JP2003192848A - Oil-resistant thermoplastic elastomer composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which has excellent thermal ageing resistance, weather resistance, low temperature physical properties, oil resistance and flexibility, and to provide a molded article, such as a hose, using the thermoplastic elastomer composition. <P>SOLUTION: This thermoplastic elastomer composition is obtained by dynamically thermally treating a mixture comprising (A) an olefinic resin, (B) an unsaturated group-containing acrylic rubber, and (D) an inorganic filler in the presence of (E) a cross-linking agent and is characterized in that the component (B) comprises (B1) 55 to 94.99 wt.% of constituent units originated from an alkyl acrylate and/or an alkoxyalkyl acrylate monomers, (B2) 0.01 to 20 wt.% of constituent units originated from a monomer having a carbon-carbon double bond in a side chain, (B3) 5 to 30 wt.% of constituent units originated from an unsaturated acrylonitrile monomer, and (B4) 0 to 30 wt.% of constituent units originated from a monomer capable of being copolymerized with the above-described monomers, and a molded article produced from the thermoplastic elastomer composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition having excellent heat aging resistance, weather resistance, low temperature physical properties, oil resistance, and flexibility, and a molded article using the same.

[0002]

2. Description of the Related Art A hose is known in which an inner pipe, a reinforcing layer and an outer pipe are laminated in this order in an annular shape. These hoses have inner and outer pipes made of rubber such as vulcanized rubber or polyurethane.
It is made of resin such as polyester and nylon, and the reinforcing layer is braided in a braid or spiral shape with fibers such as nylon, polyester, rayon, vinylon, and aramid fibers, and rubber cement or urethane adhesive is used between layers. Have been treated with adhesive. However, a so-called rubber hose using rubber for the inner and outer pipes requires a vulcanization process, which complicates the manufacturing process and inevitably results in a high price. A so-called resin hose in which a thermoplastic resin is simply used for the inner and outer tubes has a problem that the hose is hard and inferior in flexibility, and a kink phenomenon occurs when the hose is bent. As a proposal for solving such a problem, at least a part of a vulcanized thermoplastic resin such as an olefin-based thermoplastic resin, a vinyl chloride-based thermoplastic resin, an amide-based thermoplastic resin, or an ester-based thermoplastic resin is crosslinked. A hose using a thermoplastic elastomer composition in which a rubber phase is dispersed has been proposed (see, for example, JP-A-6-64102). However, from the viewpoint of an oil-resistant hose, a general olefin-based thermoplastic elastomer composition is composed of polypropylene and ethylene-propylene-based rubber and does not have a polar group in its molecular structure, and therefore has a high oil resistance. It has the disadvantage of being scarce. On the other hand, in order to improve oil resistance, a thermoplastic elastomer composed of polypropylene and acrylonitrile-butadiene rubber, and a thermoplastic elastomer composed of ethylene-acrylic ester copolymer rubber and polyolefin have been proposed, but the former Although it is excellent in oil resistance, it has a drawback that it is inferior in heat resistance and weather resistance because it has a double bond in the molecular structure, and the latter is excellent in heat resistance and weather resistance. Since it has an ethylene part in its molecular structure, its oil resistance is insufficient, and it is hardly usable in fuel oil systems, which is a drawback.
As a compromise between these, a ternary blend system of polypropylene / acrylonitrile-butadiene rubber / ethylene-acrylic ester copolymer rubber has been devised. However, the balance between heat resistance and oil resistance was insufficient.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic elastomer composition having excellent heat aging resistance, weather resistance, low temperature physical properties, oil resistance, and flexibility, and a molded article using the same. And

[0004]

Means for Solving the Invention As a result of intensive studies aimed at achieving the above object, the inventors of the present invention have contained (A) an olefin resin, (B) a specific acrylic rubber, and (D) an inorganic filler. By dynamically heat-treating the mixture in the presence of (E) a cross-linking agent, it was found that a thermoplastic elastomer composition having excellent heat aging resistance, weather resistance, low temperature physical properties, oil resistance, and flexibility can be obtained, The present invention has been completed.

That is, the present invention provides the following thermoplastic elastomer composition and molded articles using the same. [1] Obtained by dynamically heat treating a mixture containing (A) an olefin resin, (B) an unsaturated group-containing acrylic rubber, and (D) an inorganic filler in the presence of (E) a cross-linking agent. Thermoplastic elastomer composition, wherein component (B) is (B1) acrylic acid alkyl ester and / or acrylic acid alkoxyalkyl ester monomer-derived structural unit 55 to 94.99% by weight, (B2) carbon-carbon Structural unit 0.01 to 2 derived from monomer having double bond in side chain
0% by weight, (B3) 5 to 30% by weight of a structural unit derived from an unsaturated acrylonitrile monomer, and (B4) 0 to 30% by weight of a structural unit derived from a monomer copolymerizable therewith (however,
A thermoplastic elastomer composition comprising (B1) + (B2) + (B3) + (B4) = 100% by weight. [2] The thermoplastic elastomer composition according to the above [1], wherein the olefin resin (A) is a propylene resin. [3] The thermoplastic elastomer composition according to the above [1] or [2], wherein the inorganic filler (D) is silica. [4] The above [1] which further comprises (C) a compatibilizing agent.
~ The thermoplastic elastomer composition according to any one of [3]. [5] The (C) compatibilizer is at least one selected from the group consisting of an ethylene-acrylic acid ester copolymer, a functional group-containing polyolefin, and a polyolefin-glycol (meth) acrylate. The thermoplastic elastomer composition according to [4]. [6] The thermoplastic elastomer composition according to any one of the above [1] to [5], which further comprises (F) a plasticizer having a molecular weight of 400 to 1000. [7] The thermoplastic elastomer composition according to any one of [1] to [6], which further comprises (G) an extender oil. [8] Further comprises (H) an aromatic oligomer [1]
~ The thermoplastic elastomer composition according to any one of [7]. [9] A molded product using the thermoplastic elastomer composition according to any one of [1] to [8]. [10] The molded product according to [9], which is a hose.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the thermoplastic elastomer composition of the present invention will be specifically described below. The thermoplastic elastomer composition of the present invention comprises a mixture containing (A) an olefin resin, (B) an unsaturated group-containing acrylic rubber, and (D) an inorganic filler in the presence of (E) a cross-linking agent. 55 to 94.99% by weight of the constituent unit derived from the (B1) acrylic acid alkyl ester and / or acrylic acid alkoxyalkyl ester monomer, which is a thermoplastic elastomer composition obtained by heat treatment ,
(B2) 0.01 to 20% by weight of a structural unit derived from a monomer having a carbon-carbon double bond in a side chain, (B3) 5 to 30% by weight of a structural unit derived from an unsaturated acrylonitrile monomer, and ( B4) 0 to 30% by weight of structural units derived from monomers copolymerizable with these (provided that (B1) + (B2) + (B3)
+ (B4) = 100% by weight). Hereinafter, each component will be described more specifically.

(A) Olefin Resin The (A) olefin resin (hereinafter also referred to as “(A) component”) used in the present invention has 2 to 2 carbon atoms.
0 homo- or copolymers of α-olefins. Specific examples of the olefin resin include the following (co) polymers. (1) Ethylene homopolymer (manufacturing method may be low-pressure method or high-pressure method) (2) Copolymerization of ethylene with 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate or ethyl acrylate Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 20 mol% or less of other α-olefin (5) Propylene and 30 mol%
The following block copolymers with other α-olefins (6)
1-Butene homopolymer (7) Random copolymer of 1-butene and 10 mol% or less of other α-olefin (8) 4−
Methyl-1-pentene homopolymer (9) 4-methyl-1-
Random copolymer of pentene and 20 mol% or less of other α-olefin. Specific examples of the α-olefin include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Among the above-mentioned olefin resins, a propylene homopolymer and a random copolymer of propylene and 20 mol% or less of another α-olefin are particularly preferable. The above-mentioned olefin resins can be used alone or in combination.

When the olefin resin used in the present invention is a crystalline olefin resin, the crystallinity determined by X-ray method is usually 50% or more, preferably 55% or more. The density is 0.89 g / cm ³ or higher, more preferably at maximum peak temperature by differential scanning calorimetry it is preferable that the crystalline olefin resin be 0.90~0.94g / cm ^3, i.e. the melting point (hereinafter It is preferable that “Tm” is 100 ° C. or higher (more preferably 120 ° C. or higher). If Tm is less than 100 ° C, sufficient heat resistance and strength tend not to be exhibited. In addition, the melt flow rate (hereinafter simply referred to as “MFR”) (temperature 2
30 ° C., load 2.16 kg) is preferably 0.1-10
It is 0 g / 10 minutes, more preferably 0.5 to 80 g / 10 minutes. If the MFR is less than 0.1 g / 10 minutes, the kneading processability and extrusion processability of the elastomer composition tend to be insufficient. On the other hand, if it exceeds 100 g / 10 minutes, the strength tends to decrease.

Therefore, the olefin resin used in the present invention has a crystallinity of 50% or more and a density of 0.89 g / cm.
³ or more, the content of ethylene units is 20 mol% or less, Tm is 140 to 170 ° C., MFR is 0.1 to 100 g / 10 minutes, and polypropylene and /
Alternatively, it is particularly preferable to use a copolymer of propylene and ethylene.

As the olefin resin, besides the above crystalline olefin resin, an amorphous olefin resin may be used.

As the amorphous olefin resin, homopolymers such as atactic polypropylene and atactic poly-1-butene, propylene (containing 50 mol% or more) and other α-olefins (ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-
Octene, 1-decene, etc.), 1-butene (containing 50 mol% or more) and other α-olefins (ethylene, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc.) and the like.

The melt viscosity of the amorphous olefin resin at 190 ° C. is not more than 50,000 cSt, preferably 100.
To 30,000 cSt, more preferably 200 to 20,0
00cSt. Further, the crystallinity by X-ray diffraction measurement is less than 50%, preferably 30% or less, more preferably 20% or less. Density is 0.85-0.89g / c
m ^3, it is more preferably at 0.85~0.88g / cm ^3. Furthermore, G of amorphous olefin resin
The number average molecular weight Mn in terms of PC method polystyrene conversion is 100.
0 to 20,000 (more preferably 1500 to 15,000)
0) is preferable.

Usually, the amorphous olefin resin is used in combination with the crystalline olefin resin, but only one of them may be used.

The proportion of the component (A) in the thermoplastic elastomer composition is preferably 10 to 70% by weight, more preferably 10 to 50%, when the total amount of (A) and (B) is 100% by weight. % By weight, most preferably 15-30
% By weight. If it is less than 10% by weight, the phase structure (morphology) of the thermoplastic elastomer composition finally obtained
However, the good sea-island structure [olefin resin is the sea (matrix), cross-linked rubber is the island (domain)], which is a characteristic of the dynamically cross-linked thermoplastic elastomer, may cause deterioration of molding processability and mechanical properties. If it exceeds 70% by weight, the flexibility and rubber elasticity of the finally obtained thermoplastic elastomer composition will be decreased, which is not preferable.

(B) Unsaturated Group-Containing Acrylic Rubber The (B) unsaturated group-containing acrylic rubber used in the present invention (hereinafter, also referred to as “component (B)”) is (B1) an alkyl acrylate and / or A structural unit derived from an acrylic acid alkoxyalkyl ester monomer (hereinafter,
(Also referred to as "B1 component") 55 to 94.99% by weight,
(B2) Structural unit derived from a monomer having a carbon-carbon double bond in the side chain (hereinafter, also referred to as "B2 component") 0.01 to
20% by weight and (B3) unsaturated acrylonitrile monomer-derived structural unit (hereinafter, also referred to as "B3 component") 5 to 3
It is composed of 0% by weight and (B4) 0 to 30% by weight of a structural unit derived from a monomer copolymerizable therewith (hereinafter, also referred to as "B4 component"). However, (B1), (B
The total of 2), (B3) and (B4) is 100% by weight. The component (B) is prepared by copolymerizing a monomer mixture in the presence of a radical polymerization initiator.

Examples of the alkyl acrylate as the component B1 after the copolymerization include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate. , Hexyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, and the like, and these can be used alone or in combination of two or more. Of these, ethyl acrylate and n-butyl acrylate are particularly preferable.

Examples of the alkoxyalkyl acrylate as the component B1 after copolymerization include methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate, Examples thereof include butoxyethyl acrylate, and these can be used alone or in combination of two or more kinds. Of these, methoxymethyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, and ethoxyethyl acrylate are particularly preferable.

The constituent ratio of the component B1 in the component (B) [copolymerization ratio in the component (B)] is 55 to 94.9.
It is 9% by weight, preferably 60 to 94.98% by weight.
If this proportion is less than 55% by weight, the thermoplastic elastomer composition obtained will have excessive hardness and will not have a suitable elastic state. On the other hand, if this proportion exceeds 94.99% by weight, the oil resistance becomes poor.

The monomer having a carbon-carbon double bond in the side chain as the B2 component after copolymerization is a monomer for introducing a cross-linking point into the (B) component, for example, dihydrodicyclo acrylate. Pentenyl, dihydrodicyclopentenyl methacrylate, dihydrodicyclopentenyl itaconate, dihydrodicyclopentenyl maleate, dihydrodicyclopentenyl fumarate, dihydrodicyclopentenyloxyethyl acrylate (DCPEA), dihydrodicyclopentenyloxyethyl methacrylate , Dihydrodicyclopentenyloxyethyl itaconate, dihydrodicyclopentenyloxyethyl maleate, dihydrodicyclopentenyloxyethyl fumarate, vinyl methacrylate (CAS No. 4245-38-8), vinyl acrylate (CAS N .2177-18-6), methacrylic acid 1,1-dimethyl propenyl, acrylic acid 1,1
-Dimethylpropenyl, 3,3-dimethylbutenyl methacrylate, 3,3-dimethylbutenyl acrylate, divinyl itaconate, divinyl maleate, divinyl fumarate, dicyclopentadiene, methyldicyclopentadiene, ethylidene norbornene, 1, 1-dimethylpropenyl methacrylate, 1,1-dimethylpropenyl acrylate, 3,3-dimethylbutenyl methacrylate,
3,3-Dimethylbutenyl acrylate, vinyl 1,1
-Dimethylpropenyl ether, vinyl 3,3-dimethylbutenyl ether, 1-acryloyloxy-1-phenylethene, 1-acryloyloxy-2-phenylethene, 1-methacryloyloxy-1-phenylethene, 1-methacryloyloxy- Examples thereof include 2-phenylethene, and these can be used alone or in combination of two or more kinds. Among these, dihydrodicyclopentenyl acrylate, dihydrodicyclopentenyl methacrylate, dihydrodicyclopentenyloxyethyl acrylate, dihydrodicyclopentenyloxyethyl methacrylate, vinyl methacrylate and vinyl acrylate are particularly preferable.

The composition ratio of the B2 component in the component (B) [copolymerization ratio in the component (B)] is 0.01 to 20.
% By weight, preferably 0.02 to 8% by weight. If this proportion is less than 0.01% by weight, the thermoplastic elastomer composition obtained will have an insufficient degree of crosslinking and an insufficient tensile strength, and will not have suitable mechanical strength. On the other hand, if this proportion exceeds 20% by weight, the hardness of the resulting thermoplastic elastomer composition becomes excessively high, which is not preferable.

Examples of the unsaturated acrylonitrile monomer serving as the B3 component after the copolymerization include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These can be used alone or in combination of two or more. Of these, acrylonitrile is particularly preferable. The proportion of the B3 component used [the copolymerization proportion of the component (B)] is 5 to 30% by weight, preferably 10 to 30% by weight. When it is less than 5% by weight, the oil resistance of the obtained thermoplastic elastomer composition is insufficient, while when it exceeds 30% by weight, the hardness of the obtained thermoplastic elastomer composition becomes high, which is not preferable.

The other copolymerizable monomer to be the B4 component after copolymerization is particularly preferably a monomer copolymerizable with the above-mentioned monomers to be the B1 component, B2 component and B3 component. It is not limited, for example, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 1-methylcyclohexyl methacrylate, cyclohexyl methacrylate, chlorobenzyl methacrylate, 1-phenylethyl methacrylate, 1,2-diphenylethyl methacrylate, diphenylmethyl methacrylate, furfuryl. Monofunctional methacrylates such as methacrylate, 1-phenylcyclohexyl methacrylate, pentachlorophenyl methacrylate, pentabromophenyl methacrylate; styrene, vinyltoluene, vinylpyridyl , Α-methylstyrene, vinylnaphthalene, halogenated styrene, acrylamide, methacrylamide, N-methylolacrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, (meth) acrylic acid ester of alicyclic alcohol (eg cyclohexyl acrylate), (Meth) acrylic acid ester of aromatic alcohol (for example, benzyl acrylate) and the like can be mentioned. By adding monofunctional methacrylate,
After polymerization of the component (B), the crumbs obtained do not have blocking and are easy to handle. Further, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, 1,6 hexanediol-di (meth) acrylate, trimethylolpropane-di (meth) acrylate. , Pentaerythritol tri (meta)
Acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, diisopropenylbenzene, trivinylbenzene, hexamethylene di (meth)
Examples thereof include polyfunctional unsaturated monomers such as acrylate. Copolymers of polyfunctional unsaturated monomers become partially crosslinked rubber, which improves the skin of molded products and reduces the amount of crosslinking agents and crosslinking aids added during dynamic crosslinking. This is effective for cost reduction. As the B4 component, methyl methacrylate, benzyl methacrylate and phenyl methacrylate are preferable, and methyl methacrylate is particularly preferable. The constituent ratio of the component B4 in the component (B) is 0 to 30% by weight, preferably 0 to 10% by weight.

The radical polymerization initiator used in copolymerizing the monomer mixture is not particularly limited, and examples thereof include peroxides such as potassium persulfate, p-menthane hydroperoxide, and methyl isopropyl ketone peroxide. And azo compounds such as azobisisobutyronitrile. The amount of the radical polymerization initiator to be used is 0.1 per 100 parts by weight of the monomer mixture.
001 to 1.0 parts by weight.

The copolymerization reaction for obtaining the component (B) can be carried out by a usual polymerization method such as suspension polymerization method, emulsion polymerization method or solution polymerization method. As the emulsifier in the emulsion polymerization method, any substance can be used as long as it can emulsify and disperse the monomer mixture, and for example, salts of alkyl sulfate, alkyl aryl sulfonate, and higher fatty acid can be used. The reaction temperature is usually 0 to
It is 80 ° C., and the reaction time is usually about 0.01 to 30 hours. The component (B) obtained as described above has a Mooney viscosity [ML1 + 4 (100 ° C.)] of 10 to 15.
It is preferably 0.

The proportion of the component (B) in the thermoplastic elastomer composition is preferably 90 to 30% by weight, more preferably 90 to 50%, when the total amount of (A) and (B) is 100% by weight. % By weight, particularly preferably 85-70
% By weight. (B) 30 unsaturated group-containing acrylic rubber
If it is less than wt%, the oil resistance of the finally obtained thermoplastic elastomer tends to deteriorate. On the other hand, if it exceeds 90% by weight, the phase structure (morphology) of the finally obtained thermoplastic elastomer composition is a good sea-island structure characteristic of the dynamically crosslinkable thermoplastic elastomer because the amount of the (A) olefin resin is small. (The polyolefin resin does not form the sea (matrix) and the crosslinked rubber particles do not form islands (domains), and the moldability and mechanical properties tend to deteriorate.

(C) Compatibilizer In the thermoplastic elastomer composition of the present invention, since the (A) olefin resin and the (B) unsaturated group-containing acrylic rubber are essentially incompatible or incompatible, It is preferable to add a compatibilizer having a structure similar to those of both components.
As the (C) compatibilizer (hereinafter, also referred to as “(C) component”) in the present invention, the solubility parameter (SP value) is (A) olefin resin (SP value: 7 to 8) and (B) unsaturated. Polymer in the middle of the group-containing acrylic rubber (SP value: 9 to 10), specifically, the solubility parameter (SP
A polymer having a (value) in the range of 7.2 to 9.5 is used. The SP value used here is the polymer handbook second edition (Polymer Handbook; Seco).
nd Edition: BRANDRUP) 339
It is calculated by the method of HOY described on the page. Examples of polymers falling within this range include ethylene-acrylic acid ester copolymers, functional group-containing polyolefins, polyolefin-glycol (meth) acrylates, low nitrile-containing acrylonitrile-butadiene rubber or hydrogenated products thereof, and styrene-butadiene blocks. Copolymer or hydrogenated product thereof, styrene-isoprene block copolymer or hydrogenated product thereof, styrene-butadiene rubber, butadiene rubber, isoprene rubber, epichlorohydrin rubber, chloroprene rubber, chlorinated ethylene-α-olefin copolymer, Examples thereof include ethylene / vinyl ester copolymers and chlorosulfonated polyethylene. Among these, particularly ethylene-acrylic acid ester copolymers, functional group-containing polyolefins and polyolefin-glycols (meth)
At least one selected from the group consisting of acrylates is preferable.

The ethylene-acrylic acid ester copolymer has ethylene as an essential component and has 1 to 8 carbon atoms.
Of an alkyl acrylate having an alkyl group, an alkoxy group having 1 to 4 carbon atoms, and an alkoxyalkyl acrylate having an alkylene group having 1 to 4 carbon atoms. Polymers may be mentioned. Further, a copolymer having ethylene, an acrylic ester and vinyl acetate as a main skeleton, or a copolymer of ethylene and an acrylic ester and a carboxyl group-containing monomer and / or an epoxy group-containing monomer as a crosslinking point. Can be mentioned. This copolymer may be a copolymer of another copolymerizable monomer that can be copolymerized with the above-mentioned monomer, such as acrylonitrile.

Specific examples thereof include carboxyl group-containing monomers such as ethylene-methyl acrylate copolymer, ethylene-methyl acrylate-acrylic acid copolymer and ethylene-methyl acrylate-methacrylic acid copolymer. Epoxy group-containing monomer such as copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl acrylate copolymer, ethylene-methyl acrylate-allyl glycidyl ether copolymer Copolymer, ethylene-alkyl acrylate-vinyl acetate copolymer, ethylene-alkyl acrylate-vinyl acetate-glycidyl methacrylate copolymer, ethylene-alkyl acrylate-vinyl acetate-glycidyl acrylate copolymer, ethylene-alkyl acrylate − Vinegar And a copolymer of an epoxy group-containing monomers such as vinyl chromatography allyl glycidyl ether copolymer. The number average molecular weight of the copolymer is preferably 3,000 to 500,000. More preferably, the Mooney viscosity [ML1 + 4 (100 ° C)] is 10 to 10.
It is preferable to use the one of 150. These ethylene-acrylic acid ester copolymers may be used alone or in combination of two or more.

The functional group-containing polyolefin means a polymer obtained by modifying a polyolefin resin or a polyolefin rubber with a functional group. The polyolefin resin or polyolefin rubber is a resin or rubber polymerized mainly with α-olefin. As α-olefin, ethylene, propylene, 1-butene, 4
-Methyl-1-butene, 4-methyl-1-pentene and the like can be mentioned, with preference given to ethylene and propylene.
These α-olefins can be used alone or in combination of two or more. Examples of the polyolefin rubber include ethylene-propylene rubber and ethylene-propylene-diene rubber. As a functional group,
It is preferably at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, an acid anhydride, and a hydroxyl group. Examples thereof include functional group-containing polyolefins graft-modified with unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether. Further, specific examples of the functional group-containing compound used for modification, maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, maleic anhydride, fumaric anhydride,
Itaconic anhydride and the like are preferable, and maleic anhydride is preferable. As the modification method, a polyolefin resin or a polyolefin rubber is grafted with a functional group-containing compound by using a radical initiator in an alkylaromatic hydrocarbon solvent at a temperature of 115 ° C. or higher, or an extremely small amount of an alkyl peroxide. Examples thereof include a method of kneading an oxide, preferably an aliphatic bifunctional peroxide, a functional group-containing compound, and a polyolefin resin and / or a polyolefin rubber at a temperature of 200 ° C. or higher. Specific examples of the functional group-containing polyolefin include maleic anhydride-modified LDP
E (Low density polyethylene), Maleic anhydride modified HDP
E (high density polyethylene), maleic anhydride modified LLD
Examples thereof include PE (linear low-density polyethylene), maleic anhydride-modified EVA (ethylene-vinyl acetate copolymer), maleic anhydride-modified PP (polypropylene), and the like, preferably maleic anhydride-modified LLDPE.

As the polyolefin-glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, ethoxy polyethylene. Examples thereof include glycol mono (meth) acrylate, methoxy polypropylene glycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, and the like. These may be used alone or in combination of two or more. The degree of polymerization of polyolefin glycol is 2-10.

The blending amount of the component (C) is 0.5 / 9 in terms of the weight ratio of the component (C) and the component (B) ((C) / (B)).
9.5-20 / 80, preferably 1 / 99-10 / 9
0, and more preferably 2/98 to 7.5 / 92.5.

(D) Inorganic filler As the inorganic filler (D) used in the present invention (hereinafter also referred to as “component (D)”), an inorganic filler of a usual rubber composition can be used. Silica, ground calcium carbonate, gourd powder, light calcium carbonate, ultrafine activated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin, calcined clay, pyrolite clay, silanized clay, synthetic calcium silicate, synthetic silica Magnesium acid, synthetic aluminum silicate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, kaolin, sericite, talc, fine powder talc, wollastonite, zeolite, bentonite, mica, asbestos, PMF (Processed Min)
eal fiber, sepiolite, potassium titanate, elestadite, gypsum fiber, glass balun, silica balun, hydrotalcite, fly ash balun, silas balun, carbon balun, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, etc. . These may be used alone or in admixture of two or more. Among these, silica is particularly preferable because of its high oil absorption.

The amount of the component (D) added is 0.1 to 5 with respect to 100 parts by weight of the total amount of the components (A) and (B).
It is 0 part by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight. If the amount is less than 0.1 parts by weight, the viscosity of the component (B) decreases at high temperature, so that the component (B) easily sticks to the rotor, casing, etc. of the mixer. The oil absorption becomes insufficient and the adhesion during kneading becomes severe. On the other hand, if it exceeds 50 parts by weight, the viscosity becomes excessively high, or the compression set, which is an index of flexibility of the obtained thermoplastic elastomer composition, becomes large, which is not preferable.

When silica is used, a silane coupling agent is usually used for the surface treatment of silica. The silane coupling agent is not particularly limited,
For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltrichlorosilane, vinyltriacetoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-amino. Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropyltris (β-methoxyethoxy) silane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxylane, methyltriethoxylane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, N- [β Examples include-(N-vinylbenzalamino) ethyl] -γ-aminopropyltrimethoxysilane-hydrochloride. These silane coupling agents can be used alone or in combination of two or more. The blending amount of the silane coupling agent is
It is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B).
Parts by weight. In this case, if the amount of the silane coupling agent is less than 0.1 parts by weight, the thermoplastic elastomer composition obtained may have insufficient tensile properties, compression set, etc., and if it exceeds 10 parts by weight. However, the physical properties of the crosslinked rubber may be deteriorated and the rubber elasticity may be impaired.

The silica filler has a pH of 2 to 10, preferably 3 to 8, and particularly preferably 4 to 6. If the pH is lower than 2, the crosslinking rate will be slow, and if it is higher than 10, scorch tends to occur. The oil absorption (cc / 100g) is 150 to 300, preferably 200 to 300. When it is less than 150, the viscosity at the time of mixing the component (B) and the component (F) in the production process of the thermoplastic elastomer of the present invention is low and the tackiness becomes severe, which is a practical problem. On the other hand, if it exceeds 300, the viscosity becomes excessively high, which is not preferable.

(E) Crosslinking Agent The (E) crosslinking agent (hereinafter referred to as "(E)" used in the present invention.
(Also referred to as “component”) is a compound capable of cross-linking at least one unsaturated group-containing acrylic rubber in the composition by dynamic heat treatment at a temperature equal to or higher than the melting point of the olefin resin. The cross-linking agent is not particularly limited as long as it is a cross-linking agent capable of cross-linking a polymer compound having a double bond in the molecule, and examples thereof include sulfur, organic sulfur-containing compounds, organic peroxides, and resins. , Quinone derivatives, polyhalides, bis (dioxotriazoline) derivatives, aldehydes, epoxy compounds, amine-borane complex,
Dipolar compounds are mentioned. Further, methylhydrogensiloxane used for platinum crosslinking by hydrosilylation reaction in the presence of a platinum catalyst can be mentioned. Among these cross-linking agents, sulfur, organic sulfur-containing compounds, organic peroxides,
Methyl hydrogen siloxane is preferable, and organic peroxide is more preferable. Component (E) can be used alone or in 2
A mixture of two or more species can be used. The amount of these crosslinking agents used is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, relative to 100 parts by weight of the component (B) of the present invention.

The organic peroxide preferably has a decomposition temperature of 150 ° C. or higher for obtaining a one-minute half-life (half-life of 1 minute). Specifically, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-)
Di-t-butylperoxycyclohexyl) propane,
1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t
-Butyl peroxylaurate, 2,5-dimethyl-
2,5-di (m-toluoyl peroxy) hexane, t
-Butyl peroxyisopropyl monocarbonate, t
-Butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-bis ( t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′bis (T-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 Diisopropylbenzene hydroperoxide, t- butyl trimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t
-Hexyl hydroperoxide, t-butyl hydroperoxide and the like. The amount of the organic peroxide added is 0.3 to 100 parts by weight of the component (B) of the present invention.
15 parts by weight, preferably 0.5 to 10 parts by weight.
If the amount is less than 0.3 parts by weight, the crosslinking time becomes very long and the crosslinking tends to be insufficient. If the amount added exceeds 15 parts by weight, the crosslinked product tends to be hard and brittle.

The above organic peroxides can be used alone or in admixture of two or more. In the present invention, a uniform and gentle crosslinking reaction can be carried out by using the organic peroxide in combination with a suitable crosslinking aid. Examples of such a cross-linking aid include powdered sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, sulfur such as dipentamethylene thiuram tetrasulfide, or sulfur compounds; p-quinone oxime, p, p′-diamine. Oxime compounds such as benzoylquinone oxime; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N, N'-m
Examples thereof include polyfunctional monomers such as phenylene bismaleimide, N, N′-toluylene bismaleimide, maleic anhydride, divinylbenzene and zinc di (meth) acrylate. Among these crosslinking aids, p, p '
-Dibenzoylquinone oxime, N, N'-m-phenylene bismaleimide, divinylbenzene are preferred. In addition, N, N'-m-phenylene bismaleimide can act as a cross-linking agent alone. The cross-linking aids can be used alone or in admixture of two or more. The amount of the crosslinking aid used is 0 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the component (B). When sulfur is used as a cross-linking agent, thiazoles such as mercaptobenzothiazole, thiurams such as tetramethylthiuram disulfide, guanidines such as diphenylguanidine, and dithiocarbamate salts such as zinc dimethyldithiocarbamate serve as cross-linking accelerators. It can be used effectively. When an organic sulfur-containing compound is used as the cross-linking agent, for example, tetramethylthiuram disulfide or 4,4'-dithiomorpholine which are thiuram type accelerators can be effectively used as the cross-linking accelerator. The amount of these crosslinking accelerators used is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the component (B) of the present invention.

(F) Plasticizer The thermoplastic elastomer composition of the present invention may further contain (F) a plasticizer, if necessary, in addition to the components (A) and (B). Used in the present invention (F)
As the plasticizer (hereinafter, also referred to as “(F) component”), an ordinary plasticizer of a rubber composition can be used, but a plasticizer having excellent heat resistance is preferable, and examples thereof include an ether type and an ether having excellent heat resistance. Examples thereof include ester type and trimellitic acid type plasticizers. Examples of ether plasticizers include aliphatic dicarboxylic acids condensed with alkoxypolyoxyethylene alcohols. Specific examples include Adeka Sizer RS-705 manufactured by Asahi Denka Kogyo Co., Ltd., Monosizer W-264 manufactured by Dainippon Ink and Chemicals, Inc., and the like. The ether ester plasticizer is not particularly limited with regard to its production method, but it is easily obtained by reacting 2-ethylhexylic acid and ether glycol at a molar ratio of 2: 1. For example, it can be obtained by reacting a mixed ether glycol containing a predetermined amount of pentaethylene glycol, hexaethylene glycol, heptaethylene glycol or the like with 2-ethylhexylic acid by a conventional method, but pentaethylene glycol, hexaethylene glycol or heptaglycol It can also be produced by separately mixing ethylene glycol and the like with 2-ethylhexyl acid by a conventional method and mixing them so that the average degree of polymerization of polyethylene glycol becomes 5 to 10. Specifically, Asahi Denka Kogyo KK Adeka Sizer RS-107, RS-10
00, RS-735, RS-700, etc. are applicable. Examples of the trimellitic acid plasticizer include trimellitic acid esters formed by condensing three carboxylic acids of trimellitic acid with alcohols. For example, trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, triamyl trimellitate, trihexyl trimellitate,
Triheptyl trimellitate, Tri-n trimellitate
-Octyl, Tri-2-ethylhexyl trimellitate, Trinonyl trimellitate, Tris (decyl) trimellitate, Tris (dodecyl) trimellitate, Tris (tetradecyl) trimellitate, Tris trimellitate (C8-C12 mixture) Alkyl), tris trimellitate (C7 to C9 mixed alkyl), trilauryl trimellitate and the like. Specifically, Asahi Denka Kogyo KK Adeka Sizer C-8, C-880, C-79, C8
10, C-9N, C-10, etc. are applicable. The molecular weight of these plasticizers is preferably 400-1000. More preferably, it is 500-900. Below 400,
The heat resistance is insufficient, and if it exceeds 1000, the cold resistance and compression set are poor, which is not preferable. The plasticizers can be used alone or in combination of two or more kinds. The above-mentioned plasticizer is used as the component (A) and the component (B) during the production of the thermoplastic elastomer composition.
It may be added to the component or may be added to the component (B) in advance.

The blending amount of the above plasticizer can be 0 to 100 parts by weight, preferably 5 to 70 parts by weight, more preferably 10 parts by weight, per 100 parts by weight of the total amount of the components (A) and (B). ˜50 parts by weight. If it exceeds 100 parts by weight, the plasticizer tends to bleed out from the finally obtained thermoplastic elastomer composition, and the mechanical strength and rubber elasticity tend to decrease.

(G) Extending oil The thermoplastic elastomer composition of the present invention may further contain (G) an extending oil, if necessary. The extender oil used in the present invention (hereinafter also referred to as “(G) component”) is
Extending oils normally used in rubber compositions can be used, but aromatic and naphthenic extending oils are preferred. In particular, ASTM D3238-95 (2000
Aroma carbon (CA%), naphthene carbon (CN%), and paraffin carbon (CF%) in the ring analysis by the n-d-M method described in (Yearly Reapproval) are 3 to 60, 20 to 50, and 0 to 6, respectively.
0 (however, CA + CN + CF = 100) is more preferable. If the CF exceeds 60%, the mechanical strength of the thermoplastic elastomer composition of the present invention and the surface texture of the molded product may be poor. The amount of the component (G) is 0 per 100 parts by weight of the total amount of the components (A) and (B).
-50 parts by weight, preferably 1-20 parts by weight.

(H) Aromatic Oligomer The thermoplastic elastomer composition of the present invention may further contain (H) aromatic oligomer, if necessary. The aromatic oligomer used in the present invention (hereinafter, also referred to as “(H) component”) has a weight average molecular weight of 200.
To about 10,000 aromatic oligomers, and examples thereof include resins mainly containing an aromatic ring skeleton. Specific examples thereof include coumarone indene resin, xylene resin,
Examples thereof include phenol novolac resin, styrenated phenol resin, naphthalene resin, and the like, and coumarone indene resin and naphthalene resin are preferable. If the weight average molecular weight is less than 200, the mechanical strength of the molded product is insufficient, and 1
When it exceeds 50,000, the kneading property is deteriorated. The blending amount of the component (G) is 0 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the total amount of the components (A) and (B). If it exceeds 20 parts by weight, the tackiness may be increased and the kneading property may be deteriorated.

Further, various compounding agents can be added to the thermoplastic elastomer composition of the present invention within a range that does not impair the performance of the thermoplastic elastomer composition of the present invention. Compounding agents include lubricants, metal oxides, reinforcing agents,
Examples of the softening agent other than the component (G), an antiaging agent, and the like.

Examples of the lubricant include stearic acid, oleic acid, lauric acid, dibutylammonium oleate, zinc stearate, calcium stearate, potassium stearate, sodium stearate, stearylamine and the like. These may be used alone or in admixture of two or more. Examples of the metal oxide include zinc white, activated zinc white, surface-treated zinc white, zinc carbonate, complex zinc white, complex active zinc white, surface-treated magnesium oxide, magnesium oxide, calcium hydroxide, ultrafine calcium hydroxide, Examples thereof include lead monoxide, red lead and lead white. These may be used alone or in admixture of two or more.

Examples of the softener include petroleum-based softeners other than the above component (G), vegetable oil-based softeners, and sub-softeners. Examples of the vegetable softener include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, and wax. Examples of the sub include black sub, white sub, candy sub, and the like. Anti-aging agents include naphthylamine-based, diphenylamine-based, p-phenylenediamine-based, quinoline-based, hydroquinone derivative-based, mono, bis, tris, polyphenol-based, thiobisphenol-based, hindered phenol-based, phosphite-based, imidazole System, nickel dithiocarbamic acid salt-based, phosphoric acid-based antiaging agents and the like.
These may be used alone or in combination of two or more.

Examples of the reinforcing agent include carbon black, specifically, SAF carbon black and ISAF.
Examples thereof include carbon black, HAF carbon black, FEF carbon black, GPF carbon black, SRF carbon black, FT carbon black, MT carbon black, acetylene carbon black and Ketjen black. These alone or 2
A mixture of two or more species can be used.

Method for Producing Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention allows the rubber to be crosslinked while kneading the thermoplastic resin and the rubber composition. It is a thermoplastic elastomer composition produced by crosslinking. By using such a production method, the obtained thermoplastic elastomer composition is such that at least a part of the crosslinked rubber phase, which is a discontinuous phase, is finely dispersed in a thermoplastic resin phase, which is a continuous phase. The resulting thermoplastic elastomer composition behaves in the same manner as the crosslinked rubber, and at least the continuous phase is the thermoplastic resin phase. Is possible.

In the production of the thermoplastic elastomer composition of the present invention, the components (A), (B), (D) and (E), and optionally (C), (F), (G),
The machine used for kneading the components such as (H) is not particularly limited, but a screw extruder, a kneader, a Banbury mixer, a twin-screw kneading extruder and the like are exemplified. Examples of the kneading processing method include the following two methods. (1) Components (B), (C), (D), (F), (G),
(H) is charged into a closed-type kneader (kneader, Banbury mixer, etc.) and kneaded by heating (150 to 160 ° C.), then component (A) is charged and melt-kneaded, and then pelletized by an extruder. To mold. Next, using a twin-screw kneading extruder, the pellets and the (E) cross-linking agent for dynamic cross-linking or further a cross-linking aid are kneaded, and the component (B) is dynamically mixed while being heated and melted (about 200 ° C) Crosslink. (2) First, the component (A) molded into pellets is charged from the first charging port of the twin-screw kneading extruder, and mixed and heated / melted by the twin screw. Ingredients (B), (C),
For (D), (F), (G), and (H), a kneading machine for rubber such as Banbury mixer is used, and if necessary, a lubricant, a reinforcing agent, an antiaging agent, etc. are added and kneaded. It is made into a so-called masterbatch that does not contain, and is prepared by pelletizing with a pelletizer for rubber. As described above, the component (A) is added to 2
After being heated and melted by a shaft kneading extruder, the pellets (B), (C), (D), (F),
Pellets of the rubber component containing (G) and (H) are charged from the second charging port of the twin-screw kneading extruder to disperse the rubber component in the component (A). After that, (E) a cross-linking agent or a cross-linking auxiliary agent is charged from the third and fourth charging ports of the twin-screw kneading extruder, and the (B) component is cross-linked (dynamically cross-linked) under kneading. Let By carrying out the crosslinking in this way,
Crosslinking can be performed in a state where the component (B) is sufficiently dispersed in the component (A), and the component (B) is in a sufficiently fine state.
A thermoplastic elastomer composition is prepared in which the component (B) is stably dispersed as the dispersed phase (domain) in the component (A) forming the continuous phase (matrix). In such a thermoplastic elastomer composition, the particle diameter of the crosslinked rubber composition as the dispersed phase is preferably 50 μm or less, and more preferably 10 to 1 μm.

Further, a reinforcing material, a softening agent,
When a compounding agent such as an antioxidant is added, the compounding agent for the component (B) may be added during the above kneading, but the compounding agents other than the crosslinking agent are mixed in advance before the above kneading. Is good.
The compounding agent for the component (A) may be mixed in advance before the kneading, or may be added during the kneading.

As the conditions for melt-kneading the components (A) and (B), or the components (A), (B) and components (C), the kneading temperature is, for example, 150 to 250 ° C., and particularly 1
It is preferably 50 to 200 ° C., and the shear rate at the time of kneading is 500 to 7000 / sec, particularly 500 to 2000 / sec.
Seconds are preferred. The entire melt-kneading time is 30 seconds to 10 minutes, and the crosslinking time after adding the crosslinking agent is 15 seconds to
It is preferably 5 minutes.

The thermoplastic elastomer composition of the present invention thus obtained is excellent in heat resistance, oil resistance, low temperature physical properties and flexibility. The application of such a thermoplastic elastomer composition of the present invention is not particularly limited, but it is preferably used when oil resistance and heat resistance are required. For example, not only various hose materials such as fuel oil, lubricating oil type oil resistant hose, oil cooler hose, air duct hose, power steering hose, control hose, intercooler hose, torque converter hose, oil return hose, vacuum sensing hose, heat resistant hose, etc. , Bearing seals, valve stem seals, various oil seals,
In addition to O-rings, packing, sealing materials such as gaskets, shock absorbing materials such as seismic isolation rubber and damping rubber, automobiles that require oil resistance and heat resistance such as belts, rolls, rubber plates, various diaphragms and oil level gauges. It is also suitable for parts around the engine.

[0052]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Parts and% in the examples and comparative examples are based on weight unless otherwise specified. Further, various measurements in Examples and Comparative Examples were based on the following methods. Preparation of Thermoplastic Elastomer Composition Olefin Resin, Unsaturated Group-Containing Acrylic Rubber, Compatibilizer, Inorganic Filler, Plasticizer, Crosslinking Agent, Extending Oil,
Aromatic oligomers and other additives were used.

(A) Olefin Resin Polypropylene Polymer "PP1": Density 0.90 g / c
m ³ , MFR (temperature 230 ° C, load 21N) 3g / 10
min, manufactured by Nippon Polychem, product name “Novatech PP M
A4 "

(B) Unsaturated Group-Containing Acrylic Rubber An unsaturated group-containing acrylic rubber was synthesized by the method described below. Synthesis Example 1 Ion-exchanged water 20 was placed in a nitrogen-substituted autoclave.
Add 0 parts and add ethyl acrylate (EA) 83.5
Parts, acrylonitrile (AN) 12.5 parts, dihydrodicyclopentenyloxyethyl acrylate (DCPE)
A) 100 parts of a monomer mixture consisting of 4 parts, 4 parts of sodium laurate, 0.25 part of p-menthane hydroperoxide, 0.01 part of ferrous sulfate and 0.025 sodium ethylenediaminetetraacetate. And 0.04 part of sodium formaldehyde sulfoxylate,
The emulsion was polymerized at a reaction temperature of 30 ° C. Polymerization conversion rate is almost 1
When it reached 00%, 0.5 part of N, N-diethylhydroxylamine was added to the reaction system to stop the copolymerization reaction (reaction time 1 hour). Then, the reaction product (latex) was taken out, and an aqueous calcium chloride solution (0.25%) was added to the reaction product to coagulate the unsaturated group-containing acrylic rubber. After thoroughly washing this coagulated product with water, about 90
An unsaturated group-containing acrylic rubber with Mooney viscosity [ML1 + 4 (100 ° C.)] 72 (this is referred to as ANM1) was obtained by drying at 3 ° C. for 3 to 4 hours. Synthetic Examples 2 and 3 and Comparative Synthetic Examples 1 and 2 In the same manner, the monomer mixtures shown in Table 1 below were copolymerized A
NM2 and ANM3 were obtained. In Synthesis Example 2, n-butyl acrylate (BA) and methyl methacrylate (MMA) were used. As a comparative sample for comparison with the present invention, the monomer mixture shown in Table 1 was similarly copolymerized to obtain an acrylic rubber A which was not the component (B) of the present invention.
CM1 and ACM2 were obtained.

[0055]

[Table 1]

(C) Compatibilizer ethylene-ethyl acrylate copolymer (C1): Showa Denko DuPont, product name "VAMAC-G" acrylonitrile-butadiene rubber (C2): AN content 20% by weight, JSR Corporation Made, product name "N250
S ”polypropylene glycol monomethacrylate (C
3): NOF CORPORATION, product name "Blenmer PP1000" Maleic anhydride-modified ethylene-propylene rubber (C
4): Mitsui Chemicals, product name "Tufmer MP0610" (D) Inorganic filler silica: Nippon Silica, product name "Nipseal NS" (E) Crosslinking agent 2,5-dimethyl-2,5-di (t- Butyl peroxy) hexane: manufactured by NOF CORPORATION, product name “Perhexa 25B
-40 "2,5-dimethyl-2,5-di (t-butylperoxy) hexine: manufactured by NOF CORPORATION, product name" Perhexin 25 "
B-40 "(F) Plasticizer trimellitic acid plasticizer: Asahi Denka Kogyo KK, product name" Adeka Sizer C-79 "Ether ester plasticizer: Asahi Denka Kogyo KK, product name" Adeka Sizer RS735 " Plasticizer: Asahi Denka Kogyo Co., Ltd., product name "ADEKA CIZER RS1000" (G) Extension oil: Fuji Kosan Co., Ltd., product name "Fuccol FLE"
X # 2050N "The analysis value by the nd-M method was CA 6%, CN 39%, C
P55%. (H) Aromatic oligomer: Nippon Steel Chemical Co., Ltd., product name “Cumaron Indene Resin G-90” Other additives Crosslinking aid (1): Sankyo Kasei: Divinylbenzene (purity 56%) Crosslinking aid (2) : Nippon Oil & Fats Co., Ltd. product name "TMPA" Antiaging Agent (1): 4,4 '(α, α-Dimethylbenzyl) diphenylamine: Ouchi Shinko Chemical Co., Ltd. Product Name "Nocrac CD" Antiaging Agent (2) : Pentaerythrityl-tetrakis [3- (3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate]: Ciba Specialty Chemicals, product name "Irganox 1010" Processing aid (1): Kao , Stearic acid processing aid (2): Kao, product name "Farmin 80" Lubricant: NOF Corporation, product name "PEG4000" Silane coupling agent: Toshiba Shi Corn Co., Ltd., trade name "T
SL8370 "

Example 1 20 parts by weight of "PP1" as the olefin resin (A) and "ANM as the acrylic rubber containing the unsaturated group (B)"
80 parts by weight of "1" as a compatibilizer (C) "VAMAC
-G ", 5 parts by weight, (D) an inorganic filler," Nipseal NS "10 parts by weight, (F) a plasticizer" Adeka Sizer RS735 "20 parts by weight, and other additives such as an antioxidant. 1.2 parts by weight, processing aid 1.5 parts by weight, lubricant 0.5 part by weight, silane coupling agent 0.
Using 5 parts by weight, the mixture was put into a 10-liter double-arm pressure kneader (manufactured by Moriyama Co., Ltd.) heated to 160 ° C., and kneaded at 40 rpm for 20 minutes. Then, the composition in molten state is
Pelletization was performed using a feeder ruder (manufactured by Moriyama Co., Ltd.) set at 0 ° C. and 40 rpm. Further, to the obtained pellets, 3 parts by weight of "Perhexa 25B-40" as a cross-linking agent and divinylbenzene (purity 56
%) 9 parts by weight (5 parts by weight as divinylbenzene), and mixed for 30 seconds with a Henschel mixer, a twin-screw extruder (manufactured by Ikegai Co., Ltd., model “PCM-45”, same direction complete meshing type screw Screw flight length L
And a screw diameter D ratio (L / D) of 33.5) are used to extrude while performing a dynamic heat treatment under the conditions of staying at 230 ° C. and 300 rpm for 2 minutes to obtain a pellet-like dynamic crosslinking type heat. A plastic elastomer composition was obtained.

Preparation of Thermoplastic Elastomer Test Pieces The obtained thermoplastic elastomer pellets were injection-molded using an injection molding machine (trade name N-100, manufactured by Nippon Steel Co., Ltd.) to obtain a thickness of 2 mm, a length of 120 mm and a width. A 120 mm sheet was prepared and subjected to various evaluations.

Evaluation of Thermoplastic Elastomer The kneadability of the obtained thermoplastic elastomer was measured with a kneader of 10 liters, and the fluidity was measured as a melt flow rate at 230 ° C. under a load of 10 kg. I wrote it in. Further, using the molded sheet of the thermoplastic elastomer obtained, hardness, mechanical properties (tensile rupture strength,
Tensile elongation at break) and oil resistance were evaluated by the following methods and are shown in Table 3. Hardness: Measured according to JIS-K6253 as an index of flexibility. Tensile breaking strength and tensile breaking elongation: JIS-K6251
It was measured according to. Oil resistance: In accordance with JIS-K6258, the rate of change in volume (ΔV) by the immersion test at 23 ° C. for 70 hours using Fuel C test oil and the rate of change in elongation in the tensile test (Sc
(EB)) The rate of change in strength (Sc (TB)) and the rate of change in hardness (CH) were determined. Heat resistance: According to JIS-K6257, a tensile test is performed after leaving the gear oven at 140 ° C. for 200 hours.
The rate of change in tensile breaking strength (Ac (TB)), the rate of change in tensile breaking elongation (Ac (EB)), and the change in hardness (AH) were measured. Compression set: 120 according to JIS-K6262
The value after 25% compression at 22 ° C. for 22 hours was measured. Low temperature test: Based on JIS-K6261, an impact embrittlement test was carried out under the condition of -20 ° C to examine the presence or absence of abnormality. Weather resistance: According to JIS-K6259, ozone concentration 5
The presence / absence of cracks was evaluated by evaluation under the conditions of 00 pphm, 40 ° C., 200 hours and static 40% elongation.

Examples 2 to 10 and Comparative Examples 1 to 5 Pelletized crosslinked thermoplastic elastomer compositions and test pieces were prepared in the same proportions as in Example 1 with the blending ratios shown in Table 2. However, in the case of Comparative Example 4, a large shrinkage was not obtained, and in the case of Comparative Example 5, pellets were not obtained due to poor kneading property in a kneader. Table 3 shows the evaluation results of the obtained thermoplastic elastomer composition.

[0061]

[Table 2]

[0062]

[Table 3]

From Table 3, it can be seen that Examples 1 to 10 are excellent in heat aging resistance, weather resistance, low temperature physical properties and oil resistance. The acrylic rubber (ACM1) of Comparative Example 1 is inferior in oil resistance and tensile strength, which are the features of the present invention, because the structural unit derived from the unsaturated acrylonitrile monomer is not copolymerized. The acrylic rubber (ACM2) of Comparative Example 2 is inferior in tensile strength and compression set because a structural unit derived from a monomer having a carbon-carbon double bond in its side chain is not copolymerized. Comparative Example 3 uses an acrylonitrile-butadiene rubber and an ethylene-acrylic ester copolymer rubber as rubber components in place of the unsaturated group-containing acrylic rubber of the present invention. In this case, oil resistance and heat resistance Inferior in sex. Comparative Example 4 was kneaded in the absence of a cross-linking agent, a good molded product was not obtained, and the evaluation of physical properties was impossible. Comparative Example 5
Since the component (D) was not contained in the sample, the tackiness during kneading was severe and the kneading could not be performed.

[0064]

The thermoplastic elastomer composition of the present invention is excellent in heat aging resistance, weather resistance, low temperature physical properties and oil resistance, and therefore requires oil resistance and heat resistance. For example, fuel oil and lubricating oil system oil resistance. Suitable for various hose materials such as heat hose, oil cooler hose, air duct hose, power steering hose, control hose, intercooler hose, torque converter hose, oil return hose, vacuum sensing hose, heat resistant hose.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tsukasa Toyoshima             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F term (reference) 3H111 AA02 BA15 BA34 CB02 CB14                       DA09 DA11 DA12 DB08 DB19                 4F071 AA10 AA14X AA20 AA33                       AA33X AB26 AE02 AE04                       AE17 AF02 AF45 AF46 AF57                       AH07 BA01 BB06 BC05                 4J002 BB03W BB05W BB06W BB07W                       BB073 BB12W BB13W BB14W                       BB17W BG04X BG073 BP03W                       DA036 DA047 DE076 DE146                       DE186 DE236 DE266 DG026                       DG046 DG056 DJ006 DJ016                       DJ026 DJ036 DJ046 DJ056                       DL006 EA019 EA029 EA039                       EH148 EK007 FD016 FD028                       FD147 FD203 FD209 GN00

Claims (10)

[Claims] 1. A mixture containing (A) an olefin resin, (B) an unsaturated group-containing acrylic rubber, and (D) an inorganic filler is dynamically heat treated in the presence of (E) a cross-linking agent. The resulting thermoplastic elastomer composition, wherein the component (B) is (B1) an acrylic acid alkyl ester and / or an acrylic acid alkoxyalkyl ester monomer-derived structural unit (55 to 94.99% by weight), and (B2) carbon. A constituent unit 0.01 derived from a monomer having a carbon double bond in the side chain
˜20% by weight, (B3) 5 to 30% by weight of a structural unit derived from an unsaturated acrylonitrile monomer, and (B4) 0 to 30% by weight of a structural unit derived from a monomer copolymerizable with these (provided that (( B1) + (B2) + (B3) + (B4) = 100
% By weight). 2. The thermoplastic elastomer composition according to claim 1, wherein the olefin resin (A) is a propylene resin. 3. The thermoplastic elastomer composition according to claim 1, wherein the inorganic filler (D) is silica. 4. The thermoplastic elastomer composition according to claim 1, further comprising (C) a compatibilizing agent. 5. The (C) compatibilizer is at least one selected from the group consisting of ethylene-acrylic acid ester copolymers, functional group-containing polyolefins and polyolefin-glycol (meth) acrylates. The thermoplastic elastomer composition according to claim 4. 6. (F) having a molecular weight of 400 to 1000.
The thermoplastic elastomer composition according to any one of claims 1 to 5, which comprises a plasticizer. 7. The thermoplastic elastomer composition according to claim 1, further comprising (G) an extender oil. 8. The thermoplastic elastomer composition according to claim 1, further comprising (H) an aromatic oligomer. 9. A molded article using the thermoplastic elastomer composition according to claim 1. 10. A hose, which is a hose.
The molded product described in.