JP2006232983A - Method for producing thermoplastic elastomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a thermoplastic elastomer allowing a reaction to proceed in a short time to prevent degradation of a rubber main chain and physical properties, and to provide a thermoplastic elastomer which has excellent recyclability and is excellent in mechanical strengths, particularly tensile properties and compression-set resistance. <P>SOLUTION: The method for producing a thermoplastic elastomer comprises allowing an elastomeric polymer having a side chain containing a cyclic acid anhydride group to react with a compound capable of introducing an imino group and/or a compound capable of introducing a nitrogen-containing heterocyclic ring in a single screw and/or a twin screw extruder to obtain a thermoplastic elastomer having a side chain containing an imino group and/or a nitrogen-containing heterocyclic ring and a carbonyl-containing group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a thermoplastic elastomer and a thermoplastic elastomer composition. Specifically, the present invention has a characteristic (hereinafter sometimes simply referred to as “recyclability”) capable of repeatedly reproducing cross-linking and dissociation by temperature change. The present invention relates to a thermoplastic elastomer having and a method for producing a thermoplastic elastomer composition containing the same.

In recent years, reuse of used materials is desired from the standpoints of environmental protection and resource saving. Cross-linked rubber (vulcanized rubber) has a stable three-dimensional network structure in which a polymer substance and a cross-linking agent (vulcanizing agent) are covalently bonded, and exhibits very high strength. Reforming is difficult. On the other hand, a thermoplastic elastomer utilizes physical cross-linking and can be easily molded by heating and melting without requiring a complicated vulcanization / molding process including pre-molding.
A typical example of such a thermoplastic elastomer includes a resin component and a rubber component, and at room temperature, the microcrystalline resin component serves as a hard segment serving as a crosslinking point of a three-dimensional network structure, and the rubber component (soft segment) Thermoplastic elastomers that prevent plastic deformation of the resin and that are plastically deformed by softening or melting of the resin component by increasing the temperature are known. However, since such a thermoplastic elastomer contains a resin component, the rubber elasticity tends to be lowered. Therefore, a material that can impart thermoplasticity without containing a resin component is required.

  In response to such a problem, the present inventor has previously proposed that a hydrogen-bonding thermoplastic elastomer comprising an elastomeric polymer having a carbonyl group-containing group and a heterocyclic amine-containing group in the side chain is subjected to a temperature change utilizing hydrogen bonds. The hydrogen bondable thermoplastic elastomer comprising the elastomeric polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in the side chain. As a method for producing the thermoplastic elastomer, an elastomeric polymer having a cyclic acid anhydride group in the side chain and a heterocyclic amine-containing compound are synthesized, and the heterocyclic amine-containing compound is chemically synthesized with a cyclic acid anhydride group. Have proposed a method for producing a thermoplastic elastomer that is obtained by reacting at a temperature at which it can be mechanically bonded (see, for example, Patent Document 1). See).

  The thermoplastic elastomer having such characteristics has high industrial utility value and environmental protection value, and further has high cross-linking strength, and there is no change in physical properties even after repeated cross-linking and cross-linking. It is expected as a material with excellent recyclability.

JP 2000-169527 A

However, the thermoplastic elastomer described in the above-mentioned Patent Document 1 is released after being compressed after being compressed for a predetermined time even when a filler or the like is blended, and mechanical strength as a composition, especially tensile properties (modulus, elongation at break, breaking strength). In some cases, the compression set at that time was not sufficient.
In addition, in the method for producing a thermoplastic elastomer described in Patent Document 1, the reaction (mixing) of an elastomeric polymer having a cyclic acid anhydride group in the side chain and a heterocyclic amine-containing compound results in poor shear efficiency. In some cases, it may take a long time, which may cause deterioration of the main rubber chain and deterioration of physical properties.

  Therefore, the present invention enables a reaction in a short time, maintains a method for producing a thermoplastic elastomer capable of preventing deterioration of the main chain of the rubber and deterioration of physical properties and excellent recyclability, and has a mechanical strength, particularly It is an object to provide a thermoplastic elastomer excellent in tensile properties and compression set.

  Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that an elastomeric polymer containing a cyclic acid anhydride group in the side chain and a compound capable of introducing a predetermined functional group are uniaxially and / or Or, by reacting in a twin-screw extruder, it has been found that a reaction in a short time is possible, and it is possible to unexpectedly suppress the deterioration of the main chain, and contains a predetermined structure obtained by this method. The present inventors have found that a thermoplastic elastomer having a side chain capable of maintaining good recyclability and excellent physical properties such as mechanical strength, tensile properties, and compression set resistance has been achieved. That is, the present invention relates to a method for producing a thermoplastic elastomer described in the following (I) to (XVI), a method for producing a thermoplastic elastomer composition described in (XVII), a thermoplastic elastomer described in (XVIII) and ( A thermoplastic elastomer composition as described in (XIX) and (XX) is provided.

  (I) An elastomeric polymer containing a cyclic acid anhydride group in the side chain, and a compound capable of introducing an imino group and / or a compound capable of introducing a nitrogen-containing heterocyclic ring, in a single-screw and / or twin-screw extruder. To produce a thermoplastic elastomer having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group (first embodiment).

  (II) The method for producing a thermoplastic elastomer according to (I), wherein the nitrogen-containing heterocycle of the compound into which the nitrogen-containing heterocycle can be introduced is a 5- or 6-membered ring.

  (III) The thermoplastic elastomer according to (II) above, wherein the nitrogen-containing heterocycle of the compound into which the nitrogen-containing heterocycle can be introduced is a triazole ring, thiadiazole ring, pyridine ring, thiazole ring, imidazole ring or hydantoin ring. Production method.

  (IV) The method for producing a thermoplastic elastomer according to any one of (I) to (III), wherein the side chain contains a structure represented by the following formula (1) and / or the following formula (2).

  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, and E is a nitrogen-containing heterocyclic ring.

  (V) The above side chain containing a structure represented by the following formula (3) or (4) and / or the following formula (5) or (6) bonded to the main chain at the α-position or β-position ( A method for producing a thermoplastic elastomer according to IV).

  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, and E is a nitrogen-containing heterocyclic ring.

  (VI) Production of the thermoplastic elastomer according to the above (IV), wherein the side chain contains a structure represented by the following formula (7), the following formula (8) or (9), or the following formula (10). Method.

  In the formula, 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. And 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.

  (VII) Any one of the following formula (11) or (12), the following formulas (13) to (16), or the following formula (17) or ( The manufacturing method as described in said (VI) containing the structure represented by 18).

  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.

  (VIII) The thermoplastic elastomer has another side chain containing a covalently bonded cross-linking site, and the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether in the covalently cross-linked site The method for producing a thermoplastic elastomer according to any one of (I) to (VII), wherein the thermoplastic elastomer can be crosslinked by at least one bond selected from the above.

  (IX) The thermoplastic elastomer has another side chain containing a covalent crosslinking site, and the crosslinking at the covalent crosslinking site is from amide, ester, lactone, urethane, ether, thiourethane and thioether. The method for producing a thermoplastic elastomer according to any one of the above (I) to (VII), which is formed by at least one bond selected from the group consisting of:

  (X) The method for producing a thermoplastic elastomer according to the above (IX), wherein the crosslinking at the covalent crosslinking site contains a tertiary amino group.

  (XI) The thermoplastic elastomer according to (IX) or (X) above, wherein the crosslinking at the covalent crosslinking site contains at least one structure represented by any of the following formulas (19) to (21): Manufacturing method.

  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.

  (XII) The above-described (XI), wherein the cross-linking at the covalent cross-linking site contains at least one structure represented by any one of the following formulas (22) to (24) bonded to the main chain at the α-position or β-position. ) For producing a thermoplastic elastomer.

  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.

  (XIII) The method for producing a thermoplastic elastomer according to (XI) or (XII) above, wherein any T in the formulas (19) to (24) contains a tertiary amino group.

  (XIV) The crosslinking according to any one of (IX) to (XIII) above, wherein the crosslinking at the covalent crosslinking site is formed by a reaction between a cyclic acid anhydride group and a hydroxyl group or an amino group and / or an imino group. A method for producing a thermoplastic elastomer.

  (XV) The method for producing a thermoplastic elastomer according to any one of (I) to (XIV) above, wherein the reaction time of the reaction is 30 seconds to 30 minutes.

  (XVI) The method for producing a thermoplastic elastomer according to any one of (I) to (XV) above, wherein the reaction temperature of the reaction is 60 to 250 ° C.

  (XVII) In the method for producing a thermoplastic elastomer according to any one of (I) to (XVI), a thermoplastic elastomer composition containing the thermoplastic elastomer by performing the reaction in the presence of an uncrosslinked polymer. A method for producing a thermoplastic elastomer composition for obtaining a product (second embodiment).

  (XVIII) A thermoplastic elastomer obtained by the method for producing a thermoplastic elastomer according to any one of (I) to (XVI) (third aspect).

  (XIX) A thermoplastic elastomer composition obtained by the method for producing a thermoplastic elastomer composition described in (XVII) above (fourth aspect).

  (XX) A thermoplastic elastomer composition containing the thermoplastic elastomer according to (XVIII) above (fifth aspect).

  As described below, according to the present invention, a method for producing a thermoplastic elastomer capable of reacting in a short time and preventing deterioration of the main chain of rubber and deterioration of physical properties and excellent recyclability are maintained. It is also useful because it can provide a thermoplastic elastomer having excellent mechanical strength, particularly tensile properties and compression set resistance. Moreover, the composition containing this thermoplastic elastomer also has the same effect and is very useful because its value is extremely high.

The present invention is described in detail below.
The method for producing a thermoplastic elastomer according to the first aspect of the present invention comprises introducing an elastomeric polymer containing a cyclic acid anhydride group in the side chain, a compound capable of introducing an imino group and / or a nitrogen-containing heterocyclic ring. A thermoplastic elastomer having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group by reacting the resulting compound with a compound in a single-screw and / or twin-screw extruder It is a manufacturing method.
The method for producing a thermoplastic elastomer composition according to the second aspect of the present invention is the method for producing a thermoplastic elastomer according to the first aspect, wherein the reaction is carried out in the presence of an uncrosslinked polymer. It is a manufacturing method of the thermoplastic elastomer composition which obtains the thermoplastic elastomer composition containing an elastomer.
Hereinafter, a method for producing a thermoplastic elastomer according to the first aspect of the present invention and a method for producing a thermoplastic elastomer composition according to the second aspect of the present invention (hereinafter referred to as “the present” unless otherwise specified. The elastomeric polymer containing a cyclic acid anhydride group in the side chain, a compound capable of introducing an imino group and a compound capable of introducing a nitrogen-containing heterocycle, and uniaxial and / Or reaction in a twin-screw extruder, and the thermoplastic elastomer obtained by the production method of the present invention and the thermoplastic elastomer composition containing the same (hereinafter, these are collectively referred to as “the thermoplastic elastomer (composition) of the present invention). ”Will be described in detail.

<Elastomeric polymer containing cyclic acid anhydride group in side chain>
The “elastomeric polymer containing a cyclic acid anhydride group in the side chain” used in the production method of the present invention means that the cyclic acid anhydride group has a chemically stable bond (covalent bond) to the atom forming the main chain. It is obtained by reacting an elastomeric polymer with a compound capable of introducing a cyclic acid anhydride group.

(Elastomeric polymer)
In the present invention, the elastomeric polymer is not particularly limited as long as it 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.
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), olefinic rubbers such as chlorosulfonated polyethylene, acrylic rubber, fluororubber, polyethylene rubber, polypropylene rubber; epichlorohydrin rubber; polysulfide rubber; silicone rubber; urethane rubber; Be mentioned

  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. The use of the resulting thermoplastic elastomer (composition) of the present invention, and the physical properties required for these. It can be appropriately selected according to the like.
When emphasizing the fluidity when the resulting thermoplastic elastomer (composition) of the present invention is heated (decrosslinked), the elastomeric polymer is preferably in the form of a liquid, such as isoprene rubber or butadiene rubber. The diene rubber preferably has a weight average molecular weight of 1,000 to 100,000, particularly preferably about 1,000 to 50,000.
On the other hand, when emphasizing the strength of the thermoplastic elastomer (composition) of the present invention obtained, the elastomeric polymer is preferably in a solid state. For example, in diene rubbers such as isoprene rubber and butadiene rubber, The average molecular weight is preferably 100,000 or more, 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. The mixing ratio of the respective elastomeric polymers in this case depends on the use in which the obtained thermoplastic elastomer (composition) of the present invention is used, the physical properties required for the obtained thermoplastic elastomer (composition) of the present invention, and the like. Any ratio can be set.
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. When the glass transition point of the elastomeric polymer is within this range, the resulting molded article made of the thermoplastic elastomer (composition) of the present invention is preferably rubbery elastic at room temperature.
In the present invention, the glass transition point is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry). The temperature raising rate is preferably 10 ° C./min.

  Such elastomeric polymers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), Diene rubber such as butyl rubber (IIR); Olefin rubber such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM); Since the obtained molded product made of the thermoplastic elastomer (composition) of the present invention exhibits rubber-like elasticity at room temperature, it is preferable. Further, when the olefinic rubber is used, the tensile strength when the thermoplastic elastomer (composition) of the present invention obtained is cross-linked is improved, and deterioration of the composition is suppressed because there is no double bond.

In the present invention, the amount of bound styrene of the styrene-butadiene rubber (SBR), the hydrogenation rate of the hydrogenated elastomeric polymer and the like are not particularly limited, and the resulting thermoplastic elastomer (composition) of the present invention is used. The ratio can be adjusted to any ratio according to the intended use and the physical properties required of the resulting thermoplastic elastomer (composition) of the present invention.
When ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM) is used as the main chain of the elastomeric polymer, its ethylene content Is preferably 10 to 90 mol%, more preferably 40 to 90 mol%. It is preferable for the ethylene content to be in this range because it is excellent in compression set resistance and mechanical strength when used as a thermoplastic elastomer (composition).

(Compound capable of introducing a cyclic acid anhydride group)
In the present invention, specific examples of the compound capable of introducing the 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 formed by the usual method, for example, the above-mentioned elastomeric polymer under the usual conditions such as stirring under heating. The cyclic acid anhydride exemplified for the compound capable of introducing an acid anhydride group may be produced by graft polymerization, or a commercially available product may be used.
Examples of commercially available products include maleic anhydride-modified isoprene rubber such as LIR-403 (manufactured by Kuraray Co., Ltd.) and LIR-410A (Kuraray Co., Ltd.); modified isoprene rubber such as LIR-410 (manufactured by Kuraray Co., Ltd.); Clinac 110 , 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.); , 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 (Takeda Pharmaceutical Co., Ltd.)), Bondine (Maleic anhydride modified EEA (Atofina)), Tuftec (Maleic anhydride modified SEBS, M1943 (Asahi Kasei) Manufactured)), Kraton (maleic anhydride modified SEBS, FG1901X (manufactured by Kraton Polymer)), tufprene (maleic anhydride modified SBS, 912 (Asahi Kasei)), Septon (maleic anhydride modified SEPS (manufactured 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>
The “compound capable of introducing an imino group” used in the production method of the present invention includes 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 thereof include N-methylaminoethanol, N-ethylaminoethanol, Nn-propylaminoethanol, Nn-butylaminoethanol, Nn-pentylaminoethanol, Nn-hexylaminoethanol, Nn-heptylaminoethanol, Nn-octylaminoethanol, Nn-nonylaminoethanol, Nn-decylaminoethanol, N- n-undecylaminoethanol, Nn-dodecylaminoethanol, N- (2-ethylhexyl) aminoethano , Alkylamino alcohols such as N-methylaminopropanol and N-methylaminobutanol; aromatic aminoalcohols such as N-phenylaminoethanol, N-toluylaminoethanol, N-phenylaminopropanol and N-phenylaminobutanol Alkylamino such as N-methylaminoethanethiol, N-ethylaminoethanethiol, Nn-propylaminoethanethiol, Nn-butylaminoethanethiol, N-methylaminopropanethiol, N-methylaminobutanethiol Thiols; Aromatic aminothiols such as N-phenylaminoethanethiol, N-toluylaminoethanethiol, N-phenylaminopropanethiol, N-phenylaminobutanethiol; N-methylethylene Alkyl such as amine, N-ethylethylenediamine, Nn-propylethylenediamine, N-methylpropanediamine, N-ethylpropanediamine, N-methylbutanediamine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine Diamines; aromatic diamines such as N-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 heterocycle” used in the production method of the present invention may be the nitrogen-containing heterocycle itself exemplified below, or a substituent that reacts with a cyclic acid anhydride group such as maleic anhydride. It may be a nitrogen-containing heterocyclic ring having a group (for example, a hydroxyl group, a thiol group, an amino group, etc.).

In the present invention, the nitrogen-containing heterocycle may have a heteroatom other than a nitrogen atom in the heterocycle, for example, a sulfur atom, an oxygen atom, a phosphorus atom, etc., as long as it contains a nitrogen atom in the heterocycle. Can be used. 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 thermoplastic elastomer (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; and the like can be mentioned, and these can be used in combination. The substitution position of these substituents is not particularly limited, and the number of substituents is not limited.
Further, the nitrogen-containing heterocyclic ring may or may not have aromaticity, but the thermoplastic elastomer (composition) of the present invention obtained when having aromaticity. This is preferable because the tensile strength at the time of crosslinking becomes higher and the mechanical strength is further improved.

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, those that are a triazole ring, a thiadiazole ring, a pyridine ring, a thiazole ring, an imidazole ring, and a hydantoin ring can be recycled and compression resistance of the resulting thermoplastic elastomer (composition) of the present invention. It is preferable because of its excellent permanent set, mechanical strength and hardness.

<Reaction in single screw and / or twin screw extruder>
In the production method of the present invention, the elastomeric polymer containing the cyclic acid anhydride group in the side chain, the compound capable of introducing the imino group and / or the compound capable of introducing the nitrogen-containing heterocycle are simply combined. A thermoplastic elastomer having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group can be obtained by reacting (mixing) in a screw and / or twin screw extruder.
By reacting in a single screw and / or twin screw extruder, the resulting thermoplastic elastomer (composition) of the present invention retains excellent recyclability, and has mechanical strength, particularly tensile properties and compression set resistance. Excellent.
This is because the resulting thermoplastic elastomer contains an imino group and / or a nitrogen-containing heterocycle and a carbonyl-containing group in the side chain, so that the imino group and / or the nitrogen-containing heterocycle and the carboxylic acid or carbonyl group This is thought to be because it forms a strong hydrogen bond and can act as a strong cross-linking point.In addition, the reaction in the extruder introduces an imino group rather than the reaction while kneading with a kneader or the like. As a result, the dispersibility of the compound capable of introducing a nitrogen-containing heterocycle is improved, so that the kneading efficiency is high, the kneading and reaction can be performed in a short time, and the heat history is small, so that the main component of the elastomeric polymer is surprising. It is thought that the chain was not broken and the physical properties such as recyclability, mechanical strength, tensile properties and compression set were prevented from being lowered.
In addition, by reacting in a single-screw and / or twin-screw extruder, kneading can be performed in a sealed environment, so that oxidative deterioration is suppressed, recyclability, mechanical strength, tensile properties, compression set resistance, etc. The physical properties of the are improved.

  The “single screw and / or twin screw extruder” used in the production method of the present invention is not particularly limited as long as it is a known extruder as a normal continuous extruder.

In the production method of the present invention, a single-screw and / or twin-screw extruder can be used, but a twin-screw extruder is preferably used. Moreover, as a twin screw extruder, it can be used whether the two screws mesh with each other, or those that do not mesh with each other, and use a screw that meshes with the two screws rotating in the same direction. Is more preferable.
Specifically, as such a twin screw extruder, for example, GT manufactured by Ikegai Co., Ltd., KTX manufactured by Kobe Steel Co., Ltd., TEX manufactured by Nippon Steel Co., Ltd., TEM manufactured by Toshiba Machine Co., Ltd., ZSK manufactured by Warner Co., Ltd. Trademark) and the like.

  Moreover, in the manufacturing method of this invention, since reaction time of the said reaction changes also with axial lengths, it is not specifically limited, It is preferable that it is 30 seconds-30 minutes, and it is more preferable that it is 5 to 20 minutes. If the reaction time is within this range, the main chain of the elastomeric polymer is not cut because the heat history is small, and deterioration of physical properties can be prevented. Therefore, mechanical strength, especially tensile properties, is maintained while maintaining excellent recyclability. Further, the compression set resistance is further improved.

  Furthermore, in the manufacturing method of this invention, it is preferable that the reaction temperature of the said reaction is 60-250 degreeC, and it is more preferable that it is 100-230 degreeC. If the reaction time is within this range, the main chain of the elastomeric polymer is not cut because the heat history is small, and deterioration of physical properties can be prevented. Therefore, mechanical strength, especially tensile properties, is maintained while maintaining excellent recyclability. Further, the compression set resistance is further improved.

In the production method of the present invention, the reaction in the single-screw and / or twin-screw extruder can specifically introduce the elastomeric polymer containing the cyclic acid anhydride group in the side chain and the imino group. This is a reaction with a compound and / or a compound capable of introducing the nitrogen-containing heterocycle.
The reaction of the elastomeric polymer containing the cyclic acid anhydride group in the side chain with the compound capable of introducing the imino group (hereinafter referred to as “reaction A”), the cyclic acid anhydride group side The description will be divided into the reaction between the elastomeric polymer contained in the chain and the compound capable of introducing the nitrogen-containing heterocycle (hereinafter referred to as “reaction B”).

(Reaction A)
In the reaction 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 temperature at which the compound and the cyclic acid anhydride group can chemically bond ( For example, the reaction is performed at 60 to 250 ° C. (cyclic acid anhydride group is opened).
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, the tensile strength at the time of crosslinking is sufficiently developed, and the compression set resistance is further improved.

(Reaction B)
In the reaction B, a compound capable of introducing a nitrogen-containing heterocyclic ring 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. This is a step of reacting at a temperature (for example, 60 to 250 ° C.) (opening a cyclic acid anhydride group).
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.

In the production method of the present invention, when both the compound capable of introducing the imino group and the compound capable of introducing the nitrogen-containing heterocycle are used together, the reaction A and The above reaction B occurs together.
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, tensile properties, compression set resistance, and tensile strength at the time of crosslinking are further improved while maintaining recyclability.
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.

On the other hand, in the method for producing a thermoplastic elastomer composition according to the second aspect of the present invention, the reaction in the single-screw and / or twin-screw extruder is performed in the presence of an uncrosslinked polymer.
Here, the uncrosslinked polymer is not particularly limited as long as the softening temperature is lower than the temperature at which it can chemically bond in the reactions A and B. Specific examples thereof include natural rubber (NR), isoprene rubber (IR), butadiene. Diene such as rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM) Rubbers and hydrogenated products thereof: ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), chlorosulfonated polyethylene, acrylic rubber, fluorine rubber, polyethylene rubber, polypropylene rubber, etc. Olefin rubber; Epichlorohi Phosphorous rubber; Polysulfide rubber; Silicone rubber; Urethane rubber; Hydrogenated polystyrene elastomeric polymer (for example, SBS, SIS, SEBS, etc.); Polyolefin elastomeric polymer; Polyvinyl chloride elastomeric polymer; Polyurethane Preferable examples include a series elastomeric polymer; a polyester series elastomeric polymer; a polyamide series elastomeric polymer;
Such an uncrosslinked polymer is preferably present in an amount of 5-1000 parts by mass, more preferably 5-500 parts by mass, per 100 parts by mass of the elastomeric polymer containing the cyclic acid anhydride group in the side chain. More preferred.
In the method for producing the thermoplastic elastomer composition according to the second aspect of the present invention, the reaction in the single-screw and / or twin-screw extruder is not limited to the uncrosslinked polymer, but may be carbon black, silica, etc., which will be described later. You may carry out in presence of various additives. In addition, even if the quantity which makes various additives exist with respect to 100 mass parts of elastomeric polymers which contain a cyclic acid anhydride group in a side chain is the same level as content with respect to 100 mass parts of the thermoplastic elastomer of this invention. Good.

  In the production method of the present invention, each group (structure) of the side chain of the resulting thermoplastic elastomer, that is, an unreacted cyclic acid anhydride group, the above formulas (3), (4), (5) and (6) ) Can be confirmed by commonly used analytical means such as NMR and IR spectra.

<Thermoplastic elastomer (composition) of the present invention>
The thermoplastic elastomer according to the third aspect of the present invention (hereinafter referred to as “the thermoplastic elastomer of the present invention”) is a thermoplastic elastomer obtained according to the first aspect of the present invention, and contains an imino group and / or an imino group. A thermoplastic elastomer having a side chain containing a nitrogen heterocycle and a carbonyl-containing group.
The thermoplastic elastomer composition according to the fourth aspect of the present invention is a thermoplastic elastomer composition obtained according to the second aspect of the present invention, and at least the thermoplastic elastomer obtained according to the first aspect and It is a thermoplastic elastomer composition containing a crosslinked polymer.
Furthermore, the thermoplastic elastomer composition according to the fifth aspect of the present invention is a thermoplastic elastomer composition containing the thermoplastic elastomer of the present invention.
Hereinafter, unless otherwise specified, the thermoplastic elastomer composition according to the fourth aspect of the present invention and the thermoplastic elastomer composition according to the fifth aspect of the present invention are collectively referred to as “the thermoplastic elastomer composition of the present invention”. That's it.

(Thermoplastic elastomer)
The thermoplastic elastomer of the present invention has a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group in an elastomeric polymer of a natural polymer or a synthetic polymer.
In the present invention, “side chain” refers to a side chain and a terminal of an elastomeric polymer. Further, “having an imino group and / or a side chain containing a nitrogen-containing heterocycle 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 / or Or it means that the nitrogen-containing heterocyclic ring and the carbonyl-containing group have a chemically stable bond (for example, covalent bond, ionic bond, etc.).

  The thermoplastic elastomer of the present invention preferably has a side chain containing a structure represented by the following formula (1) and / or the following formula (2) in the above-mentioned elastomeric polymer.

  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, and E is a nitrogen-containing heterocyclic ring.

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, since it is an alkyl group, especially a butyl group, an octyl group, a dodecyl group, an isopropyl group, and 2-ethylhexyl group, the processability of the thermoplastic elastomer (composition) of the present invention to be obtained becomes good. preferable.

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); An alkylene group having 1 to 20 carbon atoms or an aralkylene group which may contain a group; an alkylene ether group having 1 to 20 carbon atoms having such an atom or group as a terminal (an alkyleneoxy group such as —O—CH ₂ CH ₂ - 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 Group, an amino group (NH), an alkyleneamino group (—NH—CH ₂ — group, —NH—CH ₂ CH ₂ — group, —NH—CH ₂ CH ₂ CH ₂ — group), alkylene ether A group (—O—CH ₂ — group, —O—CH ₂ CH ₂ — group, —O—CH ₂ CH ₂ CH ₂ — group) is particularly preferred.

  Specific examples of the nitrogen-containing heterocyclic ring E include the nitrogen-containing heterocyclic rings exemplified above.

  The thermoplastic elastomer of the present invention has a structure represented by the following formula (3) or (4) in which a side chain containing the structure represented by the above formula (1) is bonded to the main chain at the α-position or β-position. The side chain containing the structure represented by the above formula (2) is preferably bonded to the main chain at the α-position or β-position, and the following formula (5) or (6 It is preferable that it has as a side chain containing the structure represented by this.

  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, and E is a nitrogen-containing heterocyclic ring.

Here, the substituent A is basically the same as the substituent A of the above formula (1), and the substituents B and D are each independently the same as the substituent B of the above formula (1). The nitrogen-containing heterocycle E is basically the same as the nitrogen-containing heterocycle E of the above formula (2).
However, the substituent D in the above formula (4) 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 (4). 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 addition, the substituent D in the 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).

The side chain containing the structure represented by the above formula (1) and / or the above formula (2), or the above formula (3) or (4) and / or the above formula (5) or (6) 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 conductive polymer. If it is less than 0.1 mol%, the strength at the time of crosslinking may not be sufficient, and if it exceeds 50 mol%, the crosslinking density may increase and rubber elasticity may be lost. When the introduction ratio is within this range, the interaction between the side chains of the elastomeric polymer occurs between molecules or within the molecule, and these are formed in a well-balanced manner. Therefore, the thermoplastic elastomer (composition) of the present invention to be obtained High tensile strength at the time of cross-linking, excellent recyclability, and good compression set resistance. 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 particular, in the case of a side chain containing both the structures represented by the above formula (1) and the above formula (2), or the above formula (3) or (4) and the above formula (5) or (6), These introduction ratios to the chain (the above formula (2) or the side chain containing the structure represented by the above formula (5) or (6) / the above formula (1) or the above formula (3) or (4) The side chain containing the structure represented) is more preferably 1/99 to 99/1, still more preferably 10/90 to 90/10. When the introduction rate and the introduction ratio are within this range, the tensile strength at the time of crosslinking is high, the recyclability is excellent, and the mechanical strength such as tensile strength is maintained while maintaining the property of good compression set resistance. Further improvement is also possible, and coloring of the thermoplastic elastomer (composition) derived from the introduced nitrogen-containing heterocycle can also be suppressed, which is preferable.

  Further, when the thermoplastic elastomer of the present invention has a side chain containing a triazole ring, an imidazole ring or a thiazole ring as a side chain containing the nitrogen-containing heterocycle, the side chain containing the nitrogen-containing heterocycle is It is preferable to have 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 has a side chain containing a structure represented by the following formula (11) or (12), any of the following formulas (13) to (16), or the following formula (17) or (18). It is more preferable.

  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 (2), (5) and (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.

  The thermoplastic elastomer of the present invention preferably has a glass transition point of 25 ° C. or lower. When the thermoplastic elastomer has two or more glass transition points, or when two or more thermoplastic elastomers are used in combination, glass is used. At least one of the transition points is preferably 25 ° C. or lower. When the glass transition point is 25 ° C. or lower, the molded article exhibits rubber-like elasticity at room temperature.

The bonding position of the nitrogen-containing heterocycle in the case where the thermoplastic elastomer of the present invention has a side chain containing the nitrogen-containing heterocycle 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 of the present invention, the bonding position of the nitrogen-containing n-membered ring compound bonded to the copolymer directly or via an organic group is not particularly limited, and 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, making it easy to recycle. Excellent, excellent mechanical properties.

  The thermoplastic elastomer of the present invention preferably has another side chain containing a covalent crosslinkable site, in which the amide, ester, lactone, urethane, ether, thiourethane and More preferably, it can be crosslinked by at least one bond selected from the group consisting of thioethers. Further, the thermoplastic elastomer 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 methylene diamine, ethylene diamine, propylene diamine, 1,2-diaminopropane, 1,3-diaminopentane, hexamethylene diamine, diaminoheptane, diaminododecane, diethylenetriamine, and 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 when two or more types are used in combination is an arbitrary ratio depending on the use in which the thermoplastic elastomer (composition) of the present invention is used, the physical properties required for the thermoplastic elastomer (composition) of the present invention, and the like. Can be adjusted.

  Among the polyamine compounds exemplified above, hexamethylenediamine, N, N′-dimethyl-1,6-hexanediamine, diaminodiphenylsulfone, 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 alicyclic polyisocyanates such as; 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.
The thermoplastic elastomer of the present invention has at least one crosslink in this molecule, ie, a crosslink by a covalent bond between the functional group and the above-mentioned “compound that generates a covalent bond”. In particular, when at least one bond selected from the group consisting of lactones, urethanes, ethers, thiourethanes and thioethers forms a crosslink, it is preferable to have 2 or more. It is more preferable to have -20, and it is still more preferable to have 2-10.
In the present invention, the crosslinking at the covalent crosslinking site contains a tertiary amino group (-N =). The compression set of the resulting thermoplastic elastomer (composition) of the present invention is resistant to compression. And it is preferable because the mechanical strength (breaking elongation, breaking strength) is further improved. This is considered to be due to the tertiary amino group being further hydrogen-bonded (interacted) with the carbonyl-containing group and the nitrogen-containing heterocyclic ring to further improve 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).

（式中、ｌは、１以上の整数を表す。）

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

（式中、ｌ、ｍおよびｎは、それぞれ独立に１以上の整数を表す。）

(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.

(Thermoplastic elastomer composition)
Next, the thermoplastic elastomer composition of the present invention will be described.
The thermoplastic elastomer composition according to the fourth aspect of the present invention contains at least one thermoplastic elastomer of the present invention and the above-mentioned uncrosslinked polymer.
The thermoplastic elastomer composition according to the fifth aspect of the present invention contains one or more thermoplastic elastomers of the present invention.
In the thermoplastic elastomer composition of the present invention, the mixing ratio in the case of containing two or more thermoplastic elastomers of the present invention is an arbitrary ratio depending on the use of the composition, the physical properties required for the composition, etc. It can be.

The thermoplastic elastomer composition of the present invention preferably contains carbon black and / or silica as a reinforcing agent. 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. In the present invention, it is particularly preferable to use hard carbon having strong reinforcing properties.
The content of carbon black (when used alone) is 1 to 200 parts by weight, preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the thermoplastic elastomer of the present invention. More preferably, it is part 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 the thermoplastic elastomer of this invention, 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 and 10 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer of the present invention. It is preferably 20 to 80 parts by mass.

  If necessary, the thermoplastic elastomer composition of the present invention is a polymer other than the thermoplastic elastomer of the present invention, a reinforcing agent (filler) other than carbon black and silica, an amino acid, as long as the object of the present invention is not impaired. A filler obtained by introducing a group (hereinafter simply referred to as “amino group-introducing filler”), an amino group-containing compound other than the amino group-introducing filler, and a compound containing a metal element (hereinafter simply referred to as “metal salt”). .), Maleic anhydride modified polymer, anti-aging agent, antioxidant, pigment (dye), plasticizer, thixotropic agent, UV absorber, flame retardant, solvent, surfactant (including leveling agent), dispersion Various additives such as an additive, a dehydrating agent, a rust preventive agent, an adhesion imparting agent, an antistatic agent, and a filler 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 of the present invention, 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), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butyl rubber ( IIR), ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), polystyrene-based elastomeric polymer that may be hydrogenated (for example, SBS, SIS, SEBS, etc.), polyolefin-based elastomeric polymer, polyvinyl chloride-based elastomeric polymer, polyurethane-based elastomeric polymer, polyester-based elastomeric polymer, polyamide-based elastomeric polymer, etc. R, EPM, no unsaturated bond polymer or unsaturated bonds less polymer EBM (e.g., EPDM) are preferred. A polymer having a site capable of hydrogen bonding is also preferable, and examples thereof include polyester, polylactone, and polyamide.
Further, in the thermoplastic elastomer composition of the present invention, the polymer other than the thermoplastic elastomer of the present invention may contain one or more kinds, and the content of the polymer is the thermoplastic elastomer 100 of the present invention. It is preferable that it is 0.1-100 mass parts with respect to a mass part, and it is more preferable that it is 1-50 mass parts.

  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 of the present invention.

  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 of the present invention and being effectively dispersible in the thermoplastic elastomer, a heterocyclic amino group and a mixed amino group containing a heterocyclic amino group are included. It is preferably a group or an aliphatic amino group, and preferably a heterocyclic amino group or an aliphatic amino group.

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 of the present invention 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 of the present invention 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 are used in combination can be any ratio depending on the application in which the thermoplastic elastomer composition of the present invention is used, the physical properties required for the thermoplastic elastomer composition of the present invention, and the like. .
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 or more with respect to 100 parts by mass of the thermoplastic elastomer of the present invention. It is particularly preferred that

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 it can form two or more cross-linking bonds with the thermoplastic elastomer of the present invention 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 ⁺ <), and may be used for physical properties such as recyclability, compression set resistance, mechanical strength and hardness required for the thermoplastic elastomer composition of the present invention. It can be arbitrarily selected depending on the case. 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 thermoplastic elastomer composition of the present invention obtained is excellent in recyclability and compression set resistance, and is excellent 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 of the present invention (particularly, the carboxy group that is a carbonyl-containing group) is strengthened, and is excellent. Recyclability may be impaired.

  That is, considering the bonding strength between the functional group in the thermoplastic elastomer of the present invention and the amino group in the amino group-containing compound, the series and number of amino groups and the structure of the amino group-containing compound are appropriately adjusted and selected. be able to.

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 of these polymers, such as average molecular weight, molecular weight distribution, and viscosity, are not particularly limited, depending on the application in which the thermoplastic elastomer composition of the present invention is used, the physical properties required for the thermoplastic elastomer composition of the present invention, and the like. And can have any physical property.

  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 are used in combination can be any ratio depending on the application in which the thermoplastic elastomer composition of the present invention is used, the physical properties required for the thermoplastic elastomer composition of the present invention, and the like. .

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 of the present invention, as in the case of the amino group-containing compound. Depending on the structure and molecular weight of the polymer compound, there may be an amino group that cannot effectively form an interaction with the thermoplastic elastomer.
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 of the present invention. It is particularly preferable that the amount is not less than part by mass.

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.

  Among these, from the viewpoint of further improving the compression set of the resulting thermoplastic elastomer composition of the present invention, the metal element is preferably Ti, Al, or Zn, and the metal salt is an acetate or stearic acid thereof. C1-C20 saturated fatty acid salts such as salts, metal alkoxides (reactants with alcohols having 1 to 12 carbon atoms), oxides, hydroxides, complexes with diketones are preferred, and carbon numbers such as stearates 1-20 saturated fatty acid salts, metal alkoxides (reactants with alcohols having 1-12 carbon atoms), and complexes with diketones are particularly preferred.

  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 are used in combination can be any ratio depending on the application in which the thermoplastic elastomer composition of the present invention is used, the physical properties required for the thermoplastic elastomer composition of the present invention, and the like. .

  The content of the metal salt is preferably 0.05 to 3.0 equivalents and more preferably 0.1 to 2.0 equivalents with respect to the carbonyl group contained in the thermoplastic elastomer of the present invention. Preferably, it is 0.2-1.0 equivalent. When the content of the metal salt is within this range, the thermoplastic elastomer composition of the present invention obtained 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. .

（式中、Ｘはエチレン残基またはプロピレン残基であり、ｌ、ｍおよびｎはそれぞれ独立に０．１〜８０の数を表す。）

(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 are used in combination can be any ratio depending on the application in which the thermoplastic elastomer composition of the present invention is used, the physical properties required for the thermoplastic elastomer composition of the present invention, and the like. .

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 of the present invention. When the content of the maleic anhydride-modified polymer is within this range, the processability and mechanical strength of the resulting thermoplastic elastomer 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 thermoplastic elastomer 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 plasticizer include benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid, and other polyesters. , Polyether, epoxy and the like.
Specific examples of the thixotropic agent include benton, silicic anhydride, silicic acid derivatives, urea derivatives, 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 solvent include hydrocarbons such as hexane and toluene; halogenated hydrocarbons such as tetrachloromethane; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; ethyl acetate. And ester systems such as
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.

  The content of the plasticizer is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer of the present invention. The content of other additives is preferably 0.1 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer of the present invention.

Some of the thermoplastic elastomers of the present invention can self-crosslink, but vulcanizing agents, vulcanization aids, vulcanization accelerators, vulcanization retarders, etc. can be used in combination as long as the object of the present invention is not impaired. .
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 of the present invention.

  The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited. For example, the thermoplastic elastomer of the present invention, and various additives that may be contained as necessary, a roll, a kneader, an extruder, What is necessary is just to mix by a universal stirrer.

  Curing conditions when the thermoplastic elastomer 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 thermoplastic elastomer (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 thermoplastic elastomer (composition) of the present invention that has been softened and given 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 thermoplastic elastomer (composition) of the present invention exhibits recyclability.

  The thermoplastic elastomer (composition) of the present invention can be used for various rubber applications utilizing, for example, rubber elasticity. Moreover, since it can improve heat resistance and recyclability, it is preferable to use it as a hot melt adhesive or as an additive contained therein. The thermoplastic elastomer (composition) of the present invention can be suitably used around an automobile or the like.

  Specific examples of the above-mentioned automobile surroundings include, for example, tire treads, carcass, sidewalls, inner liners, undertreads, belt portions, and the like; exterior radiator grilles, side moldings, garnishes (pillars, rears, cowls) Top), aero parts (air dam, spoiler), wheel cover, weather strip, cow belt grille, air outlet louver, air scoop, hood bulge, vent parts, anti-corrosion parts (over fender, side seal panel, molding ( Window, hood, door belt)), marks, etc .; interior window frame parts such as door, light, wiper weather strip, glass run, glass run channel; air duct hose, radiator hose, brake hose; crankshaft Lubricant, valve stem seal, head cover gasket, A / T oil cooler hose, mission oil seal, P / S hose, P / S oil seal and other lubricating oil parts; fuel hose, emission control hose, inlet filler hose, diaphragm Fuel system parts such as engine parts; Anti-vibration parts such as engine mounts and in-tank pump mounts; Boots such as CVJ boots and rack and pinion boots; Air conditioning parts such as A / C hoses and A / C seals; Belt parts such as timing belts and auxiliary belts; sealers such as windshield sealers, vinyl plastisol sealers, anaerobic sealers, body sealers, spot weld sealers; and the like.

  Further, when a rubber modifier, for example, a flow preventing agent, is included in a resin or rubber that causes a cold flow at room temperature, it is possible to prevent a flow during extrusion or a cold flow.

  Furthermore, the thermoplastic elastomer composition of the present invention comprising the thermoplastic elastomer of the present invention and carbon black and / or silica has improved tensile strength, tear strength and bending strength, and in particular, tires, hoses, belts, sheets, Vibration rubber, roller, lining, rubberized cloth, sealing material, gloves, fender, medical rubber (syringe gasket, tube, catheter), gasket (for home appliances, construction), asphalt modifier, hot melt adhesive , Boots, grips, toys, shoes, sandals, keypads, gears, PET bottle cap liners and the like.

  The thermoplastic elastomer (composition) of the present invention is excellent in compression set resistance while maintaining the same level of recyclability and mechanical properties as compared with conventional thermoplastic elastomers. Among them, it is suitably used for applications that require particularly recyclability and compression set resistance.

EXAMPLES Next, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited to these.
Example 1
A dry blend of 100 parts of maleic anhydride modified ethylene-propylene copolymer (TX-1215, manufactured by Mitsui Chemicals, hereinafter abbreviated as “maleinized EPM”) and 100 parts of SEBS (manufactured by Asahi Kasei), 4H-3- A dry blend of 0.86 amino-1,2,4-triazole (ATA, manufactured by Nippon Carbide), 6 parts of carbon black (N660, manufactured by Tokai Carbon) and 60 parts of talc (talc F, manufactured by Nippon Talc) Was fed into a twin screw extruder (TEX30, manufactured by JSW) at a feeder speed of 6 kg / h, extruded into a strand shape at a screw rotation speed of 104 / min, and a thermoplastic elastomer composition 1 was prepared using a strand cutter. . The discharge rate of the twin screw extruder was 6 kg / h, and this was the production rate.

(Example 2)
A thermoplastic elastomer composition 2 was prepared in the same manner as in Example 1 except that the amount of SEBS was 30 parts and talc was not added.

(Example 3)
Dry blend of 100 parts maleated EPM and 100 parts SEBS (Asahi Kasei), 0.82 parts 4H-3-amino-1,2,4-triazole (ATA, Nippon Carbide) and Nn-octylamino Ethanol (Naymin C-201, manufactured by Nippon Oil & Fats Co., Ltd.) (0.42 parts) was charged into a twin screw extruder (TEX30, manufactured by JSW) at a feeder speed of 6 kg / h, and formed into a strand at a screw speed of 104 / min. The thermoplastic elastomer composition 3 was prepared by extrusion and using a strand cutter. The discharge rate of the twin screw extruder was 6 kg / h, and this was the production rate.

Example 4
100 parts of maleated EPM and 0.10 parts of Nn-octylaminoethanol (Nymene C-201, manufactured by NOF Corporation) are charged into a twin screw extruder (TEX30, manufactured by JSW) at a feeder speed of 6 kg / h. Then, it was extruded into a strand shape at a screw rotation speed of 104 / min, and the thermoplastic elastomer 1 was prepared using a strand cutter. The discharge rate of the twin screw extruder was 6 kg / h, and this was the production rate.

(Comparative Example 1)
100 parts of maleated EPM and 100 parts of SEBS (manufactured by Asahi Kasei) are put into a heat sealed kneader (pressure kneader, manufactured by Moriyama Co., Ltd.) having a capacity of 4 L. After kneading for several minutes, 4H-3- 0.86 part of amino-1,2,4-triazole (ATA, manufactured by Nippon Carbide) was added, and further 6 parts of carbon black (N660, manufactured by Tokai Carbon Co.) and talc (talc F, manufactured by Nippon Talc) 60 While adding several tens of minutes, it was added little by little and kneaded. After kneading for about 1 hour, a thermoplastic elastomer composition 4 was obtained. The mixing amount at this time was 2 kg, and this was defined as the production rate.

(Comparative Example 2)
A thermoplastic elastomer composition 5 was prepared in the same manner as in Comparative Example 1 except that the SEBS content was 30 parts and no talc was added.

  The obtained thermoplastic elastomer compositions 1 to 5 and the thermoplastic elastomer 1 were hot press molded at 200 ° C. for 10 minutes, and MFR (melt flow rate), hardness, tensile properties, and compression set were determined by the measurement methods described later. Were measured and evaluated. The results are shown in Table 1 below.

<MFR>
The obtained thermoplastic elastomer compositions 1 to 5 and the thermoplastic elastomer 1 were 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 1 cm was produced. This flat plate sample was cut into 3 mm squares to obtain MFR measurement samples.
The MFR of this measurement sample at 230 ° C. and a load of 2.16 kg was measured according to JIS K7210. Specifically, 3 to 6 g of a measurement sample is filled in a cylinder of an MFR measuring apparatus (melt indexer, manufactured by Toyo Seiki Co., Ltd.) whose temperature is constant for 15 minutes or more, and a prescribed load is applied after preheating for 4 minutes, The measurement was started after another 2 minutes.

<JIS-A hardness>
The obtained thermoplastic elastomer compositions 1 to 5 and the thermoplastic elastomer 1 were 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 flat plate samples were stacked and hot-pressed at 200 ° C. for 20 minutes, and JIS-A hardness was measured according to JIS K6253.

<Tensile properties>
The obtained thermoplastic elastomer compositions 1 to 5 and the thermoplastic elastomer 1 were 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, and 100% modulus (M ₁₀₀ ) [MPa] breaking strength (T _B ) [MPa], The elongation at break (E _B ) [%] was measured at room temperature.

<Compression set (C-Set)>
The obtained thermoplastic elastomer compositions 1 to 5 and the thermoplastic elastomer 1 were hot-pressed at 200 ° C. for 10 minutes to produce a sheet having a thickness of 2 mm, and then the seven sheets were stacked and heated at 200 ° C. for 20 minutes. The sample was pressed to produce a cylindrical sample (diameter 29 × thickness 12.5 mm).
This cylindrical sample was compressed 25% with a dedicated jig and allowed to stand at 70 ° C. for 22 hours, and then the compression set was measured according to JIS K6262.

  As apparent from Table 1 above, the thermoplastic elastomer compositions and thermoplastic elastomers obtained in Examples 1 to 4 were obtained by kneading with a kneader without using an extruder (comparison). Compared to Examples 1 and 2), it was found that the production rate was high and the mechanical strength, particularly tensile properties and compression set resistance were excellent. Moreover, it turned out that the thermoplastic elastomer composition and the thermoplastic elastomer obtained in Examples 1 to 4 both have excellent recyclability.

Claims (20)

  Reacting an elastomeric polymer containing a cyclic acid anhydride group in the side chain with a compound capable of introducing an imino group and / or a compound capable of introducing a nitrogen-containing heterocycle in a single screw and / or twin screw extruder. By this, the manufacturing method of the thermoplastic elastomer which obtains the thermoplastic elastomer which has a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring, and a carbonyl-containing group.   The method for producing a thermoplastic elastomer according to claim 1, wherein the nitrogen-containing heterocycle of the compound into which the nitrogen-containing heterocycle can be introduced is a 5- or 6-membered ring.   The method for producing a thermoplastic elastomer according to claim 2, wherein the nitrogen-containing heterocycle of the compound into which the nitrogen-containing heterocycle can be introduced is a triazole ring, a thiadiazole ring, a pyridine ring, a thiazole ring, an imidazole ring or a hydantoin ring. The manufacturing method of the thermoplastic elastomer in any one of Claims 1-3 in which the said side chain contains the structure represented by following formula (1) and / or following formula (2).

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, and E is a nitrogen-containing heterocyclic ring. The side chain contains a structure represented by the following formula (3) or (4) and / or the following formula (5) or (6) bonded to the main chain at the α-position or β-position. A method for producing a thermoplastic elastomer.

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, and B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups, and E is a nitrogen-containing heterocyclic ring. The method for producing a thermoplastic elastomer according to claim 4, wherein the side chain contains a structure represented by the following formula (7), the following formula (8) or (9), or the following formula (10).

Wherein 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 which may contain 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.) In the following formula (11) or (12), the following formulas (13) to (16), or the following formula (17) or (18) in which the side chain is bonded to the main chain at the α-position or β-position. The manufacturing method of Claim 6 containing the structure represented.

Wherein 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.)   The thermoplastic elastomer has another side chain containing a covalent crosslinkable site, and the covalent crosslinkable site is selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. The method for producing a thermoplastic elastomer according to claim 1, wherein the thermoplastic elastomer can be crosslinked by at least one bond.   The thermoplastic elastomer has another side chain containing a covalent crosslinking site, and the crosslinking at the covalent crosslinking site is selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether. The method for producing a thermoplastic elastomer according to any one of claims 1 to 7, wherein the thermoplastic elastomer is formed by at least one selected bond.   The method for producing a thermoplastic elastomer according to claim 9, wherein the cross-linking at the covalent cross-linking site contains a tertiary amino group. The method for producing a thermoplastic elastomer according to claim 9 or 10, wherein the crosslinking at the covalent crosslinking site contains at least one structure represented by any of the following formulas (19) to (21).

Wherein 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; or these And T is an hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom, and may be branched.) The bridge | crosslinking in the said covalent bond bridge | crosslinking site | part contains at least 1 structure represented by either of following formula (22)-(24) couple | bonded with a principal chain in (alpha) position or (beta) position. A method for producing a thermoplastic elastomer.

Wherein 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; or these And T is an hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom, and may be branched.)   The method for producing a thermoplastic elastomer according to claim 11 or 12, wherein any T in the formulas (19) to (24) contains a tertiary amino group.   The method for producing a thermoplastic elastomer according to any one of claims 9 to 13, wherein the covalent crosslinking site is formed by a reaction between a cyclic acid anhydride group and a hydroxyl group or an amino group and / or an imino group. .   The method for producing a thermoplastic elastomer according to any one of claims 1 to 14, wherein a reaction time of the reaction is 30 seconds to 30 minutes.   The reaction temperature of the said reaction is 60-250 degreeC, The manufacturing method of the thermoplastic elastomer in any one of Claims 1-15.   The method for producing a thermoplastic elastomer according to any one of claims 1 to 16, wherein the reaction is carried out in the presence of an uncrosslinked polymer to obtain a thermoplastic elastomer composition containing the thermoplastic elastomer. A method for producing the composition.   The thermoplastic elastomer obtained by the manufacturing method of the thermoplastic elastomer in any one of Claims 1-16.   The thermoplastic elastomer composition obtained by the manufacturing method of the thermoplastic elastomer composition of Claim 17.   A thermoplastic elastomer composition comprising the thermoplastic elastomer according to claim 18.