JP2002105341A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an easily producible hot-melt composition capable of obtaining a low hardness product. SOLUTION: This thermoplastic elastomer composition comprises a crosslinked product of an organic polymer obtained by crosslinking the organic polymer (a) having a crosslinkable function group at the molecular end [(A) component] and one or more substances selected from hot-melt resins, thermoplastic resins and plasticizers [(B) component]. The composition is easily producible and can afford a low hardness elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic elastomer composition containing a crosslinked organic polymer.

[0002]

2. Description of the Related Art Thermoplastic elastomers can be molded in the same manner as thermoplastic resins, and the resulting molded article is a polymer material exhibiting rubber-like elasticity at room temperature. Since they are unnecessary and easy to recycle, they have recently been used in a wide range of fields such as automobile parts, home electric parts, electric wire covering materials, medical parts, sundries, footwear and the like.

[0003] Techniques for compounding an organic polymer such as rubber for improving the performance of a thermoplastic elastomer have been known for a long time. In particular, olefin elastomers such as PP and styrene elastomers such as SEBS have been used. EPDM
Many studies have been made on a technique for compounding a crosslinked product of NR and IIR. For example, in the case of an olefin-based thermoplastic elastomer, a crystalline olefin resin or an olefin-based rubber is crosslinked using an organic peroxide. A technique (JP-B-53-21021), a technique of crosslinking using a phenol resin (JP-B-58-46138), and a technique of crosslinking using a hydrosilyl group (JP-A-11-16675, JP-A-11-181172) have been reported. In addition, use of a special structure isobutylene rubber (Japanese Patent Application Laid-Open No. Hei 9-137007) has been reported. In each case, EPDM and IIR in which double bonds are randomly present as crosslink points in an olefin polymer as a rubber component. And the like, and the crosslinking is not uniform, and it is difficult to reduce the hardness.

[0004]

An object of the present invention is to provide a thermoplastic elastomer composition containing a crosslinked product of an organic polymer, which has low hardness.

[0005]

Means for Solving the Problems The present inventor has proposed a crosslinked organic polymer (a) which is obtained by crosslinking an organic polymer (a) having a crosslinkable functional group at a molecular terminal, A thermoplastic elastomer composition containing one or more substances (component (B)) selected from a hot melt resin, a thermoplastic resin, and a plasticizer can be easily produced and has a low hardness. Was found.

Further, an organic polymer (a) having a crosslinkable functional group at a molecular terminal [hereinafter, simply referred to as an organic polymer (a)]. The organic polymer (a) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and having a silicon-containing group which can be crosslinked by forming a siloxane bond.
1) an organic polymer having a carbon-carbon double bond-containing group selected from alkenyl groups and (meth) acryl groups (a
2) The organic polymer (a3) having a hydroxyl group is particularly effective, and the thermoplastic elastomer thus produced can be used for a gasket material, a sheet material, a vibration control material, and a sealing plug. Was found.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The present invention relates to a crosslinked organic polymer (a) obtained by crosslinking an organic polymer (a) having a crosslinkable functional group at a molecular terminal, a hot melt resin, a thermoplastic resin, And a thermoplastic elastomer composition containing one or more substances [component (B)] selected from plasticizers.

In the present invention, the organic polymer (a) having a crosslinkable functional group at the molecular terminal has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and is crosslinked by forming a siloxane bond. An organic polymer (a1) having at least one silicon-containing group, an alkenyl group,
Organic polymer (a) having at least one carbon-carbon double bond-containing group selected from (meth) acryl groups in the molecule
2) or an organic polymer (a3) having at least one hydroxyl group.

In the present invention, the substantial crosslinking method comprises the steps of: (a) an organic polymer having at least one alkenyl group; and (b) a siloxane having at least one hydrosilyl group in the molecule. The thermoplastic elastomer composition according to any one of claims 1 and 3, wherein the thermoplastic elastomer composition is obtained by crosslinking the compound (c) having a structure.

Further, in the present invention, the organic polymer (a) having a crosslinkable functional group at the molecular terminal is preferably a saturated hydrocarbon polymer.

In the present invention, the component (B) is SBS
(Styrene-butadiene-styrene block polymer),
From SIS (styrene-isoprene-styrene block polymer), SEBS (styrene-ethylenebutylene-styrene block polymer), SEPS (styrene-ethylenepropylene-styrene block polymer), SIBS (styrene-isobutylene-styrene block polymer) It is preferably a hot melt resin selected from the group consisting of: In the present invention, the component (B) is preferably a thermoplastic resin composed of a polyolefin resin. In the present invention, the component (B) is SEBS (styrene-
Ethylene butylene-styrene block polymer), SEP
It is preferably a hot melt resin selected from the group consisting of S (styrene-ethylene propylene-styrene block polymer) and SIBS (styrene-isobutylene-styrene block polymer).

In the present invention, the organic polymer (a) having a crosslinkable functional group at the molecular terminal contains 80% by weight or more of a repeating unit derived from isobutylene, or has a number average molecular weight of at least 80% by weight. It is preferably a saturated hydrocarbon polymer of 500 to 100,000 or a saturated hydrocarbon polymer having a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.01 to 1.50.

In the present invention, when the thermoplastic elastomer composition is produced, it is preferable to mix the composition containing the component (A) with the composition containing the component (B).

In the present invention, when the thermoplastic elastomer composition is produced, the organic polymer (a) is preferably crosslinked in a mixture of the organic polymer (a) and the component (B).

In the present invention, when producing the thermoplastic elastomer composition, it is preferable to crosslink the organic polymer (a) in a state where the organic polymer (a) and the component (B) are kneaded.

Further, the present invention provides an organic polymer (a) having a crosslinkable functional group at a molecular terminal and one or more substances selected from a hot melt resin, a thermoplastic resin, and a plasticizer [( B) The molded product of the thermoplastic elastomer composition obtained by molding the mixture of the component] and then crosslinking the organic polymer (a) having a crosslinkable functional group at the molecular terminal.

The thermoplastic elastomer composition of the present invention may be used, for example, in gasket materials, sheet materials,
Vibration control materials and sealing plugs can be mentioned.

The present invention also relates to an organic polymer (a) having a crosslinkable functional group at a molecular terminal, and one or more substances selected from a hot melt resin, a thermoplastic resin, and a plasticizer [( B) Component].

The main chain skeleton of the organic polymer (a) of the present invention is
There is no particular limitation as long as the above conditions are satisfied, and the main chain skeleton of the organic polymer can be selected from, for example, saturated hydrocarbons, polyethers, polyesters, acrylics, and the like. Saturated hydrocarbon-based polymers are desirable in that they have excellent stability at high temperatures.

The polymer constituting the skeleton of the saturated hydrocarbon polymer may be prepared by (1) polymerizing an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene or the like as a main monomer; 2) butadiene,
It can be obtained by homopolymerizing a diene-based compound such as isoprene or copolymerizing the above-mentioned olefin-based compound, followed by hydrogenation. However, it can be obtained by a method such as isobutylene-based polymer or hydrogenated polybutadiene-based polymer. The coalescing is particularly preferable because a functional group can be easily introduced into the terminal, the molecular weight can be easily controlled, and the number of terminal functional groups can be increased. An isobutylene-based polymer is more preferable from the viewpoint of easy synthesis.

In the present invention, the isobutylene-based polymer is defined as 50% by weight of a repeating unit derived from isobutylene.
It refers to the polymer contained above. Isobutylene-based polymer,
All of the monomer units may be formed from isobutylene units or may be copolymers with other monomers, but contain at least 80% by weight of a repeating unit derived from isobutylene isobutylene from the viewpoint of rubber properties. Preferably, it is

A saturated hydrocarbon polymer, preferably an isobutylene polymer or a hydrogenated polybutadiene polymer, has a number average molecular weight of 500 to 100, from the viewpoint of availability.
It is preferably about 000, and particularly preferably about 1,000 to 50,000 from the viewpoint of fluidity.

The value of the molecular weight distribution (weight average molecular weight / number average molecular weight) of the organic polymer (a) of the present invention is not particularly limited, but is preferably 2 or less from the viewpoint of fluidity. Particularly preferred is 5 or less.

As a method for synthesizing the organic polymer (a), various polymerization methods have been reported, and in recent years many so-called living polymerizations have been developed. In the case of a saturated hydrocarbon polymer, especially an isobutylene polymer, Kenn
edy et al. (JPP.
Kennedy et al. Polymer Sci. , P
polymer Chem. Ed. 15,2843
(1977)), it can be easily produced, and has a molecular weight of about 500 to 100,000,
It is known that polymerization can be performed with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced into molecular terminals.

The functional group of the organic polymer (a) can be used without any particular limitation depending on the purpose. For example, it has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and forms a siloxane bond. And a carbon-carbon double bond-containing group such as a silicon-containing group, an alkenyl group, and a (meth) acrylic group, a hydroxyl group, a carboxyl group, and a glycidyl group.

As a method for introducing the functional group of the organic polymer (a), various existing methods can be used. In particular, in the case of a saturated hydrocarbon-based polymer, particularly an isobutylene-based polymer, it is known that after polymerization by the above-described inifer method, many functional groups can be introduced.
Alkenyl groups (JP-A-63-105005;
248406, WO90 / 15081, JP-A-4-28
8309 etc.), (meth) acrylic group (Japanese Unexamined Patent Publication No. 2-886)
14), a hydroxyl group (Ivan et al., J. Polymer)
Sci. , Polymer Chem. Ed. 1
8, 3177 (1980), JP-A-4-20501, JP-A-11-302320, JP-A-2000-11933
0, JP-A-2000-103810, etc.), carbonyl group (JP-A-2000-150076, JP-A-2000-169)
518), a glycidyl group (US Pat. No. 4,429,099)
Etc.).

Further, based on the introduced functional group,
Hydrolyzable silicon groups (JP-A-63-006041, JP-A-63-6003, JP-A-1-197509, JP-A-4
-103606, JP-A-7-532882, etc.) and hydrosilyl groups (JP-A-3-152164, JP-A-3-1815)
65) can be easily synthesized.

The above functional groups can be used alone or in combination of two or more kinds. Organic polymers having two or more kinds of functional groups in one molecule or different kinds of functional groups are contained in one molecule. Is also possible.

The above functional groups can be freely selected according to the purpose. Among them, from the viewpoint of easy availability and easy control of the reaction, the functional group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom. An organic polymer having a silicon-containing group capable of crosslinking by forming a siloxane bond (a
1), an organic polymer (a2) having an alkenyl group, and an organic polymer (a3) having a hydroxyl group are particularly preferable.

The reactive silicon group of the organic polymer (a1) having a silicon-containing group which can be crosslinked by forming a siloxane bond includes those described in JP-A-63-6041 and JP-A-6-604.
3-6003, JP-A-1-197509, JP-A-4-1
03606, various silicon functional groups described in JP-A-7-53882 and the like can be used and can be selected according to use conditions. However, from the viewpoint of availability, an alkoxysilyl group or an alkylalkoxy group is preferable. In view of the above, a trimethoxysilyl group, a methyldimethoxysilyl group, a triethoxysilyl group, and a methyldiethoxysilyl group are particularly preferable, and a methyldimethoxysilyl group is more preferable in terms of a balance between reactivity and storage stability.

As a method for obtaining a crosslinked product as the component (A) by a curing reaction of the organic polymer (a1) having a silicon-containing group which can be crosslinked by forming a siloxane bond,
For example, there can be mentioned a method in which a reactive siloxane group of the organic polymer (a1) is reacted with a hydroxyl group-containing compound (such as water or silanol) in the presence of a silanol condensation catalyst to form a siloxane bond.

Examples of the silanol condensation catalyst include acids, base catalysts, divalent and tetravalent tin-based curing catalysts, titanium-based curing catalysts, aluminum-based curing catalysts, and amine-based curing catalysts.

Specific examples of the tetravalent tin curing catalyst include tetravalent tin carboxylate salts such as dibutyltin bisacetylacetonate, dibutyltin dialkoxide, dibutyltin dilaurate, dibutyltin maleate and dibutyltin diacetate. can give. Specific examples of the silanol condensation catalyst other than the above-mentioned tetravalent tin curing catalyst include tin octylate and the like.
Divalent tin-based curing catalyst; titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum-based curing catalysts such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetyl Acetonate; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, Triethylenediamine, guanidine, diphenylguanidine, 2,4,6
-Tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0)
Amine curing catalyst such as undecene-7 (DBU); low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane; −
A known silanol condensation catalyst such as a silane coupling agent having an amino group such as (β-aminoethyl) aminopropylmethyldimethoxysilane;

These catalysts may be used alone,
Two or more kinds may be used in combination.

The alkenyl group of the alkenyl group-containing organic polymer (a2) of the present invention is described in JP-A-63-105.
005, JP-A-1-248406, WO90 / 1508
1. Various functional groups described in JP-A-4-288309 and the like can be used and can be selected according to the conditions of use. However, from the viewpoint of reactivity, an α-olefin structure is preferable, and availability is low. Thus, an allyl group is particularly preferred.

The method for crosslinking the alkenyl group of the alkenyl group-containing organic polymer (a2) of the present invention into a crosslinked product as the component (A) includes peroxide crosslinking, sulfur crosslinking,
A crosslinking method generally known in rubber crosslinking such as phenol resin crosslinking, a crosslinking method by a radical reaction such as crosslinking by light, radiation or electron beam, and a hydrosilylation reaction with a hydrosilyl group (JP-A-3-152164, JP-A-3-1864)
1565, JP-A-11-166075, JP-A-11-1
81172) can be used, and a hydrosilylation reaction with a hydrosilyl group is particularly preferred because of easy control of the reaction.

The compounds capable of hydrosilylation reaction with the alkenyl group of the alkenyl group-containing organic polymer (a2) of the present invention are described in JP-A-3-152164 and JP-A-3-152164.
181565, JP-A-11-166075, JP-A-11-11675
Compounds described in US Pat. No. 181172 are exemplified, but from the viewpoint of availability, it is preferably a compound (c) containing a hydrosilyl group and having a siloxane structure in the molecule, and is compatible with other components. In view of the above, methylhydropolysiloxane or a compound obtained by reacting methylhydropolysiloxane with an alkyl α-olefin and / or aromatic vinyl, a dimethylpolysiloxane-methylhydropolysiloxane copolymer, and an alkyl α-olefin thereof And / or compounds reacted with aromatic vinyl, methylhydrocyclopolysiloxane, its alkyl alpha olefins, and / or compounds reacted with aromatic vinyl.

It is known that the reaction of the alkenyl group of the alkenyl group-containing organic polymer (a2) of the present invention with a compound capable of performing a hydrosilylation reaction is promoted by the coexistence of a radical polymerization catalyst or a hydrosilyl catalyst. From the standpoint of high reactivity, use of a hydrosilyl catalyst is preferred, and platinum-based catalysts and rhodium-based catalysts described in JP-A-3-152164, JP-A-3-181565, JP-A-11-16675, and JP-A-11-181172 are particularly preferred. From the viewpoint of availability, a platinum vinylsiloxane catalyst and chloroplatinic acid are more preferable.

The organic polymer having a hydroxyl group of the present invention (a
The hydroxyl group of 3) is described in Ivan et al. Polymer S
ci. , Polymer Chem. Ed. 1
8, 3177 (1980), JP-A-4-20501, JP-A-11-302320, JP-A-2000-11933
0, synthesized by a method described in JP-A-2000-103810 and the like, and can be selected according to the conditions of use. However, from the viewpoint of reactivity, a hydroxyl group bonded to an alkyl group is preferable.

The organic polymer having a hydroxyl group of the present invention (a
As a method of crosslinking the hydroxyl group of 3) to form a crosslinked product as the component (A), the compound is reacted with an isocyanate group-containing compound,
A method of forming an urethane bond, reacting with a hydrosilyl group-containing compound, forming an alkoxysilicon bond, reacting with a carbonyl group-containing compound, and forming an ester bond is exemplified. A method of reacting to form a urethane bond is preferred. Isocyanate group-containing compounds used in the present invention are not particularly limited, and aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates and the like can be used. From the viewpoint of availability, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene Examples include diisocyanate, norbornane diisocyanate, hexyl diisocyanate, and isophorone dissocyanate.

The number of functional groups per molecule of the organic polymer (a) of the present invention is not particularly limited. However, from the viewpoint of controlling physical properties, particularly rubber hardness, 0.4 to 10 per molecule is usually used. The number is preferably 0.5 to 3 per molecule, and more preferably 1.1 to 3 per molecule. The position of the functional group is not particularly limited, except that at least one of the functional groups is present at the molecular terminal, but is preferably present at the molecular terminal from the viewpoint of controlling physical properties, particularly rubber hardness.

As an organic polymer suitable for the organic polymer (a) of the present invention, a product named Epion (Kanebuchi), which is a polyisobutylene having a dimethoxysilyl group or an allyl group at the molecular terminal, which is produced by the inifer method Chemical Industry) is available.

In the present invention, the content of the crosslinked organic polymer as the component (A) in the thermoplastic elastomer composition is not limited as long as physical properties and fluidity are compatible. Of the fluid components inside, 5
80% by weight is preferable, and 20 to 60% by weight is more preferable.

The “crosslinked organic polymer” as the component (A) of the present invention may be produced using only the organic polymer (a). An organic polymer having a crosslinkable functional group in the main chain (although it has no functional group at the terminal) may be used in combination. Organic polymers having a crosslinkable functional group having no functional group at the terminal include, but are not limited to, US Pat. No. 4,130,534 and US Pat.
0535, US Pat. No. 4,311,628, US Pat.
628, U.S. Pat. No. 4,448,074, JP-A-9-1370
Organic polymers exemplified in EP-07-07 can be used, and from the viewpoint of availability, copolymers with EPDM, butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and isobutylene-P-alkylstyrene are preferred.

The hot melt resin as the component (B) is not limited as long as it meets the purpose of the present invention, and includes, for example, butyl rubber, partially crosslinked butyl, polyisobutylene, styrene block polymer, EVA, olefin, and polyester. ,
Examples thereof include polyamide-based and reactive urethane-based hot-melt resins, and styrene-based block polymers are particularly preferable in view of the balance of physical properties. More specific examples of the styrenic block polymer that can be used in the present invention include S
BS (styrene-butadiene-styrene block polymer), SIS (styrene-isoprene-styrene block polymer), SEBS (styrene-ethylenebutylene-
Styrene block polymer), SEPS (styrene-ethylene propylene-styrene block polymer), SIBS
(Styrene-isobutylene-styrene block polymer)
In particular, from the viewpoint of heat resistance and weather resistance, a styrene-based block polymer containing a saturated hydrocarbon is preferable as a rubber component, and from the viewpoint of availability, SEBS (styrene-ethylenebutylene-styrene block polymer) is preferable. ), SE
PS (styrene-ethylene propylene-styrene block polymer) and SIBS (styrene-isobutylene-styrene block polymer) are more preferable. The thermoplastic resin as the component (B) is not limited within a range suitable for the purpose of the present invention, and for example, a polyolefin resin, a polystyrene resin, a vinyl chloride resin, an acrylic resin, a fluororesin, or the like can be used. In view of the above, a polyolefin resin is particularly preferable. Examples of the polyolefin resin suitable for the present invention include semi-crystalline polyolefins. More specifically, homopolymer types such as polypropylene and polyethylene (low density, high density, linear low density, etc.), vinyl acetate, acrylic acid , Methyl acrylate, ethyl acrylate and the like. Also,
A new olefin resin using a single-site catalyst recently developed is also exemplified. These polyolefin resins can be used singly or in combination depending on the price and performance, but HPDE and polypropylene are particularly preferred. The plasticizer of the component (B) is not limited as long as it meets the purpose of the present invention, and includes, for example, polyvinyl oligomers such as polybutene, hydrogenated polybutene, hydrogenated α-olefin oligomer and atactic polypropylene; biphenyl, triphenyl and the like. Aromatic oligomers such as No .; hydrogenated polyene oligomers such as hydrogenated liquid polybutadiene; paraffinic oligomers such as paraffin oil and chlorinated paraffin oil; cycloparaffinic oligomers such as naphthenic oil; dibutyl phthalate, diheptyl phthalate, di ( Phthalates such as 2-ethylhexyl) phthalate, butylbenzyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate and diundecyl phthalate; di (2-ethylhexyl) adipate, di n Octyl adipate, diisononyl adipate, diisodecyl adipate, di (2-ethylhexyl) Sebashiketo, non-aromatic dibasic acid esters such as tetrahydrophthalic di-2-ethylhexyl phthalate; trimellitic acid 2-
Aromatic esters such as ethylhexyl and triisodecyl trimellitate; fatty acid esters such as butyl oleate, methyl acetyl ricinoleate and pentaerythritol ester; polyalkylene glycol esters such as diethylene glycol benzoate and triethylene glycol dibenzoate; Phosphoric esters such as cresyl phosphate and tributyl phosphate; and epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil can be used. These may be used alone or in combination of two or more.

The component (B) has a structure, a composition, an added amount,
The combination or the like affects the properties of the thermoplastic elastomer at room temperature, such as the fluidity at a high temperature and the compression recovery ratio.

Each of the components (B) can be used alone or in combination, and can be selected according to the intended use.

The method for producing the thermoplastic elastomer composition containing the components (A) and (B) is not particularly limited, and the composition containing the component (A) is prepared.
A method of mixing with the composition containing the component (B), and in the composition containing the organic polymer (a) and the component (B),
(A) a method of forming a crosslinked body of an organic polymer as a component,
In the composition containing the component (B), for example, a method of mixing a composition obtained by forming a crosslinked product of the organic polymer as the component (A) with the composition containing the component (B) is exemplified. Is done. In any method, it is important to select the composition, temperature, curing speed, mechanical performance, and the like so as to satisfy the manufacturing conditions such as mixing and kneading operations. For example, an organic polymer (a) having a crosslinkable functional group at a molecular terminal is cross-linked in a plasticizer as a component (B) at normal temperature to obtain a cross-linked product of the organic polymer as a component (A). Thus, the thermoplastic elastomer composition of the present invention can be easily produced by kneading the composition containing the hot melt resin and the thermoplastic resin as the component (B) at a high temperature using a kneading apparatus. In addition to the components described above, necessary additives such as an antioxidant, an adhesion-imparting agent, a filler, a surfactant and the like can be freely added to each composition under conditions that can be produced.

The composition containing the component (A) and the composition containing the component (B) are mixed. In a mixture of the organic polymer (a) and the component (B), the organic polymer (a) is mixed. The organic polymer (a) having a crosslinkable functional group at a molecular terminal, which crosslinks the organic polymer (a) in a state in which the organic polymer (a) and the component (B) are kneaded, and (B) )) A method of forming a mixture of components and then crosslinking the organic polymer (a) having a crosslinkable functional group at the molecular terminal is relatively simple.
Easy and preferred.

The thermoplastic elastomer composition of the present invention contains, in addition to the components (A) and (B) described above, a tackifier, a filler, a flexibility control agent, an antioxidant, and a silane coupling agent. , A physical property adjuster for adjusting the tensile properties of the resulting cured product, a photocurable resin, an anti-sagging agent, a solvent, a flame retardant, a lubricant, a pigment, a spacer shape retainer, a flow improver, etc. Various additives are added.
In addition, a reactive silicon group-containing organic polymer can be added for the purpose of improving properties.

These additional components are manufacturable, and
It is possible to add at any stage of the production process as long as the physical properties can be expressed, for example, a method used together with the production of the component (A), or after mixing the components (A) and (B). Etc. are exemplified.

Examples of the tackifier include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, hydrogenated alicyclic hydrocarbon resins, alicyclic hydrocarbon resins, cumarone resins, terpene resins, Rosin derivatives and the like can be mentioned.

Examples of the filler include wood powder, parve, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, terra alba, fumed silica, and precipitated silica. , Silicic anhydride, carbon black, calcium carbonate, clay,
Talc, titanium oxide, magnesium carbonate, quartz, aluminum fine powder, flint powder, zinc dust, polyethylene,
Polypropylene, high styrene resin, cyclized rubber, cumarone-indene resin, phenol-formaldehyde resin, modified melamine resin, petroleum resin, styrene copolymer,
Lignin and the like. Among these fillers, precipitated silica, fumed silica, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. These fillers may be used alone or in combination of two or more.

Examples of the flexibility control agent include polybutene, polybutadiene, and non-reactive polyisobutylene.

The antioxidants include phenolic antioxidants, aromatic amine antioxidants, sulfur hydroperoxide decomposers, phosphorus hydroperoxide decomposers,
Examples include benzotriazole-based UV absorbers, salicylate-based UV absorbers, benzophenone-based UV absorbers, hindered amine-based light stabilizers, and nickel-based light stabilizers.

Specific examples of the phenolic antioxidants include 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, and 2,6-di-t-butyl-4.
-Methylphenol, 2,5-di-t-butylhydroquinone, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate],
2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-t -Butylphenol) and the like.

Specific examples of the aromatic amine antioxidant include N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-.
Examples thereof include dihydroquinoline.

Specific examples of the sulfur-based hydroperoxide decomposer include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate. Pionate and the like can be exemplified.

Specific examples of the phosphorus hydroperoxide decomposer include diphenylisooctyl phosphite,
Examples include triphenyl phosphite.

Specific examples of the benzotriazole-based ultraviolet absorber include 2- (3,5-di-tert-butyl-2-).
(Hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole and the like can be exemplified.

Specific examples of the salicylate-based ultraviolet absorber include 4-t-butylphenyl salicylate,
Examples thereof include 4-di-t-butylphenyl-3,5′-di-t-butyl-4′-hydroxybenzoate.

Specific examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone,
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and the like.

Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4
-Piperidyl) sebacate, bis (1,2,2,6,
6, -pentamethyl-4-piperidyl) sebacate, 1
-{2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4-
[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,
6,6, -tetramethylpiperidine and the like can be exemplified.

Specific examples of the nickel light stabilizer include nickel dibutyldithiocarbamate, [2,2
'-Thiobis (4-t-octylphenolate)]-2
-Ethylhexylamine nickel (II), [2.2
'-Thiobis (4-t-octylphenolate)]-n
-Butylamine nickel (II) and the like.

These antioxidants may be used alone or in combination of two or more. It may work more effectively when used in combination than when used alone.

Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- ( 2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2
-Aminoethyl) aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-
Benzyl-γ-aminopropyltrimethoxysilane, N
Amino-containing silanes such as -vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane Mercapto group-containing silanes such as silane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silanes such as trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2
Carboxysilanes such as -methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ Silanes containing a vinyl-type unsaturated group such as acroyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; -Containing isocyanate groups such as isocyanate propyl trimethoxy silane, γ-isocyanate propyl triethoxy silane, γ-isocyanate propyl methyl diethoxy silane, and γ-isocyanate propyl methyl dimethoxy silane. Silanes and the like. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated amino silane complexes, blocked isocyanate silanes, phenylamino long-chain alkyl silanes, amino silylated silicones, silylated polyesters, and the like, which are modified derivatives thereof, are also used as silane coupling agents. Can be used.

The above silane coupling agents may be used alone or in combination of two or more.

In the thermoplastic elastomer composition of the present invention, an adhesion-imparting agent other than the silane coupling agent can be used.

The thermoplastic elastomer composition of the present invention comprises:
As a thermoplastic elastomer composition that can be reduced in hardness and is easy to manufacture, it can be used in various applications as a substitute for conventional thermoplastic elastomer products, and can be used for sheets, molded products,
It is molded into an adhesive or foam, and can be expected to be used in a wide range of fields such as automobile parts, home electric parts, electric wire covering materials, medical parts, miscellaneous goods and footwear. Particularly, it is effective for a gasket material, a vibration control material, and a sealing plug which conventionally used a large amount of a plasticizer to reduce hardness.

[0071]

Embodiments of the present invention will be described below. (Example 1) 100 parts by weight of SEBS resin (Taftec 1031 manufactured by Asahi Kasei) as a component (B), isobutylene polymer having a methyldimethoxysilyl group at a molecular terminal as a component (a1), and paraffin as a component (B) System process oil PS
Epion EP303S containing -32 (made by Idemitsu Kosan)
After mixing 100 parts by weight (manufactured by Kanebuchi Chemical Co., Ltd.) of Mark AO-50 (manufactured by Asahi Denka) as an antioxidant, using a Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.) set at 160 ° C.,
In order to crosslink the isobutylene polymer having reactive silicon as the component (a1) and synthesize the component (A), a silanol condensation catalyst Scat-27 (manufactured by Sankyoki Chemical Co., Ltd.)
After adding 2 parts by weight and 1 part by weight of water, the mixture was kneaded for 20 minutes.
The JIS-A hardness at 23 ° C. of this molded product was 45. (Example 2) Epion EP400A (Kanebuchi Chemical Industry) containing 100 parts by weight of SEBS resin (Taftec 1031 manufactured by Asahi Kasei Corporation) as the component (B) and isobutylene polymer having an allyl group at the molecular terminal as the component (a2) 100 parts by weight), Mark AO-50 (manufactured by Asahi Denka) as an antioxidant, 3 parts by weight of CR100 (manufactured by Kanegafuchi Chemical Industry), which is a modified methylhydropolysiloxane (c), were added at 140 ° C. After mixing using a mill (manufactured by Toyo Seiki Co., Ltd.), (a
1) In order to crosslink the isobutylene polymer having reactive silicon as a component and form the component (A), 50 μl of platinum vinyl siloxane (3%, manufactured by Degussa Huls) and 25 μl of dimethyl malate are dissolved in 1 ml of toluene. Kneaded for 20 minutes. JIS-
The A hardness was 52. (Example 3) 100 parts by weight of SEBS resin (ToughTech 1031 manufactured by Asahi Kasei) as the component (B), and JP-A 20 as the component (a3)
Isobutylene polymer having a hydroxyl group at the molecular terminal (number average molecular weight 53
00, molecular weight distribution 1.5, about 90% of molecular weight terminal end contains hydroxyl group) 100 parts by weight, mark AO as antioxidant
-50 (manufactured by Asahi Denka) was mixed using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set at 140 ° C., and then (a1)
In order to crosslink the isobutylene polymer having reactive silicon as a component and form the component (A), 2 g of diphenylmethane-4,4'-diisocyanate and 0.5 g of dibutyltin laurate are dissolved in 1 ml of toluene, and
Kneaded for 0 minutes. The JIS-A hardness at 23 ° C. of the molded product was 60. (Example 4) Epion EP400A (Kanebuchi Chemical Industry) containing 100 parts by weight of SEBS resin (Taftec 1031 manufactured by Asahi Kasei) as the component (B) and isobutylene polymer having an allyl group at the molecular terminal as the component (a2) 100 parts by weight)
(B) Hydrocarbon Plasticizer PAO-5010 as Component
40 parts by weight (manufactured by Idemitsu Petrochemical), and Ao-50 (manufactured by Asahi Denka) as an antioxidant were mixed with Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.) set at 140 ° C. After lowering the temperature to 100 ° C., 3 parts by weight of CR100 (manufactured by Kaneka Corporation), which is a modified methylhydropolysiloxane (c),
Platinum vinyl siloxane (3%, manufactured by Degussa Huls) 1
After adding and mixing 0 μl and 25 μl of dimethyl malate, the mixture taken out quickly was crosslinked with an isobutylene polymer having a molecular allyl group as the component (a2),
To form the component (A), the mixture was sandwiched between heated bracelets heated to 160 ° C. and heated for 1 hour. The JIS-A hardness at 23 ° C. of this molded product was 45. (Comparative Example 1) Tuftec 1031 (Asahi Kasei) 10 as the component (A)
0 parts by weight of Mark AO-50 (manufactured by Asahi Denka) as an antioxidant was mixed using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set at 160 ° C. to obtain a uniform composition. The JIS-A hardness at 23 ° C. of this molded product was 80.

[0072]

According to the present invention, it is possible to obtain a thermoplastic elastomer composition which can be reduced in hardness without adding a large amount of oil and which can be easily produced. As an alternative, it can be used in a wide range of fields such as automobile parts, home appliance parts, electric wire covering materials, medical parts, miscellaneous goods, footwear, etc.In particular, gasket materials, which used to use a large amount of plasticizer to reduce hardness, Effective for vibration control materials and sealing plugs.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/04 C08L 83/04 F term (Reference) 4F070 AA06 AA12 AA18 AA60 AA78 AB05 AB07 AB08 AB09 AB11 AB16 AC43 AC48 AC55 AC73 AC75 AC76 AC87 AC94 AE02 AE08 GA06 GB02 GB03 GC02 GC03 GC04 GC05 4J002 BB03X BB06X BB07X BB08X BB12X BB17X BB20W BC03X BD03X BD12X BG00X BL01X BP01X CD16X CP03W CP06W CP12H146 016 016 016

Claims (21)

[Claims] 1. A crosslinked organic polymer (a) which is obtained by crosslinking an organic polymer (a) having a crosslinkable functional group at a molecular terminal, a hot melt resin, a thermoplastic resin,
One or more substances selected from plasticizers [(B)
Component]. 2. The organic polymer (a) according to claim 1, which has a crosslinkable functional group at the molecular terminal, has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and forms a siloxane bond. The thermoplastic elastomer composition according to claim 1, which is an organic polymer (a1) having at least one crosslinkable silicon-containing group. 3. The organic polymer (a) having a crosslinkable functional group at the molecular terminal according to claim 1, wherein a carbon-carbon double bond-containing group selected from an alkenyl group and a (meth) acryl group is contained in the molecule. The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer composition is an organic polymer (a2) having at least one polymer. 4. The thermoplastic elastomer according to claim 1, wherein the organic polymer (a) having a crosslinkable functional group at the molecular terminal according to claim 1 is an organic polymer (a3) having at least one hydroxyl group. Composition. 5. An organic polymer (a2) having at least one alkenyl group and a compound having at least one hydrosilyl group in the molecule and having a siloxane structure in the molecule, wherein the substantial crosslinking method is used. 4. The thermoplastic elastomer composition according to claim 1, which is obtained by crosslinking (c). 6. The thermoplastic elastomer composition according to claim 1, wherein the organic polymer (a) having a crosslinkable functional group at a molecular terminal is a saturated hydrocarbon polymer. 7. Component (B) is SBS (styrene-butadiene-styrene block polymer), SIS (styrene-isoprene-styrene block polymer), SEBS
A hot melt resin selected from the group consisting of (styrene-ethylenebutylene-styrene block polymer), SEPS (styrene-ethylenepropylene-styrene block polymer), and SIBS (styrene-isobutylene-styrene block polymer). 7. The thermoplastic elastomer composition according to 1 to 6. 8. The thermoplastic elastomer composition according to claim 1, wherein the component (B) is a thermoplastic resin comprising a polyolefin resin. 9. Component (B) is SEBS (styrene-ethylene butylene-styrene block polymer), SEPS
9. The thermoplastic elastomer composition according to claim 1, which is a hot melt resin selected from the group consisting of (styrene-ethylene propylene-styrene block polymer) and SIBS (styrene-isobutylene-styrene block polymer). 10. The organic polymer (a) having a crosslinkable functional group at a molecular terminal contains a repeating unit derived from isobutylene in an amount of 80% by weight or more.
The thermoplastic elastomer composition as described in the above. 11. The thermoplastic elastomer according to claim 1, wherein the organic polymer (a) having a crosslinkable functional group at a molecular terminal is a saturated hydrocarbon polymer having a number average molecular weight of 500 to 100,000. Composition. 12. The organic polymer (a) having a crosslinkable functional group at a molecular terminal is a saturated hydrocarbon polymer having a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.01 to 1.50. The thermoplastic elastomer composition according to any one of claims 1 to 11. 13. The method for producing a thermoplastic elastomer composition according to claim 1, wherein the composition containing the component (A) and the composition containing the component (B) are mixed. 14. The thermoplastic elastomer composition according to claim 1, wherein the organic polymer (a) is cross-linked in a mixture of the organic polymer (a) and the component (B). Method. 15. The thermoplastic elastomer composition according to claim 1, wherein the organic polymer (a) is crosslinked while the organic polymer (a) and the component (B) are kneaded. how to. 16. An organic polymer (a) having a crosslinkable functional group at a molecular terminal, and one or more substances selected from a hot melt resin, a thermoplastic resin, and a plasticizer [component (B)] ] The molded article of the thermoplastic elastomer composition obtained by molding the mixture and then crosslinking the organic polymer (a) having a crosslinkable functional group at the molecular terminal. 17. A gasket material comprising the thermoplastic elastomer composition according to claim 1. Description: 18. A sheet material comprising the thermoplastic elastomer composition according to claim 1. Description: 19. A vibration control material comprising the thermoplastic elastomer composition according to claim 1. Description: 20. A sealing plug comprising the thermoplastic elastomer composition according to claim 1. Description: 21. An organic polymer (a) having a crosslinkable functional group at a molecular terminal, and one or more substances selected from a hot melt resin, a thermoplastic resin, and a plasticizer [component (B)] ] The curable composition containing these.