer composition of the present invention, the rubber particles are dispersed in the matrix. In other words, in the rubber particle-containing elastomer composition of the present invention, rubber particles are dispersed like an island phase with respect to the sea phase comprising the matrix. Therefore, it can be said that the rubber particle-containing elastomer composition of the present invention has a so-called sea-island structure. Such a dispersed state can be confirmed by electron microscope measurement.

The content of such rubber particles is preferably 1 to 1000 parts by mass (more preferably 10 to 900 parts by mass, still more preferably 20 to 800 parts by mass) with respect to 100 parts by mass of the matrix. If the content of such rubber particles is less than the above lower limit, the effect of the compression set resistance tends to be lowered, while if it exceeds the above upper limit, the thermoplastic property is lowered and the formability tends to be lowered.

In addition, the content of such rubber particles is 1 to 1000 parts by mass (more preferably 10 to 900 parts by mass, further preferably 20 to 800 parts by mass) with respect to 100 parts by mass of the thermoplastic resin. preferable. If the content of such rubber particles is less than the above lower limit, the effect of the compression set resistance tends to be lowered, while if it exceeds the above upper limit, the thermoplastic property is lowered and the formability tends to be lowered.

Furthermore, the content of such rubber particles is preferably 1 to 1000 parts by mass (more preferably 10 parts by mass) with respect to 100 parts by mass of the polymer component (when the polymer component is the elastomer component, 100 parts by mass of the elastomer component). The preferred range is about 900 parts by weight, more preferably 20 to 800 parts by weight. If the content of such rubber particles is less than the above lower limit, the effect of the compression set resistance tends to be lowered, while if it exceeds the above upper limit, the thermoplastic property is lowered and the formability tends to be lowered.

In the present invention, other components that can be used for the thermoplastic elastomer may be appropriately used within the range that does not impair the effects of the present invention (for example, various additives in the matrix as described above) And other components may be contained).

In addition, the rubber particle-containing elastomer composition of the present invention is, for example, an elastomer product for use in any application selected from the group consisting of civil engineering and construction materials, industrial parts, electric and electronic parts and household goods. It can be suitably used as a material or the like. In addition, these applications (the civil engineering / building materials, the industrial parts, the electric / electronic parts, the daily items) are not particularly limited, but for example, various gaskets and sheets for civil engineering / building, gap filling Materials (for example, joint materials), sealing materials for construction, sealing materials for pipe joints, sealing materials for construction sash, piping protection materials, wiring protection materials, heat insulation materials, packing materials, shock absorbing materials, automotive parts (for example, rubber for automobiles described above) Parts, interior and exterior parts of automobiles, constant velocity joint boots, weather strips, dampers, wiper blades, insulating covers, hood seal rubbers, body panels, side shields, packing materials (for automobiles: for example, automobile engine packings), etc. Parts for agricultural machinery, agricultural materials, conveyor belts, contact rubber sheets, electrical insulators, various electrical Equipment housing and internal parts, wire coverings, connectors, caps, plugs, sports and leisure products (fins for swimming, underwater glasses, golf club grips, baseball bat grips, etc.), footwear (shoe soles, sandals, etc.), miscellaneous goods (shoes etc) Packaging materials, garden hoses, anti-slip tapes for stairs, cleaning tools, cosmetics, etc. can be mentioned. Moreover, since the rubber particle-containing elastomer composition of the present invention can reduce the compression set at a higher level compared to the conventional thermoplastic elastomer composition, it is particularly suitable for civil engineering and construction. Various gaskets, building sealing materials, building sash sealing materials, packing materials, shock absorbing materials, automobile parts (for example, the above-mentioned automobile rubber parts, automobile interior / exterior parts, constant velocity joint boots, weather strips, dampers, wiper blades It is particularly useful for applications such as insulation covers, hood seal rubbers, body panels, side shields, packing materials (for automobiles: for example, automobile engine packings).

Although the rubber particle-containing elastomer composition of the present invention has been described above, the method for producing the first to fourth rubber particle-containing elastomer compositions of the present invention will be described below.

[Method of Producing First Rubber Particle-Containing Elastomer Composition (First Method)]
In such a first production method, a thermoplastic resin having no chemically bondable crosslinking site and a rubber particle-containing thermoplastic elastomer (I) containing rubber particles;
Polymer (A) having a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or less, and hydrogen bond to the side chain At least one polymer component (more preferably a carbonyl-containing group and selected from the group consisting of polymers (B) containing a reactive crosslinking site and a covalent crosslinking site and having a glass transition temperature of 25 ° C. or less) And / or an elastomeric polymer (A) having a side chain (a) containing a hydrogen bonding crosslinking site having a nitrogen-containing heterocyclic ring and having a glass transition point of 25 ° C. or less, and a hydrogen bonding crosslinking to the side chain At least one kind of elastomer selected from the group consisting of elastomeric polymers (B) which contain a site and a covalent crosslinking site and have a glass transition temperature of 25 ° C. or less Thermoplastic comprising a tomer component) and clay having a content ratio of 20 parts by mass or less based on 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component) An elastomeric composition (II);
By mixing
The thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), and 100 parts by mass of the polymer component (when the polymer component is the elastomer component, the elastomer component) A rubber particle-containing elastomer composition is obtained, which comprises a clay having a content ratio of not more than 20 parts by mass with respect to 100 parts by mass) and rubber particles. Hereinafter, after explaining each component used for such a 1st manufacturing method, the process employ | adopted by a 1st manufacturing method is demonstrated.

(Rubber particle-containing thermoplastic elastomer (I))
The rubber particle-containing thermoplastic elastomer (I) used in the first production method contains a thermoplastic resin having no chemically bondable crosslinking site and rubber particles. The thermoplastic resin having no chemically bondable crosslinking site and the rubber particles are the same as those described as the components in the rubber particle-containing elastomer composition of the present invention described above. From the viewpoint of flowability, heat resistance and availability, polyethylene and polypropylene are preferred as the thermoplastic resin having no chemically bondable crosslinking site in such elastomer (I), and polypropylene is particularly preferred.

In such rubber particle-containing thermoplastic elastomer (I), the content of the thermoplastic resin is preferably 1 to 99% by mass, and more preferably 5 to 80% by mass. If the content of such a thermoplastic resin is less than the lower limit, the flowability tends not to be sufficiently obtained, while if it exceeds the upper limit, the rubber property tends to be lost.

Further, in such rubber particle-containing thermoplastic elastomer (I), the content of the rubber particles is preferably 1 to 99% by mass, and preferably 10 to 80% by mass. If the content of such rubber particles is less than the above lower limit, the rubber property tends to be low, while if it exceeds the above upper limit, the thermoplasticity (formability) tends to be low. From the same viewpoint, the content of the rubber particles is preferably 1 to 1000 parts by mass (more preferably 10 to 500 parts by mass) with respect to 100 parts by mass of the thermoplastic resin.

Further, as such a rubber particle-containing thermoplastic elastomer (I), one in which rubber particles are dispersed in a thermoplastic resin is preferable. That is, as said rubber particle containing thermoplastic elastomer (I), what has a sea-island structure which makes a thermoplastic resin a matrix (sea phase) and makes a rubber particle an island phase is preferable. The rubber particle-containing thermoplastic elastomer (I) in which rubber particles are dispersed in such a thermoplastic resin is crosslinked to a thermoplastic resin having no chemically bondable crosslinking site (for example, PP, PE, etc.) So-called dynamically crosslinked thermoplastic elastomers (TPV: Thermo Plastic Vulcanizate) in which rubber particles (eg EPDM etc.) are dispersed are preferred.

Further, such rubber particle-containing thermoplastic elastomer (I) may appropriately contain various additives used for the thermoplastic elastomer. Such additives are not particularly limited as long as they can be used for a thermoplastic elastomer composition, and known additives can be appropriately used (additives in the above matrix) The same as described above is preferred). Among the additives that the rubber particle-containing thermoplastic elastomer (I) may contain, a slip agent, an antioxidant, an ultraviolet light absorber, a light stabilizer, a conductivity imparting agent, an antistatic agent, a dispersant, The well-known additive normally added to rubber | gum, such as a flame retardant, a microbicide, a neutralizing agent, a softener, a filler, a coloring agent, a thermally conductive filler, can be used suitably. In addition, when the rubber particle-containing thermoplastic elastomer (I) contains an additive, the content of the additive is 0. 0. 100 parts by mass of the thermoplastic resin having no chemically bondable crosslinking site. The amount is preferably 1 to 100 parts by mass (more preferably 1 to 10 parts by mass).

The method for producing such a rubber particle-containing thermoplastic elastomer (I) (preferably, a dynamically crosslinked thermoplastic elastomer) is not particularly limited, and a known method (for example, a method described in Japanese Patent No. 6000714) may be used. It can be adopted appropriately. As a method of producing such rubber particle-containing thermoplastic elastomer (I), when preparing a dynamically cross-linked thermoplastic elastomer suitable as a rubber particle-containing thermoplastic resin, for example, the chemically bondable crosslinking site is possessed. Thermoplastic resin, diene rubber having no hydrogen bondable crosslinking site, and the crosslinking agent (peroxide crosslinking agent, phenol resin crosslinking agent, sulfur crosslinking agent and silane crosslinking agent) The method of melt-kneading at least 1 sort (s) selected from a group, and making it dynamic-crosslink, and preparing a dynamic-crosslinking-type thermoplastic elastomer can be employ | adopted suitably. In addition, at the time of melt-kneading, according to the design of the object of elastomer (I), you may contain the said additive suitably. Thermoplastic resins not having such chemically bondable crosslinking sites, diene rubbers not having hydrogen bondable crosslinking sites, crosslinking agents (peroxide based crosslinking agents, phenolic resin based crosslinking agents, sulfur based crosslinking agents And at least one selected from the group consisting of silane-based crosslinking agents, and additives are the same as those described for the rubber particle-containing elastomer composition of the present invention above (also preferred examples thereof) The same). When the components are melt-kneaded as described above, it is preferable to mix (knead) using a twin-screw extruder, a screw extruder, a kneader, a Banbury mixer or the like. Moreover, well-known conditions can be suitably employ | adopted as conditions for making it bridge | crosslink dynamically. For example, a method of mixing for 1 minute to 1 hour at a temperature (preferably 100 to 250 ° C.) higher than the melting point of the added resin component may be adopted. The conditions of the shear force applied at this time are not particularly limited, and the conditions may be appropriately set so as to enable dynamic crosslinking, but the shear rate is adjusted to 1 to 100 sec ^-1. It is preferable to do.

In addition, when preparing the dynamically crosslinked thermoplastic elastomer as described above, the amount of the diene rubber used is 1 to 1000 parts by mass (more preferably 10 to 900 parts by mass) with respect to 100 parts by mass of the thermoplastic resin. It is more preferable to set it as a mass part). If the amount of such a diene rubber used is less than the above lower limit, the rubber property tends to be low, while if it exceeds the above upper limit, the thermoplasticity (moldability) tends to be low.

In addition, when preparing a dynamically crosslinked thermoplastic elastomer as described above, the amount of the crosslinking agent used is 0.1 to 20 parts by mass (more preferably 0. 0 to 20 parts by mass) with respect to 100 parts by mass of the diene rubber. More preferably, it is 3 to 15 parts by mass. If the amount of such a crosslinking agent used is less than the above lower limit, the crosslink density tends to be low, while if it exceeds the above upper limit, the crosslink density tends to be too high.

Furthermore, when preparing a dynamically crosslinked thermoplastic elastomer as described above, as an additive, a slip agent, an antioxidant, an ultraviolet light absorber, a light stabilizer, a conductivity imparting agent, an antistatic agent, a dispersant, It is preferable to further use known additives which are usually added to rubber, such as flame retardants, fungicides, neutralizing agents, softeners, fillers, colorants, heat conductive fillers and the like. When such an additive is used, the amount of the additive used (the amount of each additive used when combining a plurality of types) is 0 with respect to 100 parts by mass of the thermoplastic resin. More preferably, the amount is from 1 to 100 parts by mass (more preferably 0.5 to 30 parts by mass). If the amount of such an additive used is less than the lower limit, the effect of the additive tends to be low, while if the amount is more than the upper limit, the effect of the additive tends to be too high.

In addition, as such a rubber particle-containing thermoplastic elastomer (I), any one containing a thermoplastic resin having no chemically bondable crosslinking site and rubber particles may be used, and a commercially available product is appropriately used. You may For example, a commercially available product of the dynamically crosslinked thermoplastic elastomer (TPV) suitable as the rubber particle-containing thermoplastic elastomer (I) (trade name "Milastomer" manufactured by Mitsui Chemicals, Inc .; trade name "Santoprene" manufactured by Exxon Mobil "Geolast", "Trefcine"; trade name "Sumitomo TPE" manufactured by Sumitomo Chemical Co., Ltd .; trade name "Thermoran" manufactured by Mitsubishi Chemical Corp., "Zelas"; trade name "Actymar" manufactured by Riken Technos, etc. You may use suitably.

In the case where the dynamically crosslinked thermoplastic elastomer (TPV) is used as the rubber particle-containing thermoplastic elastomer (I), such a dynamically crosslinked thermoplastic elastomer and a thermoplastic polymer composition (II) described later (II) And the matrix component (including the thermoplastic resin) in the dynamically crosslinked thermoplastic elastomer and the components in the thermoplastic polymer composition (II) described later. It becomes possible to easily manufacture a composition in the state where rubber particles are dispersed in its matrix as a mixture of them and, as a result, efficiently manufacture the rubber particle-containing elastomer composition of the present invention. Is possible.

(Thermoplastic polymer composition (II))
The thermoplastic polymer composition (II) used in the first production method comprises the polymer component (more preferably the elastomer component) and 100 parts by mass of the polymer component (when the polymer component is the elastomer component, the elastomer component) And clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass). In addition, as a thermoplastic polymer composition (II), a thermoplastic elastomer composition (II) comprising the elastomer component and a clay having a content ratio of 20 parts by mass or less based on 100 parts by mass of the elastomer component Is preferred. The polymer component (more preferably, the elastomer component) and the clay in such composition (II) are the same as those described as the components in the rubber particle-containing elastomer composition of the present invention described above (its preferred Conditions are the same).

The content (content ratio) of the clay in such a thermoplastic polymer composition (II) is 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component) In contrast, it is 20 parts by mass or less. When the content of such clay exceeds the above upper limit, the tensile properties are degraded. The content of such clay is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component) The amount is more preferably 0.05 to 5 parts by mass, and particularly preferably 0.08 to 3 parts by mass. If the content of such a clay is less than the above lower limit, the content of the clay is too small to obtain sufficient effects, while if it exceeds the above upper limit, the crosslink becomes too strong and the elongation or strength is rather Tend to be difficult to use for various applications (the practicability decreases). In the thermoplastic polymer composition (II), as described above, the polymer component (more preferably the elastomer component) and the clay are the polymer components (more preferably the elastomer) using the surface of the clay. The present inventors speculate that the component is in a state of surface cross-linking.

In addition, as such clay, clay in the form of a monolayer (clay of monolayer) is present in the thermoplastic polymer composition (II) (more preferably, in the thermoplastic elastomer composition (II)) preferable. The presence of such clay in the form of a monolayer is confirmed by measuring the surface of the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)) by transmission electron microscopy (TEM). You may Furthermore, in the thermoplastic polymer composition (II) of the present invention (more preferably, the thermoplastic elastomer composition (II)), 5.63 μm ² of any three or more points on the surface of the composition (II) When the measurement points of the size are measured by a transmission electron microscope (TEM), 50% or more (more preferably 70% or more, more preferably 80% or more) of the total clay based on the number at all measurement points. 100%, particularly preferably 85 to 100%) are preferably present as monolayer clays. If the content of clay in the single layer is less than the above lower limit, the breaking elongation and breaking strength tend to be reduced. In addition, as a measuring method of the abundance ratio (ratio) of such a clay of a single layer, the method similar to the method described in patent 5918878 is employable. In addition, when clay of a single layer is contained in the above-mentioned ratio (presence ratio) in a composition, clay is more dispersed and contained rather than multilayer clay being dispersed as it is. Since it is in the state (the multilayer clay is decomposed to form a monolayer clay), it is possible to disperse the clay in the composition with higher dispersibility. As described above, when the single layer is present in the above proportion in the composition, the clay has higher dispersibility than the existing in the form of multilayer, and the heat resistance and the breaking strength are higher. It is possible to Therefore, it is more preferable that the clay in a single layer state is contained at the ratio as described above, whereby the clay is more dispersed, and it is possible to more efficiently improve the heat resistance and the breaking strength.

Further, in the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)), measuring points of any three or more points of 5.63 μm ² on the surface of the composition When it is measured by a transmission electron microscope, it is preferable that 1 to 100 (more preferably 3 to 80, still more preferably 5 to 50) particles be dispersed per 1 μm ^{2 at} all measurement points. If the number of clays in such a single layer is less than the above lower limit, the amount of clay is too small, and a sufficient effect tends not to be obtained. In addition, the number of pieces of clay of such a single layer can be calculated | required by confirming a TEM image by the method similar to the measurement of the abundance (rate) of the clay of a single layer.

Moreover, as such a thermoplastic polymer composition (II) (more preferably, a thermoplastic elastomer composition (II)), various additives used for a thermoplastic resin may be suitably contained. Such additives are not particularly limited as long as they can be used for a thermoplastic polymer composition (more preferably, a thermoplastic elastomer composition), and are not particularly limited, and known additives may be appropriately It can be used (preferred to the ones described as additives in the matrix above).

As the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)), it is preferable to further contain a styrene block copolymer having no chemically bondable crosslinking site. Such a styrene block copolymer is the same as that described in the rubber particle-containing elastomer composition of the present invention described above. As for the content ratio of such a styrene block copolymer, 100 parts by mass of the polymer component in the thermoplastic polymer composition (II) (the thermoplastic polymer composition (II) is the thermoplastic elastomer composition (II) Is preferably 1 to 1000 parts by mass, and more preferably 5 to 800 parts by mass with respect to 100 parts by mass of the elastomer component in the thermoplastic elastomer composition (II). If the content ratio is less than the lower limit, oil bleeding tends to occur easily, and if the content ratio exceeds the upper limit, physical properties tend to decrease.

Further, as the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)), one further containing the paraffin oil is preferable. Such paraffin oil is similar to that described in the rubber particle-containing elastomer composition of the present invention described above. As for the content ratio of such paraffin oil, 100 parts by mass of the polymer component in the thermoplastic polymer composition (II) (the thermoplastic polymer composition (II) is the thermoplastic elastomer composition (II) In this case, the amount is preferably 10 to 1000 parts by mass, more preferably 30 to 900 parts by mass, and 50 to 800 parts by mass with respect to 100 parts by mass of the elastomer component in the thermoplastic elastomer composition (II). It is more preferably part, and particularly preferably 75 to 700 parts by mass. If the content of such paraffin oil is less than the above lower limit, the content of paraffin oil is too small, and in particular, there tends to be no sufficient effect in terms of flowability and processability, and on the other hand, the above upper limit is exceeded And, it tends to be easy to induce the bleeding of paraffin oil.

In addition, as the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)), the polymer component (more preferably, the ester component) from the viewpoint of the balance between moldability and mechanical properties. It is more preferable to contain a combination of a styrene block copolymer having no chemically bondable crosslinking site and paraffin oil together with paraffin oil and clay.

The thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)) is an α-olefin having no chemically bondable crosslinking site from the viewpoint of moldability (flowability). It is preferable to further contain a resin. The term "α-olefin resin" as used herein refers to homopolymers of α-olefins and copolymers of α-olefins, and "α-olefins" have a carbon-carbon double bond at the α-position. And alkenes such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. As the α-olefin resin having no such chemically bondable crosslinking site, for example, those described in paragraphs [0204] to [0214] of JP-A-2017-57322 can be suitably used.

In addition, as an α-olefin resin having no such chemically bondable crosslinking site, it becomes a matrix of the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)) From the viewpoint of compatibility with the polymer component (more preferably, the elastomer component), polypropylene, polyethylene, ethylene-propylene copolymer, and ethylene-butene copolymer are preferable. Further, as an α-olefin resin having no such chemically bondable crosslinking site, an α-olefin resin (polypropylene, an ethylene-propylene copolymer, ethylene, etc.) having a degree of crystallinity of 10% or more can be mentioned, among others. -A butene copolymer, polyethylene, polybutene etc. can be used suitably. The method for producing the α-olefin resin having no such chemically bondable crosslinking site is not particularly limited, and a known method can be appropriately adopted. Moreover, as such an α-olefin resin, a commercially available product may be used. The α-olefin resins having no such chemically bondable crosslinking site may be used alone or in combination of two or more.

The content ratio of the α-olefin resin having no such chemically bondable crosslinking site can be appropriately changed according to the intended application and design, and is not particularly limited. For example, the content is 250 parts by mass or less (more preferably 5 to 250 parts by mass, more preferably 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component)) It is more preferable to use 10 to 225 parts by mass, particularly preferably 25 to 200 parts by mass, and most preferably 35 to 175 parts by mass. If the content is less than the lower limit, the flowability tends not to be sufficiently obtained. On the other hand, if the content exceeds the upper limit, the rubber elasticity is reduced and the resin property is increased (the hardness becomes higher than necessary) Tend to

The method for preparing the thermoplastic polymer composition (II) is not particularly limited, and known methods can be appropriately adopted. In addition, the method for preparing the thermoplastic elastomer composition (II), which can be suitably used as such a thermoplastic polymer composition (II), is not particularly limited, and known methods can be suitably adopted, for example, The methods for producing the thermoplastic elastomer composition described in Japanese Patent No. 5918878, Japanese Patent Application Laid-Open No. 2016-193970, Japanese Patent Application Laid-Open No. 2017-057323, International Publication No.

Moreover, as a method for producing such a thermoplastic polymer composition (II) (more preferably, a thermoplastic elastomer composition (II)), among them, a polymer having a cyclic acid anhydride group in a side chain (more preferably a cyclic An elastomeric polymer having an acid anhydride group in a side chain); a compound (i) which reacts with the cyclic acid anhydride group to form a hydrogen bonding crosslinking site; and the compound (i) and the cyclic acid anhydride A raw material compound of at least one of the mixed raw materials of the compound (ii) which reacts with a substance group to form a covalent bond crosslinking site; 100 parts by mass of the total amount of the polymer and the raw material compound And mixing the clay with a content ratio of 20 parts by mass or less with respect to the total of 100 parts by mass of the elastomeric polymer and the raw material compound). By and,
The polymer (A) is obtained by reacting the polymer having the cyclic acid anhydride group in the side chain (more preferably, the elastomeric polymer having the cyclic acid anhydride group in the side chain) and the raw material compound. At least one polymer component (more preferably, the elastomeric polymer (A) selected from the group consisting of the polymer (B), and at least one polymer selected from the group consisting of the elastomeric polymer (B)) Form the elastomeric component)
Clay having a content ratio of 20 parts by mass or less based on the polymer component (more preferably, the elastomer component) and 100 parts by mass of the polymer component (when the polymer component is the elastomer component, 100 parts by mass of the elastomer component) It is preferable to adopt a method of obtaining a thermoplastic polymer composition (II) (more preferably a thermoplastic elastomer composition (II)) comprising

Here, "a polymer having a cyclic acid anhydride group in a side chain" means a polymer having a cyclic acid anhydride group having a chemically stable bond (covalent bond) to an atom forming the main chain of the polymer. For example, those obtained by reacting a polymer capable of forming the main chain portion of the polymers (A) to (B) with a compound capable of introducing a cyclic acid anhydride group are preferable. It can be used to As such a polymer having a cyclic acid anhydride group in a side chain, for example, a polyolefin polymer having a cyclic acid anhydride group in a side chain (eg, high density polyethylene having a cyclic acid anhydride group in a side chain (HDPE) Polypropylene (PP) having cyclic acid anhydride group in side chain, ethylene-propylene copolymer having cyclic acid anhydride group in side chain, ethylene butylene copolymer having cyclic acid anhydride group in side chain, cyclic acid anhydride group The ethylene-octene copolymer which has a side chain, the polyolefin-type elastomeric polymer etc. which have a cyclic acid anhydride group in a side chain etc. are mentioned.

In addition, the “elastomeric polymer having a cyclic acid anhydride group in a side chain, which is suitable as a polymer having a cyclic acid anhydride group in a side chain, has a cyclic acid anhydride group at an atom forming the main chain of the polymer Chemically stable (covalently bonded) elastomeric polymers, such as polymers capable of forming the main chain portion of the above-mentioned elastomeric polymers (A) to (B) What is obtained by making it react with the compound which can introduce an acid anhydride group can be used suitably. As an elastomeric polymer having a cyclic acid anhydride group in a side chain, which is suitable as a polymer having such a cyclic acid anhydride group in a side chain, known ones (for example, paragraph [0183] of Patent No. 5918878) Those described in paragraph [0193] can be used as appropriate. Moreover, as an elastomeric polymer having a cyclic acid anhydride group in a side chain, which is suitable as a polymer having such a cyclic acid anhydride group in a side chain, maleic anhydride modified from the viewpoint of high molecular weight and high strength. Ethylene-propylene rubber and maleic anhydride-modified ethylene-butene rubber are more preferable.

Further, as the compound (i) which reacts with the cyclic acid anhydride group to form a hydrogen bondable crosslinking site, a compound which forms a hydrogen bondable crosslinking site described in the rubber particle-containing elastomer composition of the present invention The same compounds as those capable of introducing a nitrogen-containing heterocyclic ring can be suitably used. For example, the nitrogen-containing heterocycle itself described in the conductive thermoplastic elastomer composition of the present invention may be itself, or a substituent which reacts with the nitrogen-containing heterocycle with a cyclic acid anhydride group such as maleic anhydride. It may be a compound (a nitrogen-containing heterocyclic ring having the above-mentioned substituent) in which (for example, a hydroxyl group, a thiol group, an amino group, etc.) is bonded. In addition, as such a compound (i), a compound which forms both a hydrogen bondable crosslinking site and a covalent bond crosslinking site (it is possible to simultaneously introduce both a hydrogen bondable crosslinking site and a covalent bond crosslinking site The side chain having both a hydrogen bonding crosslinking site and a covalent bonding crosslinking site can be said to be a preferable form of a side chain having a hydrogen bonding crosslinking site.

Further, as the compound (ii) which reacts with the cyclic acid anhydride group to form a covalent crosslinking site, the “compound forming the covalent crosslinking site” described in the rubber particle-containing elastomer composition of the present invention The same compounds as (compound forming a covalent bond) ”can be suitably used (the same as the compound is also preferable).

Moreover, as such a compound (ii), a compound which forms both a hydrogen bondable crosslinking site and a covalent bond crosslinking site (it is possible to simultaneously introduce both a hydrogen bondable crosslinking site and a covalent bond crosslinking site The side chain having both the hydrogen bondable crosslinking site and the covalent bond crosslinking site can be said to be one preferable form of the side chain having the covalent bond crosslinking site. As a compound which forms both of such a hydrogen bondable crosslinking site and a covalent bond crosslinking site, trishydroxyethyl isocyanurate and 2,4-diamino-6-phenyl-1,3,5-triazine are particularly preferable.

As such raw material compounds (compound (i) and compound (ii)), for example, compounds described in paragraphs [0203] to [0207] of Japanese Patent No. 5918878 can be appropriately used. Moreover, as said raw material compound (compound (i) and / or compound (ii)), the above-mentioned compound (X) is more preferable. Furthermore, the addition amount of the compound (i) and the compound (ii) (total amount of them: when only one compound is used, it is the amount of one compound thereof) and the addition method are not particularly limited, It can be set appropriately according to the target design (for example, the design may be changed with reference to paragraphs [0208] to [0210] of Japanese Patent No. 5918878).

Moreover, as such raw material compounds (compound (i) and / or compound (ii)), from the viewpoint of compression set resistance, trishydroxyethyl isocyanurate, sulfamide, pentaerythritol, 2,4-diamino- 6-phenyl-1,3,5-triazine and polyether polyol are preferable, and pentaerythritol, 2,4-diamino-6-phenyl-1,3,5-triazine and trishydroxyethyl isocyanurate are more preferable.

Further, a polymer having the cyclic acid anhydride group in a side chain (more preferably, an elastomeric polymer having the cyclic acid anhydride group in a side chain) and the raw material compound (compound (i) and / or compound (ii)) And 100 parts by mass of the polymer having the cyclic acid anhydride group in the side chain (when the polymer is the elastomeric polymer, 100 parts by mass of the elastomeric polymer). Is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and still more preferably 0.5 to 5.0 parts by mass. If the addition amount (the amount based on the mass part) of such a raw material compound is less than the above lower limit, there is a tendency that the raw material compound is too small to increase the crosslink density and desired physical properties are not expressed. There is a tendency for the number of branches to increase and the crosslink density to decrease.

A polymer having a cyclic acid anhydride group in a side chain (more preferably, an elastomeric polymer having the cyclic acid anhydride group in a side chain) and the raw material compound (compound (i) and / or compound (ii)) When reacted, the cyclic acid anhydride group possessed by the polymer is ring-opened to chemically bond the cyclic acid anhydride group to the raw material compound (the compound (i) and / or the compound (ii)). Thereby, at least one polymer component selected from the group consisting of the polymer (A) and the polymer (B) (more preferably, the elastomeric polymer (A), and the elastomeric polymer (B) At least one elastomeric component selected from the group consisting of There are no particular restrictions on the temperature conditions at which such a polymer and the starting compound (the compound (i) and / or the compound (ii)) are reacted (ring opening of the cyclic acid anhydride group). Depending on the type of cyclic acid anhydride group, the temperature may be adjusted to a temperature at which they can react, for example, from the viewpoint of accelerating the reaction instantaneously by softening, it is preferable to set to 100 to 250 ° C. It is more preferable to set it as 230 degreeC.

Further, the method of such mixing is not particularly limited, and known methods can be appropriately adopted. For example, a method of mixing using a roll, a kneader, an extruder, a universal stirrer or the like can be adopted. Furthermore, the addition order of the respective components is not particularly limited, but from the viewpoint of further improving the dispersibility of the clay, a polymer having a cyclic acid anhydride group in a side chain in advance (more preferably a cyclic acid anhydride group) After plasticizing the elastomeric polymer having a side chain, clay is added to obtain a mixture, and the above-mentioned raw material compound (compound (i) and / or compound (ii)) is added and mixed there Is preferred. In addition, when various additives (such as a styrene block copolymer having no chemically bondable crosslinking site, paraffin oil, an α-olefin resin having no chemical bondable crosslinkable site, etc.) are added. A mixture containing a polymer having the cyclic acid anhydride group in a side chain (more preferably, an elastomeric polymer having the cyclic acid anhydride group in a side chain) so that the clay is sufficiently dispersed, and various additives It is preferable to add clay after preparing in advance, and then to add and mix the raw material compounds (compound (i) and / or compound (ii)). In addition, in the case of such mixing, a polymer having a cyclic acid anhydride group in a side chain (more preferably, an elastomer having a cyclic acid anhydride group in a side chain) from the viewpoint of further improving the dispersibility of clay. Polymer component) and, of the various additives optionally added, are preferably plasticized. The method of such plasticization is not particularly limited, and a known method can be appropriately adopted. For example, a roll, a kneader, or the like at a temperature (for example, about 100 to 250 ° C.) which makes it possible to plasticize these. A method of kneading using an extruder, a universal stirrer or the like can be appropriately adopted. In the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)), the thermoplastic polymer composition (II) containing the polymer (A) as a polymer component (more preferably, it is elastomeric) Thermoplastic elastomer composition (II) having polymer (A) as an elastomer component, and thermoplastic polymer composition (II) having polymer (B) as a polymer component (more preferably elastomer polymer (B)) Thermoplastic polymer composition (II) (II) containing (A) and (B) as polymer components after separately preparing the component thermoplastic elastomer composition (II) and separately mixing them More preferably, heat containing elastomeric polymers (A) and (B) as said elastomeric component It may be plastically elastomer composition (II)).

As mentioned above, although each component utilized for a 1st manufacturing method was demonstrated, the process of a 1st manufacturing method is demonstrated hereafter.

(About the process of the first production process)
In the first production method, by mixing the rubber particle-containing thermoplastic elastomer (I) with the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)); The thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), and 100 parts by mass of the polymer component (when the polymer component is the elastomer component, the elastomer component) A rubber particle-containing elastomer composition is obtained which contains a clay and a rubber particle in a content ratio of 20 parts by mass or less with respect to 100 parts by mass).

The method of mixing the rubber particle-containing thermoplastic elastomer (I) and the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)) is not particularly limited. Known methods and the like can be appropriately adopted. For example, a method of mixing using a roll, a kneader, an extruder, a universal stirrer and the like can be adopted. Moreover, in the case of such a mixing step, the rubber particle-containing thermoplastic elastomer (I) and the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)) are plasticized and mixed. It is preferable to do. The method of such plasticization is not particularly limited, and a known method can be appropriately adopted, and mixing (kneading) under temperature conditions of 100 to 250 ° C. (more preferably 120 to 230 ° C.) is more preferable. If such temperature is less than the lower limit, it tends to be difficult to disperse each component sufficiently (difficult to mix and disperse each component uniformly), while if it exceeds the upper limit, deterioration occurs There is a tendency.

In addition, the mixing ratio of the rubber particle-containing thermoplastic elastomer (I) and the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)) is particularly limited in the mixing step. Although not preferred, the content of the composition (II) relative to 100 parts by mass of the elastomer (I) is preferably 1 to 1000 parts by mass. From the viewpoint of further improving the 100% modulus and the 300% modulus, the content of the composition (II) is 10 to 1000 parts by mass (more preferably 100 to 1000 parts by mass) with respect to 100 parts by mass of the elastomer (I). The content of the composition (II) is preferably 1 to 700 parts by mass with respect to 100 parts by mass of the elastomer (I) from the viewpoint that mechanical strength such as breaking strength and elongation at break is further improved. (More preferably 10 to 500 parts by mass) is more preferable.

Further, in the mixing step, the amount of the rubber particle-containing thermoplastic elastomer (I) used is the same as that in the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)). The amount is preferably 1 to 15000 parts by mass with respect to 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component), and 100% modulus and 300% modulus are From the viewpoint of further improving, 1 to 700 parts by mass (more preferably 10 to 500 parts by mass) is more preferable, and on the other hand, from the viewpoint of improving mechanical strength such as breaking strength and breaking elongation And 1000 to 10000 parts by mass (more preferably 2000 to 9000 parts by mass). It is more preferable.

Furthermore, in the mixing step, the thermoplastic resin in the rubber particle-containing thermoplastic elastomer (I) is 100 parts by mass of the polymer component in the thermoplastic polymer composition (II) (the thermoplastic polymer When the composition (II) is the thermoplastic elastomer composition (II), it is 1 to 10000 parts by mass with respect to 100 parts by mass of the elastomer component in the thermoplastic elastomer composition (II) From the viewpoint of further improving the 100% modulus and the 300% modulus, it is more preferable to mix in an amount of 1 to 900 parts by mass (more preferably 10 to 800 parts by mass). On the other hand, from the viewpoint of further improving the mechanical strength such as the breaking strength and the breaking elongation, To 8000 parts by weight (more preferably from 500 to 7000 parts by weight) and more preferably mixed as a.

By mixing in this manner, a rubber particle-containing elastomer composition containing the thermoplastic resin, the polymer component (more preferably the elastomer component), the clay, and rubber particles can be obtained. When TPV is used as the rubber particle-containing thermoplastic elastomer (I), the thermoplastic resin, the polymer component (more preferably the elastomer component), and the clay are derived from the TPV structure. Thus, the rubber particle-containing elastomer composition of the present invention in which the rubber particles are dispersed in the resulting matrix can be produced more efficiently.

In the rubber particle-containing elastomer composition thus obtained, the thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), the clay, and the rubber particles The content is preferably the same as the content of each component described in the rubber particle-containing elastomer composition of the present invention. When the rubber particle-containing elastomer composition thus obtained is made to contain the additive, the content thereof is the rubber particle-containing elastomer composition of the present invention in the rubber particle-containing elastomer composition finally obtained. It is preferable to adjust suitably so that it may become the quantity similar to content of each component already demonstrated as a component in things. Thus, each component can be easily made into content as above-mentioned by suitably adjusting the usage-amount of the raw material (component) to utilize at the time of manufacture of a rubber particle containing elastomer composition.

In addition, when using what contains the alpha-olefin resin which does not have the said chemically bondable crosslinking site as said thermoplastic polymer composition (II) (more preferably, said thermoplastic elastomer composition (II)) In the rubber particle-containing elastomer composition obtained, since the α-olefin resin having no chemically bondable crosslinking site is a kind of thermoplastic resin having no chemically bondable crosslinkable site, After mixing), the α-olefin resin having no chemically bondable crosslinking site is contained in the rubber particle-containing elastomer composition as one component of the thermoplastic resin. As mentioned above, although the 1st manufacturing method was demonstrated, the 2nd manufacturing method is demonstrated hereafter.

[Method of Producing Second Rubber Particle-Containing Elastomer Composition (Second Method)]
The method for producing a second rubber particle-containing elastomer composition of the present invention (second production method) is
A polymer having a cyclic acid anhydride group in a side chain (more preferably an elastomeric polymer having a cyclic acid anhydride group in a side chain); the compound (i), and the compound (i) and the compound (ii) A total of 100 parts by mass of at least one of the raw material compounds of the mixed raw materials; a total of 100 parts by mass of the polymer and the raw material compound (when the polymer is the elastomeric polymer, a total of 100 mass parts of the elastomeric polymer and the raw material compound Mixing 20 parts by weight or less of clay and rubber particle-containing thermoplastic elastomer (I) containing a thermoplastic resin having no chemically bondable crosslinking site and rubber particles; A polymer having the cyclic acid anhydride group in the side chain (more preferably, an elastomeric polymer having the cyclic acid anhydride group in the side chain) Mer) and reacted with said raw material compound, the polymer component (more preferably forms the elastomer component),
The thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), and 100 parts by mass of the polymer component (when the polymer component is the elastomer component, the elastomer component) A rubber particle-containing elastomer composition is obtained, which comprises a clay having a content ratio of not more than 20 parts by mass with respect to 100 parts by mass) and rubber particles.

A polymer having a cyclic acid anhydride group in a side chain (more preferably, an elastomeric polymer having a cyclic acid anhydride group in a side chain) used in such a second production method, a starting compound (compound (i), a compound (ii) ), Clay and rubber particle-containing thermoplastic elastomer (I) are the same as those described in the first production method (the preferred ones are also the same).

In the second production method, a polymer having the cyclic acid anhydride group in the side chain (more preferably, an elastomeric polymer having the cyclic acid anhydride group in the side chain); the raw material compound; the clay; the rubber The method for mixing the particle-containing thermoplastic elastomer (I) is not particularly limited, and a known mixing method can be appropriately adopted. For example, a method of mixing using a roll, a kneader, an extruder, a universal stirrer, etc. Can be adopted.

Further, in the mixing step of the second production method, the addition order of the respective components is not particularly limited, a method of adding each component once (simultaneously) and mixing, and sequentially adding and mixing each component Method: The polymer having the cyclic acid anhydride group in the side chain (more preferably, the elastomeric polymer having the cyclic acid anhydride group in the side chain) is mixed and reacted with the starting compound, and then other components are mixed. As a result, the method may be such as mixing the respective components. In addition, in such a mixing step, from the viewpoint of further improving the dispersibility of the clay, a polymer having a cyclic acid anhydride group in a side chain (more preferably, an elastomer having a cyclic acid anhydride group in a side chain) It is preferable to add a clay after preparing a mixture of a polymer) and the rubber particle-containing thermoplastic elastomer (I), and then add and mix the raw material compounds. In addition, when various additives (such as a styrene block copolymer having no chemically bondable crosslinking site, paraffin oil, an α-olefin resin having no chemical bondable crosslinkable site, etc.) are added. A polymer having the cyclic acid anhydride group in the side chain (more preferably, an elastomeric polymer having the cyclic acid anhydride group in the side chain) and the rubber particle-containing thermoplastic elastomer (the elastomeric polymer having the cyclic acid anhydride group in the side chain) Preferably, the clay is added after preparing a mixture containing I) and various additives, and then the raw material compounds are added and mixed. In addition, in the case of such mixing, from the viewpoint of further improving the dispersibility of the clay and the viewpoint of sufficiently dispersing the rubber particles, a component to be plasticized (for example, the cyclic acid anhydride group is used as a side chain) It is preferable to plasticize the polymer (more preferably, the elastomeric polymer having a cyclic acid anhydride group in the side chain), the rubber particle-containing thermoplastic elastomer (I), the polymer component in various additives, and the like.

Further, in such a mixing step, the polymer having the cyclic acid anhydride group in the side chain (more preferably, the elastomeric polymer having the cyclic acid anhydride group in the side chain) is reacted with the raw material compound. Thus, the temperature conditions for reacting the polymer having the cyclic acid anhydride group in the side chain (more preferably, the elastomeric polymer having the cyclic acid anhydride group in the side chain) and the raw material compound are the same as described above. It is preferable to set the temperature to 100 to 250 ° C. (more preferably 120 to 230 ° C.) under the same conditions as described in the first production method of From such a viewpoint, a polymer having the cyclic acid anhydride group in a side chain (more preferably, an elastomeric polymer having the cyclic acid anhydride group in a side chain); the raw material compound; the clay; the rubber When mixing the particle-containing thermoplastic elastomer (I), it is preferable to mix under the temperature condition of 100 to 250 ° C. (more preferably 120 to 230 ° C.). By mixing in this manner, the polymer having the cyclic acid anhydride group in the side chain (more preferably, the elastomeric polymer having the cyclic acid anhydride group in the side chain) and the raw material compound (compound (i) and / or By reacting the compound (ii) with the polymer (A), and at least one polymer component selected from the group consisting of the polymer (B) (more preferably, the elastomeric polymer (A)) And at least one elastomer component selected from the group consisting of the above-mentioned elastomeric polymers (B).

In the second production method, the amount of the clay used is the total of 100 parts by mass of the polymer having the cyclic acid anhydride group in the side chain and the raw material compound (compound (i), compound (ii)) (the above When the polymer having a cyclic acid anhydride group in the side chain is an elastomeric polymer having the cyclic acid anhydride group in the side chain, the elastomeric polymer having the cyclic acid anhydride group in the side chain and the starting compound (compound It is necessary to make it 20 mass parts or less with respect to (i) and a total amount of 100 mass parts of compounds (ii)). In such a content ratio, 100 parts by mass of the polymer component (when the polymer component is an elastomer component) in the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)) The content of clay with respect to 100 parts by mass of the elastomer component can be 20 parts by mass or less. In addition, when the usage-amount of such a clay exceeds the said upper limit, a tensile property will fall. The amount of such clay used is a total of 100 parts by mass of the polymer having the cyclic acid anhydride group in the side chain and the raw material compound (a polymer having the cyclic acid anhydride group in the side chain is the cyclic acid anhydride When it is an elastomeric polymer having a side chain, the amount is 0.01 to 10 parts by mass with respect to the total amount of 100 parts by mass of the elastomeric polymer having the cyclic acid anhydride group in the side chain and the raw material compound). Is more preferable, 0.05 to 5 parts by mass is more preferable, and 0.08 to 3 parts by mass is particularly preferable.

In addition, the amounts of the raw material compounds (compound (i) and compound (ii)) used are the same as in the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)) used in the first production method 100 parts by mass of the polymer having the cyclic acid anhydride group in the side chain (the elastomer having the cyclic acid anhydride group in the side chain having the cyclic acid anhydride group in the side chain) for the same reason as the explained reason When it is a hydrophobic polymer, it is preferably 0.1 to 10 parts by mass, preferably 0.3 to 7 parts by mass, with respect to 100 parts by mass of the elastomeric polymer having the cyclic acid anhydride group in the side chain) Is more preferably 0.5 to 5.0 parts by mass.

In the second production method, the amount of the rubber particle-containing thermoplastic elastomer (I) used is the total of the polymer having the cyclic acid anhydride group in the side chain and the raw material compound (mass of polymer component to be obtained) 100 Parts by mass (when the polymer having the cyclic acid anhydride group in the side chain is an elastomeric polymer having the cyclic acid anhydride group in the side chain, an elastomeric polymer having the cyclic acid anhydride group in the side chain and the The amount is preferably 1 to 15,000 parts by mass with respect to 100 parts by mass of the total amount of raw material compounds (the mass of the obtained elastomer component), and from the viewpoint of further improving 100% modulus and 300% modulus, 1 to 700 It is more preferable to use parts by mass (more preferably 10 to 500 parts by mass), and on the other hand, machines such as breaking strength and breaking elongation From the viewpoint of a strength it is further improved, and more preferably to 1,000 to 10,000 parts by weight (more preferably 2,000 to 9,000 parts by weight).

Further, in the mixing step of the second production method, a polymer having the above cyclic acid anhydride group in a side chain (more preferably, an elastomeric polymer having the above cyclic acid anhydride group in a side chain), a raw material compound, clay, etc. It is preferable to use the styrene block copolymer which does not have the said chemically bondable crosslinking site as the said additive with each component of. The addition amount of such a styrene block copolymer is 100 parts by mass of the total amount of the polymer and the raw material compound (the mass of the polymer component to be obtained) (when the polymer is the elastomeric polymer, the elastomeric polymer and The amount is preferably 1 to 1000 parts by mass, and more preferably 10 to 800 parts by mass with respect to the total amount of the raw material compounds (the mass of the obtained elastomer component). If the content ratio is less than the lower limit, oil bleeding tends to occur easily. If the content ratio exceeds the upper limit, mechanical properties such as breaking strength tend to decrease.

Moreover, in the mixing step of the second production method, it is preferable to use the paraffin oil as the additive together with each of the above components. The addition amount of such paraffin oil is 100 parts by mass of the total amount of the polymer having the cyclic acid anhydride group in the side chain and the raw material compound (mass of the polymer component to be obtained) (the cyclic acid anhydride group in the side chain When the polymer having the cyclic acid anhydride group is an elastomeric polymer having a side chain, the total content of the elastomeric polymer having the cyclic acid anhydride group in a side chain and the raw material compound (mass of the obtained elastomer component) 100 Preferably 10 to 600 parts by mass, more preferably 50 to 550 parts by mass, still more preferably 75 to 500 parts by mass, and 100 to 400 parts by mass. Particularly preferred. If the content of such paraffin oil is less than the above lower limit, the content of paraffin oil is too small, and in particular, there tends to be no sufficient effect in terms of flowability and processability, and on the other hand, the above upper limit is exceeded And, it tends to be easy to induce the bleeding of paraffin oil.

In addition, in the mixing step of the second production method, it is preferable to use an α-olefin resin having no chemically bondable crosslinking site as the additive together with the above respective components. The amount of such α-olefin resin added is 100 parts by mass of the total amount of the polymer having the cyclic acid anhydride group in the side chain and the raw material compound (mass of the polymer component to be obtained) (the cyclic acid anhydride group When the polymer having in the side chain is an elastomeric polymer having the cyclic acid anhydride group in the side chain, the total amount of the elastomeric polymer having the cyclic acid anhydride group in the side chain and the raw material compound (elastomer component obtained 250 parts by mass or less (more preferably 5 to 250 parts by mass, still more preferably 10 to 225 parts by mass, particularly preferably 25 to 200 parts by mass, most preferably 35 to 175 parts by mass) per 100 parts by mass) It is more preferable to use it as If the content is less than the lower limit, the flowability tends not to be sufficiently obtained. On the other hand, if the content exceeds the upper limit, the rubber elasticity is reduced and the resin property is increased (the hardness becomes higher than necessary) Tend to

Thus, the polymer having the cyclic acid anhydride group in the side chain (more preferably, the elastomeric polymer having the cyclic acid anhydride group in the side chain); the raw material compound; and the cyclic acid anhydride group The total of 100 parts by mass of the polymer having a side chain and the raw material compound (when the polymer having a cyclic acid anhydride group in a side chain is an elastomeric polymer having a cyclic acid anhydride group in a side chain, the cyclic acid anhydride is The content ratio of 20 parts by mass or less with respect to the total amount of the elastomeric polymer having side groups in the material group and the raw material compound) and the rubber particle-containing thermoplastic elastomer (I); Forming the polymer component (more preferably the elastomer component), the thermoplastic resin, and the polymer component (more preferably the elastomer) A rubber component and a clay having a content ratio of 20 parts by mass or less based on 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component) And rubber particle-containing elastomer compositions can be obtained. In the rubber particle-containing elastomer composition thus obtained, the thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), the clay, and the rubber particles The content is preferably the same as the content of each component described in the rubber particle-containing elastomer composition of the present invention. When the rubber particle-containing elastomer composition thus obtained is made to contain the additive, the rubber particle-containing elastomer composition of the present invention is also contained in the rubber particle-containing elastomer composition finally obtained. It is preferable to adjust suitably so that it may become the quantity similar to content of each component already demonstrated as a component in things. As mentioned above, although 2nd manufacturing method was demonstrated, the 3rd manufacturing method is demonstrated hereafter.

[Method of Producing Third Rubber Particle-Containing Elastomer Composition (Third Method)]
The third method for producing a rubber particle-containing elastomer composition of the present invention (third method) is
A polymer having a cyclic acid anhydride group in a side chain (more preferably, an elastomeric polymer having a cyclic acid anhydride group in a side chain); the compound (i), and the compound (i) and the compound (ii) And 100 parts by mass of the total of the polymer and the raw material compound (when the polymer is the elastomeric polymer, the total amount 100 of the elastomeric polymer and the raw material compound) 20% by mass or less of a clay with respect to the mass part), a thermoplastic resin having no chemically bondable crosslinking site, and a diene rubber having no hydrogen bondable crosslinking site; Agents (at least one selected from the group consisting of peroxide-based crosslinking agents, phenol resin-based crosslinking agents, sulfur-based crosslinking agents, and silane-based crosslinking agents); By case,
The polymer component (more preferably, the elastomer component) is reacted by reacting the polymer having the cyclic acid anhydride group in the side chain (more preferably, the elastomeric polymer having the cyclic acid anhydride group in the side chain) and the raw material compound. Forming a rubber particle comprising a crosslinked product of a diene-based rubber by reacting the diene-based rubber not having the hydrogen bondable crosslinking site with the crosslinking agent.
The thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), and 100 parts by mass of the polymer component (when the polymer component is the elastomer component, the elastomer component) A rubber particle-containing elastomer composition is obtained, which comprises a clay having a content ratio of not more than 20 parts by mass with respect to 100 parts by mass) and rubber particles.

A polymer having a cyclic acid anhydride group in a side chain (more preferably, an elastomeric polymer having a cyclic acid anhydride group in a side chain) used in such a third production method, a starting compound (compound (i), a compound (ii) )), Clay, thermoplastic resin having no chemically bonding crosslinking site, diene rubber having no hydrogen bonding crosslinking site, crosslinking agent (peroxide crosslinking agent, phenol resin crosslinking agent, sulfur system) The crosslinking agent and at least one selected from the group consisting of silane crosslinking agents are the same as those components described in the first production method and the rubber particle-containing elastomer composition of the present invention, respectively. (The preferred one is similar as well).

In addition, in the mixing step of the third production method, the addition order of the respective components is not particularly limited, and a method of adding the respective components once (simultaneously) and mixing them; sequentially adding the respective components and mixing them Method for mixing and reacting other components, after previously mixing and reacting the polymer having the cyclic acid anhydride group in the side chain (more preferably, the elastomeric polymer having the cyclic acid anhydride group in the side chain) and the raw material compound A method of mixing the respective components as a result by mixing; a thermoplastic resin which does not have the crosslinking site of the chemical bonding property in advance, a diene rubber which does not have the hydrogen bonding crosslinking site, and the crosslinking Agent (a peroxide type crosslinking agent, a phenol resin type crosslinking agent, at least one selected from the group consisting of a sulfur type crosslinking agent and a silane type crosslinking agent) is mixed to react the diene rubber with the above-mentioned crosslinking agent After By mixing the ingredients, or a method such as to mix the results in each of the components.

In addition, in the mixing step of the third production method, a known mixing method or the like can be appropriately adopted. Further, in the third production method, the addition order of the respective components is not particularly limited, but from the viewpoint of further improving the dispersibility of clay and from the viewpoint of sufficiently dispersing the formed rubber particles. A polymer having the cyclic acid anhydride group in the side chain (more preferably, an elastomeric polymer having the cyclic acid anhydride group in the side chain), a thermoplastic resin having no chemically bondable crosslinking site, and the hydrogen Diene-based rubber having no bondable crosslinking site; clay; the raw material compound; the crosslinking agent (peroxide-based crosslinking agent, phenolic resin-based crosslinking agent, sulfur-based crosslinking agent, and silane-based crosslinking agent selected from the group consisting of It is preferable to add and mix in order of at least one of In addition, when various additives (a styrene block copolymer having no chemically bondable crosslinking site, paraffin oil, etc.) are added, the additive; a polymer having the cyclic acid anhydride group in a side chain (More preferably, the elastomeric polymer having the cyclic acid anhydride group in the side chain), a thermoplastic resin having no chemically bonding crosslinking site, and a diene rubber having no hydrogen bonding crosslinking site; clay The raw material compound; the crosslinking agent (at least one selected from the group consisting of a peroxide crosslinking agent, a phenol resin crosslinking agent, a sulfur crosslinking agent, and a silane crosslinking agent) are sequentially added and mixed Is preferred. The conditions for the addition amount of the styrene block copolymer having no chemically bondable crosslinking site, paraffin oil, etc. suitable as an additive are preferably the same as those described in the second production method.

Moreover, in such a mixing step, a polymer having the cyclic acid anhydride group in the side chain (more preferably, an elastomeric polymer having the cyclic acid anhydride group in the side chain) is reacted with the raw material compound. Form a polymer component (more preferably an elastomeric component). It is preferable to make it the same as the conditions demonstrated in the said 2nd manufacturing method as conditions of such mixing. Furthermore, in the third production method, in the mixing step, the diene rubber having no hydrogen bondable crosslinking site is reacted with the crosslinking agent to form rubber particles composed of a crosslinked product of the diene rubber. . In such a reaction, mixing may be carried out under such temperature conditions that a crosslinked product of a diene rubber is simultaneously formed, and the polymer having a cyclic acid anhydride group in a side chain (more preferably, the cyclic acid anhydride) The same conditions as the temperature conditions at the time of forming the polymer component (more preferably, the elastomer component) by reacting an elastomeric polymer having a substance group in a side chain with the raw material compound can be suitably used. In the third production method, at least the thermoplastic resin and the hydrogen bondable crosslinking site among the respective components from the viewpoint that the formed rubber particles are sufficiently dispersed in the mixing step. It is preferable to melt-knead and dynamically crosslink the diene rubber which does not have and the crosslinking agent. From the viewpoint of melt-kneading in this way, mixing is preferably carried out using a twin-screw extruder, a screw extruder, a kneader, a Banbury mixer or the like. In addition, well-known conditions (For example, the conditions as described in patent 6000714) can be employ | adopted suitably as conditions for making it dynamically bridge | crosslink. For example, a method of mixing for 1 minute to 1 hour at a temperature (preferably 100 to 250 ° C.) higher than the melting point of the added resin component may be adopted. The shear force applied at this time is also not particularly limited, and conditions may be appropriately set so as to allow dynamic crosslinking, but it is preferable to prepare so that the shear rate is 1 to 100 sec ^-1. .

In the third production method, the amount of the clay used is the total of 100 parts by mass of the polymer having the cyclic acid anhydride group in the side chain and the raw material compound (the polymer having the cyclic acid anhydride group in the side chain 20 parts by mass or less with respect to the total amount of 100 parts by mass of the elastomeric polymer having the cyclic acid anhydride group in the side chain and the raw material compound, when the elastomeric polymer has the cyclic acid anhydride group in the side chain You need to Such a content ratio is the same as the conditions described in the second production method (note that the preferable conditions are also the same).

In the third production method, the amount of the thermoplastic resin used is 100 parts by mass of the total amount of the polymer having the cyclic acid anhydride group in the side chain and the raw material compound (mass of the polymer component to be obtained) When the polymer having an anhydride group in the side chain is an elastomeric polymer having the cyclic acid anhydride group in the side chain, the total amount of the elastomeric polymer and the raw material compound (the mass of the obtained elastomer component) 100 parts by mass) The amount is preferably 1 to 10000 parts by mass, and from the viewpoint of further improving the 100% modulus and 300% modulus, it is more preferably 1 to 900 parts by mass (more preferably 10 to 800 parts by mass). On the other hand, from the viewpoint of further improving the mechanical strength such as the breaking strength and the breaking elongation, 400 to 800 Parts by weight (more preferably from 500 to 7000 parts by weight) and more preferably in the.

In the third production method, the amount of the diene rubber used is more preferably 1 to 1000 parts by mass (more preferably 10 to 900 parts by mass) with respect to 100 parts by mass of the thermoplastic resin. If the amount of such a diene rubber used is less than the above lower limit, the rubber property tends to be low, while if it exceeds the above upper limit, the thermoplasticity (moldability) tends to be low.

In the third production method, the amount of the crosslinking agent used is 0.1 to 20 parts by mass (more preferably 0.3 to 15 parts by mass) with respect to 100 parts by mass of the diene rubber. preferable. If the amount of such a crosslinking agent used is less than the above lower limit, the crosslink density tends to be low, while if it exceeds the above upper limit, the crosslink density tends to be too high.

In this manner, the respective components are mixed to form the polymer component (more preferably the elastomer component) and the rubber particles, whereby the thermoplastic resin and the polymer component (more preferably the elastomer component) A rubber containing 20 parts by mass or less of a content ratio of 20 parts by mass or less based on 100 parts by mass of the polymer component (100 parts by mass of the elastomer component when the polymer component is the elastomer component) Particulate-containing elastomeric compositions can be obtained. In the rubber particle-containing elastomer composition thus obtained, the thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), the clay, and the rubber particles The content is preferably the same as the content of each component described in the rubber particle-containing elastomer composition of the present invention. When the rubber particle-containing elastomer composition thus obtained is made to contain the additive, the rubber particle-containing elastomer composition of the present invention is also contained in the rubber particle-containing elastomer composition finally obtained. It is preferable to adjust suitably so that it may become the quantity similar to content of each component already demonstrated as a component in things. In addition, in such a third production method, since the rubber particles are formed by reaction at the time of mixing, the rubber particle-containing elastomer composition of the present invention in which the rubber particles are dispersed in the matrix by such mixing step It is also possible to produce efficiently. The third manufacturing method has been described above, and the fourth manufacturing method will be described below.

[Method of Producing Fourth Rubber Particle-Containing Elastomer Composition (Fourth Method)]
The fourth method for producing a rubber particle-containing elastomer composition of the present invention (fourth production method) is
A thermoplastic resin having no chemically bondable crosslinking site; a diene rubber not having a hydrogen bondable crosslinking site; a crosslinking agent (peroxide crosslinking agent, phenol resin crosslinking agent, sulfur crosslinking agent, By mixing at least one member selected from the group consisting of silane based crosslinking agents; and the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II));
The diene rubber having no hydrogen bondable crosslinking site is reacted with the crosslinking agent to form a rubber particle comprising a crosslinked product of diene rubber,
The thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), and 100 parts by mass of the polymer component (when the polymer component is the elastomer component, the elastomer component) A rubber particle-containing elastomer composition is obtained, which comprises a clay having a content ratio of not more than 20 parts by mass with respect to 100 parts by mass) and rubber particles.

A thermoplastic resin having no chemically bondable crosslinking site, a diene rubber having no hydrogen bondable crosslinking site, and a crosslinking agent (peroxide crosslinking agent, phenol resin) used in the fourth production method The thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II)) is at least one selected from the group consisting of a crosslinking agent, a sulfur-based crosslinking agent and a silane-based crosslinking agent; The components are the same as those described in the rubber particle-containing elastomer composition of the present invention and the first production method described above (the preferred ones are also the same).

Also, in the mixing step of the fourth production method, the addition order of the respective components is not particularly limited, and each component is added once (simultaneously) and mixed; the respective components are sequentially added and mixed Method: Thermoplastic resin not having the crosslinking site having the chemical bonding property in advance, diene rubber having no the hydrogen bonding crosslinking site, and the crosslinking agent (peroxide crosslinking agent, phenolic resin crosslinking agent And the thermoplastic polymer composition (II) after mixing the diene rubber and the crosslinking agent by mixing at least one selected from the group consisting of a sulfur crosslinking agent and a silane crosslinking agent; Preferably, the thermoplastic elastomer composition (II) may be added and mixed, and as a result, the respective components may be mixed; As described above, in the mixing step of the fourth production method, the addition order of the respective components is not particularly limited, but from the viewpoint of sufficiently dispersing the formed rubber particles, the crosslink site having the chemical bonding property A thermoplastic resin having no hydrogen bondable crosslinking site, the crosslinker, and the thermoplastic polymer composition (II) (more preferably, the thermoplastic elastomer composition (II) )) Is preferably added at once and melt mixed. Thus, by melting and mixing, it is possible to cause the so-called dynamic crosslinking by reacting the diene rubber having no hydrogen bondable crosslinking site at the time of mixing with the crosslinking agent, so that the formed rubber particles are formed. It is possible to obtain a rubber particle-containing elastomer composition in a state of being sufficiently dispersed. Further, even when various additives are added, the order of addition is not particularly limited, and the additives may be appropriately added so as to achieve the intended design.

In addition, when melt-mixing each component as described above, conditions are adopted that can dynamically crosslink the diene rubber and the crosslinking agent that do not have the hydrogen bondable crosslinking site at the time of the melt mixing. It is preferable that a known method (conditions) of dynamic crosslinking can be adopted as appropriate. For example, using either a twin-screw extruder, a screw extruder, a kneader, or a Banbury mixer as a mixer, each component is added once (simultaneously) and a resin component (including an elastomer component) added A method of mixing at a temperature above the melting point (preferably 100 to 250 ° C.) for 1 minute to 1 hour may be employed. The shear force applied at this time is also not particularly limited, and conditions may be appropriately set so as to allow dynamic crosslinking, but it is preferable to prepare so that the shear rate is 1 to 100 sec ^-1. . In the fourth production method, when the final product is produced by melt-mixing as described above, such a method is a so-called dynamic method using the thermoplastic resin, the diene rubber and the crosslinking agent. It can be said that the thermoplastic elastomer composition (II) is further added to produce a final product when producing a dynamically crosslinked elastomer. Therefore, as the production conditions, the conditions adopted in the method of producing a so-called dynamically crosslinked elastomer (for example, the method described in Japanese Patent No. 6000714) may be adopted appropriately. According to such a method, it is also possible to efficiently produce a rubber particle-containing elastomer composition in which rubber particles are sufficiently dispersed.

In the fourth production method, the amount of the thermoplastic resin used is the polymer component in the thermoplastic polymer composition (II) (in addition, the thermoplastic polymer composition (II) is the thermoplastic elastomer composition ( In the case of II), it is preferable to be 1 to 10000 parts by mass with respect to 100 parts by mass of the elastomer component in the thermoplastic elastomer composition (II), and 100% modulus and 300% modulus are further improved From the viewpoint, it is more preferable to use 1 to 900 parts by mass (more preferably 10 to 800 parts by mass), and from the viewpoint of further improving the mechanical strength such as the breaking strength and the breaking elongation, 400 to 8000. It is more preferable to use parts by mass (more preferably 500 to 7000 parts by mass). In the fourth production method, the conditions for the amount of the diene rubber used and the amount of the crosslinking agent used are preferably the same as the conditions for the amounts used in the third production method.

In addition, in the fourth production method, when various additives are added, the amount of the additives used (the amount of each of the additives used when combining a plurality of types) The amount is more preferably 0.1 to 100 parts by mass (more preferably 0.5 to 30 parts by mass) with respect to 100 parts by mass of the thermoplastic resin. If the amount of such an additive used is less than the lower limit, the effect of the additive tends to be low, while if the amount is more than the upper limit, the effect of the additive tends to be too high. As additives to be added together with the above-mentioned thermoplastic resin in the fourth production method, a slip agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a conductivity imparting agent, an antistatic agent, a dispersant, a flame retardant, an antifungal agent The well-known additive normally added to rubber | gum, such as an agent, a neutralizing agent, a softener, a filler, a coloring agent, a thermally conductive filler, is preferable.

Thus, by mixing the components to form the rubber particles in the mixture, 100 parts by mass of the thermoplastic resin, the polymer component (more preferably the elastomer component), and the polymer component When the polymer component is the elastomer component, it is possible to obtain a rubber particle-containing elastomer composition containing clay and a rubber particle in a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the elastomer component) . In the rubber particle-containing elastomer composition thus obtained, the thermoplastic resin having no chemically bondable crosslinking site, the polymer component (more preferably the elastomer component), the clay, and the rubber particles The content is preferably the same as the content of each component described in the rubber particle-containing elastomer composition of the present invention. When the rubber particle-containing elastomer composition thus obtained is made to contain the additive, the rubber particle-containing elastomer composition of the present invention is also contained in the rubber particle-containing elastomer composition finally obtained. It is preferable to adjust suitably so that it may become the quantity similar to content of each component already demonstrated as a component in things. Furthermore, in such a fourth production method, the rubber particles are contained in the rubber particle-containing elastomer composition of the present invention in which the rubber particles are dispersed in the matrix by the mixing step, since the rubber particles are formed by reaction during mixing. It is also possible to produce efficiently.

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

<JIS-A hardness>
Using the rubber particle-containing elastomer composition obtained in each Example and each Comparative Example, first, the rubber particle-containing elastomer composition is heat-pressed at 200 ° C. for 10 minutes, and the sheet is made to have a thickness of about 2 mm. Prepared. Next, the sheet obtained in this manner was punched into a disk shape having a diameter of 29 mm, seven sheets were stacked, and a sample was prepared so that the height (thickness) was 12.5 ± 0.5 mm. Using the samples thus obtained, JIS-A hardness was measured in accordance with JIS K6253 (issued in 2012).

<100% modulus, 300% modulus, breaking strength, breaking elongation>
Using the rubber particle-containing elastomer composition obtained in each Example and each Comparative Example, first, the rubber particle-containing elastomer composition was heated at a temperature of 200 ° C. for 3 minutes of preheating thickness 2 mm, length 150 mm After putting in a mold of 150 mm in width, pressure is applied by a heating press under the conditions of temperature: 200 ° C., pressure: 18 MPa, pressurization time: 5 minutes, then pressure: 18 MPa in a water-cooled cooling press: pressurization time A 2 mm thick sheet (thickness 2 mm, length 150 mm, width 150 mm) was formed by applying pressure under conditions of 2 minutes and taking it out of the mold. Next, a No. 3 dumbbell-shaped test piece is punched out of the sheet obtained in this manner, and a tensile test at a tensile speed of 500 mm / min is performed according to JIS K6251 (issued in 2010), 100% modulus (M ₁₀₀ ) [unit: MPa], 300% modulus (M ₃₀₀ ) [unit: MPa], breaking strength (T _B ) [unit: MPa], and breaking elongation (E _B ) [unit:%] at room temperature (%) It measured at 25 degreeC.

<Compression set (C-Set)>
Using the rubber particle-containing elastomer composition obtained in each Example and each Comparative Example, first, the rubber particle-containing elastomer composition is heat-pressed at 200 ° C. for 10 minutes, and the sheet is made to have a thickness of about 2 mm. Prepared. The sheet thus obtained was punched into a disk shape having a diameter of 29 mm, and seven sheets were stacked, and a sample was prepared so that the height (thickness) was 12.5 ± 0.5 mm. The compression set (unit:%) after compression at a rate of 25% with a dedicated jig and leaving at 70 ° C. for 22 hours was measured according to JIS K6262 (issued in 2013) using the sample thus obtained. did. As a compression device, a trade name "Vulcanized rubber compression set tester SCM-1008L" manufactured by Dumbbell Co., Ltd. was used.

<Measurement of Average Particle Size of Rubber Particles in Composition>
The average particle sizes of the rubber particles in the rubber particle-containing elastomer compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were measured as follows. That is, for each rubber particle-containing elastomer composition, the cross section of the composition is observed using a transmission electron microscope (TEM, trade name "SU-70" manufactured by Hitachi High-Technologies Corporation) and included in the cross section. The average particle size of the rubber particles was determined by calculating and averaging the diameters of 30 optional rubber particles. In the measurement, the diameter of the largest circumscribed circle of the outer shape of the rubber particles in the cross section was measured as the diameter of the rubber particles. In addition, at the time of such measurement, the diameter was determined for each particle by dragging the portion of the largest diameter of each particle on the screen from the start point to the end point using the length measurement function of the above-mentioned apparatus (the TEM). . Furthermore, in the case of such measurement, the rubber particle-containing elastomer composition is heat-pressed at 200 ° C. for 10 minutes using the rubber particle-containing elastomer composition obtained in each example and each comparative example. A sheet is prepared to have a size of about 2 mm, a sample piece is cut out from the sheet having a thickness of about 2 mm, and a temperature of −80 ° C. so that the cut surface becomes an observation surface using a cryomicrotome from the sample piece. Under the conditions, an ultrathin section with a thickness of 100 nm was cut out and prepared, and this was used as a sample for measurement, and the cut surface was observed as a cross section of the composition. Further, the magnification of the transmission electron microscope at the time of measurement of the diameter of the rubber particles (during measurement) was set to 10000 times. In addition, regarding the rubber particle-containing elastomer composition obtained in Example 1, a transmission electron micrograph of a cross section of the composition (TEM photograph at a magnification of 3000 times: composition confirmed in measurement of average particle diameter of rubber particles) A photograph showing the state of the cross section of the object is shown in FIG. 1, and an enlarged view of a part of the cross section shown in FIG. 1 (a TEM photograph at a magnification of 10000) is shown in FIG.

Synthesis Example 1: Preparation of Thermoplastic Elastomer Composition (A)
First, a styrene block copolymer (styrene-ethylene-butylene-styrene block copolymer (hereinafter sometimes referred to as “SEBS”), trade name “G1633” manufactured by Kraton, molecular weight: 400,000 to 500,000, styrene Content: 30% by mass) 10 g is put into a pressure kneader, and while kneading under conditions of 180 ° C., 20 g of paraffin oil (trade name "YUBASE8J" manufactured by SK Lubricants) is dropped in the pressure kneader, The SEBS and paraffin oil were mixed for 1 minute. Then, in the pressure kneader, maleic anhydride-modified ethylene-butene copolymer (trade name "Tafmer MH 5040" manufactured by Mitsui Chemicals, Inc., crystallinity degree: 4%, hereinafter sometimes referred to as "maleated EBM" ) Add 5 g of polyethylene (HDPE: trade name "HJ 590N" made by Japan Polyethylene) and 0.12 g of anti-aging agent (trade name "AO-50" made by Adeka Co., Ltd.), and set the temperature to 180 ° C. The mixture was kneaded for 2 minutes and plasticized to obtain a first mixture. Next, to the first mixture in the pressure kneader, 0.006 g of organically modified clay (trade name "Esben WX" manufactured by Hojun Co., Ltd.) is further added, and the mixture is kneaded at 180 ° C for 4 minutes. A second mixture was obtained. Next, 0.051 g of pentaerythritol (trade name "Nylizer P" manufactured by Mitsubishi Chemical Corporation) is added to the second mixture in the pressure kneader, and the mixture is mixed at 180 ° C. for 8 minutes to obtain a thermoplastic elastomer composition ( A) was prepared. The elastomer component in the thermoplastic elastomer composition (A) was a reaction product of maleated EBM and pentaerythritol. Further, for convenience, the thermoplastic elastomer composition (A) obtained in Synthesis Example 1 is hereinafter sometimes referred to as "TPE- (A)".

Synthesis Example 2: Preparation of Thermoplastic Elastomer Composition (B)
Synthesis Example 1 except that 0.141 g of 2,4-diamino-6-phenyl-1,3,5-triazine (trade name “benzoguanamine” manufactured by Nippon Shokuhin Co., Ltd.) was used instead of using 0.051 g of pentaerythritol The thermoplastic elastomer composition (B) was obtained in the same manner as in the above. The elastomer component in the thermoplastic elastomer composition (B) was a reaction product of maleated EBM and benzoguanamine. Further, for convenience, the thermoplastic elastomer composition (B) obtained in Synthesis Example 2 is hereinafter sometimes referred to as "TPE- (B)".

Synthesis Example 3 Preparation of Thermoplastic Elastomer Composition (C)
A thermoplastic elastomer composition in the same manner as in Synthesis Example 1 except that 0.131 g of trishydroxyethyl isocyanurate (trade name "Tanac P" manufactured by Nichise Sangyo Co., Ltd.) is used instead of using 0.051 g of pentaerythritol. I got (C). The elastomer component in the thermoplastic elastomer composition (C) was a reaction product of maleated EBM and trishydroxyethyl isocyanurate. Further, for convenience, the thermoplastic elastomer composition (C) obtained in Synthesis Example 3 is hereinafter sometimes referred to as "TPE- (C)".

(Composition example 4)
Do not use polyethylene, change the amount of antioxidant used to 0.0524 g, change the amount of SEBS used to 12 g, change the amount of paraffin oil used to 40 g, maleic anhydride modified ethylene-butene co-weight The amount of coalescence was changed to 0.4 g, the amount of 2,4-diamino-6-phenyl-1,3,5-triazine was changed to 0.01128 g, and the amount of organic clay used was 0.0004 g A thermoplastic elastomer composition (D) was obtained in the same manner as in Synthesis Example 2 except that the composition was changed to The elastomer component in the thermoplastic elastomer composition (D) was a reaction product of maleated EBM and benzoguanamine. Further, for convenience, the thermoplastic elastomer composition (D) obtained in Synthesis Example 4 is hereinafter sometimes referred to as “TPE- (D)”.

(Composition example 5)
Instead of using maleic anhydride modified ethylene-butene copolymer (maleated EBM), maleic anhydride modified high density polyethylene (trade name "Husabond E 265" manufactured by DuPont Co., Ltd., density 0.95 g / cm ³ , In some cases, 7 g of “maleated HDPE” is used, the usage of trishydroxyethyl isocyanurate is changed to 0.0623 g, the usage of paraffin oil is changed to 21 g, and the usage of polyethylene is changed to 14 g And the amount of SEBS was changed to 14 g, the amount of organophilic clay was changed to 0.007 g, and the amount of anti-aging agent was changed to 0.168 g. Thermoplastic polymer composition (E) was obtained. The polymer component in the thermoplastic polymer composition (E) was a reaction product of maleated HDPE and trishydroxyethyl isocyanurate. In addition, the thermoplastic polymer composition (E) obtained in Synthesis Example 5 is hereinafter sometimes referred to as “TPC- (E)” for convenience.

Synthesis Example 6
Instead of using maleic anhydride modified ethylene-butene copolymer (maleated EBM) alone, 3.7 g of maleic anhydride modified ethylene-butene copolymer (maleated EBM) and maleic anhydride modified high density polyethylene ( Maleated HDPE: Using a mixture of 6.3 g of trade name “Husabond E 265” manufactured by DuPont Co., Ltd., the amount of trishydroxyethyl isocyanurate was changed to 0.176 g, and the amount of SEBS used was 6.52 g Change the amount of paraffin oil used to 15.22 g, change the amount of organic clay used to 0.01 g, and use 15 g of polyethylene (HDPE: trade name "HJ590N" made by Japan Polyethylene) Change the polyethylene (HDPE: trade name "HJ 590 N" made by Japan Polyethylene) In addition to 15 g of the polyethylene, 5.22 g of ethylene-butene copolymer (trade name “Tafmer DF7350” manufactured by Mitsui Chemicals, hereinafter sometimes referred to as “EBM”) is also added together with 15 g of the polyethylene. A thermoplastic polymer composition (F) was obtained in the same manner as in Synthesis Example 3, except that the amount of the anti-aging agent used was changed to 0.117 g. The polymer component in the thermoplastic polymer composition (F) was a reaction product of maleated HDPE and trishydroxyethyl isocyanurate, and a reaction product of maleated EBM and trishydroxyethyl isocyanurate. In addition, the thermoplastic polymer composition (F) obtained in Synthesis Example 6 is hereinafter sometimes referred to as “TPC- (F)” for convenience.

The compositions of TPE- (A) to TPE- (D) and TPC- (E) to (F) are shown in Table 1. All numerical values in Table 1 indicate parts by mass.

(About the abbreviation of the dynamically crosslinked thermoplastic elastomer used in each example and comparative example)
The abbreviation of the dynamic crosslinking thermoplastic elastomer (TPV) used in each Example etc. is shown below.

TPV- (1): trade name "Santoprene 121-75 M100" manufactured by Exxon Mobil;
TPV- (2): trade name "Santoprene 121-50M100" manufactured by Exxon Mobil;
TPV- (3): trade name "Milastomer 4010 NS" manufactured by Mitsui Chemicals, Inc .;
TPV- (4): trade name "Milastomer 6020NS" manufactured by Mitsui Chemicals, Inc .;
TPV- (5): trade name "Milastomer 7030NS" manufactured by Mitsui Chemicals, Inc.

(Examples 1 to 8)
40 g of a thermoplastic elastomer composition selected from TPE- (A) to TPE- (D) or a thermoplastic polymer selected from TPC- (E) and TPC- (F) Using 40 g of the composition and 10 g of one dynamically cross-linked thermoplastic elastomer selected from TPV- (1) to TPV- (5) in the combinations shown in Table 2, these are pressurized The mixture was charged into a kneader and mixed at a temperature of 180 ° C. for 10 minutes to obtain 50 g of the rubber particle-containing elastomer composition.

(Comparative Examples 1 to 5)
As shown in Table 2, TPV- (1) to TPV- (5) were used as they were as rubber particle-containing elastomer compositions for comparison (Comparative Example 1: TPV- (1), Comparative Example 2: TPV- (2), Comparative Example 3: TPV- (3), Comparative Example 4: TPV- (4), Comparative Example 5: TPV- (5)).

The properties of the rubber particle-containing elastomer compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 are shown in Table 2. In addition, about TPE- (A)-(D), TPC- (E)-(F), and TPV- (1)-(5) in Table 2, a numerical value shows mass ratio (mass%), The symbol " "-" Indicates that the component is not used (the amount of the component used is 0% by mass).

As apparent from the results shown in Table 2, TPE- (A) to TPE were obtained for each TPV as compared with the case where TPV- (1) to TPV- (5) were used as they were (Comparative Examples 1 to 5). In the rubber particle-containing elastomer compositions (Examples 1 to 8) obtained by mixing one selected from (D) and TPC- (E) to (F), each of them is compressed It has been found that the resistance to permanent set is at a higher level. In addition, in consideration of the components used in each example, the rubber particle-containing elastomer composition obtained in each example is a polymer component (a polymer in Examples 1 to 3, 5 and 7 to 8). It is apparent that the rubber particles have a structure in which rubber particles are dispersed in a matrix containing an elastomer component suitable as a component, a clay and a thermoplastic resin.

(Example 9)
First, 10 g of a styrene block copolymer (SEBS, trade name "G1633" manufactured by Kraton Co., Ltd.) is introduced into a pressure kneader and kneaded under the conditions of 180 ° C in a paraffin oil (SK Lubricants Co., Ltd.) 20g of brand names "YUBASE8J" (trade name) manufactured by Japan Electronics Co., Ltd. was dropped, and SEBS and paraffin oil were mixed for 1 minute. Next, 5 g of maleated EBM (trade name "Tafmer MH 5040" manufactured by Mitsui Chemicals, Inc.), 7.5 g of TPV- (1), and an antiaging agent (trade name "AO-50 manufactured by Adeka Co., Ltd." in the pressure kneader. 0.12 g was further added, and the mixture was kneaded at a temperature of 180 ° C. for 2 minutes for plasticization to obtain a first mixture. Next, to the first mixture in the pressure kneader, 0.006 g of organically modified clay (trade name "Esben WX" manufactured by Hojun Co., Ltd.) is further added, and the mixture is kneaded at 180 ° C for 4 minutes. A second mixture was obtained. Next, 0.051 g of pentaerythritol (trade name "Nylizer P" manufactured by Mitsubishi Chemical Corporation) is added to the second mixture in the pressure kneader, and the mixture is mixed at 180 ° C for 8 minutes to obtain a rubber particle-containing elastomer The composition was obtained. In the composition obtained, the elastomer component was a reaction product of maleated EBM and pentaerythritol, and the rubber particles were derived from the rubber particles in TPV- (1).

(Example 10)
A rubber particle-containing elastomer composition was obtained in the same manner as in Example 9 except that 7.5 g of TPV- (2) was used instead of 7.5 g of TPV- (1). In the composition obtained, the elastomer component was a reaction product of maleated EBM and pentaerythritol, and the rubber particles were derived from the rubber particles in TPV- (2).

(Comparative example 6)
Instead of using 7.5 g of TPV- (1), an ethylene-butene copolymer (trade name “Tafmer DF7350” manufactured by Mitsui Chemicals, Inc .; hereinafter sometimes referred to as “EBM”) which is a thermoplastic resin; An elastomer composition for comparison was obtained in the same manner as in Example 9 except that 5 g was used. In the composition obtained, the elastomer component was a reaction product of maleated EBM and pentaerythritol. In addition, as is clear from the components used for production, the obtained elastomer composition does not contain rubber particles.

(Example 11)
Instead of using 7.5 g of TPV- (1), 7.5 g of TPV- (3) was used, and instead of using 0.051 g of pentaerythritol, 2,4-diamino-6-phenyl-1,3,5- was used. A rubber particle-containing elastomer composition was obtained in the same manner as in Example 9 except that 0.141 g of triazine (trade name "benzoguanamine" manufactured by Nippon Shokubai Co., Ltd.) was used. In the composition obtained, the elastomer component is a reaction product of maleated EBM and 2,4-diamino-6-phenyl-1,3,5-triazine, and the rubber particles are TPV- (3). It was derived from rubber particles.

(Example 12)
A rubber particle-containing elastomer composition was obtained in the same manner as in Example 11 except that 7.5 g of TPV- (4) was used instead of 7.5 g of TPV- (3). In the composition obtained, the elastomer component is the reaction product of maleated EBM and 2,4-diamino-6-phenyl-1,3,5-triazine, and the rubber particles are TPV- (4). It was derived from rubber particles.

(Comparative example 7)
An elastomer composition for comparison was prepared in the same manner as in Example 11 except that 7.5 g of EBM (trade name "Tafmer DF7350" manufactured by Mitsui Chemicals, Inc.) was used instead of using 7.5 g of TPV- (3). Obtained. In the composition obtained, the elastomer component was a reaction product of maleated EBM and 2,4-diamino-6-phenyl-1,3,5-triazine. In addition, as is clear from the components used for production, the obtained elastomer composition does not contain rubber particles.

(Example 13)
Instead of using 7.5 g of TPV- (1), 7.5 g of TPV- (5) was used, and instead of using 0.051 g of pentaerythritol, trishydroxyethyl isocyanurate (trade name “TANAC manufactured by Nichise Sangyo Co., Ltd. A rubber particle-containing elastomer composition was obtained in the same manner as in Example 9 except that 0.131 g of P ′ ′) was used. In the composition obtained, the elastomer component was a reaction product of maleated EBM and trishydroxyethyl isocyanurate, and the rubber particles were derived from the rubber particles in TPV- (5).

(Comparative example 8)
An elastomer composition for comparison was prepared in the same manner as in Example 13 except that 7.5 g of EBM (trade name “Tafmer DF7350” manufactured by Mitsui Chemicals, Inc.) was used instead of using 7.5 g of TPV- (5). Obtained. In the composition obtained, the elastomer component was a reaction product of maleated EBM and trishydroxyethyl isocyanurate. In addition, as is clear from the components used for production, the obtained elastomer composition does not contain rubber particles.

The properties of the compositions obtained in Examples 9 to 13 and Comparative Examples 6 to 8 are shown in Table 3. In the composition description in Table 3, the numerical values indicate parts by mass, and the symbol "-" indicates that the component is not used (the amount of the component used is 0 parts by mass).

From the results shown in Table 3, considering first the case where the elastomer component is a reaction product of maleated EBM and pentaerythritol (the rubber particle elastomer composition obtained in Examples 9 to 10 and Comparative Example 6) When using TPV as compared with the case where only thermoplastic resin (EBM) not containing rubber particles (EBM) is used without using TPV (Comparative Example 6) (Example 9) It was found that the resistance to compression set of the resulting composition is higher in (10).

Also, from the results shown in Table 3, it is considered that the case where the elastomer component is a reaction product of maleated EBM and 2,4-diamino-6-phenyl-1,3,5-triazine (Examples 11 to 12) When the obtained rubber particle elastomer composition and the elastomer composition obtained in Comparative Example 7 are compared with each other, the case where a thermoplastic resin (EBM) not containing rubber particles is simply used without using TPV (Comparative Example) In comparison with 7), it was found that the resistance to compression set of the resulting composition was higher when TPV was used (Examples 11 to 12).

Further, from the results shown in Table 3, when considering that the elastomer component is a reaction product of maleated EBM and trishydroxyethyl isocyanurate (obtained from the rubber particle elastomer composition obtained in Example 13 and Comparative Example 8). In the case of using TPV as compared with the case of using only thermoplastic resin (EBM) containing no rubber particles without using TPV and comparing with the case of using the elastomer composition (Comparative Example 8) (Example) It was found in 13) that the resistance to compression set of the resulting composition was higher.

From these results (Table 3), rubber particles containing a thermoplastic resin derived from TPV, an elastomer component, a clay having a content ratio of 20 parts by mass or less based on 100 parts by mass of the elastomer component, and rubber particles According to the contained elastomer compositions (Examples 9 to 13), it was confirmed that the resistance to compression set of the resulting composition is higher. In addition, in consideration of the components used in Examples 9 to 13, the rubber particle-containing elastomer composition obtained in each Example was that the rubber particles were dispersed in the matrix containing the elastomer component, the clay and the thermoplastic resin. It is clear that it has a structure.

As described above, according to the present invention, a rubber particle-containing elastomer composition capable of reducing compression set at a higher level, and such a rubber particle-containing elastomer composition are efficiently produced. It is possible to provide a method of producing a rubber particle-containing elastomer composition that can be As described above, since the rubber particle-containing elastomer composition of the present invention can make the resistance to compression set to a higher level, in particular, various gaskets for civil engineering and construction, sealing materials for construction, and construction sash sealing materials , Packing materials, shock absorbing materials, automobile parts and the like.

Claims

A matrix and rubber particles dispersed in the matrix, and
A thermoplastic resin wherein the matrix does not have a chemically bondable crosslinking site;
Polymer (A) having a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or less, and hydrogen bond to the side chain At least one polymer component selected from the group consisting of a polymer (B) containing an anionic crosslinking site and a covalent crosslinking site and having a glass transition temperature of 25 ° C. or less
Clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component,
Containing
Rubber particle containing elastomer composition characterized by the above-mentioned.
The rubber particle-containing elastomer composition according to claim 1, wherein an average particle diameter of the rubber particles is 0.01 to 20.0 μm.
The rubber particle is at least one selected from the group consisting of a diene rubber having no hydrogen bondable crosslinking site, a peroxide crosslinker, a phenol resin crosslinker, a sulfur crosslinker, and a silane crosslinker. The rubber particle-containing elastomer composition according to claim 1 or 2, which is made of a cross-linked product of a diene rubber which is a reaction product with a cross-linking agent of a kind.
A rubber particle-containing thermoplastic elastomer (I) containing a thermoplastic resin having no chemically bondable crosslinking site and rubber particles;
Polymer (A) having a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or less, and hydrogen bond to the side chain At least one polymer component selected from the group consisting of a polymer (B) containing an anionic crosslinking site and a covalent crosslinking site and having a glass transition temperature of 25 ° C. or less, and 100 parts by mass of the polymer component And a thermoplastic polymer composition (II) comprising a clay having a content ratio of 20 parts by mass or less;
By mixing
Rubber particles containing: thermoplastic resin having no chemically bondable crosslinking site, the polymer component, clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component, and rubber particles A method of producing a rubber particle-containing elastomer composition, comprising obtaining an elastomer composition.
A polymer having a cyclic anhydride group in the side chain;
Compound (i) which reacts with the cyclic acid anhydride group to form a hydrogen bondable crosslinking site, and compound which reacts with the compound (i) and the cyclic acid anhydride group to form a covalent crosslinking site (Ii) at least one starting compound of the mixed starting materials;
Clay having a content of 20 parts by mass or less based on 100 parts by mass of the total amount of the polymer and the raw material compound;
A rubber particle-containing thermoplastic elastomer (I) containing a thermoplastic resin having no chemically bondable crosslinking site and rubber particles;
By mixing
The polymer having the cyclic acid anhydride group in the side chain is reacted with the raw material compound to have a side chain (a) having a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring. And a polymer (A) having a glass transition temperature of 25 ° C. or less, and a polymer having a hydrogen bonding crosslinking site and a covalent crosslinking site in the side chain and having a glass transition temperature of 25 ° C. or less (B) Form at least one polymer component selected from the group consisting of
Rubber particles containing: thermoplastic resin having no chemically bondable crosslinking site, the polymer component, clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component, and rubber particles A method of producing a rubber particle-containing elastomer composition, comprising obtaining an elastomer composition.
A polymer having a cyclic anhydride group in the side chain;
Compound (i) which reacts with the cyclic acid anhydride group to form a hydrogen bondable crosslinking site, and compound which reacts with the compound (i) and the cyclic acid anhydride group to form a covalent crosslinking site (Ii) at least one starting compound of the mixed starting materials;
Clay having a content of 20 parts by mass or less based on 100 parts by mass of the total amount of the polymer and the raw material compound;
A thermoplastic resin having no chemically bondable crosslinking site;
A diene rubber having no hydrogen bondable crosslinking site;
At least one crosslinker selected from the group consisting of peroxide crosslinkers, phenolic resin crosslinkers, sulfur crosslinkers and silane crosslinkers;
By mixing
The polymer having the cyclic acid anhydride group in the side chain is reacted with the raw material compound to have a side chain (a) having a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocyclic ring. And a polymer (A) having a glass transition temperature of 25 ° C. or less, and a polymer having a hydrogen bonding crosslinking site and a covalent crosslinking site in the side chain and having a glass transition temperature of 25 ° C. or less (B) And at least one polymer component selected from the group consisting of: a rubber comprising a crosslinked product of a diene rubber by reacting the diene rubber not having the hydrogen bondable crosslinking site with the crosslinking agent. Form particles,
Rubber particles containing: thermoplastic resin having no chemically bondable crosslinking site, the polymer component, clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component, and rubber particles A method of producing a rubber particle-containing elastomer composition, comprising obtaining an elastomer composition.
A thermoplastic resin having no chemically bondable crosslinking site;
A diene rubber having no hydrogen bondable crosslinking site;
At least one crosslinker selected from the group consisting of peroxide crosslinkers, phenolic resin crosslinkers, sulfur crosslinkers and silane crosslinkers;
Polymer (A) having a side chain (a) containing a hydrogen bondable crosslinking site having a carbonyl-containing group and / or a nitrogen-containing heterocycle and having a glass transition point of 25 ° C. or less, and hydrogen bond to the side chain At least one polymer component selected from the group consisting of a polymer (B) containing an anionic crosslinking site and a covalent crosslinking site and having a glass transition temperature of 25 ° C. or less, and 100 parts by mass of the polymer component And a thermoplastic polymer composition (II) comprising a clay having a content ratio of 20 parts by mass or less;
By mixing
The diene rubber having no hydrogen bondable crosslinking site is reacted with the crosslinking agent to form a rubber particle comprising a crosslinked product of diene rubber,
Rubber particles containing: thermoplastic resin having no chemically bondable crosslinking site, the polymer component, clay having a content ratio of 20 parts by mass or less with respect to 100 parts by mass of the polymer component, and rubber particles A method of producing a rubber particle-containing elastomer composition, comprising obtaining an elastomer composition.