JP2006241231A - Thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which is less prone to deterioration in physical properties such as resistance to compression set and excellent in fluidity and processability at high temperatures. <P>SOLUTION: The thermoplastic elastomer composition contains (A) a thermoplastic elastomer having a side chain containing an imino group and/or a nitrogen-containing heterocyclic ring and a carbonyl group and a thermoplastic elastomer composition containing (B) an uncrosslinked polymer. A specific relationship exists between the thermoplastic elastomer (A) and the uncrosslinked polymer (B). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic elastomer composition.

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

  In response to this problem, the present inventors have previously described that a hydrogen-bonding thermoplastic elastomer composed of an elastomeric polymer having a carbonyl group-containing group and a heterocyclic amine-containing group in the side chain has a temperature utilizing hydrogen bonding. It is found that cross-linking and dissociation can be repeated by change, and hydrogen bonding heat comprising an elastomeric polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in the side chain. A plastic elastomer is proposed, and as a method for producing the thermoplastic elastomer, an elastomeric polymer having a cyclic acid anhydride group in the side chain and a heterocyclic amine-containing compound are used, and the heterocyclic amine-containing compound is a cyclic acid anhydride group. Has been proposed for producing a thermoplastic elastomer by reacting with a compound at a temperature at which it can chemically bond with (for example, a thermoplastic elastomer). See Patent Document 1).

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

JP 2000-169527 A

However, although the thermoplastic elastomer described in Patent Document 1 is excellent in physical properties such as compression set resistance, there is a problem in that fluidity at high temperatures is lowered and workability may be lowered.
On the other hand, when liquid low molecular weight polymers are added for the purpose of improving fluidity and workability at high temperatures, physical properties such as compression set resistance may be greatly reduced or adhesiveness may be reduced. there were.

  Accordingly, an object of the present invention is to provide a thermoplastic elastomer composition which is less deteriorated in physical properties such as compression set resistance and excellent in fluidity, workability and adhesion at high temperatures.

  As a result of intensive studies on the above problems, the inventor has added a specific uncrosslinked polymer to a thermoplastic elastomer having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group. The present invention was completed by discovering that a thermoplastic elastomer composition having little deterioration in physical properties such as permanent distortion and excellent fluidity at high temperature, workability, and adhesion was obtained.

（式中、Ａは炭素数１〜３０のアルキル基、炭素数７〜２０のアラルキル基または炭素数６〜２０のアリール基であり、Ｂは単結合；酸素原子、アミノ基ＮＲ′（Ｒ′は水素原子または炭素数１〜１０のアルキル基である。）またはイオウ原子；あるいはこれらの原子または基を含んでもよい有機基である。）
（５）前記式（１）で表される構造を含有する側鎖が、α位またはβ位で主鎖に結合する下記式（２）または（３）で表される構造を含有する上記（４）に記載の熱可塑性エラストマー組成物。

（式中、Ａは炭素数１〜３０のアルキル基、炭素数７〜２０のアラルキル基または炭素数６〜２０のアリール基であり、ＢおよびＤはそれぞれ独立に単結合；酸素原子、アミノ基ＮＲ′（Ｒ′は水素原子または炭素数１〜１０のアルキル基である。）またはイオウ原子；あるいはこれらの原子または基を含んでもよい有機基である。）
（６）前記側鎖が、下記式（４）で表される構造を含有する上記（１）または（３）に記載の熱可塑性エラストマー組成物。

（式中、Ｅは含窒素複素環であり、Ｂは単結合；酸素原子、アミノ基ＮＲ′（Ｒ′は水素原子または炭素数１〜１０のアルキル基である。）またはイオウ原子；あるいはこれらの原子または基を含んでもよい有機基である。）
（７）前記式（４）で表される構造を含有する側鎖が、α位またはβ位で主鎖に結合する下記式（５）または（６）で表される構造を含有する上記（６）に記載の熱可塑性エラストマー組成物。

（式中、Ｅは含窒素複素環であり、ＢおよびＤはそれぞれ独立に単結合；酸素原子、アミノ基ＮＲ′（Ｒ′は水素原子または炭素数１〜１０のアルキル基である。）またはイオウ原子；あるいはこれらの原子または基を含んでもよい有機基である。）
（８）前記含窒素複素環が、５または６員環である上記（１）、（３）、（６）または（７）に記載の熱可塑性エラストマー組成物。
（９）前記含窒素複素環が、トリアゾール環、チアジアゾール環、ピリジン環、イミダゾール環またはヒダントイン環である上記（８）に記載の熱可塑性エラストマー組成物。
（１０）前記式（４）で表される構造を含有する側鎖が、下記式（７）または下記式（８）もしくは（９）で表される構造を含有する上記（６）に記載の熱可塑性エラストマー組成物。

（式中、Ｂは単結合；酸素原子、アミノ基ＮＲ′（Ｒ′は水素原子または炭素数１〜１０のアルキル基である。）またはイオウ原子；あるいはこれらの原子または基を含んでもよい有機基であり、ＧおよびＪはそれぞれ独立に水素原子、炭素数１〜３０のアルキル基、炭素数７〜２０のアラルキル基または炭素数６〜２０のアリール基である。）
（１１）前記式（４）で表される構造を含有する側鎖が、α位またはβ位で主鎖に結合する下記式（１０）〜（１５）のいずれかで表される構造を含有する上記（１０）に記載の熱可塑性エラストマー組成物。

（式中、ＢおよびＤはそれぞれ独立に単結合；酸素原子、アミノ基ＮＲ′（Ｒ′は水素原子または炭素数１〜１０のアルキル基である。）またはイオウ原子；あるいはこれらの原子または基を含んでもよい有機基であり、ＧおよびＪはそれぞれ独立に水素原子、炭素数１〜３０のアルキル基、炭素数７〜２０のアラルキル基または炭素数６〜２０のアリール基である。）
（１２）前記未架橋ポリマー（Ｂ）は、メルトマスフローレイト（ＭＦＲ）が０．００１ｇ／１０ｍｉｎ以上である上記（１）〜（１１）のいずれかに記載の熱可塑性エラストマー組成物。
（１３）前記熱可塑性エラストマー（Ａ）の重量平均分子量Ｍｗ（Ａ）と、前記未架橋ポリマー（Ｂ）の重量平均分子量Ｍｗ（Ｂ）との比（Ｍｗ（Ａ）／Ｍｗ（Ｂ））が、０．５〜２０である上記（１）〜（１２）のいずれかに記載の熱可塑性エラストマー組成物。 That is, the present invention provides the following (1) to (13).
(1) A thermoplastic elastomer composition comprising a thermoplastic elastomer (A) having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group, and an uncrosslinked polymer (B). ,
The monomer constituting the thermoplastic elastomer (A) and the monomer constituting the uncrosslinked polymer (B) include at least one monomer (m) of the same kind,
A thermoplastic elastomer composition in which the thermoplastic elastomer (A) and the uncrosslinked polymer (B) satisfy the following formulas (I) and (II).
0.97 ≦ Sp (A) / Sp (B) ≦ 1.03 (I)
(In formula (I), Sp (A) is the Sp value of the thermoplastic elastomer (A), and Sp (B) is the Sp value of the uncrosslinked polymer (B).)
0.7 ≦ M (A) / M (B) ≦ 1.2 (II)
(In the formula (II), M (A) is the ratio (mol%) of the monomer (m) in the monomer constituting the thermoplastic elastomer (A), and M (B) is the uncrosslinked polymer ( (It is the ratio (mol%) of the monomer (m) in the monomer constituting B).)
(2) The thermoplastic elastomer composition according to (1), wherein the side chain contains an imino group and a carbonyl-containing group.
(3) The thermoplastic elastomer composition according to (1), wherein the side chain contains an imino group, a nitrogen-containing heterocyclic ring, and a carbonyl-containing group.
(4) The thermoplastic elastomer composition according to any one of (1) to (3), wherein the side chain contains a structure represented by the following formula (1).

Wherein A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups.
(5) The above side chain containing a structure represented by the following formula (2) or (3) in which the side chain containing the structure represented by the formula (1) is bonded to the main chain at the α-position or the β-position ( The thermoplastic elastomer composition according to 4).

Wherein A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups.
(6) The thermoplastic elastomer composition according to the above (1) or (3), wherein the side chain contains a structure represented by the following formula (4).

Wherein E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; An organic group that may contain any atom or group of
(7) The above side chain containing a structure represented by the following formula (5) or (6) in which the side chain containing the structure represented by the formula (4) is bonded to the main chain at the α-position or the β-position ( The thermoplastic elastomer composition as described in 6).

(Wherein E is a nitrogen-containing heterocyclic ring, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)) or A sulfur atom; or an organic group that may contain these atoms or groups.)
(8) The thermoplastic elastomer composition according to the above (1), (3), (6) or (7), wherein the nitrogen-containing heterocycle is a 5- or 6-membered ring.
(9) The thermoplastic elastomer composition according to (8), wherein the nitrogen-containing heterocycle is a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring, or a hydantoin ring.
(10) The side chain containing the structure represented by the formula (4) is described in the above (6), which contains a structure represented by the following formula (7) or the following formula (8) or (9) Thermoplastic elastomer composition.

Wherein B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic which may contain these atoms or groups. G and J are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)
(11) The side chain containing the structure represented by the formula (4) contains a structure represented by any one of the following formulas (10) to (15) bonded to the main chain at the α-position or the β-position. The thermoplastic elastomer composition according to (10) above.

Wherein B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or these atoms or groups G and J are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)
(12) The thermoplastic elastomer composition according to any one of (1) to (11), wherein the uncrosslinked polymer (B) has a melt mass flow rate (MFR) of 0.001 g / 10 min or more.
(13) The ratio (Mw (A) / Mw (B)) of the weight average molecular weight Mw (A) of the thermoplastic elastomer (A) and the weight average molecular weight Mw (B) of the uncrosslinked polymer (B) is The thermoplastic elastomer composition according to any one of (1) to (12), which is 0.5 to 20.

  The thermoplastic elastomer composition of the present invention has little deterioration in physical properties such as compression set resistance, and is excellent in fluidity, workability and adhesiveness at high temperatures.

Hereinafter, the present invention will be described in more detail.
The thermoplastic elastomer composition of the present invention (hereinafter also referred to as “the composition of the present invention”) is a thermoplastic elastomer having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group (A ) And an uncrosslinked polymer (B), wherein the monomer constituting the thermoplastic elastomer (A) and the monomer constituting the uncrosslinked polymer (B) are the same monomer. A thermoplastic elastomer composition containing at least one kind of (m), wherein the thermoplastic elastomer (A) and the uncrosslinked polymer (B) satisfy the formulas (I) and (II).
Below, the thermoplastic elastomer (A) used for the composition of this invention, an uncrosslinked polymer (B), and the relationship between a thermoplastic elastomer (A) and an uncrosslinked polymer (B) are explained in full detail in order.

<Thermoplastic elastomer (A)>
The thermoplastic elastomer (A) used in the composition of the present invention has a side chain containing an imino group and / or a nitrogen-containing heterocyclic group and a carbonyl-containing group on an elastomeric polymer of a natural polymer or a synthetic polymer. Have. In the thermoplastic elastomer (A), as described later, the monomer constituting the thermoplastic elastomer (A) contains at least one monomer (m) of the same type as the monomer constituting the uncrosslinked polymer (B). And satisfying the formulas (I) and (II).
In the present invention, “side chain” refers to a side chain and a terminal of an elastomeric polymer. Further, “having a side chain containing an imino group and / or a nitrogen-containing heterocyclic group and a carbonyl-containing group” means that an atom (usually a carbon atom) forming the main chain of the elastomeric polymer has an imino group and It means that the nitrogen-containing heterocyclic group and the carbonyl-containing group have a chemically stable bond (for example, covalent bond, ionic bond, etc.).

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

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

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

In the present invention, the elastomeric polymer may be used alone or in combination of two or more. When two or more kinds are used in combination, the mixing ratio of the respective elastomeric polymers can be any ratio depending on the use of the composition of the present invention, the physical properties required for the composition of the present invention, and the like. .
The glass transition point of the elastomeric polymer is preferably 25 ° C. or less as described above. When the elastomeric polymer has two or more glass transition points, or two or more elastomeric polymers are mixed. When used, at least one of the glass transition points is preferably 25 ° C. or lower. When the glass transition point of the elastomeric polymer is within this range, a molded product made of the composition of the present invention is preferable because it exhibits rubber-like elasticity at room temperature.
In the present invention, the glass transition point is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry). The temperature raising rate is preferably 10 ° C./min.

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

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

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

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

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

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

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

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

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

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

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

  In the present invention, a side chain containing an imino group and a carbonyl-containing group (specifically, a side chain containing a structure represented by the above formula (1) or the above formula (2) or (3)) is It is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the elastomeric polymer. When the introduction ratio is within this range, the interaction between the side chains of the elastomeric polymer occurs between molecules or within the molecule, and these are formed in a well-balanced manner, so that the tensile strength during crosslinking of the resulting composition of the present invention is , High recyclability, and good compression set. It is more preferable that the side chain is introduced at a ratio of 0.1 to 30 mol%, and that the side chain is introduced at a ratio of 0.5 to 20 mol% in terms of these characteristics being more excellent. Further preferred.

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

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

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

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

The nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring.
Specific examples of such nitrogen-containing heterocycle include pyrrololine, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl, phthalimidine, β -Isoindigo, monoporphyrin, diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyroerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone Hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, in , Indoline, oxylindole, carbazole, phenothiazine, indolenine, isoindole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine , Pyrazine, phenazine, tetrazine, benzoxazole, benzoisoxazole, anthranyl, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthrazolin, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline, triazine, histidine , Triazolidine, melamine, adenine, guanine, thymine, cytosine And derivatives thereof. Among these, particularly the nitrogen-containing 5-membered ring is preferably exemplified by the following compound, a triazole derivative represented by the following formula (16) and an imidazole derivative represented by the following formula (17). These may have the above-described various substituents, or may be hydrogenated or eliminated.

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

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

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

  Among such nitrogen-containing heterocycles, a triazole ring, a pyridine ring, a thiadiazole ring, an imidazole ring, and a hydantoin ring are suitable for the recyclability, compression set, mechanical strength, and hardness of the resulting composition of the present invention. It is preferable because it is excellent.

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

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

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

  When the thermoplastic elastomer (A) used in the composition of the present invention has a side chain containing a triazole ring or an imidazole ring as a side chain containing the nitrogen-containing heterocycle, it is represented by the above formula (4). It is preferable to have a side chain containing a structure as a side chain containing a structure represented by the following formula (7) or the following formula (8) or (9). It is more preferable to have a side chain containing a structure represented by any one of the following formulas (10) to (15) bonded to the main chain.

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

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

  In the present invention, a side chain containing a nitrogen-containing heterocyclic ring and a carbonyl-containing group (specifically, a side chain containing a structure represented by the above formula (4) or the above formula (5) or (6)). ) Is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the elastomeric polymer. If it is less than 0.1 mol%, the strength at the time of crosslinking may not be sufficient, and if it exceeds 50 mol%, the crosslinking density may increase and rubber elasticity may be lost. When the introduction ratio is within this range, the interaction between the side chains of the elastomeric polymer occurs between molecules or within the molecule, and these are formed in a well-balanced manner, so that the tensile strength during crosslinking of the resulting composition of the present invention is , High recyclability, and good compression set. It is more preferable that the side chain is introduced at a ratio of 0.1 to 30 mol%, and that the side chain is introduced at a ratio of 0.5 to 20 mol% in terms of these characteristics being more excellent. Further preferred.

Further, in the present invention, when having a side chain containing a nitrogen-containing heterocycle and a carbonyl-containing group together with a side chain containing an imino group and a carbonyl-containing group, these side chains are added together to give the elastomeric property. It is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the monomer constituting the polymer, and the ratio of introduction into the side chain (the side containing the nitrogen-containing heterocycle) The chain / side chain containing the structure represented by the above formula (1) or the above formula (2) or (3) is more preferably 1/99 to 99/1, and more preferably 10/90 to 90 /. More preferably, it is 10.
When the introduction rate and the introduction ratio are within this range, the tensile strength at the time of crosslinking is high, the recyclability is excellent, and the mechanical strength such as tensile strength is maintained while maintaining the property of good compression set resistance. This is preferable because it can be further improved and coloring of the composition derived from the introduced nitrogen-containing heterocycle can be suppressed.

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

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

  In addition, the thermoplastic elastomer (A) used in the composition of the present invention preferably has a glass transition point of 25 ° C. or lower, and the thermoplastic elastomer (A) has a glass transition point of 2 or more or When two or more thermoplastic elastomers (A) are used in combination, at least one of the glass transition points is preferably 25 ° C. or lower. When the glass transition point is 25 ° C. or lower, the molded article exhibits rubber-like elasticity at room temperature.

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

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

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

In the present invention, the elastomeric polymer containing a cyclic acid anhydride group in the side chain is prepared by subjecting the cyclic polymer to a cyclic acid under the usual conditions such as stirring under heating. An anhydride may be produced by a graft polymerization method, or a commercially available product may be used.
Examples of commercially available products include maleic anhydride-modified isoprene rubbers such as LIR-403 (manufactured by Kuraray Co., Ltd.) and LIR-410A (Kuraray Co., Ltd.); modified isoprene rubbers such as LIR-410 (manufactured by Kuraray Co., Ltd.); Clinac 110 , 221 and 231 (manufactured by Policer), etc .; carboxy-modified polybutenes such as CPIB (manufactured by Nisseki Chemical Co., Ltd.), HRPIB (manufactured by Nisseki Chemical Co., Ltd.); Nucrel (manufactured by DuPont Mitsui Polychemical Co., Ltd.) , Maleic anhydride-modified ethylene-propylene rubber such as Yucaron (manufactured by Mitsubishi Chemical Co., Ltd.), Tuffmer M (for example, MA8510 (manufactured by Mitsui Chemicals)), etc. Anhydrous maleic such as Tuffmer M (for example, MH7020 (manufactured by Mitsui Chemicals)) Acid-modified ethylene-butene rubber; Adtex series (maleic anhydride-modified EVA, anhydrous Inacid-modified EMA (manufactured by Nippon Polyolefin Co., Ltd.), HPR series (maleic anhydride-modified EEA, maleic anhydride-modified EVA (manufactured by Mitsui / Jupon Polyolefin)), Bond Fast series (maleic anhydride-modified EMA (Sumitomo Chemical Industries, Ltd.) Manufactured)), Dumiran series (maleic anhydride modified EVOH (manufactured by Takeda Pharmaceutical Co., Ltd.)), Bondine (maleic anhydride modified EEA (manufactured by Atofina)), Tuftec (maleic anhydride modified SEBS, M1943 (manufactured by Asahi Kasei)) ), Kraton (maleic anhydride modified SEBS, FG1901X (manufactured by Clayton Polymer)), Tufprene (maleic anhydride modified SBS, 912 (manufactured by Asahi Kasei)), Septon (maleic anhydride modified SEPS (manufactured by Kuraray)), Lex Pearl (maleic anhydride modified EEA, ET 182G, 224M, 234M (manufactured by Nippon Polyolefin Co., Ltd.)), maleic anhydride modified polyethylene such as Aurorene (maleic anhydride modified EEA, 200S, 250S (manufactured by Nippon Paper Chemicals)); Admer (for example, QB550, LF128 (Mitsui) And maleic anhydride-modified polypropylene such as Chemical))).

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

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

(Reaction step A)
In the reaction step A, a compound capable of introducing an imino group and an elastomeric polymer containing a cyclic acid anhydride group in the side chain are mixed, and the compound and the cyclic acid anhydride group can be chemically bonded. It is a step of reacting (for example, 60 to 250 ° C.) (opening a cyclic acid anhydride group). By this reaction, the structure represented by the above formula (2) or (3) is contained in the side chain of the resulting thermoplastic elastomer (A).
Moreover, what is necessary is just to make the compound which can introduce | transduce an imino group react with a part or whole quantity of the cyclic acid anhydride group contained in the side chain of the said elastomeric polymer. The part is preferably 1 mol% or more, more preferably 50 mol% or more, particularly preferably 80 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. Within this range, high physical properties (for example, breaking properties) are sufficiently exhibited, and compression set resistance is further improved.

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

  Further, when both the compound capable of introducing the imino group and the compound capable of introducing the nitrogen-containing heterocycle are used, both the reaction step A and the reaction step B are provided. In this case, the compound capable of introducing an imino group and the compound capable of introducing a nitrogen-containing heterocyclic ring may be reacted with a part or all of the cyclic acid anhydride group contained in the side chain of the elastomeric polymer. . The reaction ratio of each compound with respect to the cyclic acid anhydride group is not particularly limited, but in total, it is preferably 1 mol% or more, more preferably 50 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. 80 mol% or more is particularly preferable. Within this range, tensile properties, compression set, and tensile strength at the time of crosslinking are further improved while maintaining recyclability.

Such a production method includes, for example, an elastomeric polymer containing a cyclic acid anhydride group in the side chain, a compound capable of introducing an imino group and / or a compound capable of introducing a nitrogen-containing heterocycle, of 60 to 250. It may be a method of mixing at 0 ° C. using a roll, a kneader, a single screw extruder, a twin screw extruder, a universal stirrer, or the like.
In such a production method, each group (structure) of the side chain of the thermoplastic elastomer (A), that is, an unreacted cyclic acid anhydride group, the above formulas (2), (3), (5) , (6) and the like can be confirmed by commonly used analytical means such as NMR and IR spectra.

<Uncrosslinked polymer (B)>
As will be described later, the uncrosslinked polymer (B) used in the composition of the present invention is such that the monomer constituting the uncrosslinked polymer (B) is the same type of monomer (m) as the monomer constituting the thermoplastic elastomer (A). Is not particularly limited as long as it satisfies the formulas (I) and (II). For example, a known uncrosslinked structure in accordance with the elastomeric polymer forming the main chain of the thermoplastic elastomer (A). It can select suitably from polymers. In particular, the same kind of elastomeric polymer as that forming the main chain of the thermoplastic elastomer (A) is preferred.

  Specifically, for example, when the elastomeric polymer forming the main chain of the thermoplastic elastomer (A) is an ethylene-propylene copolymer, the uncrosslinked polymer (B) is an ethylene-propylene copolymer, polyethylene. , Polypropylene, and copolymers of ethylene monomers and / or propylene monomers and other monomers are used, and ethylene-propylene copolymers are particularly preferably used.

The uncrosslinked polymer (B) preferably has a melt mass flow rate (MFR) of 0.001 g / 10 min or more. Within this range, the resulting composition is excellent in fluidity, workability and adhesiveness at high temperatures. In view of these characteristics, the MFR of the uncrosslinked polymer (B) is more preferably 0.01 g / 10 min or more, and further preferably 0.1 g / 10 min or more.
In addition, in this specification, MFR means MFR measured on condition of 230 degreeC and load 2.16kg according to JISK7210-1999.

  The weight average molecular weight of the uncrosslinked polymer (B) is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and still more preferably 40,000 to 300,000. When the molecular weight is in this range, a thermoplastic elastomer composition excellent in fluidity at high temperature, workability and adhesiveness can be obtained with little decrease in physical properties such as compression set resistance.

  The content of the uncrosslinked polymer (B) is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). Within this range, there is little decrease in physical properties such as compression set, and a thermoplastic elastomer composition excellent in fluidity at high temperature, workability and adhesion can be obtained. In view of these characteristics, the content of the uncrosslinked polymer (B) is more preferably 20 to 300 parts by mass, and still more preferably 30 to 200 parts by mass.

<Relationship between thermoplastic elastomer (A) and uncrosslinked polymer (B)>
The thermoplastic elastomer (A) and uncrosslinked polymer (B) used in the composition of the present invention are the same in the monomer constituting the thermoplastic elastomer (A) and the monomer constituting the uncrosslinked polymer (B). The thermoplastic elastomer (A) and the uncrosslinked polymer (B) contain at least one monomer (m) and satisfy the following formulas (I) and (II).

  0.97 ≦ Sp (A) / Sp (B) ≦ 1.03 (I)

  In formula (I), Sp (A) is the Sp value of the thermoplastic elastomer (A), and Sp (B) is the Sp value of the uncrosslinked polymer (B). When the ratio of Sp (A) to Sp (B) (Sp (A) / Sp (B)) is in the above range, the thermoplastic elastomer (A) and the uncrosslinked polymer (B) have high compatibility. , Deterioration of physical properties such as compression set can be suppressed. From the standpoint of this characteristic, the ratio of Sp (A) to Sp (B) (Sp (A) / Sp (B)) is preferably 0.98 to 1.02, more preferably 0.99. ~ 1.01.

  0.7 ≦ M (A) / M (B) ≦ 1.2 (II)

  In the formula (II), M (A) is a ratio (mol%) of the monomer (m) in the monomer constituting the thermoplastic elastomer (A), and M (B) is the uncrosslinked polymer (B ) Is a ratio (mol%) of the monomer (m) in the monomer constituting the above. If the ratio of M (A) to M (B) (M (A) / M (B)) is in the above range, the thermoplastic elastomer (A) and the uncrosslinked polymer (B) have high compatibility. , Deterioration of physical properties such as compression set can be suppressed. From the standpoint of this characteristic, the ratio of M (A) to M (B) (M (A) / M (B)) is preferably 0.8 to 1.2, more preferably 0.9. -1.1.

  The ratio (Mw (A) / Mw (B)) of the weight average molecular weight Mw (A) of the thermoplastic elastomer (A) and the weight average molecular weight Mw (B) of the uncrosslinked polymer (B) is 0.00. It is preferable that it is 5-20. Within this range, a decrease in physical properties such as compression set can be suppressed. From the point which is excellent by this characteristic, 0.5-15 are more preferable and, as for Mw (A) / Mw (B), 0.5-10 are still more preferable.

  The thermoplastic elastomer (A) and the uncrosslinked polymer (B) have excellent compatibility because they satisfy the above formulas (I) and (II). The uncrosslinked polymer (B) has high fluidity at high temperatures. Therefore, the composition of the present invention is excellent in fluidity and workability at high temperatures while suppressing a decrease in physical properties such as compression set. Moreover, it is excellent also in adhesiveness. It is considered that the reason why the composition of the present invention is excellent in adhesiveness is that the adhesiveness with the adherend is increased because of excellent fluidity at high temperatures.

  If necessary, the composition of the present invention may be a polymer other than the thermoplastic elastomer (A) and the uncrosslinked polymer (B), a reinforcing agent (filler), an amino acid, as long as the object of the present invention is not impaired. A filler obtained by introducing a group (hereinafter simply referred to as “amino group-introducing filler”), an amino group-containing compound other than the amino group-introducing filler, and a compound containing a metal element (hereinafter simply referred to as “metal salt”). .), Maleic anhydride modified polymer, anti-aging agent, antioxidant, pigment (dye), plasticizer, thixotropic agent, UV absorber, flame retardant, solvent, surfactant (including leveling agent), dispersion Various additives such as an additive, a dehydrating agent, a rust preventive agent, an adhesion-imparting agent, an antistatic agent, and a filler can be contained.

As the additive and the like, commonly used ones can be used, and specific examples thereof are shown below, but are not limited to those exemplified.
As the polymer other than the thermoplastic elastomer (A) and the uncrosslinked polymer (B), a polymer having a glass transition temperature of 25 ° C. or lower is preferable as described above. Specifically, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butyl rubber ( IIR), ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), etc., and particularly the unsaturated bond of IIR, EPM, EBM. Polymers that do not have them or polymers with low unsaturated bonds (eg EPDM) are preferred. A polymer having a site capable of hydrogen bonding is also preferable, and examples thereof include polyester, polylactone, and polyamide.
In the composition of the present invention, the polymer other than the thermoplastic elastomer may contain one kind or two or more kinds, and the content of the polymer is based on 100 parts by mass of the thermoplastic elastomer (A). And it is preferable that it is 0.1-100 mass parts, and it is more preferable that it is 1-50 mass parts.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The maleic anhydride residue is introduced (modified) into the side chain or terminal of the elastomeric polymer and is not introduced into the main chain of the elastomeric polymer. The maleic anhydride residue is a cyclic acid anhydride group, and the cyclic acid anhydride group (part) does not open.
Therefore, as the maleic anhydride-modified thermoplastic polymer, for example, as shown in the following formula (18), a cyclic acid in the side chain obtained by reacting an ethylenically unsaturated bond portion of maleic anhydride with an elastomeric polymer is used. Examples include thermoplastic elastomers having an anhydride group and no nitrogen-containing heterocycle, and specific examples thereof include those exemplified for the above-described elastomeric polymer containing a cyclic acid anhydride group in the side chain. .

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

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

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

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

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

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

Specific examples of the plasticizer include benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid, and other polyesters. , Polyether, epoxy and the like.
Specific examples of the thixotropic agent include benton, silicic anhydride, silicic acid derivatives, urea derivatives, and the like.
Specific examples of the ultraviolet absorber include 2-hydroxybenzophenone, benzotriazole, and salicylic acid ester.
Specific examples of the flame retardant include phosphorus-based materials such as TCP, halogen-based materials such as chlorinated paraffin and perchlorpentacyclodecane, antimony-based materials such as antimony oxide, and aluminum hydroxide.

Specific examples of the solvent include hydrocarbons such as hexane and toluene; halogenated hydrocarbons such as tetrachloromethane; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; Ester type; etc. are mentioned.
Specific examples of the surfactant (leveling agent) include polybutyl acrylate, polydimethylsiloxane, a modified silicone compound, and a fluorine-based surfactant.
Specific examples of the dehydrating agent include vinyl silane and the like.

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

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

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

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

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

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

The production method of the composition of the present invention is not particularly limited. For example, the thermoplastic elastomer (A), the uncrosslinked polymer (B), and various additives that may be contained as necessary, Produced by mixing using a roll, kneader, single screw extruder, twin screw extruder, universal agitator, etc., and heating (for example, hot pressing) at a temperature equal to or higher than the foaming temperature of the foaming agent added after kneading. Methods and the like.
Specifically, a method of producing by kneading at 160 to 180 ° C. for several minutes, then performing hot pressing at about 200 ° C. for several minutes to several tens of minutes in a mold, and further performing cold pressing to return to room temperature. Is preferably exemplified.

The composition of the present invention is less deteriorated in physical properties such as compression set resistance and excellent in fluidity and workability at high temperatures.
Since the composition of the present invention has excellent characteristics as described above, it can be used for various rubber applications by utilizing rubber elasticity, for example. Moreover, since it can improve heat resistance and recyclability, it is preferable to use it as a hot melt adhesive or as an additive contained therein. The composition of the present invention can be suitably used around an automobile or the like.

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

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

  Further, when the composition of the present invention contains carbon black and / or silica, etc., the tensile strength, tear strength, and bending strength are improved, and in particular, tires, hoses, belts, sheets, anti-vibration rubber, rollers, linings, rubber pulling. Cloth, sealing material, gloves, fender, medical rubber (syringe gasket, tube, catheter), gasket (for home appliances, construction), asphalt modifier, hot melt adhesive, boots, grips, toys, It is suitably used for applications such as shoes, sandals, keypads, gears, and plastic bottle cap liners.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
Example 1
First, 100 g (maleic anhydride skeleton 10.2 mmol) of maleic anhydride-modified ethylene-propylene copolymer (hereinafter abbreviated as “maleinized EPM”) was added to a kneader set at 180 ° C. and kneaded for 4 minutes. Thereafter, 1.3 g of 4H-3-amino-1,2,4-triazole (ATA, manufactured by Otsuka Chemical Co., Ltd., hereinafter abbreviated as “ATA”) was added and kneaded for 5 minutes. ) Was released. Thereafter, the released rubber was put into the kneader again and kneaded for 5 minutes to prepare a thermoplastic elastomer.
Next, 100 g of an ethylene-propylene copolymer (P0080K, manufactured by Mitsui Chemicals, Inc., hereinafter abbreviated as “EPM”) is added to the kneader and kneaded at 160 ° C. for 5 minutes together with the prepared thermoplastic elastomer. A thermoplastic elastomer composition was prepared.

(Example 2)
First, 100 g of maleated EPM was added to a kneader set at 180 ° C. and masticated for 4 minutes, and then 0.55 g of octylethanolamine (Nymine C-201, manufactured by NOF Corporation) was added and kneaded for 7 minutes. Further, after 1.1 g of ATA was added and kneaded for 5 minutes, the content (rubber) was released. Thereafter, the released rubber was put into the kneader again and kneaded for 5 minutes to prepare a thermoplastic elastomer.
Next, 100 g of EPM was added to the kneader and kneaded with the prepared thermoplastic elastomer at 160 ° C. for 5 minutes to prepare a thermoplastic elastomer composition.

(Comparative Example 1)
A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that EPM was not added.

(Comparative Example 2)
A thermoplastic elastomer composition was prepared in the same manner as in Example 2 except that EPM was not added.

(Comparative Examples 3 to 7)
A thermoplastic elastomer composition was prepared in the same manner as in Example 2 except that each uncrosslinked polymer of component B shown in Table 1 was added to the thermoplastic elastomer in the amount (g) shown in Table 1 instead of EPM. Prepared.

<Compression set (C-Set)>
The obtained thermoplastic elastomer composition was hot-pressed at 200 ° C. for 10 minutes to produce a sheet having a thickness of 2 mm. Seven sheets of the sheets were stacked and hot-pressed at 200 ° C. for 20 minutes to obtain a cylindrical sample ( Diameter 29 × thickness 12.5 mm).
The cylindrical sample was compressed by 25% with a dedicated jig and allowed to stand at 70 ° C. for 22 hours, and then the compression set was measured according to JIS K6262-1997.
The results are shown in Table 1.

<Surface morphology>
The surface of a sheet-like sample obtained by hot press molding the obtained thermoplastic elastomer composition at 200 ° C. for 10 minutes was visually observed to evaluate the surface morphology.
The case where the sheet was smooth was designated as “◎”, the sheet surface was slightly wrinkled but generally smooth as “◯”, and the case where irregularities could be visually confirmed was designated as “Δ”. In the thermoplastic elastomer composition of Comparative Example 4, the component B liquid ethylene-propylene copolymer was bleed on the surface.
The results are shown in Table 1.

<MFR>
The obtained thermoplastic elastomer composition was hot press molded at 200 ° C. for 10 minutes, and then a rubber pellet sample was produced by a commercially available pelletizer.
About this sample, MFR was measured on condition of 230 degreeC and load 2.16kg according to JISK7210-1999. In addition, when it did not flow 10 minutes after the start of measurement, it was set to “0”.
The results are shown in Table 1.

<Adhesiveness>
The obtained thermoplastic elastomer composition was press-molded and bonded to vulcanized plate-like EPDM at 200 ° C. for 10 minutes to prepare a sample.
In this sample, an incision of about 30 to 50 mm was made along the adhesion interface. This sample is fixed with a vise, etc., and the end of the obtained thermoplastic elastomer is pulled strongly at an angle of 90 degrees or more so as not to break with pliers or the like, and a knife is quickly cut at an angle of about 60 degrees. It was. At this time, the cutting with the knife reached the surface of the adherend (EPDM). The interval between the cuts was set to about 3 to 5 mm, and this operation was repeated 10 times or more. Depending on the state of the thermoplastic elastomer into which the cuts were made, the case of interfacial debonding was represented by AF, and the case of cohesive failure was represented by CF.
The results are shown in Table 1.

Each component in Table 1 is as follows. ATA, butylethanolamine, and EPM are as described above.
・ Maleinized EPM (maleic anhydride and peroxide added to EPM pellets in a twin screw extruder and reacted while kneading): TX-1023, Mitsui Chemicals, Inc. Lab Prototype ・ Liquid EP1: HC-10, manufactured by Mitsui Chemicals, Inc.-Liquid EP2: FC-3000, manufactured by Mitsui Chemicals, Inc.-PP: S119, manufactured by Mitsui Chemicals, Inc.-SEBS1: Kraton G1726, manufactured by Kraton Polymer Japan, Inc.-SEBS2: Tuftec H1013, manufactured by Asahi Kasei Corporation

For each thermoplastic elastomer and each B component in Table 1, the Sp value, Sp (A) / Sp (B), ethylene amount and its M (A) / M (B), propylene amount determined by the following method The M (A) / M (B), MFR, weight average molecular weight (Mw) and Mw (A) / Mw (B) are shown in Table 2 below.
In Table 2, Sp (A) is the Sp value of each thermoplastic elastomer in Table 1, and M (A) is the amount of ethylene (moles) in the monomer constituting each thermoplastic elastomer in Table 1. %) Or propylene content (mol%), and Mw (A) is the weight average molecular weight of each thermoplastic elastomer in Table 1. Sp (B) is the polymer Sp value of each B component in Table 2, and M (B) is the amount of ethylene (mol%) or the amount of propylene (mol%) in the monomer constituting the polymer of each B component. Mw (B) is the weight average molecular weight of the B component polymer.

(Sp value)
The Sp value was determined from the solubility parameter formula of Hansen (CM Hansen).

(MFR)
MFR was measured in the same manner as described above.

(Weight average molecular weight)
The weight average molecular weight was measured by GPC (polystyrene conversion).

As is apparent from the results shown in Table 1, the thermoplastic elastomer compositions of Examples 1 and 2 were higher in fluidity, surface morphology, and adhesion at higher temperatures than the thermoplastic elastomer compositions of Comparative Examples 1 and 2. Excellent compression properties and equivalent compression set.
In addition, the thermoplastic elastomer compositions of Comparative Examples 3 to 7 can improve the surface morphology and MFR as compared with the composition of Comparative Example 2, but the compression set resistance is greatly reduced, and the adhesion is improved. There wasn't. In contrast, the thermoplastic elastomer compositions of Example 1 and Example 2 were able to improve the surface morphology and MFR, and were excellent in compression set and adhesiveness.

Claims (13)

A thermoplastic elastomer composition comprising a thermoplastic elastomer (A) having a side chain containing an imino group and / or a nitrogen-containing heterocyclic ring and a carbonyl-containing group, and an uncrosslinked polymer (B),
The monomer constituting the thermoplastic elastomer (A) and the monomer constituting the uncrosslinked polymer (B) include at least one monomer (m) of the same kind,
A thermoplastic elastomer composition in which the thermoplastic elastomer (A) and the uncrosslinked polymer (B) satisfy the following formulas (I) and (II).
0.97 ≦ Sp (A) / Sp (B) ≦ 1.03 (I)
(In formula (I), Sp (A) is the Sp value of the thermoplastic elastomer (A), and Sp (B) is the Sp value of the uncrosslinked polymer (B).)
0.7 ≦ M (A) / M (B) ≦ 1.2 (II)
(In the formula (II), M (A) is the ratio (mol%) of the monomer (m) in the monomer constituting the thermoplastic elastomer (A), and M (B) is the uncrosslinked polymer ( (It is the ratio (mol%) of the monomer (m) in the monomer constituting B).)   The thermoplastic elastomer composition according to claim 1, wherein the side chain contains an imino group and a carbonyl-containing group.   The thermoplastic elastomer composition according to claim 1, wherein the side chain contains an imino group, a nitrogen-containing heterocyclic ring, and a carbonyl-containing group. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the side chain contains a structure represented by the following formula (1).

Wherein A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups. The side chain containing the structure represented by the formula (1) contains a structure represented by the following formula (2) or (3) bonded to the main chain at the α-position or the β-position. A thermoplastic elastomer composition.

Wherein A is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic group which may contain these atoms or groups. The thermoplastic elastomer composition according to claim 1 or 3, wherein the side chain contains a structure represented by the following formula (4).

Wherein E is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; An organic group that may contain any atom or group of The side chain containing the structure represented by said Formula (4) contains the structure represented by following formula (5) or (6) couple | bonded with a principal chain in (alpha) position or (beta) position. A thermoplastic elastomer composition.

(Wherein E is a nitrogen-containing heterocyclic ring, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)) or A sulfur atom; or an organic group that may contain these atoms or groups.)   The thermoplastic elastomer composition according to claim 1, 3, 6, or 7, wherein the nitrogen-containing heterocycle is a 5- or 6-membered ring.   The thermoplastic elastomer composition according to claim 8, wherein the nitrogen-containing heterocycle is a triazole ring, a thiadiazole ring, a pyridine ring, an imidazole ring, or a hydantoin ring. The thermoplastic elastomer composition according to claim 6, wherein the side chain containing the structure represented by the formula (4) contains a structure represented by the following formula (7) or the following formula (8) or (9). object.

Wherein B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or an organic which may contain these atoms or groups. G and J are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) The side chain containing the structure represented by the formula (4) contains a structure represented by any one of the following formulas (10) to (15) bonded to the main chain at the α-position or the β-position. 10. The thermoplastic elastomer composition according to 10.

Wherein B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom; or these atoms or groups G and J are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)   The thermoplastic elastomer composition according to any one of claims 1 to 11, wherein the uncrosslinked polymer (B) has a melt mass flow rate (MFR) of 0.001 g / 10 min or more.   The ratio (Mw (A) / Mw (B)) of the weight average molecular weight Mw (A) of the thermoplastic elastomer (A) and the weight average molecular weight Mw (B) of the uncrosslinked polymer (B) is 0.00. It is 5-20, The thermoplastic-elastomer composition in any one of Claims 1-12.