JP2002317122A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoreversibly crosslinkable thermoplastic elastomer composition having an improved shape retention ratio without detriment to recyclability. SOLUTION: The thermoplastic elastomer composition comprises a thermoplastic elastomer bearing on its side chain a carbonyl-containing group and a group containing a nitrogen-containing n-membered ring (where n>=3), the group containing a nitrogen-containing n-membered ring being bonded at its 3 to n-position to the main chain directly or via an organic group, and at least one compound of a metal selected from the group consisting of groups 2A, 3A, 4A, 5A, 6A, 7A, 8A, 1B, 2B, 3B, 4B and 5B of the periodic table.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic elastomer composition which can repeatedly reproduce cross-linking and cross-linking dissociation by a change in temperature.

[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 is difficult to remold due to crosslinkage due to strong covalent bonding. On the other hand, thermoplastic elastomers utilize physical crosslinking, and can be easily molded by heating and melting without requiring complicated vulcanization / molding steps including preliminary molding. A typical example of such a thermoplastic elastomer includes a resin component and a rubber component, and at normal temperature, the microcrystalline resin component becomes a hard segment that serves as a cross-linking point of a three-dimensional network structure, and a rubber component (soft segment). There is known a thermoplastic elastomer which prevents plastic deformation and softens or melts a resin component when the temperature rises. However, since such a thermoplastic elastomer contains a resin component, the rubber elasticity tends to decrease. Therefore, a material that can impart thermoplasticity without containing a resin component is required.

[0003] In order to address this problem, the present inventors have firstly developed an elastomer having a reactive site capable of forming a hydrogen bond,
It has been disclosed that an elastomer composition containing a reaction site of the elastomer and a compound having a reaction site capable of forming a hydrogen bond can repeat cross-link formation and cross-link dissociation by a temperature change utilizing a hydrogen bond ( JP-A-11-209524). Further, Japanese Patent Application Laid-Open No.
000-169527 discloses a hydrogen-bondable thermoplastic elastomer comprising an elastomeric polymer containing a carbonyl group-containing group and a heterocyclic amine-containing group in a side chain, which is expected to have the same effect. Further, Japanese Unexamined Patent Publication No.
No. 2,395,583, a carbonyl group-containing group and a nitrogen-containing heterocycle-containing group are contained in a side chain, and the nitrogen-containing heterocycle-containing group is bonded to the main chain directly at the 2-position to nitrogen or via an organic group. Bound organic polymers are disclosed. These elastomeric compositions or organic polymers can exhibit sufficient melt fluidity at the molding temperature of a thermoplastic resin such as an unmodified olefin resin, and at a low temperature, have excellent breaking strength due to cross-linking. It has mechanical strength and can repeatedly reproduce cross-link formation and cross-link dissociation (softening) by temperature change. Thermoplastic elastomers having such properties have extremely high industrial use value and environmental protection value, and can obtain higher crosslinking strength.
It is expected to be a material having excellent recyclability, with no change in physical properties even after repeated crosslinking and dissociation.
However, these thermoplastic elastomers did not have sufficient shape retention when a load was applied in terms of material properties. Further, the organic polymer disclosed in JP-A-8-239583, when a thermoplastic elastomer is used for the main chain,
The hardness is very low, and its properties are insufficient for use as an elastic member, such as use as a rubber material.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a temperature control device having a sufficient hardness to be used as an elastic member and an improved shape retention (compression set) without impairing excellent recyclability. An object of the present invention is to provide a thermoplastic elastomer composition capable of repeatedly reproducing curing and fluidization by a change.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve such problems, and as a result, as a thermoplastic elastomer having a carbonyl group-containing group and a nitrogen-containing heterocyclic group in a side chain, Select a thermoplastic elastomer in which the nitrogen-containing heterocyclic-containing group is bonded to the main chain at a specific site,
It has been confirmed that the above-mentioned problems can be achieved by adding a metal salt such as ZnCl ₂ or Zn (OCOC ₁₈ H ₃₇ ) ₂ thereto. That is, the present invention has a carbonyl-containing group and a nitrogen-containing n-membered ring-containing group (n ≧ 3) in the side chain, and the nitrogen-containing n-membered ring-containing group is directly located at the 3- to n-positions, or A thermoplastic elastomer bonded to the main chain through a group, and a group 2A, 3A, 4A, 5A, or 6A of the periodic table.
Group, group 7A, group 8A, group 1B, group 2B, group 3B
And a compound of at least one metal selected from the group consisting of Group 4B and Group 5B. Where n
The membered ring is a heterocyclic ring represented by the number n of atoms constituting the ring, and the nitrogen-containing heterocyclic ring and the nitrogen-containing n-membered ring are the same.

[0006] In the thermoplastic elastomer composition of the present invention, the thermoplastic elastomer preferably has a structure represented by the following formula (1) in a side chain.

Embedded image In the formula, A is a nitrogen-containing n-membered ring-containing group (n ≧ 3) bonded to the main chain via an organic group at positions 3 to n, and B is O,
It is an organic group that may contain N and S. In the thermoplastic elastomer composition of the present invention, a preferable side chain of the thermoplastic elastomer is represented by the following formula (2) or (3).

Embedded image In the formula, R is a nitrogen-containing n-membered ring-containing group (n ≧ 3) bonded to the main chain via an organic group at the 3- to n-positions, and X is O,
S is either NR 'or R' is H or an alkyl group having 1 to 10 carbon atoms.

In the thermoplastic elastomer composition of the present invention, the metal compound to be added is preferably ZnX ₂ ,
CoX ₂ , FeX ₂ , FeX ₃ , MnX ₂ , NiX ₂ ,
CuX ₂ and PbX ₂ (X is F, Cl, Br, I,
O, or at least one selected from the group consisting of OCOR [R is any one of alkyl groups having 1 to 20 carbon atoms].

The above-mentioned thermoplastic elastomers include, for example, an elastomeric polymer having a cyclic acid anhydride group in a side chain thereof and a heterocyclic amine-containing compound, wherein the heterocyclic amine-containing compound is chemically bonded to the cyclic acid anhydride group. It can be produced by reacting at a temperature capable of binding.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic elastomer composition of the present invention will be specifically described below. In the thermoplastic elastomer composition of the present invention, the thermoplastic elastomer has a carbonyl-containing group and a nitrogen-containing n-membered ring-containing group in a side chain of a natural polymer or a synthetic polymer elastomeric polymer, and contains a nitrogen-containing n-membered ring. The ring-containing group is bonded to the main chain directly at the 3- to n-positions or via an organic group. Here, having a carbonyl group-containing group and a nitrogen-containing n-membered ring-containing group in the side chain means that an atom (usually carbon) forming the main chain of the elastomeric polymer has a carbonyl group-containing group and a nitrogen-containing n-membered ring-containing group. Has a chemically stable bond (covalent bond). In addition, n of the nitrogen-containing n-membered ring-containing group
Is an integer of 3 or more in the present specification.

The elastomeric polymer serving as the main chain is a natural polymer or a synthetic polymer generally known as a rubber elastic material for vulcanization (crosslinking, curing). Specific examples of such an elastomeric polymer include, for example, natural rubber, isoprene rubber, butadiene rubber, 1,2-butadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene propylene diene rubber ( Diene rubbers such as EPDM), ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM), olefin rubbers such as chlorosulfonated polyethylene, acrylic rubber and fluororubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber And urethane rubber. Further, it may be an elastomeric polymer containing a resin component, for example, a polystyrene-based elastomeric polymer (SBS, SIS, SEBS) which may be hydrogenated, a polyolefin-based elastomeric polymer, a polyvinyl chloride-based elastomeric polymer, It may be a polyurethane-based elastomeric polymer, a polyester-based elastomeric polymer, a polyamide-based elastomeric polymer, or the like. The above-mentioned elastomeric polymer 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, and the like. However, when importance is placed on fluidity during heating (decrosslinking) of the thermoplastic elastomer, liquid rubber is preferred. For example, in a diene rubber such as isoprene rubber and butadiene rubber, the weight average molecular weight is preferably from 1,000 to 100,000, and particularly preferably from 1,000 to 50,000. on the other hand,
When importance is placed on strength, solid rubber is preferable,
For example, in diene rubbers such as isoprene rubber and butadiene rubber, the weight average molecular weight is preferably from 100,000 to 2,000,000, particularly preferably from 500,000 to 1,500,000.

In the thermoplastic elastomer of the present invention, a carbonyl-containing group is introduced into a side chain of the above-mentioned elastomeric polymer. Examples of the carbonyl-containing group include amide, ester, imide and carboxyl groups. The compound into which such a group can be introduced is not particularly limited, and examples thereof include carboxylic acid compounds and derivatives thereof. Examples of the carboxylic acid compound include organic acids having a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may be any of aliphatic, alicyclic, and aromatic carboxylic acids. Examples of the carboxylic acid derivatives include carboxylic anhydrides, esters, ketones, amino acids, amides, imides, and thiocarboxylic acids (carboxylic acids containing a mercapto group).

More 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. Acid anhydrides such as carboxylic acid and substituent-containing carboxylic acid, succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, propionic anhydride, benzoic anhydride, maleic ester, malonic ester, succinic ester , Glutaric acid ester, aliphatic ester such as ethyl acetate, phthalic acid ester, isophthalic acid ester, terephthalic acid ester, ethyl-m-aminobenzoate, methyl-
Aromatic esters such as p-hydroxybenzoate, ketones such as quinone, anthraquinone and naphthoquinone, glycine, tricine, bicine, alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N-
Amino acids such as (p-aminobenzoyl) -β-alanine, maleamide, maleamic acid (malemonoamide), succinic monoamide, 5-hydroxyvaleramide, N-acetylethanolamine, N, N′-hexamethylenebis ( Acetamide), malonamide, cycloserine, 4-acetamidophenol, amides such as p-acetamidobenzoic acid, and imides such as maleimide and succinimide. Among these, the carbonyl-containing group of the present invention is preferably derived from cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride, and particularly preferably derived from maleic anhydride. Is more preferred.

The thermoplastic elastomer of the present invention has a nitrogen-containing n-membered ring-containing group in addition to the carbonyl group-containing group in the side chain of the elastomeric polymer.
At positions -n, it is bonded to the main chain directly or via an organic group. The nitrogen-containing n-membered ring may have a structure containing a hydrogen-bonding amino group in the ring member or a structure in which a hydrogen-bonding amino group is generated. Examples of such a nitrogen-containing n-membered ring include pyrrololin, 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, indole, indolin, oxylindole, Carbazole, phenothiazine, indolenine, isoindole, oxazoles, thiazoles,
Isoxazoles, 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,
Examples include quinoxaline, triazine, histidine, triazolidine, melamine, adenine, guanine, thymine, cytosine and the like. The nitrogen-containing n-membered ring may include another hetero atom in the ring. Among such nitrogen-containing n-membered rings, particularly, for the nitrogen-containing 5-membered ring, the following compounds are preferably exemplified. These may have various substituents, and may be hydrogenated or eliminated.

[0014]

Embedded image

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

Embedded image

In addition, those obtained by condensing the above-mentioned monocyclic n-membered rings can be used, and examples thereof include the following condensed rings.

Embedded image

In the thermoplastic elastomer composition of the present invention, the carbonyl group-containing group and the nitrogen-containing n-membered ring-containing group may be bonded to the polymer main chain as side chains independent of each other, or may be linked via different groups. By bonding to the main chain, a carbonyl group-containing group and a nitrogen-containing n-membered ring-containing group may form a side chain. When one side chain is thus formed by the carbonyl group-containing group and the nitrogen-containing n-membered ring-containing group, not only the bond to the main chain but also the carbonyl group-containing group and the nitrogen-containing n-membered ring-containing group Is also chemically bonded. The carbonyl group-containing group and the nitrogen-containing n-membered ring-containing group may be bonded via any bond. Preferably, the carbonyl group-containing group and the nitrogen-containing n-membered ring-containing group are bonded via some kind of bond to form one side chain, and more preferably, the side chain is represented by the following formula (1). It has the structure shown.

Embedded image In the formula, A is a nitrogen-containing n-membered ring bonded to the main chain via an organic group at the 3- to n-positions, and B is O, N, S, or an organic group that may include these. As for A, those specifically exemplified above can be preferably used. Further, for B, specifically, an oxygen atom, a sulfur atom, an amino group, or a carbon atom of 1 which may contain O, N or S
To 20 alkyl groups or alkylene groups. In addition, an oxygen atom, a sulfur atom, and an amino group are each an ester group, a thioester group,
It is an amide group. B is preferably an amide group in combination with an adjacent carbonyl group or an N-containing alkyl or alkylene group having 1 to 10 carbon atoms.

The side chain having the structure represented by the above formula (1) is
Particularly preferred is a structure represented by the following formula (2) or (3).

Embedded image In the formula, R is a nitrogen-containing n-membered ring bonded to the main chain through an organic group at the 3- to n-positions, X is any of O, S or NR ′, and R ′ is H or carbon It is an alkyl group of Formulas 1 to 10. Here, in the formula (2), X and R are shown as being directly bonded, but an aralkyl group having 1 to 10 carbon atoms may exist between them.

The side chain composed of these groups preferably has a ratio of 0.1 to 50 mol%, preferably 1 to 15 mol%, based on 100 mol% of the main chain. Is more preferable. This ratio is, for example, when the main chain portion is isoprene rubber, the monomer having the side chain portion introduced is about 0.1 to 35 mol% per isoprene monomer unit mol. Within this range, the interaction between these side chains is well-balanced between molecules or within the molecule, and the thermoplastic elastomer has a very high tensile strength at the time of crosslinking and has rubber elasticity. . This thermoplastic elastomer has 120
Heating at a temperature of at least ° C. dissociates the three-dimensional crosslinked structure and imparts fluidity. It is considered that the interaction between side chains is weakened. If the ratio of the side chain portion to the main chain portion is 100 mol% is less than 0.1 mol%, the strength at the time of crosslinking is not sufficient, and if it exceeds 50 mol%, rubber elasticity is lost, which is not preferable. Although the ratio of the carbonyl-containing group to the nitrogen-containing n-membered ring-containing group is not particularly limited, it is 1:
A value of 1 is preferable because a complementary interaction is easily formed. Further, the thermoplastic elastomer according to the first aspect of the present invention, when it is desired to obtain a desired rubber elasticity at room temperature,
The glass transition point is preferably 25 ° C. or lower.

The method for producing the thermoplastic elastomer according to the first aspect 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 carbonyl-containing group and a nitrogen-containing n-membered ring-containing group on the same side chain include, for example, a modified carbonyl-containing group of an elastomeric polymer, By reacting with a compound capable of introducing a carbonyl group to form a covalent bond between the carbonyl-containing group and the nitrogen-containing n-membered ring-containing group. Alternatively, the compounds capable of introducing a carbonyl-containing group and a nitrogen-containing n-membered ring-containing group may be bonded to each other in advance, and then bonded to a side chain of the elastomeric polymer.

In the case of synthesizing a thermoplastic elastomer having a carbonyl-containing group and a nitrogen-containing n-membered ring-containing group independently in a side chain, when the elastomeric polymer is produced, the main component of the elastomeric polymer is used. The thermoplastic elastomer may be directly produced by copolymerizing a monomer capable of forming a chain and a copolymerizable monomer capable of introducing the above-described group, and a main chain (elastomeric polymer) is formed in advance by polymerization or the like. Then, it may be graft-modified with a compound capable of introducing the above group. In each of the above production methods, it is confirmed whether each group of the side chain of the thermoplastic elastomer is independently bonded or bonded to each other by a commonly used analytical means such as NMR and IR spectrum. be able to.

In the thermoplastic elastomer of the present invention, among the above, it is preferable that a carbonyl-containing group and a nitrogen-containing n-membered ring-containing group are bonded to the same side chain of a preformed elastomeric polymer. The elastomeric polymer having an acid anhydride in the side chain and the nitrogen-containing n-membered ring compound are reacted at a temperature at which the nitrogen-containing n-membered ring compound can chemically bond (eg, covalently bond or ionically bond) with the cyclic acid anhydride group. It is preferable to bond them by reacting. Regarding the production of the thermoplastic elastomer of the present invention, specific points are described in JP-A-2000-169527.

In the thermoplastic elastomer composition of the present invention, the nitrogen-containing n-membered ring-containing compound is bonded to the main chain at the 3-position to the n-position directly or via an organic group. That is,
In the side chain having the structure represented by the above formula (1), the nitrogen-containing n-membered ring-containing group A is bonded to the organic group B at the 3- to n-positions. In the side chain represented by the above formula (2), the nitrogen-containing n-membered ring-containing group R is bonded to X at the 3- to n-positions. In the above formula (3), the nitrogen-containing n-membered ring-containing group R is bonded to N at the 3- to n-positions. When the nitrogen-containing n-membered ring-containing group is bonded to another site, for example, JP-A-8-23958
When the compound is bonded to the main chain at the 2-position via an organic group as in the organic polymer of No. 3, between the nitrogen atom of the nitrogen-containing n-membered ring-containing group and the carbonyl group of the same side chain in the molecule Intramolecular chelate is easily formed and hydrogen bond is formed, and it is used for hydrogen bond between a carbonyl group and a nitrogen atom of a nitrogen-containing n-membered ring-containing group present between molecules, that is, different thermoplastic elastomer side chains. It is believed that the nitrogen and carbonyl groups used are reduced. As a result, it is considered that effective intermolecular hydrogen bonding decreases and the hardness of the thermoplastic elastomer decreases. Even when the nitrogen-containing n-membered ring-containing group and the carbonyl group are bonded to the main chain of the thermoplastic elastomer as independent side chains, the nitrogen-containing n-membered ring-containing group is bonded to the main chain at the 2-position. In this case, the nitrogen atom of the nitrogen-containing n-membered ring is closer to the main chain, and it is considered that it is difficult to form a hydrogen bond with a carbonyl group present in the side chain of another thermoplastic elastomer. On the other hand, in the thermoplastic elastomer composition of the present invention, the nitrogen-containing n-membered ring-containing group has 3 to
Because it is bonded to the main chain at the n-position, even when a nitrogen-containing n-membered ring and a carbonyl group are present in the same side chain, the nitrogen atom of the heterocycle and the carbonyl group are bonded at the 2-position Since they are farther apart from each other, a hydrogen bond in the molecule is hardly formed. Further, even when the nitrogen-containing n-membered ring-containing group and the carbonyl group form a side chain independently of each other, the nitrogen atom of the heterocyclic ring is separated from the main chain, Has a structure that easily forms hydrogen bonds with the carbonyl group of the thermoplastic elastomer. This makes it possible for the thermoplastic elastomer composition of the present invention to easily form a hydrogen bond between the nitrogen atom and the carbonyl group of the heterocyclic ring present in the side chains of different thermoplastic elastomers, and to obtain the obtained thermoplastic elastomer composition. It is considered that the hardness is high, which is suitable for applications such as elastic materials.

In the thermoplastic elastomer composition of the present invention,
In the 1970 IUP for thermoplastic elastomers
Based on AC nomenclature, groups 2A and 3A of the periodic table,
Group 4A, Group 5A, Group 6A, Group 7A, Group 8,
Groups 1B, 2B, 3B, 4B and 5B
At least one metal compound of the compounds of the metals
Added. Metals of these genera include Zn (II), C
o (II), Fe (II), Fe (III), Mn (II), N
selected from i (II), Cu (II) and Pb (II),
Coordination bond with a nitrogen atom having a lone pair of heterocyclic ring
Preferably, it is a metal that can be formed. Also metal compounds
Is a compound with 20 or more carbon atoms, such as formate, acetate, and stearic acid.
Carbon number of lower saturated fatty acid salt, (meth) acrylate, etc.
20 or less unsaturated fatty acid salts, nitrates, carbonates, hydrogen carbonate
Salt, chloride, oxide, hydroxide, acetylacetonato complex
Body, etc. can be used, but fluoride, chloride, bromide,
A halide such as a boride, or an oxide, or
Saturated fatty acid salts having 20 or less carbon atoms are preferred. That is,
Metal compound is ZnX_Two, CoX_Two, FeX_Two, Fe
X _Three, MnX_Two, NiX_Two, CuX_Two, PbX_Two(X is
F, Cl, Br, I, O or OCOR [R is carbon atom 1
To 20 alkyl groups]).
preferable. Among them, stearates are thermoplastic elastomers
High solubility in polymers and no deliquescence
Especially preferred because it is easy to disperse evenly in the elastomer
No.

The content of the metal compound is not particularly limited, and can be appropriately selected according to the type of the thermoplastic elastomer and the metal compound to be used. Further, different kinds of metal compounds may be added together. For example, as shown in Examples, the nitrogen-containing n-membered ring is 1,
When ZnCl ₂ is contained in the thermoplastic elastomer which is a 2,4-triazole ring, ZnCl ₂ is contained in an amount of about 0.1 to ₂ mol per 1 mol of the triazole ring in the thermoplastic elastomer. The effect is improved, and the maximum effect is achieved particularly when ZnCl ₂ is contained at a ratio of 1 mol (equimolar), and the thermoplastic elastomer contains a carbonyl group and a nitrogen-containing n-membered ring in a side chain. The formation and dissociation of cross-links can be repeatedly reproduced in accordance with the temperature change caused by the temperature change, and the mechanical properties, particularly the shape retention, are improved without impairing the properties of excellent recyclability. Further, for example, for a thermoplastic elastomer in which a nitrogen-containing n-membered ring is a triazole ring, Mn (I
I), Fe (II), Co (II), Ni (II) and Cu (I
In the case where at least one compound of the compound (I) is contained, about 0.05 to 2 mol of the compound of the metal is used per 1 mol of the triazole ring in the thermoplastic elastomer. ), The interaction between the thermoplastic elastomer and the metal compound is improved, and the maximum effect is achieved particularly when the above-mentioned metal compound is contained in a ratio of 1 mol (equimolar), and the recycling is achieved. The mechanical properties, especially the shape retention, are improved without impairing the properties.

The method of compounding the metal compound with the thermoplastic elastomer is not particularly limited, and any method can be employed. For example, a method of adding the metal compound at the time of melt-molding the thermoplastic elastomer, a method of mixing the thermoplastic elastomer with the metal compound, Examples thereof include a method in which the composition is directly mixed as it is and used for melt molding or the like, a method in which a thermoplastic elastomer and a metal compound are mixed in a solvent, and then the solvent is removed to recover the composition.

In the thermoplastic elastomer composition of the present invention obtained as described above, as described above, when the metal compound is blended with the thermoplastic elastomer, a strong interaction occurs between the thermoplastic elastomer and the metal compound. Thus, the mechanical properties, especially the compression set, are improved. This is because the lone electron pair of the nitrogen atom in the nitrogen-containing n-membered ring of the side chain of the thermoplastic elastomer and the lone electron pair present in the oxygen of the carbonyl group (—CO—) and the metal ion in the metal compound. It is considered that a strong cohesive structure accompanied by fine crystal structuring is formed in the thermoplastic elastomer due to the formation of position bonds, and in some cases, ionic bonds.

The thermoplastic elastomer composition of the present invention having such characteristics can be used for various vulcanized rubber applications by utilizing, for example, rubber elasticity. Also, when included in a hot melt adhesive, heat resistance and recyclability can be improved. Especially around automobiles, for example, tire treads, carcass; exterior radiator grills, side moldings, garnishes (pillars, rear, cowl tops), aero parts (air dams, spoilers), wheel covers, weather strips, cow belt grills, air outlets・ Louvers, air scoops, hood bulges, ventilation opening parts, anti-touch parts (over fenders, side seal panels, moldings (windows, hoods, door belts), marks; doors, lights,
Interior window frame parts such as wiper weather strip, glass run, glass run channel; air duct hose,
Lubricating oil parts such as radiator hose, brake hose; crankshaft seal, valve stem seal, head cover gasket, A / T oil cooler hose, transmission oil seal, P / S hose, P / S oil seal; fuel hose, emission control hose,
Fuel system components such as inlet filler hoses and tire frames; Vibration-proof components such as engine mounts and in-tank pump mounts; Boots such as CVJ boots, rack and pinion boots; A / C hoses, A / C seals, etc. It can be suitably used for air conditioning components; belt components such as timing belts and accessory belts; sealers such as windshield sealers, vinyl plastisol sealers, anaerobic sealers, body sealers, spot weld sealers, and the like. Further, when the resin or rubber which causes cold flow at room temperature is contained as a rubber modifier, for example, as a flow-preventing agent, flow during extrusion and cold flow can be prevented.

The thermoplastic elastomer composition of the present invention can be used as a composition by mixing with carbon black. Carbon black is appropriately selected depending on the application. 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 high reinforcement to rubber. In the present invention, it is particularly preferable to use hard carbon having a strong reinforcing property.
It is preferable that the content be from 70 to 70 parts by mass, preferably from 20 to 60 parts by mass, more preferably from 30 to 50 parts by mass.

Further, other reinforcing agents such as silica, an antioxidant, an antioxidant, a pigment and the like can be added within a range not to impair the object of the present invention. Other reinforcing agents include fumed silica, calcined silica, precipitated silica, ground silica, fused silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate And clay, kaolin clay, calcined clay and the like, and it is preferable to add 20 to 80 parts by mass, more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. Examples of the anti-aging agent include, for example, hindered phenol compounds, aliphatic and aromatic hindered amine compounds, and the like, based on 100 parts by mass of the thermoplastic elastomer.
It is preferable to add 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass. Examples of antioxidants include butylhydroxytoluene (BHT), butylhydroxyanisole
(BHA) and the like, based on 100 parts by mass of the thermoplastic elastomer, 0.1 to 10 parts by mass, more preferably 1 to 10 parts by mass.
It is preferable to add 5 parts by mass. Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate, azo pigments, and organic pigments such as copper phthalocyanine pigment. , With respect to 100 parts by mass of the thermoplastic elastomer, 0.1 to 10 parts by mass, more preferably 1 to 10 parts by mass
It is preferable to add 5 parts by mass.

Although the thermoplastic elastomer of the present invention can be crosslinked by itself, a vulcanizing agent, a vulcanization aid, a vulcanization accelerator and the like can be used in combination as long as the object of the present invention is not impaired. As a vulcanizing agent, sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, zinc white, magnesium oxide, litharge, p-Quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene, methylin dianiline and the like. As vulcanization aids, acetyl acid,
Propionic acid, butanoic acid, stearic acid, acrylic acid,
Fatty acids such as maleic acid; and zinc fatty acids such as zinc acetylate, zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, zinc maleate, and the like.
Examples of the vulcanization accelerator include tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (T
Thiurams such as ETD); aldehydes and ammonia such as hexamethylenetetramine; guanidines such as diphenylguanidine: dibenzothiazyl disulfide (D
M) and the like; sulfenamides such as cyclohexylbenzothiazylsulfenamide; and the like. Further, an alkylphenol resin or a halide thereof may be used.

The thermoplastic elastomer composition of the present invention comprises:
By including carbon black, tensile strength, tear strength and bending strength are further improved, especially tires, hoses, belts, sheets, anti-vibration rubber, rollers, linings, rubberized cloth, sealing materials, gloves, anti-glare materials It can be suitably used for applications such as.

[0033]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. <Synthesis of Thermoplastic Elastomer> Commercially available maleic anhydride-modified isoprene rubber (2.7 mol% modification, LIR-
12.73 g (6.55 mmo, 410 A, manufactured by Kuraray Co., Ltd.)
l) has 3-amino-1,2,4-triazole 0.5
51 g (6.55 mmol) was added, and the mixture was heated and stirred at 150 ° C. for 4 hours. After confirming that the solution became a homogeneous solution, the mixture was left overnight to obtain a gel-like reaction product. The reaction product was confirmed by NMR and IR to be a thermoplastic elastomer 1 (formula (4)) having the following structure. Hereinafter, similarly, a thermoplastic elastomer 2 (formula (5)) was synthesized using 4-aminopyridine as the nitrogen-containing n-membered ring-containing compound at the same ratio. As a comparative compound, the above maleic anhydride-modified isoprene rubber and 2-aminomethylpyridine were reacted at the same ratio to obtain a thermoplastic elastomer 3 (formula (6)).

Embedded image Here, m: n ≒ 358: 10.

Examples 1 to 10 After the obtained thermoplastic elastomers 1 and 2 were dissolved in a solvent, the compatibility was confirmed by adding a metal compound in an amount shown in Table 1. Then, when the solvent is distilled off, solidification occurs immediately,
A thermoplastic elastomer composition containing a metal was obtained. JIS A for the obtained thermoplastic elastomer composition
After measuring the hardness, place a 500 g weight and
Until the time, the amount of deformation was measured at each time shown in Table 1, and the shape retention was determined. The results are shown in Table 1. <Confirmation of compatibility> After addition of the metal compound, it was visually confirmed. In Table 1 below, if they are mixed,
And the case where they were uniformly mixed was evaluated as ◎. <Measurement of JIS A Hardness> The obtained thermoplastic elastomers 1 and 2 were press-molded at 150 ° C. for 60 minutes, and flat plate samples having a thickness of 1 cm × 5 cm in length × 5 cm in width were prepared. Three of the obtained flat plate samples were stacked and JIS K62
JIS A hardness was measured in accordance with No.53. <Measurement of Shape Retention> The obtained thermoplastic elastomer compositions 1 and 2 were press-molded at 100 ° C. for 20 minutes to prepare a cylindrical sample having a diameter of 29 mm and a thickness of 12.5 mm. Place a glass plate on the sample and put 500g on it
And the amount of deformation was measured up to 48 hours later. From the obtained deformation amount, the shape retention was determined using the following equation. Shape retention (%) = (thickness after elapse of predetermined time / thickness at start of measurement) × 100

Comparative Example 1 With respect to the obtained thermoplastic elastomer 1, the JIS A hardness and the shape retention were measured in the same manner as in the example without adding a metal compound. Comparative Example 2 JIS A hardness and shape retention of the obtained thermoplastic elastomer 3 were measured in the same manner as in the example.

[0036]

[0037]

[0038]

As can be seen from Table 1, the nitrogen-containing n of the present invention
In the example compound in which the member-containing group is bonded to the main chain at the 3- or 4-position via an organic group, the nitrogen-containing n-membered ring-containing group is bonded to the main chain at the 2-position via an organic group. It can be seen that the JIS A hardness is significantly higher than that of the compound of Comparative Example 2.
In addition, the thermoplastic elastomer composition of the present invention has a higher shape retention ratio than Comparative Example 1 in which the metal compound is not added, because the metal compound is added,
The decrease in the compressed shape retention over time is also small.

[0040]

As described in detail above, in the thermoplastic elastomer composition of the present invention, the nitrogen-containing n-membered ring-containing group has 3
Since it is bonded to the main chain directly or through an organic group at positions n to n, the hardness is higher than that in the case where it is bonded to the main chain at another position, for example, the second position, and an elastic material or the like is used. It is suitable for use in the field. Moreover, the shape retention rate of the thermoplastic elastomer composition of the present invention is improved by adding a metal compound. As a result, even when the cross-linking and the cross-linking dissociation are repeatedly performed due to a temperature change, excellent recyclability can be imparted without deteriorating the physical properties.

Claims (4)

[Claims] (1) a side chain having a carbonyl-containing group and a nitrogen-containing n-membered ring-containing group (n ≧ 3), wherein the nitrogen-containing n-membered ring-containing group is directly at the 3- to n-positions or A thermoplastic elastomer bonded to the main chain through a group, and a group 2A, a group 3A, a group 4A, a group 5A,
Group 6A, Group 7A, Group 8A, Group 1B, Group 2B,
A thermoplastic elastomer composition comprising: a compound of at least one metal selected from the group consisting of Group 3B, Group 4B and Group 5B. 2. The thermoplastic elastomer composition according to claim 1, wherein the elastomer has a structure represented by the following formula (1) in a side chain. Embedded image In the formula, A is a nitrogen-containing n-membered ring-containing group (n ≧ 3) bonded to the main chain via an organic group at positions 3 to n, and B is O,
It is an organic group that may contain N and S. 3. The thermoplastic elastomer composition according to claim 1, wherein the side chain is represented by the following formula (2) or (3). Embedded image In the formula, R is a nitrogen-containing n-membered ring-containing group (n ≧ 3) bonded to the main chain via an organic group at the 3- to n-positions, and X is O,
S is either NR 'or R' is H or an alkyl group having 1 to 10 carbon atoms. 4. The compound of the metal is ZnX ₂ , Co
X ₂ , FeX ₂ , FeX ₃ , MnX ₂ , NiX ₂ , Cu
X ₂ and PbX ₂ (X is F, Cl, Br, I, [the R alkyl group having 1 to 20 carbon atoms] O or OCOR any one of) claim is at least one selected from the group consisting of Item 4. The elastomer composition according to any one of Items 1 to 3.