JP2003261617A - Thermoplastic elastomer and composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer which has sufficient hardness, excellent shape retention (compression set), and surface properties as an elastic member without adversely affecting excellent recycling properties, and can repeatedly reproduce crosslink formation and crosslink dissociation by the change in temperature, and a composition comprising the thermoplastic elastomer. <P>SOLUTION: The thermoplastic elastomer has a group having a nitrogen- containing heterocycle and a metal carboxylate obtained by the condensation reaction of a carboxyl group with a metallic compound in the side chain. The thermoplastic elastomer composition comprises the thermoplastic elastomer, and a carbon and/or silica. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer capable of repeatedly reproducing crosslink formation and crosslink dissociation by a temperature change, and a composition containing the same. More specifically, it relates to a thermoplastic elastomer having excellent shape retention, surface properties and other physical properties and having recyclability due to temperature change, and a composition containing the same.

[0002]

2. Description of the Related Art In recent years, from the standpoint of environmental protection and resource saving,
Reuse of used materials is desired. Vulcanized rubber has a stable three-dimensional network structure in which a polymer substance and a vulcanizing agent are covalently bonded and exhibits extremely high strength, but remolding is difficult because of strong covalent crosslinking. On the other hand, the thermoplastic elastomer utilizes physical cross-linking, and can be easily molded by heating and melting without the need for complicated vulcanization / molding steps including preforming. 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 that serves as a cross-linking point of the three-dimensional network structure, and the rubber component (soft segment) BACKGROUND ART There is known a thermoplastic elastomer that prevents plastic deformation and plastically deforms due to softening or melting of a resin component when heated. However, in such a thermoplastic elastomer, since the resin component is included, rubber elasticity is likely to decrease. Therefore, a material that does not contain a resin component and can be imparted with thermoplasticity is required.

To address this problem, Japanese Patent Laid-Open No. 8-23958
In JP-A-3, a side chain contains a carbonyl group-containing group and a nitrogen-containing heterocycle-containing group, and the nitrogen-containing heterocycle-containing group is directly at the 2-position with respect to the ring-constituting nitrogen or via an organic group. Metal-containing organic polymeric materials containing organic polymers bound to the backbone and certain metal compounds are described. This metal-containing organic polymerized material can exhibit sufficient melt fluidity at the molding temperature of a thermoplastic resin such as an olefin resin that has not been modified, and at low temperatures it has excellent mechanical strength such as breaking strength due to cross-linking formation. It is possible to repeatedly reproduce crosslink formation and crosslink dissociation (softening) due to temperature change. The metal-containing organic polymer material having such characteristics has extremely high industrial utility value and environmental protection value, and further, high cross-linking strength can be obtained, and physical properties change even after repeated cross-link formation and cross-link dissociation. It is expected as a material with excellent recyclability. However, this metal-containing organic polymer material does not have a sufficient shape retention rate when a load is applied in terms of material properties. In addition, this metal-containing organic polymer material has a very low hardness when a thermoplastic elastomer is used for the main chain, and its properties are insufficient for use as an elastic member such as use as a rubber material. is there.

The inventors of the present invention have previously disclosed an elastomer composition containing an elastomer having a reaction site capable of forming a hydrogen bond and a compound having a reaction site capable of forming a hydrogen bond with the reaction site of the elastomer. , That it is possible to repeat cross-link formation and cross-link dissociation by changing the temperature by utilizing a hydrogen bond (JP-A-11-2095).
No. 24). In addition, JP-A-2000-169 by the present inventor
Japanese Patent No. 527 describes a hydrogen-bonding thermoplastic elastomer comprising an elastomeric polymer having a carbonyl group-containing group in its side chain and a heterocyclic amine-containing group, which is expected to have the same effect. However, recent technological innovation,
In the current situation where the physical properties and characteristics required for thermoplastic elastomers are becoming higher due to optimization of materials and shortening of manufacturing process, shape retention while maintaining excellent recyclability of these elastomer compositions is maintained. Improvement of material properties such as rate is required.

[0005]

DISCLOSURE OF THE INVENTION The present invention has a sufficient hardness, an excellent shape retention rate (compression set) and a surface texture for use as an elastic member, without impairing the excellent recyclability. It is an object of the present invention to provide a thermoplastic elastomer capable of repeatedly reproducing crosslink formation (curing) and crosslink dissociation (fluidization) due to changes and a composition containing the same.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have determined that a carboxyl group of a thermoplastic elastomer having a nitrogen-containing heterocyclic ring and a carboxyl group in a side chain is identified as a specific group. We have found a thermoplastic elastomer that has excellent shape retention (compression set) and surface properties and can repeatedly reproduce crosslink formation and crosslink dissociation due to temperature changes by condensation reaction with metal compounds to form carboxylic acid metal salts. The present invention has been completed.

That is, 1) the present invention provides a thermoplastic elastomer having, in its side chain, a nitrogen-containing heterocyclic ring-containing group; and a carboxylic acid metal salt obtained by subjecting a carboxyl group and a metal compound to a condensation reaction. . Here, in the present invention, the “side chain” refers to the side chain and terminal of the elastomeric polymer.

The metal compound may be Li, Na, K, Mg, Ca, Ba, Ti represented by the general formula Y (OQ) _q .
Mn, Fe, Co, Ni, Cu, Zn, Al and Pb
A preferred embodiment of the metal Y hydroxide, ether salt, or carboxylate selected from the group consisting of
Is one. (In the said general formula, Y is the said metal, q is an integer of 1-4, Q is a hydrogen atom, a C1-C20 hydrocarbon group, or a -CO-Q 'group. Here, Q '
Is a hydrocarbon group having 1 to 20 carbon atoms. )

It is one of the preferred embodiments that the content of the carboxylic acid metal salt is 0.1 to 1.0 mol per 1 mol of the carboxyl group.

The nitrogen-containing heterocycle-containing group is represented by the following formula (1)
The structure represented by is one of the preferred embodiments.

[Chemical 3] (In the formula, A is a nitrogen-containing heterocycle bonded to the main chain through an organic group B, and B is an oxygen atom, a sulfur atom or an amino group N.
R '(R' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or an organic group which may contain these. )

It is one of the preferred embodiments that the nitrogen-containing heterocycle-containing group and the carboxylic acid metal salt have a structure represented by the following formula (2).

[Chemical 4] (In the formula, R is a nitrogen-containing heterocycle, X is an oxygen atom, a sulfur atom or an amino group NR '(R' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or an organic group which may contain these. Yes, Y is the metal, Q is a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms or a -CO-Q 'group (Q' is a hydrocarbon group having 1 to 20 carbon atoms), and n is 1
Is an integer of 4 to 4, m is an integer of 0 to 3, and m + n is a valence of the metal Y (an integer of 1 to 4). The side chain having the structure of formula (2) is preferably introduced into the main chain at the α-position or β-position.

In one of the preferred embodiments, the nitrogen-containing heterocycle-containing group is a group containing a triazole ring, a pyridine ring or a thiadiazole ring.

Further, 2) the present invention comprises the thermoplastic elastomer according to 1); carbon and / or silica;
There is provided a thermoplastic elastomer composition containing:

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. A first aspect of the present invention is a thermoplastic elastomer having a nitrogen-containing heterocycle-containing group in a side chain and a carboxylic acid metal salt obtained by subjecting a carboxyl group and a metal compound to a condensation reaction. That is, the thermoplastic elastomer of the present invention is an elastomer having a nitrogen-containing heterocyclic ring-containing group and a carboxylic acid metal salt in the side chain of an elastomeric polymer of natural polymer or synthetic polymer. Here, in the present invention, the “side chain” refers to the side chain and terminal of the elastomeric polymer. Further, “having a nitrogen-containing heterocycle-containing group and a carboxylic acid metal salt in the side chain” means that the nitrogen-containing heterocycle-containing group and the carboxylic acid metal salt are present at the atom (usually carbon) forming the main chain of the elastomeric polymer. It means a chemically stable bond (covalent bond).

In the present invention, the formation and cleavage of hydrogen bonds can be utilized to repeatedly reproduce crosslink formation and crosslink dissociation due to temperature changes. Further, by using a carboxylic acid metal salt as the carboxyl group, excellent shape retention (compression set) and surface properties can be realized due to hydrogen bond, ionic bond, intermolecular chelate formation, and ionic interaction.

The elastomeric polymer serving as the main chain is a natural polymer or synthetic polymer generally known as a rubber elastic material for vulcanization (crosslinking and curing). Specific examples of such an elastomeric polymer include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber, nitrile rubber, and chloroprene. Diene rubbers such as rubber, butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM); olefins such as ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM), chlorosulfonated polyethylene, acrylic rubber, fluororubber Examples thereof include rubber; epichlorohydrin rubber; polysulfide rubber; silicone rubber; urethane rubber and the like. The main chain elastomeric polymer may be an elastomeric polymer containing a resin component, for example, a polystyrene-based elastomeric polymer which may be hydrogenated (SBS, SIS, SEBS),
It may be a polyolefin elastomeric polymer, a polyvinyl chloride elastomeric polymer, a polyurethane elastomeric polymer, a polyester elastomeric polymer, a polyamide elastomeric polymer, or the like.

The elastomeric polymer as described above is
It may be liquid or solid. The molecular weight is not particularly limited and can be appropriately selected depending on the purpose of use, crosslink density, etc., but when importance is attached to fluidity during heating (decrosslinking) of the thermoplastic elastomer, liquid rubber is preferable. For example, a diene rubber such as isoprene rubber or butadiene rubber has a weight average molecular weight of 1000 to 10
It is preferably 0000, and 1000 to 50000
The degree is particularly preferable. On the other hand, when strength is important, solid rubber is preferable. For example, in diene rubber such as isoprene rubber and butadiene rubber, the weight average molecular weight is preferably 100,000 to 2,000,000,
500000 to 1500000 are particularly preferable.

In the present invention, two or more kinds of the above polymers may be mixed and used. The mixing ratio in this case is
The ratio can be set arbitrarily according to the intended use, the required physical properties and the like. Further, at least one of the elastomeric polymers used in the present invention preferably has a glass transition temperature (Tg) of 25 ° C. or lower. Within this range, the mixing of the elastomer composition described below becomes uniform and the surface properties are excellent. It is also easy to handle when it is thermally dissociated.

Further, the elastomeric polymer is particularly preferably a polymer having an unsaturated bond such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR) or butyl rubber (IIR). These polymers have a glass transition temperature of 25 ° C. or lower, have unsaturated bonds, and are easily modified with carboxylic acid.

The thermoplastic elastomer of the present invention has a carboxylic acid metal salt in the side chain of the above-mentioned elastomeric polymer. The carboxylic acid metal salt is obtained by subjecting a carboxyl group and a metal compound to a condensation reaction. here,
The "carboxyl group" can be introduced into the main chain of the elastomeric polymer directly or through an organic group. In the present invention, the "carboxyl group" means a carboxyl (carbonyl) group-containing group containing the organic group. May be said.

The compound capable of introducing a carboxyl group is not particularly limited, and examples thereof include a carboxylic acid compound and its derivative. Examples of the carboxylic acid compound include organic acids having a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may be aliphatic, alicyclic, aromatic or the like. Examples of the carboxylic acid derivative include carboxylic acid anhydrides, amino acids, thiocarboxylic acids (mercapto group-containing carboxylic acids), esters, amino acids, ketones, amides, imides, dicarboxylic acids and monoesters thereof.

Specifically, malonic acid, maleic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, p-hydroxybenzoic acid, p-aminobenzoic acid, mercaptoacetic acid, etc. Carboxylic acids and substituent-containing carboxylic acids; acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, propionic anhydride, benzoic anhydride; maleic acid esters, malonic acid esters, succinic acid esters , Aliphatic esters such as glutaric acid ester and ethyl acetate; aromatic esters such as phthalic acid ester, isophthalic acid ester, terephthalic acid ester, ethyl-m-aminobenzoate, methyl-p-hydroxybenzoate; quinone, anthraquinone, naphthoquinone, etc. Ketones; glycine, tricine, bicine, Alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N-(p-aminobenzoyl)-.beta.-amino acids such as alanine, maleic amide, maleamic acid (maleic monoamide),
Succinic acid monoamide, 5-hydroxyvaleramide, N
-Acetylethanolamine, N, N'-hexamethylenebis (acetamide), malonamide, cycloserine, 4-acetamidophenol, amides such as p-acetamidobenzoic acid; and imides such as maleinimide and succinimide. Among these, as a compound capable of introducing a carboxyl group, succinic anhydride,
Cyclic acid anhydrides such as maleic anhydride, glutaric anhydride, and phthalic anhydride are preferable, and maleic anhydride is more preferable.

The metal compound forming the carboxylic acid metal salt of the present invention is not particularly limited, and various metal compounds can be used. For example, as the metal of the metal compound, 199
The first of the periodic table based on the 0 years revised IUPAC nomenclature
Tribe, 2nd, 3rd, 4th, 5th, 6th, 7th
Tribe, 8th, 9th, 10th, 11th, 12th,
Mention may be made of Group 13, Group 14 and Group 15 metals. Further, as metal compounds, saturated fatty acid salts such as formate salts, acetate salts and stearates of these metals; unsaturated fatty acid salts such as (meth) acrylate salts; ether salts; nitrates, carbonates, hydrogen carbonates, chlorides Compounds, oxides, hydroxides, acetylacetonato complexes and the like.

Ease of introduction into the side chain of the elastomeric polymer, shape retention when an elastomer composition is prepared,
From the viewpoint of excellent physical properties such as surface properties, the metal compound is preferably a metal Y hydroxide, ether salt, or carboxylate represented by the general formula Y (OQ) _q . In the above general formula, Y is a metal, q is an integer of 1 to 4, and Q is
Is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or -CO
It is a -Q 'group. Here, Q'is a hydrocarbon group having 1 to 20 carbon atoms. Further, two or more of OQ may combine to form a ring containing a metal Y (for example, oxalic acid condensate, acetylacetonato complex composed of acetylacetone and metal, etc.). Hydrocarbon groups Q and Q'having 1 to 20 carbon atoms
Are not particularly limited, and include, for example, methyl group, ethyl group, propyl group (including isomers), butyl group (including isomers), hexyl group (including isomers), allyl group, methoxymethyl group, ethoxymethyl group, Examples thereof include ethoxyethyl group, phenoxymethyl group, phenoxyethyl group, phenyl group, phenylmethyl group, furyl group and pyridinyl group. Of these, a methyl group and an ethyl group are preferable because they are easily eliminated and condensed as stable and low-boiling point methanol or ethanol, or stable acetic acid or propionic acid. Here, the "ether salt" refers to a compound in which an oxygen atom bonded to a hydrocarbon is directly bonded to a metal atom, such as a metal alkoxide, and in addition to the metal alkoxide,
It also includes a complex in which a 1,3-diketone (eg, acetylacetone) or the like is coordinated.

The metal Y is excellent in physical properties such as shape retention and surface properties when formed into an elastomer composition.
Li, Na, K, Mg, Ca, Ba, Ti, Mn, F
e, Co, Ni, Cu, Zn, Al or Pb is preferable, and the metal compound is represented by the general formula Y (OQ) _q ,
Li, Na, K, Mg, Ca, Ba, Ti, Mn, F
e, Co, Ni, Cu, Zn, Al and Pb, a hydroxide, an ether salt or a carboxylate of a metal selected from the group consisting of saturated fatty acid salts having 20 or less carbon atoms and unsaturated salts having 20 or less carbon atoms. It is preferably a saturated fatty acid salt). As the metal compound, a metal hydroxide or an acetylacetonato complex is more preferable, and when these are used, a strong aggregate structure accompanied by fine crystal structuring is formed in the thermoplastic elastomer by the carboxylic acid metal salt, and the elastomer composition is obtained. Particularly excellent in shape retention (compression set) and surface properties. Among these, Li, Na and K
Alkali metal hydroxides or acetylacetonato complexes are preferred, Na hydroxides, or Li, Na, K,
Cu and Zn acetylacetonato complexes are particularly preferred.
The metal compounds can be used as a mixture of two or more kinds, and the mixing ratio in this case can be an arbitrary ratio depending on the intended use, required physical properties and the like. As the metal compound, all hydroxides, ether salts or carboxylic acid salts of the metal can be used. For example, taking hydroxide as an example, when the metal is iron, Fe (OH) ₂ and Fe (OH) ₃ may be used alone or in combination.

The carboxylic acid metal salt of the present invention can be obtained by subjecting the above carboxyl group and the above metal compound to a condensation reaction. Examples of the condensation reaction include a dehydration reaction, dealcoholization reaction, and decarboxylic acid reaction. The condensation reaction condition is not particularly limited and may be a commonly used condition, but it is preferably carried out by heating at 100 ° C. or higher under normal pressure, more preferably by heating at 120 ° C. or higher under reduced pressure. it can. Further, a condensing agent which is usually used can also be used. The condensing agent is a reaction aid such as an acid or a base, and examples thereof include basic catalysts such as alkali hydroxide, alkali carbonate, piperidine, diethylamine, and alkali metal amides; hydrogen chloride, zinc chloride, polyphosphoric acid,
Acidic catalysts such as aluminum chloride and silica gel; ion exchange resins, molecular sieves and the like can be mentioned. In the present invention, it is preferable that the metal hydroxide is dissolved in a solvent such as water and reacted with the above-mentioned carboxyl group for the purpose of promptly dispersing the metal hydroxide. When a carboxylic acid derivative or the like is used for the introduction of a carboxyl group, it is preferably converted into a carboxyl group by hydrolysis or the like under the conditions usually performed before the reaction with a metal compound.

In the present invention, a metal compound (general formula Y
A salt in which one substituent (OQ) of (OQ) _q ) is condensed and reacted with a carboxyl group and the molar ratio of the metal compound to the carboxyl group is 1: 1 may be used, or the two substituents of the metal compound may be It may be a salt in which the molar ratio of the metal compound and the carboxyl group, which has undergone the condensation reaction with the carboxyl group, is 1: 2,
In addition, the three substituents of the metal compound are condensed with the carboxyl group, and the molar ratio of the metal compound and the carboxyl group is 1:
It may be a salt of 3. Further, it may be a mixture thereof.

The content of the carboxylic acid metal salt of the present invention is preferably 0.1 to 1.0 mol, and more preferably 0.3 to 1.0 mol, based on 1 mol of the carboxyl group. It is preferably 0.5 to 1.0 mol, and particularly preferably 0.5 to 1.0 mol.
Within this range, the shape retention (compression set) and surface properties of the elastomer (composition) are excellent.

The thermoplastic elastomer of the present invention has a nitrogen-containing heterocyclic ring-containing group at the side chain or terminal of the elastomeric polymer in addition to the above-mentioned metal salt of carboxylic acid. The nitrogen-containing heterocycle contained in the nitrogen-containing heterocycle-containing group is introduced into the main chain either directly or via an organic group. The nitrogen-containing heterocycle, if it contains a nitrogen atom in the heterocycle, other heteroatoms other than the nitrogen atom in the heterocycle, for example, sulfur atom, oxygen atom,
Those having a phosphorus atom or the like can also be used. The reason why the heterocyclic compound is used here is that the heterocyclic structure has a strong hydrogen bond, which will be described later, and the strength is improved. The heterocyclic ring may have a substituent, and examples of the substituent include an alkyl group such as a methyl group, an ethyl group, a (iso) propyl group and a hexyl group; a methoxy group, an ethoxy group and a (iso) propoxy group. An alkoxy group such as fluorine, iodine,
A group consisting of a halogen atom such as chlorine; a cyano group, an amino group, an aromatic hydrocarbon group, an ester group, an ether group, an acyl group, a thioether group and the like can be mentioned, and these can also be used in combination. These substitution positions are not particularly limited, and the number of substituents is also not limited. In addition, the heterocycle is
It may or may not have aromaticity, but if it has aromaticity, the tensile strength at the time of cross-linking is further increased, and the strength of the thermoplastic elastomer (composition) is further improved. Therefore, it is preferable.

Examples of such a 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, phylloerythrin, imidazole,
Pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone, hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, indole, indoline, oxirindole, Carbazole, phenothiazine, indolenine, isoindole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine, pyrazine, phenazine,
Tetrazine, benzoxazole, benzisoxazole, anthranil, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine,
Examples include phenanthridine, anthrazoline, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline, triazine, histidine, triazolidine, melamine, adenine, guanine, thymine and cytosine. Of these nitrogen-containing heterocycles, the following compounds are preferably exemplified especially for the nitrogen-containing 5-membered ring. These may have various substituents, and may be hydrogenated or eliminated.

[0031]

[Chemical 5]

For the nitrogen-containing 6-membered ring, the following compounds are preferably exemplified. These may also have various substituents and may be hydrogenated or eliminated.

[0033]

[Chemical 6]

The condensed ring of the above nitrogen-containing heterocycle and the benzene ring or the nitrogen-containing heterocycle can be used, and examples thereof include the following condensed rings.

[0035]

[Chemical 7]

Among these nitrogen-containing heterocycles, a triazole ring, a pyridine ring or a thiadiazole ring is used for the physical properties (hardness, shape retention rate, surface properties, etc.) when it is made into a thermoplastic elastomer (composition). It is preferable because it is excellent.

In the thermoplastic elastomer of the present invention, the carboxylic acid metal salt and the nitrogen-containing heterocyclic ring-containing group may be introduced into the polymer main chain as side chains independent from each other, and the carboxylic acid metal salt and the nitrogen-containing heterocycle may be introduced. The heterocycle-containing group may be bonded to one side chain via groups different from each other and introduced into the main chain. The nitrogen-containing heterocycle-containing group is preferably introduced into the polymer main chain as a side chain having a structure represented by the following formula (1).

[0038]

[Chemical 8] (In the formula, A is a nitrogen-containing heterocycle bonded to the main chain through an organic group B, and B is an oxygen atom, a sulfur atom or an amino group N.
R '(R' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or an organic group which may contain these. As the nitrogen-containing heterocycle A, specifically, the nitrogen-containing heterocycles exemplified above can be preferably used. Further, as the organic group B, specifically, for example, an oxygen atom, a sulfur atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); alkylene group or aralkylene group 20; with them at the end, alkylene ether group having 1 to 20 carbon atoms (alkylene group, e.g., -O-CH ₂ CH ₂ - group), an alkylene group (e.g., -NH- CH ₂ CH ₂ — group and the like) or an alkylene thioether group (alkylenethio group, for example, —S—CH ₂ CH ₂ — group); The above oxygen atom, sulfur atom and amino group are preferably combined with an adjacent carbonyl group to form an ester group, a thioester group and an amide group, respectively. The organic group B is an oxygen atom, a sulfur atom or an amino group (N
H); C1-C20 alkylene ether group, alkyleneamino group or alkylenethioether group having these at the terminal are preferred, and amino group (NH, -NH
-CH ₂ - group, -NH-CH ₂ CH ₂ - group), an alkylene ether group (-O-CH ₂ - group, -O-CH ₂ CH ₂
-Group) is particularly preferred.

Further, it is preferable that the carboxylic acid metal salt and the nitrogen-containing heterocyclic ring-containing group are chemically bonded to each other to form one side chain and be introduced into the polymer main chain. The carboxylic acid metal salt and the nitrogen-containing heterocycle-containing group are more preferably introduced into the polymer main chain at the α-position or β-position as one side chain having a structure represented by the following formula (2).

[0040]

[Chemical 9] (In the formula, R is a nitrogen-containing heterocycle, X is an oxygen atom, a sulfur atom or an amino group NR '(R' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or an organic group which may contain these. Yes, Y is the metal, Q is a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms or a -CO-Q 'group (Q' is a hydrocarbon group having 1 to 20 carbon atoms), and n is 1
Is an integer of 4 to 4, m is an integer of 0 to 3, and m + n is a valence of the metal Y (an integer of 1 to 4). Here, the nitrogen-containing heterocycle R is the same as the nitrogen-containing heterocycle A of the above formula (1), and is the nitrogen-containing heterocycle exemplified above. The organic group X is the same as the organic group B of the above formula (1), and the metal Y
The metal exemplified above can be preferably used, and Q
And Q ′ are the same as above.

The side chain portion composed of the carboxylic acid metal salt and the nitrogen-containing heterocyclic ring-containing group is preferably contained in a proportion of 0.1 to 50 mol% with respect to 100 mol% of the main chain portion, It is more preferable that the content is 1 to 30 mol%. When the carboxylic acid metal salt and the nitrogen-containing heterocyclic ring-containing group are independently introduced, both groups may be considered as a pair, and when either group is excessive, the above-mentioned groups are contained based on the larger group. Any rate will do. For example, when the main chain portion is isoprene rubber, this ratio is about 0.1 to 30 mol% of the monomer into which the side chain portion is introduced per isoprene monomer unit mole. Within this range, the interchain or intramolecular interaction of these side chains is well balanced, and the thermoplastic elastomer has a very high tensile strength at the time of crosslinking and the strength of the thermoplastic elastomer (composition) is high. It is improved and has rubber elasticity. When this thermoplastic elastomer is heated to 120 ° C. or higher, the three-dimensional crosslinked structure is dissociated and fluidity is imparted. It is considered that this is because the interaction between the side chains is weakened. If the ratio of the side chain portion to 100 mol% of the main chain portion is less than 0.1 mol%, the strength during crosslinking may not be sufficient, and if it exceeds 50 mol%, rubber elasticity may be lost. The ratio of the carboxylic acid metal salt to the nitrogen-containing heterocycle-containing group is not particularly limited, but is preferably 1: 1 because complementary interactions are likely to be formed. In addition, the thermoplastic elastomer of the present invention preferably has a glass transition point of 25 ° C. or lower when desired rubber elasticity is desired at room temperature.

The method for producing the thermoplastic elastomer of the present invention is not particularly limited, and the thermoplastic elastomer can be synthesized by an ordinary method. Among the thermoplastic elastomers of the present invention, those having a carboxylic acid metal salt and a nitrogen-containing heterocycle-containing group in the same side chain include, for example, a carbonyl-containing group modified product of an elastomeric polymer having a nitrogen-containing heterocycle-containing group. It is obtained by reacting with a compound capable of introducing a carboxylic acid, a carboxylic acid metal salt by the above method, and covalently bonding the carboxylic acid metal salt and the nitrogen-containing heterocycle-containing group. Specifically, a diene rubber such as butadiene rubber and a toluene solution containing maleic anhydride or mercaptoacetic acid are stirred at room temperature or under heating in a nitrogen atmosphere for 5 hours to precipitate the reaction mixture in methanol and dry under reduced pressure. Then, an elastomer modified with a carbonyl-containing group is obtained, and the elastomer is reacted with a compound capable of introducing a nitrogen-containing heterocycle-containing group, and then a carboxylic acid metal salt is obtained by the above-mentioned method. It can be obtained by covalently bonding to the nitrogen-containing heterocycle-containing group.

As the elastomer modified with a carbonyl-containing group, a commercially available product may be used. For example, LIR-
Maleic anhydride-modified isoprene rubber such as 403 (manufactured by Kuraray Co., Ltd.) and LIR-410A (prototype manufactured by Kuraray Co., Ltd.), LIR
-410 (manufactured by Kuraray Co., Ltd.) and other modified isoprene rubber, Clinac 110, 221, 231 (manufactured by Polycer) and other carboxyl modified nitrile rubber, CPIB (manufactured by Nisseki Chemical Co., Ltd.), HRPIB (Nisseki Chemical Lab prototype), etc. Carboxyl-modified polybutene, Nucrel (manufactured by Mitsui DuPont Polychemical Co., Ltd.), Yucaron (manufactured by Mitsubishi Chemical Co., Ltd.) and the like. In addition, after reacting compounds capable of introducing a carbonyl-containing group and a nitrogen-containing heterocyclic ring-containing group, the compound may be introduced into a side chain of an elastomeric polymer, and then the carboxylic acid metal salt may be obtained by the above method, , After reacting the compounds capable of introducing a carbonyl-containing group and a nitrogen-containing heterocyclic ring-containing group, and then a carboxylic acid metal salt by the above method,
It may be attached to a side chain of the elastomeric polymer.

When a thermoplastic elastomer having a carboxylic acid metal salt and a nitrogen-containing heterocyclic ring-containing group independently in the side chains is synthesized, the main component of the elastomeric polymer is produced during the production of the elastomeric polymer. A monomer capable of forming a chain and a copolymerizable monomer capable of introducing the above group may be copolymerized to directly produce the thermoplastic elastomer, and then the carboxylic acid metal salt may be obtained, or the main chain of the elastomeric polymer. The above-mentioned thermoplastic elastomer may be directly produced by copolymerizing a monomer capable of forming with a monomer containing a carboxylic acid metal salt, and further, a main chain (elastomer polymer) is previously formed by polymerization or the like. Then, it may be graft-modified with a compound capable of introducing the above group, and then used as a carboxylic acid metal salt. In each of the above production methods, whether each group of the side chain of the thermoplastic elastomer is independently bonded or bonded to each other is confirmed by a commonly used analysis means such as NMR or IR spectrum. be able to.

Among the above, the thermoplastic elastomer of the present invention is prepared by first synthesizing a carbonyl-containing group-modified elastomer into which a carbonyl-containing group is introduced, and then reacting it with a compound capable of introducing a nitrogen-containing heterocycle-containing group. A method in which a nitrogen heterocycle is introduced, and finally, a carboxylic acid metal salt is used is preferable. Particularly, an elastomeric polymer having a cyclic acid anhydride in a side chain and a nitrogen-containing heterocyclic compound are used. It is preferable to react the acid anhydride group at a temperature capable of forming a chemical bond (for example, a covalent bond or an ionic bond), and then to form a carboxylic acid metal salt, which is then introduced into the main chain of the elastomeric polymer. Regarding the production of the elastomer before forming the carboxylic acid metal salt, specific points are as follows.
It is described in Japanese Patent Laid-Open No. 2000-169527.

For the sake of convenience, the nitrogen-containing heterocycle contained in the nitrogen-containing heterocycle-containing group of the present invention is referred to as “nitrogen-containing n-membered ring compound (n ≧ 3)”.
Then, the bonding position of the nitrogen-containing heterocycle will be described. The bond positions (“1-n positions”) described below are based on the IUPAC nomenclature. For example, in the case of a compound having three nitrogen atoms having an unshared electron pair, the bonding position is determined by the rank based on the IUPAC nomenclature. In addition, IU
The bonding position based on the PAC nomenclature is attached to the structural formula exemplifying the nitrogen-containing heterocycle. In the thermoplastic elastomer of the present invention, the bonding position of the nitrogen-containing n-membered ring compound that is bonded to the main chain directly or via an organic group is not particularly limited, and any bonding position (1-position to n-position) may be used. Preferably, it is the 1st position or the 3rd position to the nth position. That is, in the side chain having the structure represented by the above formula (1), the nitrogen-containing n
The member ring compound A is bonded to the organic group B at the 1-position or 3-position to n-position thereof. Further, in the side chain represented by the above formula (2), the nitrogen-containing n-membered ring compound R has 1-position to 3-position to n-position.
It is bonded to the organic group X at position. Position 1 when the nitrogen-containing heterocycle contains one nitrogen atom (eg, pyridine ring) and when the nitrogen-containing heterocycle is a ring having adjacent heteroatoms (eg, imidazole). Is not preferable. This is because a chelate is easily formed in the molecule.

When the nitrogen-containing n-membered ring compound is bonded to the main chain at another site, for example, the organic polymer described in JP-A-8-239583, at the 2-position via the organic group,
An intramolecular chelate is formed between the carboxylic acid metal salt having the same side chain as the nitrogen atom of the nitrogen-containing n-membered ring compound in the molecule and a carbonyl group such as an amide bond generated when a carboxyl group or a nitrogen-containing heterocycle is introduced. It is considered that it is formed and no improvement in strength due to the intermolecular chelate can be expected. It is also used for hydrogen bonding between molecules, that is, between the nitrogen atom of the nitrogen-containing n-membered ring compound existing in different side chains of the thermoplastic elastomer and the nitrogen atom such as the carboxyl group or the amide bond. It is considered that since nitrogen atoms and hydrogen atoms are reduced, intermolecular cross-linking is reduced, resulting in lower strength and lower shape retention. As a result, effective intermolecular hydrogen bonds are reduced, and the thermoplastic elastomer (composition)
It is considered that the hardness of the is decreased. Even when the nitrogen-containing n-membered ring compound and the unreacted carboxyl group or the amide bond are bonded to the main chain of the thermoplastic elastomer as independent side chains, the nitrogen-containing n-membered ring compound is 2 When bonded to the main chain at the position, the nitrogen atom of the nitrogen-containing n-membered ring compound is present on the side closer to the main chain, and hydrogen bonds to the carbonyl group present on the side chain of another thermoplastic elastomer as well. It is thought that it is difficult to form a chelate.

On the other hand, in the thermoplastic elastomer of the present invention, the nitrogen-containing n-membered ring compound has 1 to 3 positions.
Since it is bonded to the main chain at the n-position, such as an amide bond generated when a nitrogen-containing n-membered ring compound and a carboxylic acid metal salt having the same side chain and a carboxyl group or a nitrogen-containing heterocycle are introduced into the same side chain. Even if a carbonyl group is present, since the nitrogen atom of the heterocycle and the carbonyl group such as the carboxyl group or the amide bond are far from each other, it is difficult to form a chelate in the molecule, The strength can be expected to be improved by the formation of interchelates and ionic bonds. Also,
Even when the nitrogen-containing n-membered ring compound and the carboxyl group or the amide bond or the like independently form a side chain, the nitrogen atom of the heterocycle is present distant from the main chain. The structure is such that hydrogen bonds, ionic bonds, and chelates are easily formed with carbonyl groups of other thermoplastic elastomers. As a result, the thermoplastic elastomer (composition) of the present invention has a hydrogen bond, an ionic bond, or the like between the nitrogen atom of the heterocyclic ring present on the side chains of different thermoplastic elastomers and the carboxyl group or the amide bond.
It is considered that chelate is easily formed, the recyclability is excellent, the hardness of the thermoplastic elastomer (composition) is high, and the chelate is suitable for applications such as elastic materials. Moreover, since the carboxylate of the present invention is partially ionized, it is considered that an interaction occurs between the ions. That is, when the thermoplastic elastomer (composition) of the present invention has the above-mentioned constitution, the strength of the thermoplastic elastomer (composition) is increased due to the formation of hydrogen bond, ionic bond and intermolecular chelate and interionic interaction. improves.

The thermoplastic elastomer of the present invention having such characteristics can be used for various vulcanized rubber applications by utilizing rubber elasticity, for example. When it is included in the hot melt adhesive, heat resistance and recyclability can be improved. Especially around automobiles such as tire treads, carcass; exterior radiator grills, side moldings, garnish (pillars, rears, cowl tops), aero parts (air dams, spoilers), wheel covers, weather strips, cow belt grills, air outlets. -Louvers, air scoops, hood bulges, ventilation parts, anti-corrosion parts (over fenders,
Side seal panels, moldings (windows, hoods, door belts), marks; doors, lights, wiper weather strips, glass run, interior window frame parts such as glass run channels; air duct hoses, radiator hoses, brake hoses; crankshaft seals Lubricating oil components such as valve stem seals, head cover gaskets, A / T oil cooler hoses, mission oil seals, P / S hoses, P / S oil seals; fuel hoses, emission control hoses, inlet filler hoses, tire flams, etc. Fuel system parts; engine mounts, in-tank pump mounts, etc.
Boots such as CVJ boots, rack and pinion boots;
Air conditioner parts such as A / C hoses and A / C seals; Belt parts such as timing belts and accessory belts; Windshield sealers, vinyl plastisol sealers, anaerobic sealers, body sealers, spot weld sealers, etc. It can be preferably used as a class. When a resin or rubber that causes cold flow at room temperature is included as a rubber modifier, for example, as an anti-flow agent, the flow and cold flow at the time of extrusion can be prevented.

Since the thermoplastic elastomer of the present invention has a carboxylic acid metal salt and a nitrogen-containing heterocyclic ring-containing group,
It has sufficient hardness, excellent shape retention (compression set) and surface properties to be used as an elastic member without impairing excellent recyclability, and crosslink formation (curing) and crosslink dissociation (fluidization) due to temperature change. ) Can be reproduced repeatedly.

A second aspect of the present invention is a thermoplastic elastomer composition containing the above-mentioned elastomer; carbon and / or silica.

The composition of the second aspect contains one or more of the above-mentioned thermoplastic elastomers of the present invention. When two or more kinds are contained, the mixing ratio can be an arbitrary ratio depending on the use of the composition, required physical properties and the like.

Further, the composition of the second embodiment contains carbon and / or silica as a reinforcing agent. Carbon is
There is no particular limitation, and examples thereof include carbon black, and the content thereof (when using carbon alone) is 1 to 200 parts by mass, preferably 20 to 100 parts by mass, and more preferably 100 parts by mass of the thermoplastic elastomer. Three
It is 0 to 80 parts by mass. Carbon is preferably carbon black, and the carbon black is appropriately selected according to the application. Generally, carbon black is classified into hard carbon and soft carbon based on the particle size. Soft carbon has low reinforcement to rubber, and hard carbon has high reinforcement to rubber. In the present invention,
In particular, it is preferable to use hard carbon having a strong reinforcing property.

The silica is not particularly limited, and examples thereof include fumed silica, calcined silica, precipitated silica, ground silica,
Examples of the silica include fused silica and diatomaceous earth, and the content thereof (when using silica alone) is 1 to 200 parts by mass, preferably 20 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.
It is 0 part by mass, more preferably 30 to 80 parts by mass. Of these, precipitated silica is preferred.

When carbon and silica are used in combination, the content is 1 with respect to 100 parts by mass of the thermoplastic elastomer.
To 200 parts by mass, preferably 20 to 100 parts by mass, more preferably 30 to 80 parts by mass.

The composition of the present invention, in addition to the above essential requirements,
If necessary, within a range that does not impair the object of the present invention, polymers other than the elastomer of the present invention, other reinforcing agents, antioxidants, antioxidants, pigments (dye), plasticizers, thixotropic agents, UV absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, rust preventives, adhesion promoters, antistatic agents, various additives such as fillers, etc. can be contained. .

As the additives and the like, those generally used can be used. Specific examples thereof will be given below, but the present invention is not limited to these examples. As the polymer other than the elastomer of the present invention, a polymer having a glass transition temperature of 25 ° C. or lower is preferable for the above reason,
In particular, any of those used as the main chain of the present invention is preferable. More preferably, natural rubber (N
R), isoprene rubber (IR), butadiene rubber (B
R), butyl rubber (IIR), ethylene-propylene-
Diene rubber (EPDM), ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM),
Particularly, it is preferable to use a polymer having no unsaturated bond such as IIR, EPDM, EPM and EBM or a polymer having a small amount of unsaturated bond. The other polymer may contain one kind or two or more kinds. The content of the polymer is 0.1 to 100 with respect to 100 parts by mass of the thermoplastic elastomer.
Parts by mass, more preferably 1 to 50 parts by mass.

Other reinforcing agents include, for example, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, kaolin clay and calcined clay. The content thereof is 20 to 100 parts by mass, more preferably 30 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.
~ 80 parts by mass. Examples of the antiaging agent include compounds such as hindered phenol-based, aliphatic and aromatic hindered amine-based compounds, and the content is 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer, and It is preferably 1 to 5 parts by mass. Examples of the antioxidant include butylhydroxytoluene (BH
T), butylhydroxyanisole (BHA), and the like, and the content is 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. Examples of the pigment include titanium dioxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, inorganic pigments such as iron, cobalt, aluminum, hydrochloride and sulfate, azo pigments, and organic pigments such as copper phthalocyanine pigments. The content is 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.

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 the like, polyester, polyether, Examples thereof include epoxy type. Examples of the thixotropic agent include bentone, silicic acid anhydride, silicic acid derivatives, and urea derivatives. Examples of the ultraviolet absorber include 2-hydroxybenzophenone type, benzotriazole type, salicylate type and the like. Examples of the flame retardant include phosphorus such as TCP, chlorinated paraffin, halogen such as perchlorpentacyclodecane, antimony such as antimony oxide, and aluminum hydroxide. Examples of the solvent include hydrocarbon solvents such as hexane and toluene; halogenated hydrocarbon solvents such as tetrachloromethane; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate. To be Examples of the surfactant (leveling agent) include polybutyl acrylate, polydimethyl siloxane, modified silicone compounds, fluorine-based surfactants and the like. Examples of the dehydrating agent include vinyl silane and the like. Examples of the rust preventive agent include zinc phosphate, tannic acid derivative, phosphoric acid ester, basic sulfonate, and various rust preventive pigments. 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, examples thereof include trimethoxyvinylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. As the antistatic agent, a quaternary ammonium salt or a hydrophilic compound such as polyglycol or ethylene oxide derivative is generally used. The content of the plasticizer is 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and the content of the other additives is 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. , And more preferably 1 to 5 parts by mass.

The thermoplastic elastomer of the present invention can be self-crosslinked, but a vulcanizing agent, a vulcanization aid, a vulcanization accelerator and the like can be used in combination within the range not impairing the object of the present invention. As the vulcanizing agent, powdered sulfur, precipitable sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, sulfur-based vulcanizing agents such as alkylphenol disulfide, zinc white, magnesium oxide, litharge, Examples thereof include p-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene, and methylindianiline. Vulcanization aids include fatty acids such as acetyl acid, propionic acid, butanoic acid, stearic acid, acrylic acid, maleic acid; zinc acetylate, zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, maleic acid. Fatty acid zinc such as zinc and the like can be mentioned. As the vulcanization accelerator, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (T
ETD) and other thiurams; hexamethylenetetramine and other aldehydes / ammonia; diphenylguanidine and other guanidines: dibenzothiazyl disulfide (D)
Examples thereof include thiazoles such as M); sulfenamides such as cyclohexylbenzothiazylsulfenamide; Further, an alkylphenol resin or a halide thereof can be used. The content of these vulcanizing agents and the like is 0.
It is 1 to 20 parts by mass, more preferably 1 to 10 parts by mass.

The method for producing the composition of the present invention is not particularly limited. For example, the above-mentioned thermoplastic elastomer of the present invention, carbon and / or silica and, if necessary, the above-mentioned additives and the like are rolled, kneaded or extruded. A machine, a universal stirrer, etc. may be used for mixing.

The thermoplastic elastomer composition of the present invention comprises
For example, it can be used for various rubber applications by utilizing rubber elasticity. When it is contained in or as a hot melt adhesive, heat resistance and recyclability can be improved. In particular, it can be preferably used around the above-mentioned automobile. When a resin or rubber that causes cold flow at room temperature is included as a rubber modifier, for example, as an anti-flow agent, the flow and cold flow at the time of extrusion can be prevented. Further, the elastomer composition of the present invention contains carbon and / or silica, etc., whereby the tensile strength, tear strength and bending strength are improved,
In particular, it can be particularly suitably used for applications such as tires, hoses, belts, sheets, anti-vibration rubbers, rollers, linings, rubberized cloths, sealing materials, gloves and antiglare materials.

The thermoplastic elastomer composition of the present invention comprises
By introducing a carboxylic acid metal salt and a nitrogen-containing heterocyclic ring-containing group into the thermoplastic elastomer, sufficient hardness and excellent shape retention (compression set) for use as an elastic member are obtained without impairing excellent recyclability. ) And surface properties, crosslink formation (curing) and crosslink dissociation (fluidization) can be repeatedly reproduced by temperature changes.

[0064]

EXAMPLES Next, the present invention will be described more specifically by showing examples, but the present invention is not limited to these. <Synthesis of Thermoplastic Elastomer> Commercially available maleic anhydride-modified isoprene rubber (modification rate 2.7 mol%, LIR-
410A, manufactured by Kuraray Co., Ltd.) to 869.6 g (0.448 mol of maleic anhydride skeleton), 4H-3-amino-1,
37.63 g of 2,4-triazole (0.448 mo
l) was heated and stirred at 150 ° C. for 1 hour under reduced pressure. After confirming that a uniform solution was obtained, the reaction product was allowed to stand overnight to obtain a gel-like reaction product. The reaction product was analyzed by NMR and IR.
It was confirmed to be a thermoplastic elastomer 1 (formula (3)) having the following structure. Similarly, a thermoplastic elastomer 2 (formula (4)) was synthesized using 4-aminopyridine as the nitrogen-containing heterocyclic compound at the same ratio. Similarly,
2-Aminopyridine was used as the nitrogen-containing heterocyclic compound in the same proportion to synthesize a thermoplastic elastomer 3 (formula (5)). Maleic anhydride modified isoprene rubber (modification rate 2.7 mol%, LIR-410A, manufactured by Kuraray Co., Ltd.) 1
To 5.55 g (8.0 mmol), 1.0 g of methanol
(31.25 mmol, manufactured by Kanto Chemical Co., Inc.) was added and the mixture was heated with stirring at 60 ° C. for 5 hours to synthesize half-esterified thermoplastic elastomer 4 (formula (6)).

[0065]

[Chemical 10] Here, a: b≈358: 10.

<Introduction of Carboxylic Acid Metal Salt> The obtained thermoplastic elastomers 1 to 4 and the addition amount shown in Table 1 (the addition amount in the table is the equivalent amount of the metal compound to the carboxyl group).
The metal compound of 1 was added with stirring and mixed at 80 to 120 ° C. for 1 hour. Then, the mixture was mixed at 120 ° C. for 5 hours, and the reaction was performed while condensing under reduced pressure. As an example (Example 2), 10.461 g of the elastomer 1 (formula (3))
(5.38 mmol), 2.4% of 10% NaOH aqueous solution
After adding 3 g and stirring at 80 ° C., dehydration reaction was performed under reduced pressure at 120 ° C. for 5 hours to obtain an elastomer of the present invention. The reaction product was confirmed by NMR and IR to convert the carboxyl groups of the thermoplastic elastomers 1 to 4 into carboxylic acid metal salts.

<Preparation of Thermoplastic Elastomer Composition><Examples 1 to 19> During the synthesis of the thermoplastic elastomer,
Antiaging agent 6C (Santoflex 13) 17.39g
(1 part by mass with respect to 100 parts by mass of the thermoplastic elastomer) was added, and then carboxylic acid metal salts were introduced in the combinations shown in Tables 1 and 2 to obtain a thermoplastic elastomer composition. A commercially available metal compound was used. In Table 2, "acac" means acetylacetone, and the metal compound is a salt or complex with a metal.

Example 20 A thermoplastic elastomer 1 was reacted with a metal compound to form a carboxylic acid metal salt, and further 3 g of carbon black (30 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer) was added to obtain a thermoplastic resin. An elastomer composition was prepared. Note that the antioxidant 6C (Santoflex 13) was added during the synthesis of the thermoplastic elastomer. Example 21 A thermoplastic elastomer composition was prepared in the same manner as in Example 20, except that 3 g of precipitated silica (30 parts by mass relative to 100 parts by mass of the thermoplastic elastomer) was used instead of 3 g of carbon black.

<Measurement of JIS A Hardness> The thermoplastic elastomer compositions of the respective examples and comparative examples were tested at 150 ° C. for 60 minutes.
After press molding for 1 minute, thickness 1mm x length 5cm x width 5c
A flat plate sample of m was prepared. Three obtained flat plate samples were piled up, and in accordance with JIS K6253, JIS A
Hardness was measured. The results are shown in Tables 1 and 2. <Measurement of Shape Retention Ratio> The thermoplastic elastomer compositions of Examples and Comparative Examples were press-molded at 100 ° C. for 20 minutes, and then a cylindrical sample having a diameter of 29 mm and a thickness of 12.5 mm was prepared. A glass plate was placed on the sample, a weight of 500 g was placed on the glass plate, and the amount of deformation was measured until 48 hours later. The shape retention rate was calculated from the obtained deformation amount using the following formula. The results are shown in Tables 1 and 2. Shape retention rate (%) = (thickness after a lapse of a predetermined time / thickness at the start of measurement) × 100

<Surface Properties> The thermoplastic elastomer compositions of the respective examples and comparative examples were molded into strips, and the surface condition was visually confirmed and evaluated. The results are shown in Tables 1 and 2.
Shown in the table. In Table 1, when the surface tack could not be confirmed, “◎”, when almost no surface tack was confirmed, “○”,
The case where it was confirmed only a little (feeling tackiness) (no problem at practical level) was indicated by "△", and the case where it was confirmed was indicated by "x".

<Recyclability> The lithographic sample synthesized by the above method was cut into a size of about 1 cm × 1 cm, finely divided, and press-molded again. This operation was repeated 10 times and the press formability after 10 times was confirmed. as a result,
All samples showed sufficient recyclability (specifically, moldability (press molding conditions), shape retention, surface properties, and hardness hardly changed).

Comparative Example 1 With respect to the thermoplastic elastomer 1 (added with the antioxidant 6C), the shape retention rate and hardness of the thermoplastic elastomer composition were measured in the same manner as in Example without adding the metal compound. The surface properties were evaluated. <Comparative Example 2> Thermoplastic elastomer 3 (antiaging agent 6C
Already added) and the metal salt of the addition amount shown in Table 1 (the addition amount in the table is the equivalent of the metal compound to the carboxyl group) were added with stirring and mixed at 120 ° C. for 1 hour. Then 1
The mixture was mixed at 20 ° C. for 5 hours and reacted while degassing. The obtained carboxylic acid metal salt-containing thermoplastic elastomer composition was a liquid, and the shape retention and hardness could not be measured. The surface properties were evaluated in the same manner as in the examples. <Comparative Example 3> Thermoplastic elastomer 4 (antiaging agent 6C
Already added) and 1.0 equivalent of NaOH were added and mixed.
The shape retention and hardness of the thermoplastic elastomer composition were measured in the same manner as in Examples to evaluate the surface properties.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

When the carboxylic acid metal salt is introduced into the thermoplastic elastomer, its shape retention (compression set) can be remarkably improved and its surface property can be improved. That is,
According to the present invention, without impairing the excellent recyclability,
Thermoplastic elastomer that has sufficient hardness, excellent shape retention (compression set) and surface properties to be used as an elastic member, and can repeatedly reproduce crosslink formation (curing) and crosslink dissociation (fluidization) due to temperature change. And compositions containing it can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 AC011 AC031 AC041 AC061                       AC071 AC081 AC091 AC101                       BB051 BB151 BB181 BB211                       BB271 BC051 BD121 BG041                       BP011 CF001 CH041 CK021                       CN061 CP031 DA037 DD056                       DD066 DD076 DE056 DE066                       DE226 DE236 DE246 DJ017                       EE046 EG026 EG036 EG046                       FD017 FD020 FD030 FD050                       FD100 FD130 FD140 FD150                       FD310 FD340 GJ02 GM00                       GM01 GN01                 4J100 AA06P AB02P AB02Q AM02P                       AM02Q AS01P AS02Q AS03P                       AS07P BA34H BC68H BC69H                       BC73H BC74H BC75H BC79H                       BC80H BC83H HA31 HA57                       HA61 HB20 HB29 HB36 HB37                       HB39 HC12 HC27 HC28 HC29                       HC30 HG32 JA28 JA29 JA67

Claims (7)

[Claims] 1. A thermoplastic elastomer having a nitrogen-containing heterocycle-containing group in a side chain; and a carboxylic acid metal salt obtained by subjecting a carboxyl group and a metal compound to a condensation reaction. 2. The metal compound represented by the general formula Y (OQ) _q is Li, Na, K, Mg, Ca, Ba, Ti,
Mn, Fe, Co, Ni, Cu, Zn, Al and Pb
The thermoplastic elastomer according to claim 1, which is a hydroxide, an ether salt, or a carboxylate of metal Y selected from the group consisting of: (In the said general formula, Y is the said metal, q is an integer of 1-4, Q is a hydrogen atom, carbon number 1
~ 20 hydrocarbon groups or -CO-Q 'groups. Here, Q'is a hydrocarbon group having 1 to 20 carbon atoms. ) 3. The thermoplastic elastomer according to claim 1, wherein the content of the carboxylic acid metal salt is 0.1 to 1.0 mol with respect to 1 mol of the carboxyl group. 4. The nitrogen-containing heterocycle-containing group is represented by the following formula (1):
The thermoplastic elastomer according to any one of claims 1 to 3, which has a structure represented by: [Chemical 1] (In the formula, A is a nitrogen-containing heterocycle bonded to the main chain through an organic group B, and B is an oxygen atom, a sulfur atom or an amino group N.
R '(R' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or an organic group which may contain these. ) 5. The thermoplastic elastomer according to claim 1, wherein the nitrogen-containing heterocycle-containing group and the carboxylic acid metal salt have a structure represented by the following formula (2). [Chemical 2] (In the formula, R is a nitrogen-containing heterocycle, X is an oxygen atom, a sulfur atom or an amino group NR '(R' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or an organic group which may contain these. Yes, Y is the metal, Q is a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms or a -CO-Q 'group (Q' is a hydrocarbon group having 1 to 20 carbon atoms), and n is 1
Is an integer of 4 to 4, m is an integer of 0 to 3, and m + n is a valence of the metal Y (an integer of 1 to 4). ) 6. The thermoplastic elastomer according to claim 1, wherein the nitrogen-containing heterocycle-containing group is a group containing a triazole ring, a pyridine ring or a thiadiazole ring. 7. A thermoplastic elastomer composition containing the thermoplastic elastomer according to claim 1; and carbon and / or silica.