JP2016003265A - Thermoplastic elastomer composition for non-pneumatic tire and non-pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition for a non-pneumatic tire having excellent wear resistance and compression set resistance even when used for a long period of time and to provide a non-pneumatic tire using the elastomer composition.SOLUTION: There is provided a thermoplastic elastomer composition for a non-pneumatic tire which comprises: a thermoplastic elastomer (A) having a side chain containing an imino group and/or a nitrogen-containing heterocycle and a carbonyl-containing group; and a polyol compound (B) having a melting point of 280°C or less, two or more hydroxyl groups and a hydroxyl value of 500 or more. The content of the polyol compound (B) is 0.1 to 20 pts.mass based on 100 pts.mass of the thermoplastic elastomer (A).

Description

  The present invention relates to a thermoplastic elastomer composition for a non-pneumatic tire and a non-pneumatic tire.

Pneumatic tires are mainly used for light vehicle tires such as bicycles, wheelchairs, golf carts, etc. However, in recent years, non-pneumatic tires have been proposed due to advantages such as punctures, and some of them have been put into practical use. Has been.
Since such non-pneumatic tires use a large amount of rubber, if they are disposed of at the end of their service life, the burden on the global environment is large. Therefore, from the viewpoint of protecting the global environment, high recyclability is required. ing.

  In response to such a request, for example, Patent Document 1 discloses a “non-pneumatic tire including an annular base portion and a tread portion attached to the outer peripheral side of the base portion, and the base portion and the tread portion. At least one of the materials has a side chain containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and a nitrogen-containing heterocycle, or a side chain having both a hydrogen-bonding cross-linking site and a covalent cross-linking site The material composed of the crosslinked elastomer composition and the material constituting the base part and the tread part have different breaking strengths at 100 ° C., and the ratio of the lower breaking strength to the higher breaking strength is 7/10 or less. Is a non-pneumatic tire. ”[Claim 1].

  Further, in Patent Document 2, "in a non-pneumatic tire having a tire base portion and a tire base portion partially or entirely surrounded by the tire main portion, the tread surface side of the tire is the tire main portion, Non-pneumatic tire characterized in that the tire base portion is a foam ”([Claim 1]), and at least a part of the tire body portion and / or the tire base portion is at least A thermoreversible cross-linked elastomer composition having a side chain containing a hydrogen-bonding cross-linking site having a carbonyl-containing group and a nitrogen-containing heterocycle, or a side chain having both a hydrogen-bonding cross-linking site and a covalent cross-linking site ([Claim 6]).

JP 2009-286183 A JP 2012-224134 A

  However, the present inventors have found that wear and sag are accelerated when a non-pneumatic tire produced using the thermoplastic elastomer composition described in Patent Documents 1 and 2 is used for a long period of time. did. That is, it has been clarified that there is room for improvement in wear resistance and compression set of non-pneumatic tires.

  Accordingly, the present invention provides a thermoplastic elastomer composition for non-pneumatic tires that is excellent in wear resistance and compression set resistance even when used for a long period of time, and a non-pneumatic tire using the elastomer composition. This is the issue.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by blending a specific amount of a polyol compound having a specific melting point and a hydroxyl value with respect to a predetermined thermoplastic elastomer. Invented.
That is, the present inventors have found that the above problem can be solved by the following configuration.

[1] A thermoplastic elastomer (A) having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group;
A polyol compound (B) having a melting point of 280 ° C. or lower, two or more hydroxyl groups, and a hydroxyl value of 500 or more,
The thermoplastic elastomer composition for non-pneumatic tires, wherein the content of the polyol compound (B) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).
[2] The thermoplastic elastomer composition for non-pneumatic tires according to [1], wherein the side chain of the thermoplastic elastomer (A) contains a structure represented by the following formula (1).
Wherein A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups.
[3] The thermoplastic elastomer composition for non-pneumatic tires according to [1] or [2], wherein the side chain of the thermoplastic elastomer (A) contains a structure represented by the following formula (4).
Wherein E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; An organic group that may contain any atom or group of
[4] The thermoplastic elastomer (A) has another side chain containing a covalent crosslinkable site, and the amide, ester, lactone, urethane, ether, thiourethane and thioether in the covalent crosslinkable site. The thermoplastic elastomer composition for non-pneumatic tires according to any one of [1] to [3], which can be crosslinked by at least one bond selected from the group consisting of:
[5] The thermoplastic elastomer (A) has another side chain containing a covalent crosslinking site, and the crosslinking at the covalent crosslinking site is an amide, ester, lactone, urethane, ether, thiourethane. And the thermoplastic elastomer composition for non-pneumatic tires according to any one of [1] to [3], which is formed by at least one bond selected from the group consisting of thioethers.
[6] The thermoplastic elastomer composition for non-pneumatic tires according to any one of [1] to [5], wherein the elastomeric polymer constituting the main chain of the thermoplastic elastomer (A) is a polyolefin polymer. .
[7] Furthermore, a plasticizer is contained,
The thermoplastic elastomer for non-pneumatic tires according to any one of [1] to [6], wherein the plasticizer content is 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). Composition.
[8] Further, a styrene elastomer is contained,
The thermoplasticity for non-pneumatic tires according to any one of [1] to [7], wherein the content of the styrene elastomer is 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). Elastomer composition.
[9] A non-pneumatic tire having a tire base portion and a tire base portion partially or entirely surrounded by the tire main body portion,
A non-pneumatic tire in which at least a part of the tire main body part and the tire base part is composed of the thermoplastic elastomer composition for a non-pneumatic tire according to any one of [1] to [8].

  As described below, according to the present invention, the thermoplastic elastomer composition for non-pneumatic tires that is excellent in wear resistance and compression set resistance even when used for a long period of time, and the above-described elastomer composition are used. Non-pneumatic tires can be provided.

FIG. 1 is a schematic perspective view when an example of an embodiment of a non-pneumatic tire of the present invention is cut in a tire meridian direction.

The thermoplastic elastomer composition for non-pneumatic tires of the present invention and the non-pneumatic tire of the above invention will be described below.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Thermoplastic elastomer composition for non-pneumatic tires]
The thermoplastic elastomer composition for non-pneumatic tires of the present invention (hereinafter also simply referred to as “the composition of the present invention”) has side chains containing imino groups and / or nitrogen-containing heterocycles and carbonyl-containing groups. A thermoplastic elastomer (A) having a melting point of 280 ° C. or less, a polyol compound (B) having two or more hydroxyl groups and a hydroxyl value of 500 or more.
Here, content of the said polyol compound (B) is 0.1-20 mass parts with respect to 100 mass parts of said thermoplastic elastomers (A).
Since the composition of the present invention has such a configuration, it is considered that the wear resistance and compression set are improved even when used as a non-pneumatic tire for a long time.

As described above, the composition of the present invention, together with the thermoplastic elastomer (A) having a predetermined side chain, has a melting point of 280 ° C. or less, two or more hydroxyl groups, and a hydroxyl value of 500 or more. B).
Therefore, when the imino group or nitrogen-containing heterocycle present in the side chain of the thermoplastic elastomer (A) functions as a hydrogen-bonding crosslinking site, this crosslinking site interacts with the hydroxyl group of the polyol compound (B). As a result, a strong hydrogen bond is formed. As a result, it is considered that wear resistance and compression set are improved even when used for a long time. On the other hand, when the polyol compound (B) is not contained, the hydrogen bond network changes over time, and it is considered that the initial physical properties cannot be maintained by gradually relaxing (Comparative Example). 1 and 4).
The thermoplastic elastomer (A) and polyol compound (B) used in the composition of the present invention, as well as optional styrenic elastomers, plasticizers and other additives will be described in detail below.

<Thermoplastic elastomer (A)>
The thermoplastic elastomer (A) used in the composition of the present invention has a side chain containing an imino group and / or a nitrogen-containing heterocyclic group and a carbonyl-containing group on an elastomeric polymer of a natural polymer or a synthetic polymer. Have.
In the present invention, “side chain” refers to a side chain and a terminal of an elastomeric polymer. Further, “having a side chain containing an imino group and / or a nitrogen-containing heterocyclic group and a carbonyl-containing group” means that an atom (usually a carbon atom) forming the main chain of the elastomeric polymer has an imino group and It means that the nitrogen-containing heterocyclic group and the carbonyl-containing group have a chemically stable bond (for example, covalent bond, ionic bond, etc.).

The elastomeric polymer that is the main chain of the thermoplastic elastomer (A) is a generally known natural polymer or synthetic polymer, and has a glass transition point of room temperature (25 ° C.) or lower, that is, an elastomer. If there is no particular limitation.
Specific examples of such elastomeric polymers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), and acrylonitrile. -Diene rubbers such as butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM) and hydrogenated products thereof; ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), olefin polymers such as chlorosulfonated polyethylene, acrylic rubber, fluororubber, polyethylene rubber, polypropylene rubber; epichlorohydrin rubber; polysulfide rubber; silicone rubber; urethane rubber; Cited That.

  Further, the elastomeric polymer may be an elastomeric polymer containing a resin component, and specific examples thereof may be a hydrogenated polystyrene elastomeric polymer (for example, SBS, SIS, SEBS, etc.), Examples include polyolefin-based elastomeric polymers, polyvinyl chloride-based elastomeric polymers, polyurethane-based elastomeric polymers, polyester-based elastomeric polymers, and polyamide-based elastomeric polymers.

Further, the elastomeric polymer may be liquid or solid, and the molecular weight thereof is not particularly limited, and is appropriately selected according to the use in which the composition of the present invention is used and the physical properties required for these. be able to.
When emphasizing fluidity when the composition of the present invention is heated (decrosslinked), the elastomeric polymer is preferably in a liquid state, for example, ethylene-propylene whose main component is a polyolefin such as ethylene or propylene. In the case of rubber (EPM) or the like, the weight average molecular weight is preferably 1,000 to 100,000, and particularly preferably about 1,000 to 50,000.
On the other hand, when emphasizing the strength of the composition of the present invention, the elastomeric polymer is preferably solid, and for example, ethylene-propylene rubber (EPM) has a weight average molecular weight of 100,000 or more. Is preferable, and it is particularly preferably about 500,000 to 1,500,000.
In the present invention, the weight average molecular weight is a weight average molecular weight (polystyrene conversion) measured by gel permeation chromatography (GPC). For the measurement, tetrahydrofuran (THF) is preferably used as a solvent.

In the present invention, two or more of the above elastomeric polymers can be mixed and used. In this case, the mixing ratio of the respective elastomeric polymers can be set to any ratio depending on the use of the composition of the present invention, the physical properties required for the composition of the present invention, and the like.
The glass transition point of the elastomeric polymer is preferably 25 ° C. or less as described above. When the elastomeric polymer has two or more glass transition points, or two or more elastomeric polymers are mixed. When used, at least one of the glass transition points is preferably 25 ° C. or lower.
In the present invention, the glass transition point is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry). The temperature raising rate is preferably 10 ° C./min.

  Such an elastomeric polymer is an olefin polymer such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), etc., and has a glass transition point of 25 ° C. or lower. The obtained molded product comprising the composition of the present invention is preferable because it exhibits rubber-like elasticity at room temperature. Moreover, when an olefin polymer is used, the deterioration of the composition is suppressed because there is no double bond.

  In the present invention, when ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), or ethylene-butene rubber (EBM) is used as the main chain of the elastomeric polymer, The ethylene content is preferably 10 to 90 mol%, more preferably 40 to 90 mol%. When the ethylene content is within this range, wear resistance and compression set resistance are improved when a non-pneumatic tire is formed.

  The thermoplastic elastomer (A) used in the composition of the present invention has a side chain containing an imino group and / or a nitrogen-containing heterocyclic group and a carbonyl-containing group in the elastomeric polymer. The chain preferably contains an imino group and a carbonyl-containing group, and more preferably contains an imino group, a nitrogen-containing heterocyclic ring, and a carbonyl-containing group.

  In the present invention, when the side chain contains an imino group and a carbonyl-containing group, the side chain preferably contains a structure represented by the following formula (1).

  In the formula, A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is A hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups.

The substituent A is not particularly limited as long as it is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
Specific examples of such substituent A include, for example, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a dodecyl group, and a stearyl group; an isopropyl group Branched alkyl groups such as isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl group, 2-ethylhexyl group; benzyl group Aralkyl groups such as phenethyl group; aryl groups such as phenyl group, tolyl group (o-, m-, p-), dimethylphenyl group, mesityl group; and the like.
Among these, an alkyl group, in particular, a butyl group, an octyl group, a dodecyl group, an isopropyl group, and a 2-ethylhexyl group is preferable because the processability of the resulting composition of the present invention is improved.

Substituent B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group that may contain these atoms or groups There is no particular limitation.
Specific examples of such substituent B include, for example, a single bond; an oxygen atom, a sulfur atom, or an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms); A C1-C20 alkylene group or aralkylene group which may contain a group; a C1-C20 alkylene ether group (an alkyleneoxy group such as —O—CH ₂ CH ₂₎ having these atoms or groups at its end. - group), an alkylene group (e.g., _{-NH-CH 2 CH} 2 - group) or an alkylene thioether group (alkylene thio group, for example, _{-S-CH 2 CH} 2 - group); having them end, carbon And an aralkylene ether group (aralkyleneoxy group), an aralkylene amino group, or an aralkylene thioether group;

Here, the alkyl group having 1 to 10 carbon atoms of the amino group NR ′ includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, including isomers. Group, decyl group and the like.
An oxygen atom, a sulfur atom and an amino group NR ′ of the substituent B; and; an alkylene ether group, an alkylene amino group, an alkylene thioether group, or an aralkylene having 1 to 20 carbon atoms terminated with these atoms or groups. Oxygen atom such as ether group, aralkyleneamino group, aralkylenethioether group, amino group NR 'and sulfur atom combine with adjacent carbonyl group to form conjugated ester group, amide group, imide group, thioester group, etc. It is preferable to do.
Among these, the substituent B is an oxygen atom, a sulfur atom or an amino group forming a conjugated system; an alkylene ether group having 1 to 20 carbon atoms, an alkyleneamino group or an alkylenethioether having these atoms or groups at the terminal Preferably an amino group (NH), an alkyleneamino group (—NH—CH ₂ — group, —NH—CH ₂ CH ₂ — group, —NH—CH ₂ CH ₂ CH ₂ — group), alkylene ether A group (—O—CH ₂ — group, —O—CH ₂ CH ₂ — group, —O—CH ₂ CH ₂ CH ₂ — group) is particularly preferred.

  The thermoplastic elastomer (A) used in the composition of the present invention has the following formula (2) or a side chain containing a structure represented by the above formula (1), which is bonded to the main chain at the α-position or β-position. It is preferable to have as a side chain containing the structure represented by (3).

  In the formula, A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and B and D are each independently a single bond; oxygen atom, amino group NR '(R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups.

Here, the substituent A is basically the same as the substituent A in the above formula (1), and the substituents B and D are each independently the same as the substituent B in the above formula (1). .
However, the substituent D in the above formula (3) is a C 1-20 which may contain a single bond; an oxygen atom, an amino group NR ′ or a sulfur atom, among those exemplified as the substituent B in the above formula (1). It is preferably one that forms a conjugated system with an imide nitrogen of an alkylene group or an aralkylene group, and particularly preferably an alkylene group. That is, it is preferable to form an alkyleneamino group or an aralkyleneamino group having 1 to 20 carbon atoms which may contain an oxygen atom, an amino group NR ′ or a sulfur atom together with the imide nitrogen of the above formula (3). It is particularly preferred to form
Specific examples of the substituent D include, for example, a single bond; an alkylene ether group, an alkylene amino group, and an alkylene thioether having 1 to 20 carbon atoms having an oxygen atom, a sulfur atom, or an amino group as a terminal. Group, aralkylene ether group, aralkylene amino group, aralkylene thioether group and the like; methylene group, ethylene group, propylene group, butylene group, hexylene group, phenylene group, xylylene group and the like including isomers.

  In the present invention, a side chain containing an imino group and a carbonyl-containing group (specifically, a side chain containing a structure represented by the above formula (1) or the above formula (2) or (3)) is It is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the elastomeric polymer. When the introduction ratio is within this range, the side chains of the elastomeric polymer interact with each other or within the molecule, and these are formed in a well-balanced manner. The compression set becomes better. From the viewpoint that these properties are more excellent, it is more preferable that side chains are introduced at a ratio of 0.1 to 30 mol%, and side chains are introduced at a ratio of 0.5 to 20 mol%. Further preferred.

  In the present invention, when the side chain contains a nitrogen-containing heterocyclic ring and a carbonyl-containing group, the side chain preferably contains a structure represented by the following formula (4).

  In the formula, E is a nitrogen-containing heterocyclic ring, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or sulfur. Atom; or an organic group that may contain these atoms or groups.

Here, the nitrogen-containing heterocyclic ring E specifically includes the nitrogen-containing heterocyclic rings exemplified below.
The substituents B and D are each independently the same as the substituent B in the above formula (1).

The nitrogen-containing heterocycle can be used even if it contains a nitrogen atom in the heterocycle and has a heteroatom other than the nitrogen atom in the heterocycle, such as a sulfur atom, an oxygen atom, or a phosphorus atom. Here, the reason why the heterocyclic compound is used is that if it has a heterocyclic structure, hydrogen bonds that form a bridge are strengthened, and the tensile strength of the resulting composition of the present invention is improved.
The nitrogen-containing heterocycle may have a substituent, and specific examples of the substituent include alkyl groups such as a methyl group, an ethyl group, a (iso) propyl group, and a hexyl group; Alkoxy groups such as methoxy group, ethoxy group, (iso) propoxy group; groups consisting of halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; cyano group; amino group; aromatic hydrocarbon group; ester group; An ether group; an acyl group; a thioether group; The substitution position of these substituents is not particularly limited, and the number of substituents is not limited.
Further, the nitrogen-containing heterocycle may or may not have aromaticity, but if it has aromaticity, it has wear resistance when made into a non-pneumatic tire. It is preferable because it becomes better.

The nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring.
Specific examples of such nitrogen-containing heterocycle include pyrrololine, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl, phthalimidine, β -Isoindigo, monoporphyrin, diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyroerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone Hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, in , Indoline, oxylindole, carbazole, phenothiazine, indolenine, isoindole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine , Pyrazine, phenazine, tetrazine, benzoxazole, benzoisoxazole, anthranyl, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthrazolin, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline, triazine, histidine , Triazolidine, melamine, adenine, guanine, thymine, cytosine And derivatives thereof. Among these, particularly the nitrogen-containing 5-membered ring is preferably exemplified by the following compound, a triazole derivative represented by the following formula (25) and an imidazole derivative represented by the following formula (26). These may have the above-described various substituents, or may be hydrogenated or eliminated.

  In the formula, the substituent X is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and is basically the same as the substituent A in the above formula (1). It is the same.

  Moreover, about a nitrogen-containing 6-membered ring, the following compound is illustrated preferably. These may have various substituents as described above, or may be hydrogenated or eliminated.

  Moreover, what condensed the said nitrogen-containing heterocyclic ring, a benzene ring, or nitrogen-containing heterocyclic rings can also be used, Specifically, the following condensed ring is illustrated suitably. These condensed rings may also have the above-described various substituents, and may have hydrogen atoms added or eliminated.

  Among such nitrogen-containing heterocycles, triazole ring, thiadiazole ring, pyridine ring, thiazole ring, imidazole ring and hydantoin ring are more resistant to wear and compression set when made into a non-pneumatic tire. Since it becomes favorable, it is preferable.

  The thermoplastic elastomer (A) used in the composition of the present invention has the following formula (5) or a side chain containing a structure represented by the above formula (4), which is bonded to the main chain at the α-position or β-position. It is more preferable to have as a side chain containing the structure represented by (6).

  In the formula, E is a nitrogen-containing heterocyclic ring, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or sulfur. Atom; or an organic group that may contain these atoms or groups.

Here, the nitrogen-containing heterocyclic ring E specifically includes the nitrogen-containing heterocyclic rings exemplified above.
The substituents B and D are each independently the same as the substituent B in the above formula (1).
However, the substituent D in the above formula (6) forms a conjugated system with a single bond; an imide nitrogen of an alkylene group having 1 to 20 carbon atoms or an aralkylene group which may contain an oxygen atom, an amino group NR ′ or a sulfur atom. It is preferable that it is a thing, and it is especially preferable that it is a single bond. That is, it is preferable to form an alkyleneamino group or an aralkyleneamino group having 1 to 20 carbon atoms which may contain an oxygen atom, an amino group NR ′ or a sulfur atom together with the imide nitrogen of the above formula (6). It is particularly preferable that the nitrogen-containing heterocyclic ring is directly bonded to the imide nitrogen of 6) (single bond).

  When the thermoplastic elastomer (A) used in the composition of the present invention has a side chain containing a triazole ring, an imidazole ring or a thiazole ring as the side chain containing the nitrogen-containing heterocycle, the above formula (4) ) As a side chain containing a structure represented by the following formula (7), the following formula (8) or (9), or the following formula (10). It is preferable that any one of the following formulas (11) or (12), the following formulas (13) to (16), which are bonded to the main chain at the α-position or the β-position, or It is more preferable that it has as a side chain containing the structure made.

  In the formula, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or these atoms or groups. G and J are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

Here, the substituents B and D are each independently the same as the substituents B and D in the above formulas (4) to (6).
Specific examples of the substituents G and J include, for example, a hydrogen atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, exemplified as the substituent A in the above formula (1), Linear alkyl groups such as dodecyl group and stearyl group; isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl Groups, branched alkyl groups such as 2-ethylhexyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group (o-, m-, p-), dimethylphenyl group and mesityl group Each may be the same or different.

  In the present invention, a side chain containing a nitrogen-containing heterocyclic ring and a carbonyl-containing group (specifically, a side chain containing a structure represented by the above formula (4) or the above formula (5) or (6)). ) Is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the elastomeric polymer. When the introduction ratio is within this range, the side chains of the elastomeric polymer interact with each other or within the molecule, and these are formed in a well-balanced manner. The compression set becomes better. From the viewpoint that these properties are more excellent, it is more preferable that side chains are introduced at a ratio of 0.1 to 30 mol%, and side chains are introduced at a ratio of 0.5 to 20 mol%. Further preferred.

Further, in the present invention, when having a side chain containing a nitrogen-containing heterocycle and a carbonyl-containing group together with a side chain containing an imino group and a carbonyl-containing group, these side chains are added together to give the elastomeric property. It is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the polymer, and the ratio of introduction into the side chain (nitrogen-containing heterocycle and carbonyl). The side chain containing the containing group / the side chain containing the imino group and the carbonyl containing group) is more preferably 1/99 to 99/1, and still more preferably 10/90 to 90/10.
When the introduction ratio and the introduction ratio are within this range, the tensile strength at the time of crosslinking is high, and the low heat buildup and wear resistance are improved when a non-pneumatic tire is formed.

Next, the bonding position of the nitrogen-containing heterocyclic ring in the case where the thermoplastic elastomer (A) used in the composition of the present invention has a side chain containing a nitrogen-containing heterocyclic ring will be described. For convenience, the nitrogen-containing heterocycle is referred to as “nitrogen-containing n-membered ring compound (n ≧ 3)”.
The bonding positions described below ("positions 1 to n") are based on the IUPAC nomenclature. For example, in the case of a compound having three nitrogen atoms having an unshared electron pair, the bonding position is determined by the order based on the IUPAC nomenclature. Specifically, the bonding positions are indicated on the 5-membered, 6-membered and condensed nitrogen-containing heterocycles exemplified above.
In the thermoplastic elastomer (A), the bonding position of the nitrogen-containing n-membered ring compound bonded to the copolymer directly or through an organic group is not particularly limited, and may be any bonding position (position 1 to position n). . Preferably, it is the 1-position or 3-position to n-position.

When the nitrogen-containing n-membered ring compound contains one nitrogen atom (for example, a pyridine ring), the chelate is easily formed in the molecule, and the physical properties such as tensile strength when the composition is obtained are excellent. The (n-1) position is preferred.
By selecting the bonding position of the nitrogen-containing n-membered ring compound, the thermoplastic elastomer can easily form crosslinks due to hydrogen bonds, ionic bonds, coordination bonds, etc. between the molecules of the thermoplastic elastomer, and mechanical properties. Excellent.

  The thermoplastic elastomer (A) used in the composition of the present invention may have another side chain containing a covalent crosslinkable site, and the amide, ester, lactone, More preferably, it can be crosslinked by at least one bond selected from the group consisting of urethane, ether, thiourethane and thioether. Further, the thermoplastic elastomer (A) used in the composition of the present invention may be one in which crosslinking is formed by such a bond.

The other side chain containing the covalent cross-linking site is at least selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether by reacting with “compound that forms a covalent bond”. There is no particular limitation as long as it is a side chain having a functional group capable of causing one bond as a covalent bond cross-linking site.
In the present invention, examples of the “compound that forms a covalent bond” include, for example, two or more amino groups and / or imino groups in one molecule (in the case where both amino groups and imino groups are present, these groups are added together). Polyamine compound having 2 or more); polyol compound having 2 or more hydroxyl groups in one molecule; polyisocyanate compound having 2 or more isocyanate (NCO) groups in one molecule; thiol group (mercapto group) in one molecule And a polythiol compound having two or more.

  Examples of the polyamine compound include the following alicyclic amines, aliphatic polyamines, aromatic polyamines, nitrogen-containing heterocyclic amines, and the like.

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

  Specific examples of the aliphatic polyamine include, for example, methylenediamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, 1,3-diaminopentane, hexamethylenediamine, diaminoheptane, diaminododecane, diethylenetriamine, diethylaminopropylamine. N-aminoethylpiperazine, triethylenetetramine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-dimethyl-1,3-propanediamine, N , N′-diethyl-1,3-propanediamine, N, N′-diisopropyl-1,3-propanediamine, N, N′-dimethyl-1,6-hexanediamine, N, N′-diethyl-1, 6-Hexanediamine N, N ', N' '- trimethylbis (hexamethylene) triamine, and the like.

  Specific examples of the aromatic polyamine and nitrogen-containing heterocyclic amine include diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tris (dimethylaminomethyl) phenol, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, Examples include 3-amino-1,2,4-triazole.

  In the polyamine compound, one or more of its hydrogen atoms may be substituted with an alkyl group, an alkylene group, an aralkylene group, an oxy group, an acyl group, a halogen atom, etc., and the skeleton has an oxygen atom or a sulfur atom. And may contain a heteroatom such as.

  Moreover, the said polyamine compound may be used individually by 1 type, or may use 2 or more types together. The mixing ratio in the case of using two or more kinds in combination can be adjusted to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.

  Among the polyamine compounds exemplified above, hexamethylenediamine, N, N′-dimethyl-1,6-hexanediamine, diaminodiphenylsulfone, etc. are highly effective in improving compression set resistance, mechanical strength, particularly tensile strength. preferable.

  As long as the polyol compound is a compound having two or more hydroxyl groups, the molecular weight and skeleton thereof are not particularly limited, and examples thereof include the following polyether polyols, polyester polyols, other polyols, and mixed polyols thereof. It is done.

  Specific examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3- At least one selected from polyhydric alcohols such as butanediol, 1,4-butanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxyphenylmethane, pentaerythritol, ethylene oxide, propylene oxide, butylene Polyols obtained by adding at least one selected from oxide, styrene oxide and the like; polyoxytetramethylene oxide; and the like may be used, and these may be used alone or in combination of two or more.

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

  Specific examples of other polyols include, for example, polymer polyol, polycarbonate polyol; polybutadiene polyol; hydrogenated polybutadiene polyol; acrylic polyol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, Hexanediol, polyethylene glycol laurylamine (for example, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (for example, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine) Polyethylene glycol octylamine (for example, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octyl Amines (eg, N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine ( For example, low molecular polyols such as N, N-bis (2-methyl-2-hydroxyethyl) stearylamine) may be used, and these may be used alone or in combination of two or more.

Polyisocyanate compounds include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI). ), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5 -Aromatic polyisocyanates such as naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (N DI) of an aliphatic polyisocyanate, trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (hydrogenated MDI), H ₆ TDI (hydrogenated TDI) Diisocyanate compounds such as cycloaliphatic polyisocyanates, etc .; polyisocyanate compounds such as polymethylene polyphenylene polyisocyanates; carbodiimide-modified polyisocyanates of these isocyanate compounds; isocyanurate-modified polyisocyanates of these isocyanate compounds; Urethane prepolymers obtained by reacting with the polyol compounds exemplified in the above, and the like. These may be used alone or in combination of two or more.

  As long as the polythiol compound is a compound having two or more thiol groups, its molecular weight and skeleton are not particularly limited. Specific examples thereof include methanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, , 9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1,2-propanedithiol, 1,3-propadithiol, toluene-3,4-dithiol, 3,6-dichloro-1, 2-benzenedithiol, 1,5-naphthalenedithiol, 1,2-benzenedimethanethiol, 1 3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 4,4′-thiobisbenzenethiol, 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6- Dioxaoctane, 1,5-dimercapto-3-thiapentane, 1,3,5-triazine-2,4,6-trithiol (trimercapto-triazine), 2-di-n-butylamino-4,6-dimercapto -S-triazine, trimethylolpropane tris (β-thiopropionate), trimethylolpropane tris (thioglycolate), polythiol (thiocol or thiol-modified polymer (resin, rubber, etc.)) and the like. You may use individually by 1 type or may use 2 or more types together.

  As a functional group capable of generating at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers by reacting with such “compounds that form a covalent bond” Preferred examples include a cyclic acid anhydride group, a hydroxyl group, an amino group, a carboxy group, an isocyanate group, and a thiol group.

The other side chain containing a covalent bond cross-linking site is not particularly limited as long as it is a side chain having such a functional group.
In the thermoplastic elastomer (A) used in the composition of the present invention, the crosslinking at the covalent cross-linking site, that is, the cross-linking by the covalent bond between the functional group and the above-mentioned “compound that generates a covalent bond” is 1 It is preferable to have at least one in the molecule, and in particular, when at least one bond selected from the group consisting of lactone, urethane, ether, thiourethane and thioether forms a crosslink, two or more are present. It is preferable to have 2-20, more preferably 2-10.
In the present invention, the crosslinking at the covalent crosslinking site contains a tertiary amino group (-N =). The compression set and mechanical strength of the resulting composition of the present invention ( This is preferable because the elongation at break and the strength at break are further improved. This is considered to be because the tertiary amino group is further bonded to the carbonyl-containing group and the nitrogen-containing heterocycle to form a hydrogen bond (interaction), thereby further improving the crosslinking density. Therefore, as the “compound that forms a covalent bond”, among those exemplified above, polyethylene glycol laurylamine (eg, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (eg, N , N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (eg, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octylamine (eg, N, N -Bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (for example, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine (for example, N, N- Scan is preferably (2-methyl-2-hydroxyethyl) stearylamine).

  In the present invention, it is preferable that the cross-linking at the covalent cross-linking site contains at least one structure represented by any of the following formulas (19) to (21). More preferably contains a tertiary amino group.

  In the formula, K, L, Q and R 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; It is an organic group which may contain an atom or a group, and T is a hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom and which may be branched.

Here, each of the substituents K, L, Q, and R is independently the same as the substituent B in the above formula (1).
Specific examples of the substituent T include, for example, a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, a 1,6-hexylene group, Alkylene groups such as 1,7-heptylene group, 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 1,11-undecylene group, 1,12-dodecylene group; N, N-diethyl Dodecylamine-2,2'-diyl, N, N-dipropyldodecylamine-2,2'-diyl, N, N-diethyloctylamine-2,2'-diyl, N, N-dipropyloctylamine- 2,2'-diyl, N, N-diethylstearylamine-2,2'-diyl, N, N-dipropylstearylamine-2,2'-diyl; vinylene group; 1,4-cyclohexylene group Divalent such as Alicyclic hydrocarbon group; divalent aromatic hydrocarbon group such as 1,4-phenylene group, 1,2-phenylene group, 1,3-phenylene group, 1,3-phenylenebis (methylene) group; propane Trivalent carbonization such as -1,2,3-triyl, butane-1,3,4-triyl, trimethylamine-1,1 ′, 1 ″ -triyl, triethylamine-2,2 ′, 2 ″ -triyl A hydrogen group; a tetravalent hydrocarbon group represented by the following formulas (27) and (28); and a substituent formed by combining these;

  Furthermore, in the present invention, the crosslinking at the covalent crosslinking site is represented by any one of the following formulas (22) to (24) which are bonded to the main chain of the elastomeric polymer at the α-position or β-position. It is preferable that at least one structure is contained, and it is more preferable that T in the formula contains a tertiary amino group. Specific examples of the structure represented by any one of the following formulas (22) to (24) include compounds represented by the following formulas (29) to (40).

  Here, the substituents K, L, Q and R are each independently the same as the substituents K, L, Q and R in the above formulas (19) to (21), and the substituent T is This is basically the same as the substituent T in the formula (19).

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

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

  In the present invention, the cross-linking at the covalent cross-linking site is preferably formed by a reaction between a cyclic acid anhydride group and a hydroxyl group or an amino group and / or an imino group.

  Further, the thermoplastic elastomer (A) used in the composition of the present invention preferably has a glass transition point of 25 ° C. or lower, and when the thermoplastic elastomer has two or more glass transition points, or two or more kinds. When the thermoplastic elastomer is used in combination, at least one of the glass transition points is preferably 25 ° C. or lower.

  The composition of the present invention contains one or more of such thermoplastic elastomers. The mixing ratio in the case of containing two or more kinds can be set to any ratio depending on the use in which the composition of the present invention is used, the physical properties required for the composition, and the like.

The method for producing the thermoplastic elastomer (A) used in the composition of the present invention is not particularly limited, and an ordinary method can be selected. Specifically, the elastomer contains a cyclic acid anhydride group in the side chain. A nitrogen-containing heterocycle is added to an elastomeric polymer containing a side chain of a reaction step (hereinafter simply referred to as “reaction step A”) in which a compound capable of introducing an imino group is reacted with a functional polymer. The production method preferably includes a reaction step (hereinafter simply referred to as “reaction step B”) in which a compound that can be introduced is reacted.
When both the reaction step A and the reaction step B are provided, the reaction step B may be provided as a step performed simultaneously with the reaction step A, even if it is provided before or after the reaction step A. However, it is preferably provided as a subsequent step of the reaction step A.
Hereinafter, an elastomeric polymer containing a cyclic acid anhydride group in the side chain, a compound capable of introducing an imino group, a compound capable of introducing a nitrogen-containing heterocyclic ring, and reaction steps A and B will be described in detail.

(Elastomeric polymer containing cyclic acid anhydride groups in the side chain)
An elastomeric polymer containing a cyclic acid anhydride group in the side chain is an elastomeric polymer in which the cyclic acid anhydride group has a chemically stable bond (covalent bond) to the atom forming the main chain. In other words, it is obtained by reacting the elastomeric polymer with a compound capable of introducing a cyclic acid anhydride group.
Specific examples of the compound capable of introducing a cyclic acid anhydride group include cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride.

In the present invention, the elastomeric polymer containing a cyclic acid anhydride group in the side chain is obtained by subjecting the cyclic polymer to a cyclic acid by the usual method, for example, the usual conditions such as stirring under heating. An anhydride may be produced by a graft polymerization method, or a commercially available product may be used.
Examples of commercially available products include maleic anhydride-modified isoprene rubbers such as LIR-403 (manufactured by Kuraray Co., Ltd.) and LIR-410A (Kuraray Co., Ltd.); modified isoprene rubbers such as LIR-410 (manufactured by Kuraray Co., Ltd.); , 221 and 231 (manufactured by Policer), carboxy-modified nitrile rubber; CPIB (manufactured by Nisseki Chemical), carboxy-modified polybutene such as HRPIB (manufactured by Nisseki Chemical Co., Ltd.); Nucrel (manufactured by DuPont Mitsui Polychemical) , Maleic anhydride modified ethylene-propylene rubber such as Yucaron (Mitsubishi Chemical Co., Ltd.), Tuffmer M (for example, MA8510 (Mitsui Chemicals)), etc. Anhydrous maleic such as Tuffmer M (for example, MH7020 (Mitsui Chemicals)) Acid-modified ethylene-butene rubber; Adtex series (maleic anhydride-modified E A, maleic anhydride modified EMA (manufactured by Nippon Polyolefin Co., Ltd.), HPR series (maleic anhydride modified EEA, maleic anhydride modified EVA (manufactured by Mitsui & DuPont Polyolefin)), Bond Fast series (maleic anhydride modified EMA (Sumitomo) Chemical)), Dumiran series (maleic anhydride modified EVOH (manufactured by Takeda Pharmaceutical Company Limited)), Bondine (maleic anhydride modified EEA (manufactured by Atofina)), Tuftec (maleic anhydride modified SEBS, M1943 (Asahi Kasei Corporation) Manufactured)), Kraton (maleic anhydride modified SEBS, FG1901X (manufactured by Kraton Polymer)), tufprene (maleic anhydride modified SBS, 912 (produced by Asahi Kasei)), Septon (maleic anhydride modified SEPS (produced by Kuraray)) Lexpearl (maleic anhydride modified EE ET-182G, 224M, 234M (manufactured by Nippon Polyolefin Co., Ltd.)), maleic anhydride-modified polyethylene such as Aurorene (maleic anhydride-modified EEA, 200S, 250S (manufactured by Nippon Paper Chemical Co., Ltd.)); Admer (for example, QB550, LF128 (manufactured by Mitsui Chemicals)) and the like;

(Compound capable of introducing imino group)
A compound capable of introducing an imino group is a compound having an imino group that does not constitute a part of a cyclic compound such as a heterocyclic ring and other active hydrogen groups (for example, a hydroxyl group, a thiol group, an amino group, etc.) in the molecule. Specific examples are not particularly limited, and specific examples thereof include N-methylaminoethanol, N-ethylaminoethanol, Nn-propylaminoethanol, Nn-butylaminoethanol, Nn-pentylaminoethanol, N -N-hexylaminoethanol, Nn-heptylaminoethanol, Nn-octylaminoethanol, Nn-nonylaminoethanol, Nn-decylaminoethanol, Nn-undecylaminoethanol, N- n-dodecylaminoethanol, N- (2-ethylhexyl) aminoethanol, N-methylaminopropa And alkylamino alcohols such as N-methylaminobutanol; aromatic aminoalcohols such as N-phenylaminoethanol, N-toluylaminoethanol, N-phenylaminopropanol and N-phenylaminobutanol; N-methylamino Alkylaminothiols such as ethanethiol, N-ethylaminoethanethiol, Nn-propylaminoethanethiol, Nn-butylaminoethanethiol, N-methylaminopropanethiol, N-methylaminobutanethiol; N- Aromatic aminothiols such as phenylaminoethanethiol, N-toluylaminoethanethiol, N-phenylaminopropanethiol, N-phenylaminobutanethiol; N-methylethylenediamine, N-ethylethylene Alkyl diamines such as amines, Nn-propylethylenediamine, N-methylpropanediamine, N-ethylpropanediamine, N-methylbutanediamine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine; N- And aromatic diamines such as phenylethylenediamine, N-phenylpropanediamine, N-phenylbutanediamine, and N, N′-diphenylethylenediamine;
Of these, Nn-butylaminoethanol, Nn-octylaminoethanol, and Nn-dodecylaminoethanol are preferable.

(Compound capable of introducing nitrogen-containing heterocycle)
The compound capable of introducing a nitrogen-containing heterocyclic ring may be the nitrogen-containing heterocyclic ring itself exemplified above, and a substituent that reacts with a cyclic acid anhydride group such as maleic anhydride (for example, a hydroxyl group, a thiol group, It may be a nitrogen-containing heterocyclic ring having an amino group or the like.

(Reaction step A)
In the reaction step A, a compound capable of introducing an imino group and an elastomeric polymer containing a cyclic acid anhydride group in the side chain are mixed, and the compound and the cyclic acid anhydride group can be chemically bonded. It is a step of reacting (for example, 60 to 250 ° C.) (opening a cyclic acid anhydride group). By this reaction, the structure represented by the above formula (2) or (3) is contained in the side chain of the thermoplastic elastomer obtained.
Moreover, what is necessary is just to make the compound which can introduce | transduce an imino group react with a part or whole quantity of the cyclic acid anhydride group contained in the side chain of the said elastomeric polymer. The part is preferably 1 mol% or more, more preferably 10 mol% or more, and particularly preferably 30 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. Within this range, high physical properties (for example, breaking properties) are sufficiently developed, and compression set resistance becomes better when a non-pneumatic tire is formed.

(Reaction step B)
In the reaction step B, a compound capable of introducing a nitrogen-containing heterocycle and an elastomeric polymer containing a cyclic acid anhydride group in the side chain are mixed, and the compound and the cyclic acid anhydride group are chemically bonded. This is a step of reacting (opening a cyclic acid anhydride group) at an allowable temperature (for example, 60 to 250 ° C.). By this reaction, the structure represented by the above formula (5) or (6) is contained in the side chain of the thermoplastic elastomer obtained.
Moreover, what is necessary is just to make the compound which can introduce | transduce a nitrogen-containing heterocyclic ring react with a part or whole quantity of the cyclic acid anhydride group contained in the side chain of the said elastomeric polymer. The part is preferably 1 mol% or more, more preferably 50 mol% or more, particularly preferably 80 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. Within this range, the effect of introducing a nitrogen-containing heterocyclic ring is exhibited, and mechanical strength such as tensile strength at the time of crosslinking is further improved.

Further, when both the compound capable of introducing the imino group and the compound capable of introducing the nitrogen-containing heterocycle are used, both the reaction step A and the reaction step B are provided. In this case, the compound capable of introducing an imino group and the compound capable of introducing a nitrogen-containing heterocycle may be reacted with a part or all of the cyclic acid anhydride group contained in the side chain of the elastomeric polymer. . The reaction ratio of each compound with respect to the cyclic acid anhydride group is not particularly limited, but in total, it is preferably 1 mol% or more, more preferably 50 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. 80 mol% or more is particularly preferable. Within this range, wear resistance and compression set are better when a non-pneumatic tire is used.
The ratio of the reaction ratio of each compound to the cyclic acid anhydride group (compound capable of introducing an imino group: compound capable of introducing a nitrogen-containing heterocyclic ring) is preferably 1:99 to 99: 1. It is more preferably 10:90 to 99: 1, and particularly preferably 20:80 to 90:10.

Such a production method includes, for example, an elastomeric polymer containing a cyclic acid anhydride group in the side chain, a compound capable of introducing an imino group and / or a compound capable of introducing a nitrogen-containing heterocycle, of 60 to 250. It may be a method of mixing using a roll, a kneader, a pressure kneader, a Banbury mixer, a single screw extruder, a twin screw extruder, a universal stirrer and the like at a temperature of ° C.
Further, in such a production method, each group (structure) of the side chain of the thermoplastic elastomer, that is, an unreacted cyclic acid anhydride group, the above formulas (2), (3), (5), (6 ) And the like can be confirmed by commonly used analytical means such as NMR and IR spectra.

<Polyol compound (B)>
The polyol compound (B) used in the composition of the present invention is a compound having a melting point of 280 ° C. or less, two or more hydroxyl groups, and a hydroxyl value of 500 or more.
In the present invention, the melting point is a melting point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry). The temperature raising rate is preferably 10 ° C./min.
The hydroxyl value represents the number of mg of potassium hydroxide required to acetylate a hydroxyl group in 1 g of a sample, and is a value measured according to a method (potentiometric titration method) defined in JIS K0070: 1992.

As the polyol compound (B), specifically, for example,
Catechin (melting point: 175 to 177 ° C., hydroxyl value: 967), chlorogenic acid (melting point: 208 ° C., hydroxyl value: 792), 2- (4′-hydroxy-3′-methoxyphenyl) -3,5,7- Trihydroxy-4H-2,3-dihydro-1-benzopyran (melting point: 225-227 ° C., hydroxyl value: 738), resveratrol (melting point: 267 ° C., hydroxyl value: 713), 3,4,5-tri Polyphenols such as hydroxybenzoic acid (melting point: 250 ° C., hydroxyl value: 982);
Ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, melting point: 171 ° C., hydroxyl value: 980), ethylene-vinyl alcohol copolymer (ethylene content: 44 mol%, melting point: 164 ° C., hydroxyl value: 906), Vinyl alcohols such as polyvinyl alcohol (melting point: 150 to 230 ° C., hydroxyl value: 1380);
These may be used, and these may be used alone or in combination of two or more.

  Moreover, it is preferable that melting | fusing point is 270 degrees C or less from the viewpoint that the said polyol compound (B) penetrate | invades into the hydrogen bond crosslinked structure of rubber | gum, and makes it interact.

  In the present invention, the content of the polyol compound (B) is 0.1 to 20 parts by mass and 1 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). preferable.

<Plasticizer>
In the composition of the present invention, known plasticizers used for general resin compositions and rubber compositions can be used.
Specific examples of the plasticizer include oils such as paraffin oil, process oil, and aroma oil; liquid rubbers such as liquid polyisoprene (LIR), liquid polybutadiene (LBR), and liquid ethylene-propylene rubber (LEPM); Tetrahydrophthalic acid, azelaic acid, benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid and derivatives thereof; dioctyl phthalate (DOP), dibutyl Phthalate (DBP); polybutene; dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate; adipic acid B propylene glycol polyester, adipic acid butylene glycol polyester; and the like. These may be used alone or in combination of two or more.
Of these, oil and polybutene are preferably used from the viewpoint of oil bleeding and workability.

  In the composition of the present invention, the content in the case of containing the plasticizer is preferably 1 to 500 parts by mass, and 5 to 300 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). It is more preferable that it is 10 to 200 parts by mass. When the content of the plasticizer is within this range, the flexibility and workability of the resulting composition of the present invention are improved.

<Styrenic thermoplastic elastomer>
The composition of the present invention contains a styrenic thermoplastic elastomer because the viscosity at the time of mixing and melting becomes good, and the abrasion resistance and compression set resistance become better when a non-pneumatic tire is formed. preferable.
The styrenic thermoplastic elastomer is not particularly limited, but is a known styrenic thermoplastic elastomer obtained as a block copolymer from an aromatic vinyl compound and a conjugated diene, and is composed of aromatic vinyl corresponding to a crosslinking point at the terminal. It preferably has a block polymerization portion and has a weight average molecular weight of 100,000 or more.
Specific examples of the aromatic vinyl compound include styrene, α-methyl styrene, 3-methyl styrene, 4-propyl styrene, and the like. You may use together.
Specific examples of the conjugated diene include butadiene, isoprene, and mixtures thereof.

In the present invention, the method for producing the styrenic thermoplastic elastomer is not particularly limited. For example, the polymer (block (A)) obtained by polymerizing the aromatic vinyl compound and the conjugated diene are polymerized. A method obtained by copolymerization (block copolymerization) with the obtained polymer (block (B)) is preferably exemplified.
Here, the number average molecular weight of the block (A) is preferably in the range of 3000 to 50000. When the molecular weight is within this range, the mechanical strength of the resulting styrenic thermoplastic elastomer is good, and the compression set resistance when obtaining the composition of the present invention using the styrenic thermoplastic elastomer is good.
Moreover, it is preferable that the number average molecular weights of the said block (B) are the range of 10,000-200000. When the molecular weight is within this range, the viscosity at the time of mixing and melting in obtaining the composition of the present invention using the resulting styrenic thermoplastic elastomer becomes good, and the viscosity at the time of mixing and melting of the resulting composition of the present invention is high. It becomes good.
Furthermore, the styrenic thermoplastic elastomer obtained as a block copolymer has one or more blocks (A) and one or more blocks (B), and the block form is A- (BA ) _N or (AB) _m . Among these, the form of A-B-A is preferable because the fluidity and mechanical properties are good, and the form of using AB and A-B-A together is also possible.

  In the present invention, the styrene thermoplastic elastomer preferably has a styrene content of 10 to 60% by mass, more preferably 30 to 50% by mass. When the styrene content is in this range, the wear resistance and compression set are better when a non-pneumatic tire is formed.

Specific examples of such styrenic thermoplastic elastomers include, for example, hydrogenated styrene-isoprene block copolymer (SEPS: styrene ethylene propylene styrene block copolymer), styrene ethylene ethylene propylene styrene block copolymer. (Hereinafter referred to as “SEEPS”), styrene ethylene butylene styrene block copolymer (hereinafter referred to as “SEBS”), and the like.
In the present invention, as such a styrenic thermoplastic elastomer, commercially available products such as Septon 2006 (SEPS, manufactured by Kuraray Co., Ltd.), Septon 4055 (SEEPS, manufactured by Kuraray Co., Ltd.) can be used.

  In the composition of the present invention, the content of the styrenic thermoplastic elastomer is preferably 1 to 500 parts by mass, and 30 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). More preferably, it is more preferably 50 to 150 parts by mass. When the content of the styrenic thermoplastic elastomer is within this range, the wear resistance and compression set are better when a non-pneumatic tire is formed.

<Additives>
The composition of the present invention is a filler formed by introducing a polymer other than the thermoplastic elastomer (A), a reinforcing agent (filler), and an amino group, if necessary, within a range not impairing the object of the present invention. (Hereinafter simply referred to as “amino group-introduced filler”), amino group-containing compounds other than the amino group-introduced filler, compounds containing metal elements (hereinafter simply referred to as “metal salts”), maleic anhydride-modified polymer , Antioxidants, antioxidants, pigments (dyes), UV absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrants, rust inhibitors, adhesion promoters, antistatic agents, fillers Various additives such as can be contained.

As the additive and the like, commonly used ones can be used, and specific examples thereof are shown below, but are not limited to those exemplified.
As the polymer other than the thermoplastic elastomer (A), a polymer having a glass transition temperature of 25 ° C. or lower is preferable as described above. Specifically, for example, natural rubber (NR), isoprene rubber (IR), polyethylene (PE), polypropylene (PP), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), Examples include acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), etc. A polymer having no unsaturated bond of IIR, EPM, EBM or a polymer having a low unsaturated bond (for example, EPDM) is preferred. A polymer having a site capable of hydrogen bonding is also preferable, and examples thereof include polyester, polylactone, polyamide and the like.
In the composition of the present invention, the polymer other than the thermoplastic elastomer (A) may contain one kind or two or more kinds, and the content of the polymer is 100 masses of the thermoplastic elastomer (A). The amount is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass with respect to parts.

The reinforcing agent preferably contains carbon black and / or silica. The type of the carbon black is appropriately selected according to the use. Generally, carbon black is classified into hard carbon and soft carbon based on the particle diameter. Soft carbon has low reinforcement to rubber, and hard carbon has strong reinforcement to rubber.
The content of carbon black (when used alone) is 1 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 00 parts by weight of the thermoplastic elastomer (A). More preferably, it is 80 parts by mass.

Silica is not particularly limited, and specifically, for example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, diatomaceous earth, etc., the content (when silica alone is used) is It is 1-200 mass parts with respect to 100 mass parts of said thermoplastic elastomer (A), It is preferable that it is 10-100 mass parts, and it is more preferable that it is 20-80 mass parts. Of these, precipitated silica is preferred.
When silica is used as the reinforcing agent, a silane coupling agent can be used in combination. Examples of the silane coupling agent include bis (triethoxysilylpropyl) tetrasulfide (Si69), bis (triethoxysilylpropyl) disulfide (Si75), γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and the like. Moreover, the aminosilane compound mentioned later can also be used.

  When carbon black and silica are used in combination, the content (total amount of carbon black and silica) is 1 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A), and 10 to 100 parts by mass. It is preferable that it is 20 to 80 parts by mass.

  Specific examples of reinforcing agents other than carbon black and silica include, for example, iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, and kaolin. Examples include clay and fired clay. The content of these reinforcing agents is preferably 10 to 100 parts by mass and more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).

  Examples of the filler that serves as a base for the amino group-introduced filler (hereinafter sometimes referred to simply as “filler that serves as a base”) include fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, Silicas such as diatomaceous earth; carbon black, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, kaolin clay, calcined clay, etc. Silica, carbon black, and calcium carbonate are preferable, and silica is more preferable from the viewpoint of easy introduction of groups and easy adjustment of the introduction ratio (introduction ratio).

The amino group introduced into the filler serving as the substrate (hereinafter sometimes simply referred to as “amino group”) is not particularly limited, and specific examples thereof include aliphatic amino groups, aromatic amino groups, and complex groups. Examples thereof include an amino group constituting a ring and a plurality of mixed amino groups of these amino groups.
Here, in the present invention, an amino group having an amino group in an aliphatic amine compound is bonded to an aliphatic amino group, an aromatic group having an amino group bonded to an aromatic group, and an amino group having an amino group in a heterocyclic amine compound. It is called a heterocyclic amino group.
Among these, from the viewpoint of appropriately forming an interaction with the thermoplastic elastomer (A) and being effectively dispersible in the thermoplastic elastomer, a mixture containing a heterocyclic amino group and a heterocyclic amino group An amino group or an aliphatic amino group is preferable, and a heterocyclic amino group or an aliphatic amino group is preferable.

The series of the amino group is not particularly limited, and may be any of primary (—NH ₂ ), secondary (imino group,> NH), tertiary (> N—) or quaternary (> N ⁺ <). May be.
When the amino group is primary, the interaction with the thermoplastic elastomer (A) tends to be strong, and gelation may occur depending on the conditions for preparing the composition. On the other hand, when the amino group is tertiary, the interaction with the thermoplastic elastomer (A) tends to be weak, and the improvement effect such as compression set resistance when used as a composition may be small.
From such a viewpoint, the series of the amino group is preferably primary or secondary, and more preferably secondary.

  That is, the amino group is preferably a heterocyclic amino group, a mixed amino group containing a heterocyclic amino group, or a primary or secondary aliphatic amino group, and is preferably a heterocyclic amino group or a primary or secondary amino group. Particularly preferred is an aliphatic amino group.

  It is sufficient that at least one amino group is present on the surface of the filler serving as the substrate, but it is preferable to have a plurality of amino groups from the viewpoint of excellent effect of improving compression set resistance and the like when used as a composition.

In the case of having a plurality of amino groups, at least one of the plurality of amino groups is preferably a heterocyclic amino group, and further a primary or secondary amino group (an aliphatic amino group, an aromatic amino group, a complex amino group). It is more preferable to have a cyclic amino group.
Moreover, the kind and series of an amino group can arbitrarily adjust the said amino group according to the physical property requested | required of a composition.

The amino group-introduced filler is obtained by introducing the amino group into the filler serving as the substrate.
The method for introducing the amino group is not particularly limited, and specific examples thereof include surface treatment methods generally used for various fillers, reinforcing agents, etc. (for example, surface modification methods, surface coating methods, etc.). Can be mentioned. Preferred methods include a method of reacting a compound having a functional group capable of reacting with the filler serving as the substrate and an amino group with the filler (surface modification method), and a filler serving as the substrate with a polymer having an amino group. The method of coating the surface (surface coating method) or the method of reacting a compound having an amino group or the like in the synthesis process of the filler.

The amino group-introduced fillers may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.
The content of the amino group-introduced filler is preferably 1 to 200 parts by mass, more preferably 10 parts by mass or more, and 30 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). The above is particularly preferable.

The amino group-containing compound other than the amino group-introduced filler will be described.
The amino group in the amino group-containing compound is basically the same as that described in the amino group-introduced filler, and is not particularly limited as long as the amino group content is 1 or more. It is preferable that the number is at least one because the thermoplastic elastomer (A) can form two or more crosslinks and is excellent in the effect of improving physical properties.

The series of the amino group in the amino group-containing compound is not particularly limited, and is the same as the amino group in the amino group-introduced filler, primary (—NH ₂ ), secondary (imino group,> NH), tertiary ( > N-) or quaternary (> N ⁺ <), which is optional depending on physical properties such as recyclability, compression set resistance, mechanical strength and hardness required for the composition of the present invention. Can be selected. When a secondary amino group is selected, mechanical strength tends to be excellent, and when a tertiary amino group is selected, recyclability tends to be excellent. In particular, it is preferable to have two secondary amino groups because the resulting composition of the present invention is excellent in recyclability and compression set resistance, and also in the balance of both physical properties.
In the case where the amino group-containing compound contains two or more amino groups, the number of primary amino groups in the amino group-containing compound is preferably 2 or less, and 1 or less. More preferably. When it has 3 or more primary amino groups, the (crosslinking) bond formed by the amino group and the functional group in the thermoplastic elastomer (A) (particularly, the carboxy group that is a carbonyl-containing group) becomes strong, It may impair excellent recyclability.

  That is, the series and number of amino groups and the structure of the amino group-containing compound are appropriately adjusted and selected in consideration of the bonding strength between the functional group in the thermoplastic elastomer (A) and the amino group in the amino group-containing compound. can do.

Specific examples of such an amino group-containing compound include N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-dimethyl-1,3- Propanediamine, N, N'-diethyl-1,3-propanediamine, N, N'-diisopropyl-1,3-propanediamine, N, N'-dimethyl-1,6-hexanediamine, N, N'- Secondary aliphatic diamines such as diethyl-1,6-hexanediamine and N, N ′, N ″ -trimethylbis (hexamethylene) triamine; Tertiary aliphatics such as tetramethyl-1,6-hexanediamine Diamines; polyamines containing aromatic primary amines such as aminotriazole and aminopyridine and heterocyclic amines; such as dodecylamine Tertiary heterocyclic diamines such as dipyridyl; alkyl monoamine etc., compression set, the improvement of mechanical strength is preferably exemplified by higher reasons.
Of these, secondary aliphatic diamines, polyamines containing aromatic primary amines and heterocyclic amines, or tertiary heterocyclic diamines are more preferred.

  In addition to these examples, a polymer compound having an amino group can be used as the amino group-containing compound.

The polymer compound having an amino group is not particularly limited, and specific examples thereof include polyamide, polyurethane, urea resin, melamine resin, polyvinylamine, polyallylamine, polyacrylamide, polymethacrylamide, polyaminostyrene, amino group-containing poly Examples thereof include polymers such as siloxane, and polymers obtained by modifying various polymers with a compound having an amino group.
The physical properties such as average molecular weight, molecular weight distribution, and viscosity of these polymers are not particularly limited, and may be any physical property depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like. be able to.

  The polymer compound having an amino group is preferably a polymer obtained by polymerizing (polyaddition or polycondensation) a condensable or polymerizable compound (monomer) having an amino group. A polysiloxane having an amino group which is a single condensate of a silyl compound having a group or a cocondensate of the silyl compound and a silyl compound having no amino group, is easily available, easy to produce, and has a molecular weight It is more preferable because it is easy to adjust the amino acid and the amino group introduction rate.

The silyl compound having a hydrolyzable substituent and an amino group is not particularly limited, and examples thereof include aminosilane compounds. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ An aminosilane compound having an aliphatic primary amino group such as aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane (manufactured by Nihon Unicar); N, N-bis [(3-trimethoxysilyl) propyl] amine, N, N-bis [(3-triethoxysilyl) propyl] amine, N, N-bis [(3-tripropoxysilyl) propyl] amine (Nippon Unicar Company), 3- (n-butylamino) propyltrimethoxysilane (Dyn Silane 1189 (manufactured by Degussa Huls)), N-ethyl-aminoisobutyltrimethoxysilane (Silquest A-Link 15 silane, manufactured by OSi Specialties) and other aminosilane compounds having an aliphatic secondary amino group; N-β (aminoethyl) ) Aliphatic primary such as γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane (Nihon Unicar) And aminosilane compounds having secondary amino groups; aminosilane compounds having aromatic secondary amino groups such as N-phenyl-γ-aminopropyltrimethoxysilane (Nihon Unicar); imidazole trimethoxysilane (Japan Energy) Ami And the like are; triazole and epoxysilane compound or isocyanate silane compounds and the presence or absence of a catalyst, the aminosilane compound having a heterocyclic amino group, such as triazole silane obtained by reacting at room temperature or above.
Among these, from the viewpoint of high effect of improving physical properties such as compression set resistance, the above-mentioned aminosilane compounds having an aliphatic primary amino group, aminosilane compounds having an aliphatic secondary amino group, and aliphatic primary and 2 An aminoalkylsilane compound of an aminosilane compound having a secondary amino group is preferable.

The silyl compound not having an amino group is not particularly limited as long as it is a compound different from the silyl compound having a hydrolyzable substituent and an amino group and does not contain an amino group. Examples include alkoxysilane compounds and halogenated silane compounds. Of these, alkoxysilane compounds are preferred from the viewpoints of availability, easy handling, and excellent physical properties of the resulting cocondensate.
Specific examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, and methyltriisopropoxysilane. , Phenyltrimethoxysilane, dimethyldimethoxysilane and the like.
Specific examples of the halogenated silane compound include tetrachlorosilane and vinyltrifluorosilane.
Of these, tetraethoxysilane and tetramethoxysilane are preferred from the viewpoint of low cost and safe handling.

  The silyl compound having a hydrolyzable substituent and an amino group and the silyl compound not having an amino group may be used alone or in combination of two or more.

  Such a polymer compound having an amino group may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.

Further, the content of the polymer compound having an amino group can be defined by the number of nitrogen atoms (equivalent) in the compound with respect to the side chain of the thermoplastic elastomer (A) as in the case of the amino group-containing compound. However, there may be an amino group that cannot effectively form an interaction with the thermoplastic elastomer depending on the structure and molecular weight of the polymer compound.
Therefore, the content of the polymer compound having an amino group is preferably 1 to 200 parts by mass, more preferably 5 parts by mass or more, with respect to 100 parts by mass of the thermoplastic elastomer (A). It is particularly preferably 10 parts by mass or more.

The metal salt is not particularly limited as long as it is a compound containing at least one metal element, and is composed of Li, Na, K, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Al. A compound containing one or more metal elements selected from the group is preferable.
Specific examples of the metal salt include saturated fatty acid salts having 1 to 20 carbon atoms such as formate, acetate and stearate containing one or more of these metal elements, and (meth) acrylates. And unsaturated fatty acid salts such as, metal alkoxides (reactants with alcohols having 1 to 12 carbon atoms), nitrates, carbonates, bicarbonates, chlorides, oxides, hydroxides, complexes with diketones, and the like. .
Here, the “complex with diketone” refers to a complex in which a 1,3-diketone (for example, acetylacetone) or the like is coordinated to a metal atom.

  Of these, from the viewpoint of further improving the compression set resistance of the composition of the present invention obtained, Ti, Al, and Zn are preferable as the metal element, and these acetates, stearates, and the like as the metal salts C1-C20 saturated fatty acid salts, metal alkoxides (reactants with C1-C12 alcohols), oxides, hydroxides, complexes with diketones are preferred, and C1-C20 such as stearates. Particularly preferred are saturated fatty acid salts, metal alkoxides (reactants with alcohols having 1 to 12 carbon atoms), and complexes with diketones.

  The said metal salt may be used individually by 1 type, or may use 2 or more types together. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.

  It is preferable that content of the said metal salt is 0.05-3.0 equivalent with respect to the carbonyl group contained in the said thermoplastic elastomer (A), and it is 0.1-2.0 equivalent. More preferred is 0.2 to 1.0 equivalent. When the content of the metal salt is within this range, the resulting composition of the present invention is preferably improved in physical properties such as compression set resistance, mechanical strength and hardness.

In addition, as the metal salt, any hydroxide, metal alkoxide, carboxylate, or the like that the metal can take can be used. For example, taking a hydroxide as an example, when the metal is iron, Fe (OH) ₂ and Fe (OH) ₃ may be used alone or in combination.
Further, as described above, the metal salt is one or more selected from the group consisting of Li, Na, K, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Al. Although it is preferable that it is a compound containing a metal element, you may contain metal elements other than these in the range which does not impair the effect of this invention. Although the content rate of metal elements other than these is not specifically limited, For example, it is preferable that it is 1-50 mol% with respect to all the metal elements in the said metal salt.

  The maleic anhydride-modified polymer is a polymer obtained by modifying the elastomeric polymer with maleic anhydride, and the side chain of the maleic anhydride-modified polymer is other than a maleic anhydride residue and a nitrogen-containing heterocyclic ring. However, it is preferable to have only a maleic anhydride residue.

The maleic anhydride residue is introduced (modified) into the side chain or terminal of the elastomeric polymer and is not introduced into the main chain of the elastomeric polymer. The maleic anhydride residue is a cyclic acid anhydride group, and the cyclic acid anhydride group (part) does not open.
Therefore, as the maleic anhydride-modified thermoplastic polymer, for example, as shown in the following formula (41), a cyclic acid is added to the side chain obtained by reacting an ethylenically unsaturated bond portion of maleic anhydride with an elastomeric polymer. Examples include thermoplastic elastomers having an anhydride group and no nitrogen-containing heterocycle, and specific examples thereof include those exemplified for the above-described elastomeric polymer containing a cyclic acid anhydride group in the side chain. .

(In the formula, X represents an ethylene residue or a propylene residue, and l, m and n each independently represents a number of 0.1 to 80.)

  The amount of maleic anhydride modification is preferably 0.1 to 50 mol% with respect to 100 mol% of the main chain portion of the elastomeric polymer from the viewpoint of improving compression set resistance without impairing excellent recyclability. More preferably, it is 0.3-30 mol%, Most preferably, it is 0.5-10 mol%.

  The maleic anhydride-modified polymer may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to any ratio depending on the application in which the composition of the present invention is used, the physical properties required for the composition of the present invention, and the like.

The content of the maleic anhydride-modified polymer is preferably 1 to 100 parts by mass and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). When the content of the maleic anhydride-modified polymer is within this range, the processability and mechanical strength of the resulting composition of the present invention are improved, which is preferable.
In addition, when producing the thermoplastic elastomer of the present invention, specifically, in the reaction step A or B, if an elastomeric polymer containing a cyclic acid anhydride group in the side chain remains as an unreacted product, Without removing the carbonyl-containing group-modified elastomer, the composition of the present invention can be contained as it is.

Specific examples of the anti-aging agent include hindered phenol compounds, aliphatic and aromatic hindered amine compounds, and the like.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Specific examples of the pigment include, for example, titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and other inorganic pigments, azo pigments, copper phthalocyanine pigments, and the like. Organic pigments and the like.

Specific examples of the ultraviolet absorber include 2-hydroxybenzophenone, benzotriazole, and salicylic acid ester.
Specific examples of the flame retardant include phosphorus-based materials such as TCP, halogen-based materials such as chlorinated paraffin and perchlorpentacyclodecane, antimony-based materials such as antimony oxide, and aluminum hydroxide.

Specific examples of the surfactant (leveling agent) include polybutyl acrylate, polydimethylsiloxane, a modified silicone compound, and a fluorine-based surfactant.
Specific examples of the dehydrating agent include vinyl silane and the like.

Specific examples of the rust inhibitor include zinc phosphate, tannic acid derivatives, phosphate esters, basic sulfonates, and various rust preventive pigments.
Specific examples of the adhesion imparting agent include known silane coupling agents, silane compounds having an alkoxysilyl group, titanium coupling agents, zirconium coupling agents, and the like. More specifically, trimethoxyvinylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like can be mentioned.
Generally as an antistatic agent, hydrophilic compounds, such as a quaternary ammonium salt or polyglycol and an ethylene oxide derivative, are mentioned.

  It is preferable that content of various additives other than the additive which mentions content above is 0.1-10 mass parts with respect to 100 mass parts of said thermoplastic elastomers (A), and 1-5 masses. More preferably, it is a part.

The thermoplastic elastomer (A) may be self-crosslinkable, but a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, a vulcanization retarder, etc. may be used in combination as long as the object of the present invention is not impaired. it can.
Examples of the vulcanizing agent include sulfur-based, organic peroxide-based, metal oxide-based, phenolic resin, quinone dioxime and other vulcanizing agents.
Specific examples of the sulfur vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, and the like.
Specific examples of the organic peroxide vulcanizing agent include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di- (T-Butylperoxy) hexane, 2,5-dimethylhexane-2,5-di (peroxylbenzoate) and the like.
Other examples include magnesium oxide, risurge (lead oxide), p-quinonedioxime, tetrachloro-p-benzoquinone, p-dibenzoylquinonedioxime, poly-p-dinitrosobenzene, and methylenedianiline.

Specific examples of the vulcanization aid include zinc oxide, magnesium oxide, and amines; fatty acids such as acetyl acid, propionic acid, butanoic acid, stearic acid, acrylic acid, and maleic acid; zinc acetylate, propionic acid. And fatty acid zinc such as zinc, zinc butanoate, zinc stearate, zinc acrylate, and maleate.
Specific examples of the vulcanization accelerator include thiurams such as tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (TETD); aldehydes / ammonias such as hexamethylenetetramine; guanidines such as diphenylguanidine; Thiazoles such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide (DM); sulfenes such as N-cyclohexyl-2-benzothiazylsulfenamide and Nt-butyl-2-benzothiazylsulfenamide Amide type; and the like. Furthermore, alkylphenol resins and their halides can also be used.
Specific examples of the vulcanization retarder include organic acids such as phthalic anhydride, benzoic acid, salicylic acid, and acetylsalicylic acid; N-nitrosodiphenylamine, N-nitrosophenyl-β-naphthylamine, N-nitroso- Nitroso compounds such as polymers of trimethyl-dihydroquinoline; halides such as trichloromelanin; 2-mercaptobenzimidazole; N- (cyclohexylthio) phthalimide (Santguard PVI);
The content of these vulcanizing agents is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).

  The curing conditions when the composition of the present invention is permanently crosslinked (with a vulcanizing agent) can be appropriately selected according to various components to be blended, and are not particularly limited. For example, curing conditions for curing at a temperature of 130 to 200 ° C. for 5 to 60 minutes are preferable.

When the composition of the present invention is heated to about 80 to 200 ° C., the three-dimensional crosslinked bond (crosslinked structure) is dissociated and softened to impart fluidity. This is considered to be because the interaction between the side chains formed between the molecules or within the molecule is weakened.
When the composition of the present invention softened and imparted with fluidity is allowed to stand at about 80 ° C. or less, the dissociated three-dimensional cross-linked bond (cross-linked structure) is re-bonded and cured. By repeating this, the composition of the present invention exhibits recyclability.

  The production method of the composition of the present invention is not particularly limited. For example, the thermoplastic elastomer (A), the styrenic thermoplastic elastomer, the plasticizer, and various additives that may be contained as necessary. , Rolls, kneaders, pressure kneaders, Banbury mixers, single screw extruders, twin screw extruders, universal agitators, and the like.

[Non-pneumatic tire]
The non-pneumatic tire of the present invention is a non-pneumatic tire having a tire body portion and a tire base portion partially or entirely surrounded by the tire body portion, and at least one of the tire body portion and the tire base portion. Part is a non-pneumatic tire composed of the composition of the present invention.

FIG. 1 is a schematic perspective view when an example of an embodiment of a non-pneumatic tire of the present invention is cut in a tire meridian direction.
In FIG. 1, a non-pneumatic tire 1 includes an annular tire base portion 3 and a tire main body portion (tread portion) 2 attached to the outer peripheral side thereof.
A groove portion 4 is formed on the side surface of the tire base portion 3 over the entire circumference of the tire, and is fitted to the rim of the wheel. In the illustrated example, the tire base 3 is a solid annular body, but it may be hollow to enhance the shock absorbing function. An intermediate layer may be provided between the tire base portion 3 and the tire main body portion (tread portion) 2.

In the non-pneumatic tire of the present invention, at least one material of the tire base portion and the tire main body portion (tread portion) is composed of the thermoreversible crosslinked elastomer composition of the present invention.
Moreover, when arrange | positioning an intermediate | middle layer between a tire base part and a tire main-body part (tread part), this intermediate | middle layer can also be comprised with the thermoreversible crosslinking elastomer composition of this invention.

  EXAMPLES Next, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited to these.

<Examples 1-3, Comparative Examples 1-4>
First, 100.0 g of maleic anhydride-modified ethylene-propylene copolymer (Admer QE060, manufactured by Mitsui Chemicals, hereinafter abbreviated as “maleinized EPM”) is put into a kneader set at 200 ° C. and masticated for 3 minutes. After that, 1 g of 4H-3-amino-1,2,4-triazole (ATA, manufactured by Otsuka Chemical Co., Ltd.) was added and kneaded for 10 minutes to prepare thermoplastic elastomer 1. By performing IR analysis, it was confirmed that the thermoplastic elastomer was introduced with a triazole ring.
Next, 100 g of paraffin oil (Diana Process Oil PW90, weight average molecular weight 540, manufactured by Idemitsu Kosan Co., Ltd.) is added as a plasticizer, and octadecyl-3- (3,5-di-t-butyl-4 is used as an anti-aging agent. 0.1 g of (hydroxyphenyl) propionate (AO-50, manufactured by ADEKA) was added.
Next, for Examples 1 to 3 and Comparative Examples 2 to 4, catechin (melting point: 175 to 177 ° C., hydroxyl value: 967), ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, melting point: 171 ° C., Hydroxyl value: 944), chlorogenic acid (melting point: 208 ° C., hydroxyl value: 792), nylon 11 (melting point: 187 ° C., hydroxyl value: 0), polylactic acid (melting point: 170-171, hydroxyl value: 0), and , Dihydroxyethyl bisphenol A (trade name: AE-2, hydroxyl value: 358, manufactured by Meisei Chemical Industry Co., Ltd.) is added by mass part shown in Table 1 below, and kneaded for 10 minutes until uniform. Thus, each thermoplastic elastomer composition was prepared.

<Example 4, Comparative Examples 5-6>
First, 100.0 g of maleated EPM (Admer QE060, manufactured by Mitsui Chemicals) was added to a kneader set at 200 ° C. and masticated for 3 minutes, and then 4H-3-amino-1,2,4-triazole ( 1 g of ATA (manufactured by Otsuka Chemical Co., Ltd.) was added and kneaded for another 10 minutes to prepare thermoplastic elastomer 1. By performing IR analysis, it was confirmed that the thermoplastic elastomer was introduced with a triazole ring.
Next, 100 g of paraffin oil (Diana Process Oil PW90, weight average molecular weight 540, manufactured by Idemitsu Kosan Co., Ltd.) was added as a plasticizer, and SEPS (Septon 4077, manufactured by Kuraray Co., Ltd.) was added as a styrene elastomer.
Next, for Example 4 and Comparative Example 6, an ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, melting point: 171 ° C., hydroxyl value: 944) and nylon 11 (melting point: 187 ° C., hydroxyl value: Each thermoplastic elastomer composition was prepared by adding 1 part by mass of 0) shown in Table 2 below and kneading for 10 minutes until uniform.

  The compression set, capillary viscosity, hardness, breaking strength and abrasion resistance index of each obtained thermoplastic elastomer composition were measured and evaluated by the following methods. These results are shown in Tables 1 and 2 below.

<Compression set>
Each of the obtained thermoplastic elastomer compositions was hot-pressed at 200 ° C. for 10 minutes to produce a sheet having a thickness of 2 mm, then seven sheets were superposed and hot-pressed at 200 ° C. for 20 minutes to obtain a cylindrical sample (diameter 29 × thickness 12.5 mm).
This cylindrical sample was compressed 23% with a dedicated jig, and the compression set after standing at 70 ° C. for 22 hours or 168 hours was measured according to JIS K6262: 2013.

<Capillary viscosity>
The capillary viscosity of each obtained thermoplastic elastomer composition at 230 ° C. and under a shear rate of 243 (s ⁻¹ ) was measured according to JIS K7199: 1999. When the value of the capillary viscosity is 500 Pa · s or less, the fluidity at high temperature is excellent.

<Hardness>
Each of the obtained thermoplastic elastomer compositions was hot press molded at 200 ° C. for 10 minutes, and then a flat plate sample having a thickness of 2 cm × length 15 cm × width 15 cm was produced. Three obtained flat plate samples were stacked, hot-pressed at 200 ° C. for 20 minutes, and A hardness was measured at room temperature in accordance with JIS K6253-3: 2012.

<Break strength>
Each obtained thermoplastic elastomer composition was hot-pressed at 180 ° C. for 10 minutes to produce a sheet having a thickness of 2 mm.
A No. 3 dumbbell-shaped test piece was punched from this sheet, a tensile test at a tensile speed of 500 mm / min was conducted according to JIS K6251: 2010, and a breaking strength (T _B ) [MPa] was measured at room temperature.

<Abrasion resistance index>
Each of the obtained thermoplastic elastomer compositions was hot-pressed at 180 ° C. for 10 minutes to prepare a disk-shaped test piece disk having a thickness of 2 mm and a diameter of 25 mm taken out from the outer surface portion in the thickness direction of the rubber layer.
About the produced test piece disk, the amount of wear was measured according to the “pico abrasion test” of JIS K6264-1: 2005. In Table 1 below, the index is displayed with the wear amount of Comparative Example 1 as the reference value 100, and in Table 2 below, the index is displayed with the wear amount of Comparative Example 5 as the reference value 100.
A similar evaluation was performed using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd., light source: sunshine carbon arc) at a temperature of 63 ° C. and an irradiation / rain cycle: 120 minutes irradiation / 18 minutes rainfall. The test specimens were also subjected to accelerated exposure for one day (168 hours).

As is apparent from Tables 1 and 2 above, Examples 1 to 3 blended with a polyol compound (B) having a melting point of 280 ° C. or lower, having two or more hydroxyl groups, and having a hydroxyl value of 500 or more. The thermoplastic elastomer composition has a markedly higher abrasion resistance index after sunshine weather than Comparative Example 1 (standard), and shows little change in compression set after standing for a long time. It was found that the low heat buildup and wear resistance were better when Further, even when a compound having a hydroxyl group is added, in Comparative Example 4 having a hydroxyl value of less than 500, compared to Comparative Example 1, it functions as a plasticizer because of a liquid material and becomes soft, but the compression set is large. From the improvement, it can be seen that the initial hydrogen bond-derived crosslinked structure itself is strengthened, but the wear resistance after being left for a long time is rather deteriorated.
Further, the same was found from the comparison between Example 4 in which a styrene elastomer was blended and Comparative Examples 5 and 6.

1 Non-pneumatic tire 2 Tire body (tread)
3 Tire base 4 Groove

Claims (9)

A thermoplastic elastomer (A) having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group;
A polyol compound (B) having a melting point of 280 ° C. or lower, two or more hydroxyl groups, and a hydroxyl value of 500 or more,
The thermoplastic elastomer composition for non-pneumatic tires, wherein the content of the polyol compound (B) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). The thermoplastic elastomer composition for non-pneumatic tires according to claim 1, wherein the side chain of the thermoplastic elastomer (A) contains a structure represented by the following formula (1).
Wherein A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups. The thermoplastic elastomer composition for non-pneumatic tires according to claim 1 or 2, wherein the side chain of the thermoplastic elastomer (A) contains a structure represented by the following formula (4).
Wherein E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; An organic group that may contain any atom or group of   The thermoplastic elastomer (A) has another side chain containing a covalent bond cross-linking site, and the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether in the covalent cross-link cross-linking site. The thermoplastic elastomer composition for non-pneumatic tires according to any one of claims 1 to 3, which can be crosslinked by at least one bond selected from the above.   The thermoplastic elastomer (A) has another side chain containing a covalent cross-linking site, and the cross-linking at the covalent cross-linking site is from amide, ester, lactone, urethane, ether, thiourethane and thioether. The thermoplastic elastomer composition for non-pneumatic tires according to any one of claims 1 to 3, which is formed by at least one bond selected from the group consisting of:   The thermoplastic elastomer composition for non-pneumatic tires according to any one of claims 1 to 5, wherein the elastomeric polymer constituting the main chain of the thermoplastic elastomer (A) is a polyolefin-based polymer. Furthermore, it contains a plasticizer,
The thermoplastic elastomer composition for non-pneumatic tire according to any one of claims 1 to 6, wherein a content of the plasticizer is 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). . Furthermore, containing a styrene-based elastomer,
The thermoplastic elastomer composition for non-pneumatic tire according to any one of claims 1 to 7, wherein the content of the styrene elastomer is 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). object. A non-pneumatic tire having a tire base portion and a tire base portion partially or entirely surrounded by the tire main body portion,
A non-pneumatic tire in which at least a part of the tire body portion and the tire base portion is composed of the thermoplastic elastomer composition for a non-pneumatic tire according to any one of claims 1 to 8.