• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PURPOSE: An oil-resistant thermoplastic elastomer composition and a molded product using the composition are provided, to improve the heat aging characteristics, the weather resistance, the low-temperature physical properties, the oil resistance and the flexibility. CONSTITUTION: The thermoplastic elastomer composition is obtained by dynamically heating a mixture comprising an olefin-based resin, an acryl rubber containing an unsaturated group and an inorganic filler in the presence of a crosslinking agent, wherein the acryl rubber containing an unsaturated group comprises (B1) 55-94.99 wt% of a structural unit derived from an acrylic acid alkyl ester monomer and/or an acrylic acid alkoxyalkyl ester monomer, (B2) 0.01-20 wt% of a structural unit derived from a monomer having a carbon-carbon double bond in a side chain, (B3) 5-30 wt% of a structural unit derived from an unsaturated acrylonitrile monomer, and (B4) 0-30 wt% of a structural unit derived from a monomer capable of copolymerizing (B1), (B2) and (B3). Preferably the olefin-based resin is a propylene resin; and the inorganic filler is silica.
    公开号:KR20030031441A
    申请号:KR1020020062425
    申请日:2002-10-14
    公开日:2003-04-21
    发明作者:마사끼 다까시마；가쯔따까 요꼬이；미노루 쯔네요시
    申请人:제이에스알 가부시끼가이샤；
    IPC主号:
    专利说明:

    Oil-resistant thermoplastic elastomer composition and molded article using same {Oil-Resistant Thermoplastic Elastomer Composition and Moldings Using the Same}
    [1] The present invention relates to a thermoplastic elastomer composition having excellent heat aging resistance, weather resistance, low temperature property, oil resistance and flexibility, and a molded article using the same.
    [2] Hoses are known which comprise an inner tube, a reinforcing layer and an outer tube in an annular stack in this order. In this hose, the inner tube and the outer tube are made of rubber such as vulcanized rubber and polyurethane, or resin such as polyester and nylon, and the reinforcing layer is braided or helical of fibers such as nylon, polyester, rayon, vinylon and aramid fibers. By braiding, bonding is performed using a rubber cement, a urethane adhesive, or the like in the space between the layers. However, since the vulcanization process is required for the production of so-called rubber hoses using rubber for the inner tube and the outer tube, the manufacturing steps are complicated and expensive production costs cannot be avoided. In addition, a so-called resin hose using a thermoplastic resin simply in the inner tube and the outer tube is rigid and inflexible, and there is a problem in that a kink occurs when the hose is bent. In order to solve this problem, a hose using a thermoplastic elastomer composition in which a vulcanized rubber phase having at least a part of which is crosslinked is dispersed in thermoplastic resins such as olefin thermoplastic resin, vinyl chloride thermoplastic resin, aramid thermoplastic resin and ester thermoplastic resin Is disclosed, for example, in JP 6-64102A. However, from the viewpoint of oil-resistant hose, the general olefinic thermoplastic elastomer composition is made of polypropylene and ethylene-propylene rubber and has a disadvantage in that oil resistance is insufficient because it does not have a polar group in its molecular structure. On the other hand, in order to improve oil resistance, the thermoplastic elastomer which consists of a polypropylene and an acrylonitrile butadiene type rubber, and the thermoplastic elastomer which consists of ethylene-acrylic acid ester copolymer rubber and polyolefin were proposed. However, the former has excellent oil resistance but includes double bonds in its molecular structure. This has the drawback of poor heat resistance and weather resistance of the composition. In addition, the latter is excellent in heat resistance and weather resistance but contains an ethylene moiety in its molecular structure. This has the drawback that the oil resistance of the composition is still inferior, in particular it cannot be practically used for fuel oil systems. As a compromise for this composition, a three-component blend of polypropylene, acrylonitrile-butadiene-based rubber and ethylene-acrylic acid ester rubber has been proposed. However, this three-component blend did not have a sufficient balance between heat resistance and oil resistance.
    [3] Accordingly, an object of the present invention is to provide a thermoplastic elastomer composition having excellent heat aging resistance, weather resistance, low temperature property, oil resistance and flexibility.
    [4] Another object of the present invention is to provide a molded article using such a composition.
    [5] The present inventors have studied extensively in detail to achieve the above object and found that (A) an olefinic resin, (B) a mixture containing a specific acrylic rubber and (D) an inorganic filler is dynamically heat treated in the presence of (E) a crosslinking agent. By doing this, it was found that a thermoplastic elastomer composition excellent in heat aging resistance, weather resistance, low temperature property, oil resistance, and flexibility can be obtained. The present invention has been completed based on this finding.
    [6] The present invention relates to a thermoplastic elastomer composition 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 crosslinking agent,
    [7] Said component (B)
    [8] (B1) 55 to 94.99% by weight of structural units derived from acrylic acid alkyl ester monomers and / or acrylic acid alkoxyalkyl ester monomers,
    [9] (B2) 0.01-20 weight% of the structural unit derived from the monomer which has a carbon-carbon double bond in a side chain,
    [10] (B3) 5-30 weight% of structural units derived from an unsaturated acrylonitrile monomer, and
    [11] (B4) 0-30 weight% of structural units derived from the monomer copolymerizable with said (B1), (B2), and (B3)
    [12] Wherein the sum of (B1), (B2), (B3) and (B4) is 100% by weight to provide a thermoplastic elastomer composition.
    [13] The present invention further provides a molded article using the thermoplastic elastomer composition.
    [14] The molded article is preferably a hose.
    [15] <Detailed Description of the Invention>
    [16] The thermoplastic elastomer composition according to the present invention is obtained by dynamically heat-treating a mixture containing (A) an olefinic resin, (B) an unsaturated group-containing acrylic rubber and (D) an inorganic filler in the presence of (E) a crosslinking agent,
    [17] Said component (B)
    [18] (B1) 55 to 94.99% by weight of structural units derived from acrylic acid alkyl ester monomers and / or acrylic acid alkoxyalkyl ester monomers,
    [19] (B2) 0.01-20 weight% of the structural unit derived from the monomer which has a carbon-carbon double bond in a side chain,
    [20] (B3) 5-30 weight% of structural units derived from an unsaturated acrylonitrile monomer, and
    [21] (B4) 0-30 weight% of structural units derived from the monomer copolymerizable with said (B1), (B2), and (B3)
    [22] Wherein the sum of (B1), (B2), (B3) and (B4) is a 100% by weight thermoplastic elastomer composition.
    [23] Each component is described in detail below.
    [24] (A) olefin resin
    [25] As (A) olefin resin (henceforth "component (A)") used for this invention, the homopolymer or copolymer of the C2-C20 alpha-olefin is mentioned.
    [26] Specific examples of the olefin resin include the following (co) polymers: (1) Ethylene homopolymer (the manufacturing method can be produced by any of the low pressure method and the high pressure method); (2) copolymers of ethylene and other monomers of 10 mol% or less or vinyl monomers such as vinyl acetate and ethyl acrylate; (3) propylene homopolymers; (4) random copolymers of propylene with up to 20 mol% of other α-olefins; (5) block copolymers of propylene with up to 30 mol% of other α-olefins; (6) 1-butene homopolymers; (7) random copolymers of 1-butene with up to 10 mol% of other α-olefins; (8) 4-methyl-1-pentene homopolymer; And (9) random copolymers of 4-methyl-1-pentene with up to 20 mol% of other α-olefins. Specific examples of the α-olefins mentioned above include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the like. Of the above olefin resins, propylene homopolymers and random copolymers of propylene with other alpha -olefins of 20 mol% or less are particularly preferred. Said olefin resin can be used individually or in mixture of 2 or more types.
    [27] When the olefin resin used is a crystalline olefin resin, the crystallinity of the resin measured by the X-ray method is usually 50% or more, preferably 55% or more. The density of the resin is at least 0.89 g / cm 3 , more preferably 0.90 to 0.94 g / cm 3 .
    [28] The maximum peak temperature, ie, the melting point (hereinafter, simply referred to as "Tm") by the differential scanning calorimetry of the crystalline olefin resin, is preferably 100 ° C or more, more preferably 120 ° C or more. If Tm is less than 100 ° C, heat resistance and strength tend not to be sufficiently exhibited.
    [29] Further, the melt flow rate of the crystalline olefin resin (at a temperature of 230 ° C., under a load of 2.16 kg) (hereinafter, the melt flow rate is simply referred to as “MFR”) is preferably 0.1 to 100 g / 10 minutes, more Preferably it is 0.5-80 g / 10min. If the MFR is less than 0.1 g / 10 min, there is a tendency for the mixing processability and the extrudability of the elastomer composition to be insufficient. On the other hand, when MFR exceeds 100 g / 1Omin, there exists a tendency for intensity | strength to fall.
    [30] Therefore, as olefin resin of this invention, crystallinity degree is 50% or more, density is 0.89 g / cm <3> or more, the content of an ethylene unit is 20 mol% or less, Tm is 140-170 degreeC, and MFR is 0.1, respectively. Particular preference is given to using polypropylene and / or copolymers of propylene with ethylene, which are from 100 g / 10 minutes.
    [31] As olefin resin, amorphous olefin resin can also be used other than the said crystalline olefin resin.
    [32] As an amorphous olefin resin, Homopolymers, such as atactic polypropylene and atactic poly-1-butene; Copolymers of propylene (containing 50 mol% or more) with other α-olefins (ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, etc.); And copolymers of 1-butene (containing 50 mol% or more) with other α-olefins (such as ethylene, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, etc.) Etc. can be mentioned.
    [33] The melt viscosity at 190 ° C. of the amorphous olefinic resin is 50,000 cSt or less, preferably 100 to 30,000 cSt, more preferably 200 to 20,000 cSt. The degree of crystallinity of the amorphous olefin resin by X-ray diffraction measurement is less than 50%, preferably 30% or less, and more preferably 20% or less. The density of the amorphous olefinic resin is preferably 0.85 to 0.89 g / cm 3 , more preferably 0.85 to 0.88 g / cm 3 . In addition, the number average molecular weight Mn in terms of polystyrene in the GPC method of the amorphous olefin resin is preferably 1,000 to 20,000, more preferably 1,500 to 15,000.
    [34] Usually, although amorphous olefin resin is used with crystalline olefin resin, you may use only any of these.
    [35] The proportion of component (A) in the thermoplastic elastomer composition is preferably 10 to 70% by weight, more preferably 10 to 50% by weight, most preferably 15 based on the sum of the weights of the components (A) and (B). To 30% by weight. When the proportion of component (A) is less than 10% by weight, the phase structure (form) of the finally obtained thermoplastic elastomer composition is a good sea-island structure which is characteristic of the dynamic crosslinked thermoplastic elastomer, wherein the olefinic resin Since it is not a sea (matrix) and a crosslinked rubber is an island (domain), there exists a possibility that moldability and mechanical property may deteriorate. On the other hand, when this ratio exceeds 70 weight%, the flexibility and rubber elasticity of the thermoplastic elastomer composition finally obtained fall, and it is unpreferable.
    [36] (B) unsaturated group-containing acrylic rubber
    [37] (B) unsaturated group containing acrylic rubber (henceforth "a component (B)") used for this invention is
    [38] (B1) 55 to 94.99% by weight of a structural unit derived from an acrylic acid alkyl ester monomer and / or an acrylic acid alkoxyalkyl ester monomer (hereinafter referred to as "component (B1)"),
    [39] (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 (hereinafter referred to as "component (B2)"),
    [40] (B3) 5 to 30% by weight of a structural unit derived from an unsaturated acrylonitrile monomer (hereinafter referred to as "component (B3)"), and
    [41] (B4) 0 to 30% by weight of a structural unit derived from a monomer copolymerizable with the above (B1), (B2) and (B3) (hereinafter referred to as "component (B4)")
    [42] Wherein the sum of (B1), (B2), (B3) and (B4) is 100% by weight. Component (B) is prepared by copolymerizing a monomer mixture in the presence of a radical polymerization initiator.
    [43] Examples of acrylic acid alkyl esters which form component (B1) after 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 and decyl acrylate. These acrylic acid alkyl esters may be used alone or as a mixture of two or more thereof. Among them, ethyl acrylate and n-butyl acrylate are particularly preferred.
    [44] Examples of acrylic acid alkoxyalkyl esters which form component (B1) after copolymerization are methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, ethoxypropyl Acrylate and butoxyethyl acrylate. These acrylic acid alkoxyalkyl esters can be used alone or in mixture of two or more thereof. Of these, methoxymethyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate and ethoxyethyl acrylate are particularly preferred.
    [45] The structural ratio (copolymerization ratio in component (B)) of component (B1) in component (B) is 55-94.99 weight%, Preferably it is 60-94.99 weight%. When this ratio is less than 55 weight%, desired heat resistance is not obtained in the thermoplastic elastomer composition obtained. On the other hand, when this ratio exceeds 94.99% by weight, oil resistance becomes poor.
    [46] The monomer having a carbon-carbon double bond in the side chain, which forms component (B2), is a monomer for introducing a crosslinking point into component B. Examples of monomers include dihydrodicyclopentenyl acrylate, dihydrodicyclopentenyl methacrylate, dihydrodicyclopentenyl itaconate, dihydrodicyclopentenyl maleate, dihydrodicyclopentenyl fumarate Dihydrodicyclopentenyloxyethyl acrylate (DCPEA), dihydrodicyclopentenyloxyethyl methacrylate, dihydrodicyclopentenyloxyethyl itaconate, dihydrodicyclopentenyloxyethyl maleate, Dihydrodicyclopentenyloxyethyl fumarate, vinyl methacrylate (CAS RN 4245-37-8), vinyl acrylate (CAS RN 2177-18-6), 1,1-dimethylpropenyl methacrylate, 1 , 1-dimethylpropenyl acrylate, 3,3-dimethylbutenyl methacrylate, 3,3-dimethylbutenyl acrylate, divinyl itaconate, divinyl maleate, divinyl fumarate, dicyclo Pentadiene, 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-phenyl Ethene, 1-methacryloyloxy-1-phenylethene, and 1-methacryloyloxy-2-phenylethene. These monomers may be used alone or in a mixture of two or more thereof. Among them, dihydrodicyclopentenyl acrylate, dihydrodicyclopentenyl methacrylate, dihydrodicyclopentenyloxyethyl acrylate, dihydrodicyclopentenyloxyethyl methacrylate, vinyl methacrylate and Vinyl acrylate is particularly preferred.
    [47] The structural ratio (copolymerization ratio in component (B)) of component (B2) in component (B) is 0.01-20 weight%, Preferably it is 0.02-8 weight%. When this ratio is less than 0.01% by weight, the degree of crosslinking becomes insufficient in the thermoplastic elastomer composition to be obtained, the tensile strength is excessively low, and a composition having a suitable mechanical strength is not obtained. On the other hand, when this ratio exceeds 20 weight%, hardness becomes excessively high in the thermoplastic elastomer composition obtained, and it is unpreferable.
    [48] Examples of the unsaturated nitrile that forms component (B3) after copolymerization include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile, and the like. Such unsaturated nitriles may be used alone or in admixture of two or more thereof. Among them, acrylonitrile is particularly preferred. The ratio (component copolymerization ratio in component (B)) of component (B3) in component (B) is 5-30 weight%, Preferably it is 10-30 weight%. When this ratio is less than 5 weight%, the oil resistance of the thermoplastic elastomer composition obtained is inadequate, On the other hand, when it exceeds 30 weight%, the hardness of the thermoplastic elastomer composition obtained will become high and it is unpreferable.
    [49] The other monomer forming the component (B4) after the copolymerization is not particularly limited as long as it is a monomer copolymerizable with the monomers forming the above-mentioned components (B1), (B2) and (B3), respectively. Examples of such other monomers are monofunctional methacrylates such as methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 1-methylcyclohexyl methacrylate, cyclohexyl methacrylate, chlorobenzyl methacrylate , 1-phenylethyl methacrylate, 1,2-diphenylethyl methacrylate, diphenyl methacrylate, furfuryl methacrylate, 1-phenylcyclohexyl methacrylate, pentachlorophenyl methacrylate and pentabro Mophenyl methacrylate; Styrene, vinyltoluene, vinylpyridine, α-methylstyrene, vinylnaphthalene, halogenated styrene, acrylamide, methacrylamide, N-methylol acrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, alicyclic alcohol (meth) Acrylic acid esters (e.g., cyclohexyl acrylate), (meth) acrylic acid esters (e.g., benzyl acrylate) of aromatic alcohols; By adding monofunctional methacrylate, the crum obtained after copolymerization of component (B) is not blocked and handling is facilitated. Other examples of monomers include polyfunctional unsaturated monomers such as 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 (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, diisopropenylbenzene, trivinyl Benzene, hexamethylene di (meth) acrylate, and the like. The copolymerized with the polyfunctional unsaturated monomer becomes a partially crosslinked rubber, so that the surface of the molded article can be improved, and the addition amount of the crosslinking agent and the crosslinking aid during dynamic crosslinking can be reduced, which is effective in lowering the production cost. Component (B4) is methyl methacrylate, benzyl methacrylate and phenyl methacrylate. Of these, methyl methacrylate is particularly preferred.
    [50] The composition ratio of component (B4) in component (B) becomes like this. Preferably it is 0-30 weight%, More preferably, it is 0-20 weight%.
    [51] The radical polymerization initiator used when copolymerizing the monomer mixture is not particularly limited. Examples of such initiators include peroxides such as potassium persulfate, p-mentane hydroperoxide and methyl isobutyl ketone peroxide, and azo compounds such as azobisisobutyronitrile. The amount of the radical polymerization initiator to be used is from 0.01 to 1.0 parts by weight per 100 parts by weight of the monomer mixture.
    [52] The copolymerization reaction for obtaining component (B) can be carried out by conventional polymerization methods such as suspension polymerization, emulsion polymerization and solution polymerization. Emulsifiers that can be used in the emulsion polymerization method can be any material that can emulsify and disperse the monomer mixture. Examples of emulsifiers that can be used include alkyl sulfates, alkylaryl sulfonates and higher fatty acid salts. In the copolymerization reaction, the reaction temperature is 0 to 80 ° C., and the reaction time is about 0.01 to 30 hours.
    [53] It is preferable that the Mooney viscosity [ML 1 + 4 (100 degreeC)] of the component (B) obtained by making it above is 10-150.
    [54] The proportion of component (B) in the thermoplastic elastomer composition is preferably 90 to 30% by weight, more preferably 90 to 50% by weight, most preferably based on the weight sum of the components (A) and (B). 85 to 70% by weight. When the proportion of the unsaturated group-containing acrylic rubber (B) is less than 30% by weight, the oil resistance of the finally obtained thermoplastic elastomer tends to deteriorate. On the other hand, if this ratio exceeds 90% by weight, the phase structure (form) of the finally obtained thermoplastic elastomer composition is a good sea-island structure, wherein the olefinic resin is sea (matrix), which is characteristic of the dynamic crosslinked thermoplastic elastomer. The crosslinked rubber does not become an island (domain), and the moldability and mechanical properties tend to deteriorate.
    [55] (C) compatibilizer
    [56] In the thermoplastic elastomer composition of the present invention, the (A) olefinic resin and the (B) unsaturated group-containing acrylic rubber are inherently poor- or non-commercial with each other. Therefore, it is desirable to combine compatibilizers having a structure similar to these two components. The compatibilizer (C) (hereinafter referred to as "component (C)") used in the present invention has a solubility parameter (SP value) of (A) olefin resin (SP value: 7 to 8) and (B) unsaturated group. Polymers intermediate with containing acrylic rubber (SP values: 9 to 10), in particular polymers with a solubility parameter (SP value) in the range of 7.2 to 9.5. SP values used herein are those calculated by the HOY method described on page 339 of the Polymer Handbook (Second Edition, BRANDRUP). Examples of polymers having SP values in the above defined ranges include ethylene-acrylic acid ester copolymers, functional group-containing polyolefins, polyolefin glycol (meth) acrylates, low nitrile-containing acrylonitrile-butadiene rubbers or hydrogenated materials thereof, styrene-butadiene block airborne Copolymer or its hydrogenated substance, styrene-isopropylene block copolymer or its hydrogenated substance, styrene-butadiene rubber, butadiene rubber, isoprene rubber, epichlorohydrin rubber, chloroprene rubber, chlorinated ethylene-α-olefin copolymer, ethylene-vinyl Ester copolymers, chlorosulfonated polyethylene, and the like. Among them, it is preferable to use at least one member selected from the group consisting of ethylene-acrylic acid ester copolymers, functional group-containing polyolefins and polyolefin glycol (meth) acrylates.
    [57] The ethylene-acrylic acid ester copolymer is an alkoxyalkyl acrylic having ethylene as an essential component, an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and an alkylene group having 1 to 4 carbon atoms At least one member selected from the rate. The ethylene-acrylic acid ester copolymer may further include a copolymer of ethylene, the monomer and vinyl acetate, and ethylene, the monomer, vinyl acetate and the carboxyl group-containing monomer as the crosslinking point and / or the epoxy group-containing monomer as the crosslinking point. .
    [58] Specific examples of the copolymer include copolymers of ethylene and carboxyl group-containing monomers, for example, ethylene-methyl acrylate copolymers, ethylene-methyl acrylate-acrylic acid copolymers and ethylene-methyl acrylate-methacrylic acid copolymers. ; Copolymers of ethylene with epoxy group-containing monomers such as ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl acrylate copolymer and ethylene-methyl acrylate-allyl glyc Cylyl ester copolymers; And copolymers of ethylene and epoxy group-containing monomers, such as ethylene-alkyl acrylate-vinyl acetate copolymers, ethylene-alkyl acrylate-vinyl acetate-glycidyl methacrylate copolymers, ethylene-alkyl acrylate-vinyl Acetate-glycidyl acrylate copolymers, and ethylene-alkyl acrylate-vinyl acetate-allyl glycidyl ether copolymers. The number average molecular weight of the copolymer is preferably 3,000 to 500,000. As for the Mooney viscosity [ML 1 + 4 (100 degreeC)] of a copolymer, it is more preferable that it is 10-150. These ethylene-acrylic acid ester copolymers may be used alone or in a mixture of two or more thereof.
    [59] 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 mainly a resin or rubber produced by polymerizing α-olefin. Examples of the α-olefins include ethylene, propylene, 1-butene, 4-methyl-1-butene, 4-methyl-1-pentene. Among these, ethylene and propylene are preferable. These α-olefins may be used alone or in a mixture of two or more thereof. Examples of the polyolefin rubber include ethylene-propylene rubber and ethylene-propylene-diene rubber. The functional group 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 of the functional group-containing polyolefins include those grafted-modified with unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinylglycidyl ether or allylglycidyl ether and the like. Specific examples of the functional group-containing compound used for the modification include maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, maleic anhydride, fumaric anhydride and itaconic anhydride, with maleic anhydride being preferred. Examples of the modification method include a method of grafting a polyolefin resin or a polyolefin rubber with the functional group-containing compound using a radical initiator at a temperature of 115 ° C. or higher in an alkyl aromatic hydrocarbon solvent; And very small amounts of alkyl peroxides, preferably aliphatic difunctional peroxides, functional group-containing compounds, and polyolefin resins and / or polyolefin rubbers at a temperature of 200 ° C. or more. Specific examples of the functional group-containing polyolefin include maleic anhydride modified LDPE (low density polyethylene), maleic anhydride modified HDPE (high density polyethylene), maleic anhydride modified LLDPE (linear low density polyethylene), maleic anhydride modified EVA (ethylene-vinyl acetate aerial Copolymer) and maleic anhydride modified PP (polypropylene). Among these, maleic anhydride modified LLDPE is preferred.
    [60] Examples of polyolefin glycol (meth) acrylates include polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol propylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate , Ethoxy polyethylene glycol mono (meth) acrylate, methoxy polypropylene glycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, and the like. These polyolefin-glycol (meth) acrylates can be used alone or in mixture of two or more thereof. The degree of polymerization of polyolefin glycol is 2 to 10.
    [61] The amount of component (C) is 0.5 / 99.5 to 20/80, preferably 1/99 to 10/90, more preferably in the weight ratio ((C) / (B)) of component (C) and component (B) 2/98 to 7.5 / 92.5.
    [62] (D) inorganic filler
    [63] As an inorganic filler (D) (henceforth "component (D)") used for this invention, the inorganic filler for rubber compositions can be used generally. Examples of inorganic fillers (D) include silica, heavy calcium carbonate, whistle, mild calcium carbonate, microactivated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin, calcined clay, pyrophyllite clay, silane-treated clay , Synthetic calcium silicate, synthetic magnesium silicate, synthetic aluminum silicate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, kaolin, sericite, talc, finely divided talc, wollastonite, zeolite, bentonite, mica, asbestos, PMF ( P rocessed M ineral F iber), sepiolite, potassium titanate, elestadite, stain spar, glass balun, silica balun, hydrotalcite, fly ash balun, Shirasu balun, carbon-based balun, Alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, etc. are mentioned. These inorganic fillers may be used alone or in a mixture of two or more thereof. Among these, silica is particularly preferable from the viewpoint of high oil absorption properties.
    [64] The amount of component (D) added is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the sum of the components (A) and (B). When the amount of component (D) is less than 0.1 part by weight, component (B) is likely to adhere to the rotor or casing or the like of the mixer due to the reduced viscosity of component (B) at high temperatures. In addition, when a plasticizer, a softener, or the like is added, oil absorption of the resulting composition is insufficient, and adhesion during mixing / processing becomes strong. On the other hand, when this ratio exceeds 50 parts by weight, excessively increasing the viscosity or increasing the compressive permanent distortion, which is an indicator of the flexibility of the obtained thermoplastic elastomer composition, is undesirable.
    [65] When using silica, a silane coupling agent is usually used for the surface treatment of the silica. The silane coupling agent is not particularly limited. Examples of the silane coupling agent include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (β-methoxyethoxy) silane, vinyl trichlorosilane, vinyl triacetoxysilane, N- (β-aminoethyl)- γ-aminopropyl trimethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropylmethyl dimethoxysilane, β -(3,4-epoxycyclohexyl) ethyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl tris (β-methoxyethoxy) silane, γ-mercaptopropyl tri Methoxysilane, methyltrimethoxysilane, methyltriethoxysilane, hexamethyldisilazane, γ-aminopropyl trimethoxysilane and N- [β- (N-vinylbenzalamino) ethyl] -γ-aminopropyl Trimethoxysilane hydrochloride etc. are mentioned. These silane coupling agents may be used alone or in a mixture of two or more thereof.
    [66] The blending amount of the silane coupling agent is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the sum of the components (A) and (B). If the amount of the silane coupling agent is less than 0.1 part by weight, the tensile properties and compression set distortion of the thermoplastic elastomer composition obtained may be insufficient. If the amount of the silane coupling agent is more than 10 parts by weight, the dry physical properties of the crosslinked rubber may be deteriorated, and the rubber elasticity may deteriorate. There is concern.
    [67] The pH of the silica filler is in the range of 2 to 10, preferably 3 to 8, particularly preferably 4 to 6. When the pH of the silica filler is lower than 2, the crosslinking rate is slowed, and when the pH exceeds 10, scorch is likely to occur. The oil absorption of the silica filler is 150 to 300 cc / 100 g, preferably 200 to 300 cc / 100 g. If the oil absorption of the silica filler is less than 150 cc / 100 g, the viscosity during mixing of the components (B) and (F) during the preparation of the thermoplastic elastomer composition of the present invention becomes low and the adhesion becomes severe, causing practical problems. . On the other hand, when the oil absorption exceeds 300 cc / 100 g, the viscosity becomes excessively high, which is not preferable.
    [68] (E) crosslinking agent
    [69] The crosslinking agent (E) (hereinafter referred to as "component (E)") used in the present invention is a compound capable of crosslinking at least one unsaturated group-containing acrylic rubber in the composition by dynamically heat treating the olefin resin at a temperature above the melting point. The crosslinking agent can be used without any particular limitation as long as it can crosslink a polymer compound having a double bond in the molecule. Examples of crosslinking agents include sulfur, organic sulfur containing compounds, organic peroxides, resins, quinone derivatives, polyhalides, bis (dioxotriazolin) derivatives, aldehydes, epoxy compounds, amine-borane conjugates and bipolar compounds . Another example of a crosslinking agent is methyl hydrogensiloxane (platinum crosslinking) used in the hydrosilylation reaction in the presence of a platinum catalyst. Of these crosslinking agents, sulfur, organic sulfur-containing compounds, organic peroxides and platinum crosslinking are preferred, and organic peroxides are more preferred. These crosslinking agents may be used alone or in a mixture of two or more thereof.
    [70] The amount of the crosslinking agent used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of component (B).
    [71] As an organic peroxide, it is preferable that the decomposition temperature for obtaining 1 minute half life (half life is 1 minute) is 150 degreeC or more. Examples of organic peroxides include 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t- Butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy maleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy laurate , 2,5-dimethyl-2,5-di (m-toluoyl peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl peroxy benzo Ate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxy acetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxy benzoate, n -Butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxy isophthalate, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide , 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butyl cumyl peroxide, di-t-butylper Oxide, p-mentane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyn-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1, 1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide and t-butyl hydroperoxide. The amount of the organic peroxide added is 0.3 to 15 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (B). When the amount of the organic peroxide added is less than 0.3 part by weight, the crosslinking time becomes very long and the crosslinking tends to be insufficient. On the other hand, when addition amount exceeds 15 weight part, a crosslinked material will harden | cure and it tends to become weak.
    [72] The organic peroxides may be used alone or in a mixture of two or more thereof. In the present invention, by combining the organic peroxide with a crosslinking aid, it is possible to perform a uniform and gentle crosslinking reaction. Examples of such crosslinking aids include sulfur or sulfur compounds such as powdered sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur and dipentamethylene thiuram tetrasulfide; oxime compounds such as p-quinone oxime and p, p'-dibenzoylquinone oxime; And 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, trimethyl Roll propane tri (meth) acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N, N'-m-phenylene bismaleimide, N, N'-toluylene bismaleimide, maleic acid And polyfunctional monomers such as anhydride, divinylbenzene, and zinc di (meth) acrylate. Among these crosslinking aids, p, p'-dibenzoylquinone oxime, N, N'-m-phenylene bismaleimide and divinylbenzene are preferable. N, N'-m-phenylene bismaleimide can act as a crosslinking agent even when used alone. These crosslinking aids may be used alone or as a mixture of two or more thereof. The amount of the crosslinking aid used is 0 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of component (B).
    [73] When sulfur is used as the crosslinking agent, thiazoles such as mercaptobenzothiazole, thiurams such as tetramethylthiuram disulfide, guanidines such as diphenyl guanidine, and dithiocarbamic acid such as zinc dimethyldithiocarbamate Salts and the like can be effectively used as the crosslinking aid.
    [74] When using an organic sulfur-containing sulfur compound as a crosslinking agent, tetramethylthiuram disulfide which is a thiuram type accelerator, 4,4'- dithiomorpholine, etc. can be used effectively.
    [75] The amount of such crosslinking agent is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of component (B).
    [76] (F) plasticizer
    [77] The thermoplastic elastomer composition of the present invention may optionally contain (F) plasticizer in addition to the components (A) and (B). As the plasticizer (F) (hereinafter referred to as "component (F)") that can be used, a conventional plasticizer for a rubber composition can be used, but it is preferable to use a plasticizer excellent in heat resistance. Examples of the plasticizer (F) include ether plasticizers, ether ester plasticizers and trimellitic acid plasticizers, each of which has excellent heat resistance.
    [78] As an example of an ether type plasticizer, what condensed the alkoxy polyoxyethylene alcohol to aliphatic dicarboxylic acid. Specific examples include Adekacizer RS-705 manufactured by Asahi Denka Kogyo Co., Ltd., and Monosizer W-264 manufactured by Dainippon Ink & Chemicals, Inc.
    [79] The ether ester plasticizer is not particularly limited in terms of its production method, and is easily obtained by reacting 2-ethylhexyl acid and ether glycol in a molar ratio of 2: 1. For example, ether ester plasticizers can be obtained by reacting mixed ether glycols containing a predetermined amount of pentaethylene glycol, hexaethylene glycol or hepethyleneethylene with 2-ethylhexyl acid in a conventional manner. The diester obtained by reacting pentaethylene glycol, hexaethylene glycol or hepethylene ethylene glycol with 2-ethylhexyl acid may be prepared by mixing the average degree of polymerization of polyethylene glycol to 5 to 10 by a conventional method. Specifically, Adekacizer RS-107, RS-1000, RS-735 and RS-700 manufactured by Asahi Denka Kogyo Co., Ltd. are examples of ether ester plasticizers.
    [80] Examples of trimellitic acid-based plasticizers include trimellitic acid esters in which each of three carboxylic acids of trimellitic acid is condensed with an alcohol. Examples of trimellitic acid-based plasticizers include trimellitic acid trimethyl, trimellitic acid triethyl, trimellitic acid tripropyl, trimellitic acid tributyl, trimellitic acid triamyl, trimellitic acid trihexyl, trimellitic acid triheptyl, and trimethyl Trimethyl n-octyl, tri-2-ethylhexyl trimellitic acid, trinonyl trimellitic acid, trimellitic acid tris (decyl), trimellitic acid tris (dodecyl), trimellitic acid tris (tetradecyl), Trimellitic acid tris (mixed C 8 -C 12 alkyl), trimellitic acid tris (mixed C 7 -C 9 alkyl) and trimellitic acid trilauryl. Specifically, Adekaizer C-8, C-880, C-79, C810, C-9N, C-10, etc. manufactured by Asahi Denka Kogyo Co., Ltd. correspond.
    [81] The molecular weight of the plasticizer is preferably 400 to 1,000, more preferably 500 to 900. If the molecular weight of the plasticizer is less than 400, heat resistance will be insufficient. On the other hand, when the molecular weight exceeds 1,000, cold resistance and compression set are inferior, which is not preferable. These plasticizers may be used alone or in a mixture of two or more thereof.
    [82] The plasticizer may be added to components (A) and (B) during the preparation of the thermoplastic elastomer composition or may be added to component (B) in advance.
    [83] The compounding amount of the plasticizer is 0 to 100 parts by weight, preferably 5 to 70 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the sum of the components (A) and (B). When the blending amount of the plasticizer exceeds 100 parts by weight, the plasticizer is discharged from the finally obtained thermoplastic elastomer composition, which tends to lower the mechanical strength and rubber elasticity.
    [84] (G) extender oil
    [85] If desired and necessary, the thermoplastic elastomer composition of the present invention may further comprise extender oil (G). As extender oil (hereinafter referred to as "component (G)") used in the present invention, extender oil generally used in rubber compositions can be used. The extender oil used is preferably an aromatic or naphthenic extender oil. Among them, 3 to 60 aromatic carbons (C A %), 20 to 50 naphthenic carbons (C N %) according to the ring analysis by the ndM method defined in ASTM D3238-95 (reapproved in 2000). And extender oils having 0 to 60 paraffinic carbon (C P %). When C P exceeds 60%, the mechanical strength of the thermoplastic elastomer composition of the present invention and the surface appearance of the molded article thereof may be poor.
    [86] The compounding quantity of component (G) is 0-50 weight part, Preferably it is 1-20 weight part per 100 weight part of sum total of component (A) and (B).
    [87] (H) aromatic oligomers
    [88] If desired and necessary, the thermoplastic elastomer composition of the present invention may further comprise an aromatic oligomer (H). The aromatic oligomer used in the present invention (hereinafter referred to as "component (H)") may be any aromatic oligomer as long as the weight average molecular weight is about 200 to 10,000 and includes a resin containing an aromatic skeleton. Examples of aromatic oligomers include coumarone-indene resins, xylene resins, phenol-novolac resins, styrenated phenolic acid resins and naphthenic resins. Among them, coumarone-indene resin and naphthenic resin are preferable. If the weight average molecular weight of the oligomer is less than 200, the mechanical strength of the molded article will be insufficient, while if it exceeds 10,000, the mixing properties will be poor.
    [89] The compounding quantity of component (G) is 0-20 weight part, preferably 1-10 weight part per 100 weight part of sum total of component (A) and (B). When this compounding quantity exceeds 20 weight part, adhesiveness may become strong and a mixing characteristic may worsen.
    [90] The thermoplastic elastomer composition of the present invention may further include various additives within a range not impairing its performance. Examples of additives include lubricants, metal oxides, reinforcing agents, emollients other than component (G), and anti-aging agents.
    [91] Examples of lubricants include stearic acid, oleic acid, lauric acid, dibutylammonium oleate, zinc stearate, calcium stearate, potassium stearate, sodium stearate and stearylamine. These can be used individually or in mixture of 2 or more types.
    [92] Examples of metal oxides include zinc, activated zinc, surface treated zinc, zinc carbonate, composite zinc, complex active zinc, surface treated magnesium oxide, magnesium oxide, calcium hydroxide, ultrafine calcium hydroxide, lead oxide, red lead and white lead. These metal oxides can be used alone or as a mixture of two or more thereof.
    [93] Examples of emollients include petroleum emollients other than component (G), vegetable oil emollients and facts. Examples of vegetable oil softeners include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, aja oil, coconut oil, peanut oil and Japan tallow. Examples of facts include brown facts, white factions and translucent factions.
    [94] Examples of antioxidants include naphthylamine antioxidants, diphenylamine antioxidants, p-phenylenediamine antioxidants, quinoline antioxidants, hydroquinone derivatives antioxidants, mono-, bis-, tris- or polyphenols. Antioxidants, thiobisphenol antioxidants, hindered phenol antioxidants, phosphite antioxidants, imidazole antioxidants, dithiocarbamate nickel salt antioxidants and phosphoric acid antioxidants. These antioxidants may be used alone or in a mixture of two or more thereof.
    [95] Reinforcing agents are for example carbon black, and examples of carbon black are SAF carbon black, ISAF 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 adjuvant can be used individually or in mixture of 2 or more types.
    [96] Preparation of Thermoplastic Elastomer Compositions:
    [97] The thermoplastic elastomer composition of the present invention is a thermoplastic elastomer composition produced by dynamic crosslinking, ie, dynamic crosslinking, which advances the crosslinking of rubber while mixing the thermoplastic resin and the rubber composition. By using such a manufacturing method, the obtained thermoplastic elastomer composition will be in the state in which at least one part disperse | distributed the crosslinked rubber | gum phase which is at least one part discontinuously finely. Thus, the obtained thermoplastic elastomer composition exhibits a similar behavior to that of the crosslinked rubber, and at least the continuous phase is a thermoplastic resin phase. As a result, processing according to a thermoplastic resin in molding process is possible.
    [98] In the preparation of the thermoplastic elastomer composition of the present invention, it is used for the mixing of the components (A), (B), (D) and (E), if necessary, (C), (F), (G) and (H). There is no particular restriction on the machine being used. Screw extruders, kneaders, Banbury mixers and two-axis mixed extruders can be used. Examples of the mixed processing include the following two methods.
    [99] (1) Components (B), (C), (D), (F), (G) and (H) are charged to a hermetic mixer (e.g. a kneader or banbury mixer) under heating (150 to 160 ° C) Then, component (A) is added. The mixture is melt mixed and then shaped into pellets by an extruder. The pellet is mixed with a crosslinking agent (E) and optionally a crosslinking aid for dynamic crosslinking using a two-axis mixed extruder to dynamically crosslink component (B) while heating and melting (about 200 ° C.).
    [100] (2) A component (A) molded into pellets is introduced into a first feed port of a two-axis mixing extruder, and heated and melted while mixing by a two-axis screw. Using rubber kneaders such as Banbury mixers, lubricants, reinforcing agents, anti-aging agents, and the like are added to the components (B), (C), (D), (F), (G) and (H) as necessary, By mixing, a master batch containing no crosslinking system is prepared and then pelletized by a rubber pelletizer. Component (A) is heated and melted in a two-axis mixed extruder as described above, and then pre-pelletized components (B), (C), (D), (F), (G) and (H) Pellets of the rubber component are added to the second inlet of the two-axis mixing extruder to disperse the rubber component in the component (A). A crosslinking agent (E) and optionally a crosslinking aid are added to the third and fourth inlets of the twin screw extruder, and the component (B) is crosslinked (dynamic crosslinking) under mixing. Crosslinking can be carried out in this manner so that component (B) is sufficiently dispersed in component (A) and component (B) can be crosslinked in a sufficiently fine state. Thus, a thermoplastic elastomer composition is prepared in which component (B) is stably dispersed in the component (A) as the continuous phase (matrix) as the dispersed phase (domain). In such a thermoplastic elastomer composition, the particle diameter of the crosslinked rubber composition which is discontinuous is preferably 50 µm or less, and more preferably 1 to 10 µm.
    [101] In addition, in the case of adding a compounding agent such as a reinforcing agent, a softener and an anti-aging agent to the composition of the present invention, the compounding agent may be added to component (B) during mixing, but a compounding agent other than the crosslinking agent may be mixed in advance before the mixing. much better. In addition, the compounding agent for component (A) may be mixed prior to the mixing or added during the mixing.
    [102] The melt mixing conditions of component (A) and component (B) or component (A), component (B), and component (C) are as follows. The mixing temperature is for example 150 to 250 ° C., preferably 150 to 200 ° C .; The shear rate during mixing is 500 to 7,000 / sec, preferably 500 to 2,000 / sec; The total time of melt mixing is 30 seconds to 10 minutes; Crosslinking time after addition of a crosslinking agent becomes like this. Preferably it is 15 second-5 minutes.
    [103] The thermoplastic elastomer composition of the present invention thus obtained is excellent in heat resistance, oil resistance, low temperature physical properties and flexibility. Although the use of such thermoplastic elastomer composition of this invention is not specifically limited, It is used suitably when oil resistance and / or heat resistance are needed. For example, the thermoplastic elastomer compositions of the present invention may be used in fuel oil or lubricant based oil resistant hoses, oil cooling hoses, air pipe hoses, power steering hoses, control hoses, intercooler hoses, torque converter hoses, oil return hoses, vacuum sensing hoses and heat resistant In addition to various hoses such as hoses, as well as cushioning materials such as sealing materials (for example, bearing sealing materials, valve body sealing materials, various oil sealing materials, O-rings, packings, gaskets), rubber insulation materials and damping rubbers, belts, It is also suitable for use in parts around automobile engines requiring oil resistance and / or heat resistance such as rolls, rubber sheets, various diaphragms and oil level gauges.
    [104] The invention is described in more detail with reference to the following examples, which are not intended to limit the invention.
    [105] In the examples and comparative examples below, all parts and percentages are by weight unless otherwise indicated. In addition, the various measurements in the Examples and Comparative Examples follow the following method.
    [106] Preparation of Thermoplastic Elastomer Compositions:
    [107] The following olefin resins, unsaturated group-containing acrylic rubbers, compatibilizers, inorganic fillers, plasticizers, crosslinking agents and other additives were used.
    [108] (A) olefin resin
    [109] Polypropylene polymer "PP1": Density 0.90 g / cm 3 , MFR (at a temperature of 230 ° C., under a load of 21 N): 3 g / 10 min, trade name “Novatec PP MA4” (manufactured by Japan Polychem Corporation) .
    [110] (B) unsaturated group-containing acrylic rubber
    [111] An unsaturated group containing acrylic rubber was synthesize | combined by the following method.
    [112] <Example>
    [113] Synthesis Example 1
    [114] A monomer mixture consisting of 200 parts of ion-exchanged water was introduced into a nitrogen purged autoclave, and 83.5 parts of ethyl acrylate (EA), 12.5 parts of acrylonitrile (AN) and 4 parts of dihydrodicyclopentenyloxyethyl acrylate (DCPEA) 100 parts, 4 parts of sodium lauryl, 0.25 parts of p-mentane hydroperoxide, 0.1 part of ferrous sulfate, 0.025 parts of sodium ethylenediaminetetraacetate, and 0.04 parts of sodium formaldehyde sulfoxylate were added. The resulting mixture was copolymerized at a reaction temperature of 30 ° C. When the polymerization conversion rate reached substantially 100%, 0.5 part of N, N-diethylhydroxylamine was added to the reaction system to terminate the copolymerization reaction (reaction time: 1 hour). The reaction product (latex) was extracted and an aqueous calcium chloride solution (0.25%) was added to the reaction product to solidify the unsaturated group-containing acrylic rubber. After sufficiently washing the coagulated product, it was dried at about 90 ° C. for 3 to 4 hours to obtain an unsaturated group-containing acrylic rubber having a Mooney viscosity [ML 1 + 4 (100 ° C.)] of 72 (hereinafter referred to as “ANM1”). Got it.
    [115] Synthesis Example 1 and Comparative Synthesis Examples 1 and 2
    [116] ANM2 and ANM3 were obtained by polymerizing the monomer mixture shown in Table 1 in the same manner as in Synthesis example 1. For ANM3 n-butyl acrylate (BA) and methyl methacrylate (MMA) were further used.
    [117] As comparative samples for comparison with the present invention, the monomer mixtures shown in Table 1 were respectively copolymerized to obtain ACM1 and ACM2 as acrylic rubbers other than component (B) of the present invention, respectively.
    [118] ANM1ANM2ANM3ACM1ACM2 EA83.5705747.550 BA 1047.530 AN12.52517 20 MMA 13 DCPEA4535Mooney viscosity60981106270
    [119] (C) compatibilizer
    [120] Ethylene-ethyl acrylate copolymer (C1): trade name "VAMAC-G" manufactured by Show Denko Dupont K.K
    [121] Acrylonitrile-butadiene rubber (C2): AN content: 20% by weight, trade name "N250S" manufactured by JSR Corporation
    [122] Polypropylene glycol monomethacrylate (C3): trade name: "Blemmer PP1000", manufactured by NOF Corporation
    [123] Maleic anhydride-modified ethylene-propylene rubber (C4): trade name: "Tafmer MP0610", Mitsui Chemicals, Inc. Produce
    [124] (D) inorganic filler
    [125] Silica: trade name: "Nipsil NS", Nippon Silica Industrial Co., Ltd. Produce
    [126] (E) crosslinking agent
    [127] 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane: trade name: "Perhexa 25B-40" manufactured by NOF Corporation
    [128] 2,5-dimethyl-2,5-di (t-butyl peroxy) hexyne: trade name: "Perhexyne 25B-10" manufactured by NOF Corporation
    [129] (F) plasticizer
    [130] Trimellitic acid-based plasticizer: trade name: "Adekacizer C-79", Asahi Denka Co., Ltd. Produce
    [131] Ether ester plasticizer: trade name: "Adekacizer RS735", Asahi Denka Co., Ltd. Produce
    [132] Ether ester plasticizer: trade name: "Adekacizer RS1003", Asahi Denka Co., Ltd. Produce
    [133] (G) extender oil
    [134] Naphthenic acid: trade name: "Fukkol Flex # 2050N", Fuji Kosan Co., Ltd. Produce
    [135] C A 6%, C N 39%, C P 55%
    [136] (H) aromatic oligomers
    [137] Komaron-Indene resin: Trade name: "G-90", Shin-Nittetsu Chemical Co., Ltd. Produce
    [138] Other additives
    [139] Crosslinking Aid (1): Divinylbenzene (56% Purity), Sankyo Chemical Industries, Ltd. Produce
    [140] Crosslinking aid (2): trade name: "TMPA", manufactured by NOF Corporation
    [141] Antioxidant (1): 4,4 '-(α, α'-dimethylbenzyl) diphenylamine, trade name: "Nocrac CD", Ouchishinko Chemical Industrial Co., Ltd. Produce
    [142] Anti-aging agent (2): pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], trade name: "Irganox 1010", Ciba Specialty Chemicals Ltd. Produce
    [143] Processing Agent (1): Stearic Acid, manufactured by Kao Corporation
    [144] Processing agent (2): Trade name: "Farmin 80" manufactured by Kao Corporation
    [145] Lubricant: Trade name: "PEG4000", manufactured by NOF Corporation
    [146] Silane coupling agent: trade name: "TSL8370", Toshiba Silicone Co., Ltd. Produce
    [147] Example 1
    [148] 20 parts of "PP1" as the olefinic resin (A), 80 parts of "ANM1" as the unsaturated group-containing acrylic rubber (B), 5 parts of "VAMAC-G" as the compatibilizer (C), and "nipsil" as the inorganic filler (D). 10 parts (Nipsil) NS "and 20 parts" Adekacizer RS735 "as plasticizer (F), with 1.2 parts of antioxidant, 1.5 parts of processing agent, 0.5 part of lubricant and 0.5 part of silane coupling agent as other additives 10 liters heated to 160 ° C. were introduced into a double-arm press kneader (manufactured by Moriyama Co., Ltd.). The molten composition was pelleted by a feed ruder (manufactured by Moriyama Co., Ltd.) set at 180 ° C. and 40 rpm.
    [149] The pellet thus obtained was mixed with 3 parts of "Perhexa 25B-40" as a crosslinking agent and 9 parts of divinylbenzene (purity: 56%; 5 parts of divinylbenzene) as a crosslinking aid, and then Henschel Mix for 30 seconds with a mixer. The mixture was then subjected to a two-screw extruder (model: "PCM-45", manufactured by Ikegai Corporation; ratio of screw length L and screw diameter D of the screw flight cross section (L / D) = 33.5) fully engaged in the same direction. Dynamically heat treated and extruded at 230 ° C. for 300 minutes at 300 rpm to obtain a dynamically crosslinked thermoplastic elastomer composition in pellet form.
    [150] Thermoplastic Elastomer Test Piece Preparation:
    [151] The pellets of the thermoplastic elastomer thus obtained were injection molded using an injection molding machine (trade name: N-100, manufactured by The Japan Steel Works, Ltd.) to produce sheets having a thickness of 2 mm, a length of 120 mm, and a width of 120 mm. Provided for evaluation.
    [152] Evaluation of Thermoplastic Elastomers:
    [153] The obtained thermoplastic elastomer was measured for mixing characteristics by a 10 liter kneader. Moreover, its fluidity was measured at the melt flow rate in 230 degreeC and the load conditions of 10 kg. The results obtained are shown in Table 3.
    [154] The molded sheet of the obtained thermoplastic elastomer was evaluated for hardness, mechanical properties (tensile breaking strength and tensile fracture elongation) and oil resistance by the following method. The results obtained are shown in Table 3.
    [155] (1) hardness
    [156] Measured according to JIS-K6253 as an index of flexibility
    [157] (2) tensile strength and tensile strength at break
    [158] Measured according to JIS-K6251
    [159] (3) oil resistance
    [160] Based on JIS-K-6258, the volume change rate ((DELTA) V) by the liquid immersion test of 23 hours at 23 degreeC using the Fuel C test oil, and the change rate of the elongation intensity in a tensile test were calculated | required.
    [161] (4) heat resistance
    [162] In accordance with JIS-K-6257, the molded sheet was left at 140 ° C. for 20 hours in a gear oven, and then subjected to a tension test to measure changes in tensile strength at break, tensile strength at break, and hardness.
    [163] (5) Compressive permanent distortion
    [164] In accordance with JIS-K6262, the molding sheet was pressed at a degree of 25% at 120 ° C. for 22 hours, and then the numerical value was measured.
    [165] (6) low temperature test
    [166] In accordance with JIS-K6261, the molded sheet was subjected to an impact fracture test at -20 ° C to check for abnormalities.
    [167] (7) weather resistance
    [168] In accordance with JIS-K6259, weather resistance was evaluated for 200 hours at 40 ° C under conditions of static 40% elongation at 500 ppm ozone concentration to investigate the presence of cracks.
    [169] Examples 2 to 10, and Comparative Examples 1 to 5
    [170] The crosslinked thermoplastic elastomer composition and the test piece in pellet form were obtained in the compounding ratio shown in Table 2 in the same manner as in Example 1. However, in the case of Comparative Example 4, the shrinkage ratio was so large that the test piece could not be obtained. Also, in the case of Comparative Example 5, pellets could not be obtained due to poor mixing characteristics in the kneader.
    [171] The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 3.
    [172]
    [173]
    [174] 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 of Comparative Example 1 (ACM1) is poor in oil resistance and tensile strength of the resulting composition, which is a feature of the present invention, since the structural units derived from the unsaturated acrylonitrile monomer are not copolymerized. The acrylic rubber (ACM2) of Comparative Example 2 is inferior in tensile strength and compressive permanent distortion of the resulting composition because the structural units derived from the monomer having a carbon-carbon double bond in the side chain are not copolymerized. In Comparative Example 3, an acrylonitrile-butadiene-based rubber and an ethylene-acrylic acid ester copolymer rubber were used in place of the unsaturated group-containing acrylic rubber of the present invention as the rubber component. In this case, oil resistance and heat resistance of the resulting composition are inferior. In Comparative Example 4, mixing was carried out in the absence of crosslinking agent. As a result, an excellent molded article was not obtained and its physical properties could not be evaluated. In the comparative example 5, since the component (D) was not included, the adhesiveness during mixing became strong and mixing could not be performed.
    [175] It will be apparent to those skilled in the art that various modifications may be made to the form and details of the invention presented and described above. Such changes are intended to be included within the spirit and scope of the appended claims.
    [176] This application claims priority to Japanese Patent Application No. 2001-316441 for which it applied on October 15, 2001, and the indication of this priority is integrated in its entirety by reference here.
    [177] The thermoplastic elastomer composition of the present invention has excellent heat aging resistance, weather resistance, low temperature property and oil resistance. Therefore, the composition of the present invention is a variety of hoses that require oil resistance and heat resistance, for example, oil-resistant hose for fuel oil or lubricants, oil cooling hose, air pipe hose, power steering hose, control hose, intercooler hose, torque converter hose, Suitable for oil return hose, vacuum sensing hose and heat resistant hose.
    权利要求:
    Claims (20)
    [1" claim-type="Currently amended] A thermoplastic elastomer composition obtained by dynamically heat-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 crosslinking agent,
    Said component (B)
    (B1) 55 to 94.99% by weight of structural units derived from acrylic acid alkyl ester monomers and / or acrylic acid alkoxyalkyl ester monomers,
    (B2) 0.01-20 weight% of the structural unit derived from the monomer which has a carbon-carbon double bond in a side chain,
    (B3) 5-30 weight% of structural units derived from an unsaturated acrylonitrile monomer, and
    (B4) 0-30 weight% of structural units derived from the monomer copolymerizable with said (B1), (B2), and (B3)
    Wherein the sum of (B1), (B2), (B3) and (B4) is 100% by weight.
    [2" claim-type="Currently amended] The thermoplastic elastomer composition according to claim 1, wherein the olefin resin (A) is a propylene resin.
    [3" claim-type="Currently amended] The thermoplastic elastomer composition according to claim 1, wherein the inorganic filler (D) is silica.
    [4" claim-type="Currently amended] The thermoplastic elastomer composition of claim 1, further comprising (C) a compatibilizer.
    [5" claim-type="Currently amended] The thermoplastic elastomer composition according to claim 4, wherein the compatibilizer (C) is at least one member selected from the group consisting of ethylene-acrylic acid ester copolymers, functional group-containing polyolefins and polyolefin glycol (meth) acrylates.
    [6" claim-type="Currently amended] The thermoplastic elastomer composition according to claim 1, further comprising (F) plasticizer having a molecular weight of 400 to 1,000.
    [7" claim-type="Currently amended] The thermoplastic elastomer composition according to claim 1, further comprising (G) extender oil.
    [8" claim-type="Currently amended] The thermoplastic elastomer composition according to claim 1, further comprising (H) an aromatic oligomer.
    [9" claim-type="Currently amended] A molded article using a thermoplastic elastomer composition obtained by dynamically heat-treating a mixture comprising (A) an olefin resin, (B) an unsaturated group-containing acrylic rubber and (D) an inorganic filler in the presence of (E) a crosslinking agent,
    Said component (B)
    (B1) 55 to 94.99% by weight of structural units derived from acrylic acid alkyl ester monomers and / or acrylic acid alkoxyalkyl ester monomers,
    (B2) 0.01-20 weight% of the structural unit derived from the monomer which has a carbon-carbon double bond in a side chain,
    (B3) 5-30 weight% of structural units derived from an unsaturated acrylonitrile monomer, and
    (B4) 0-30 weight% of structural units derived from the monomer copolymerizable with said (B1), (B2), and (B3)
    Wherein the sum of (B1), (B2), (B3) and (B4) is 100% by weight.
    [10" claim-type="Currently amended] The molded article using the thermoplastic elastomer composition of Claim 9 whose olefin resin (A) is a propylene resin.
    [11" claim-type="Currently amended] The molded article using the thermoplastic elastomer composition of Claim 9 whose inorganic filler (D) is silica.
    [12" claim-type="Currently amended] 10. The molded article according to claim 9, further comprising (C) a compatibilizer.
    [13" claim-type="Currently amended] 13. The molded article according to claim 12, wherein the compatibilizer (C) is at least one member selected from the group consisting of ethylene-acrylic acid ester copolymers, functional group-containing polyolefins and polyolefin glycol (meth) acrylates.
    [14" claim-type="Currently amended] The molded article using the thermoplastic elastomer composition of Claim 9 which further contains the (F) plasticizer whose molecular weight is 400-1,000.
    [15" claim-type="Currently amended] The molded article using the thermoplastic elastomer composition of Claim 9 which further contains (G) extender oil.
    [16" claim-type="Currently amended] The molded article using the thermoplastic elastomer composition of Claim 9 which further contains (H) aromatic oligomer.
    [17" claim-type="Currently amended] 10. The molded article of claim 9 which is a hose.
    [18" claim-type="Currently amended] The thermoplastic elastomer composition according to claim 2, further comprising a compatibilizer (C).
    [19" claim-type="Currently amended] The thermoplastic elastomer composition according to claim 18, wherein the inorganic filler (D) is silica.
    [20" claim-type="Currently amended] 20. The thermoplastic elastomer composition according to claim 19, further comprising extender oil (G).
    类似技术:
    公开号 | 公开日 | 专利标题
    EP0628065B1|1997-07-30|Compatibilization of dissimilar elastomer blends using ethylene/acrylate/acrylic acid terpolymers
    US5013793A|1991-05-07|Dynamically cured thermoplastic olefin polymers and process for producing the same
    KR100451602B1|2004-12-17|Olefinic Thermoplastic Elastomer, Process for Production Thereof, Olefinic Thermoplastic Elastomer Compositions, Process for Producing the Same and Moldings thereof
    EP0382401B1|1994-03-30|Ionomer composition
    EP0753027B1|1997-10-01|Thermoplastic elastomers having improved surface properties
    US5621045A|1997-04-15|Thermoplastic vulcanizates from isobutylene rubber and either EPDM or a conjugated diene rubber
    EP1441005B1|2009-08-19|Thermoplastic elastomer composition and process for producing the same
    US5589544A|1996-12-31|Soft thermoplastic elastomers having improved resistance to oil swell and compression set
    US6890990B2|2005-05-10|Co-agents for the preparation of thermoplastic elastomeric blends of rubber and polyolefins
    ES2225519T3|2005-03-16|Composition of elastomero thermoplastic.
    US7153918B2|2006-12-26|Random ethylene/alkyl acrylate copolymers, compounds and elastomeric compositions thereof with improved low temperature properties
    JP5763221B2|2015-08-12|Ethylene-vinyl alcohol thermoplastic elastomer and vulcanizate
    EP1205499B1|2009-09-09|Unsaturated nitrile-conjugated diene rubber composition and production process thereof
    US20090239014A1|2009-09-24|Rubber composition, crosslinked product and foam thereof, molded product therefrom, and use thereof
    KR20050110034A|2005-11-22|Low gloss thermoformable flooring structure
    US7943694B2|2011-05-17|Crosslinkable compositions, thermoplastic elastomers obtainable therefrom and their use
    KR100620475B1|2006-09-13|Olefinic Thermoplastic Elastomer, Process for Production Thereof, Olefinic Thermoplastic Elastomer Compositions, Process for Producing the Same and Moldings thereof
    JP2865598B2|1999-03-08|Thermoplastic elastomer composition
    US6531546B2|2003-03-11|Rubber composition
    CN101068876B|2012-03-21|Butyl material capable of vulcanized by peroxide used for manufacturing rubber products
    DE60226302T2|2009-06-25|Hose thermoplastic elastomer
    US20070173591A1|2007-07-26|Thermoplastic elastomer composition, formed article and sealing material having low hardness
    US6403713B2|2002-06-11|Method for crosslinking of isoprene-isobutylene rubber, ethylene-propylene-diene rubber containing ethylidenenorbornene as unsaturated component, or mixture thereof; and crosslinked rubber product obtained by said method
    CN101072826B|2011-02-02|Peroxide vulcanizable butyl compositions useful for rubber articles
    US7645832B2|2010-01-12|Use of metal oxides and salts to enhance adhesion to steels
    同族专利:
    公开号 | 公开日
    EP1302507A3|2003-12-10|
    DE60217048T2|2007-07-12|
    EP1302507B1|2006-12-27|
    KR100606308B1|2006-07-28|
    EP1302507A2|2003-04-16|
    CN100369969C|2008-02-20|
    CN1412231A|2003-04-23|
    US6815506B2|2004-11-09|
    US20030096071A1|2003-05-22|
    DE60217048D1|2007-02-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-10-15|Priority to JP2001316441
    2001-10-15|Priority to JPJP-P-2001-00316441
    2002-10-14|Application filed by 제이에스알 가부시끼가이샤
    2003-04-21|Publication of KR20030031441A
    2006-07-28|Application granted
    2006-07-28|Publication of KR100606308B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2001316441|2001-10-15|
    JPJP-P-2001-00316441|2001-10-15|
    [返回顶部]