WO1997017402A1 - Compositions a base d'elastomere thermoplastique - Google Patents

Compositions a base d'elastomere thermoplastique Download PDF

Info

Publication number
WO1997017402A1
WO1997017402A1 PCT/JP1996/003269 JP9603269W WO9717402A1 WO 1997017402 A1 WO1997017402 A1 WO 1997017402A1 JP 9603269 W JP9603269 W JP 9603269W WO 9717402 A1 WO9717402 A1 WO 9717402A1
Authority
WO
WIPO (PCT)
Prior art keywords
elastomer
parts
weight
styrene
polyester
Prior art date
Application number
PCT/JP1996/003269
Other languages
English (en)
Japanese (ja)
Inventor
Hideki Takahashi
Yoshio Katoh
Kazunori Yano
Hiroyoshi Kaito
Akeharu Wakayama
Original Assignee
Mitsubishi Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP28846395A external-priority patent/JPH09132700A/ja
Priority claimed from JP29518195A external-priority patent/JPH09137034A/ja
Application filed by Mitsubishi Chemical Corporation filed Critical Mitsubishi Chemical Corporation
Publication of WO1997017402A1 publication Critical patent/WO1997017402A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences

Definitions

  • the present invention relates to a thermoplastic elastomer having excellent flexibility and rubber elasticity (compression), and excellent oil resistance, heat resistance, strength and impact resistance.
  • Polyester-based elastomers have been used mainly for automotive equipment because of their excellent heat resistance, oil resistance, M ⁇ , and impact resistance.
  • polyester elastomers are inferior in flexibility and rubber elasticity (compression elongation ⁇ ), and are used in applications requiring flexibility or in areas where rubber elasticity (compression elongation ⁇ ) is required. It could not be used for vulcanized rubber applications.
  • thermoplastic elastomers have excellent flexibility and rubber elasticity (compression elongation), but are inferior in oil resistance and heat resistance. Not all of the intended uses could be replaced. In recent years, there has been a demand for thermoplastic elastomers to replace vulcanized rubber from the viewpoints of process flexibility and recycling.
  • thermoplastic elastomers because of their flexibility and rubber elasticity (compression length is good, but their compatibility is poor and they do not have a uniform and stable structure. There was a problem when oil resistance and ⁇ decreased. Also, in order for a thermoplastic elastomer to be used in industrial products and automotive parts, it must first be thermoplastic, have a high mechanical strength, and must have an elastic body to be an elastomer. It is necessary that the compression index, which is an index of, is as small as possible, the surface hardness is as low as possible, and the balance between the ⁇ ! «Target strength, the compression set, and the surface hardness is good.
  • thermoplastic polyester elastomer is a power having excellent mechanical properties, heat resistance and oil resistance.
  • thermoplastic polyester elastomer it has a drawback in that the balance between compression elongation and 5% is poor.
  • thermoplastic polyester elastomer may contain at least one functional group selected from a carboxyl group, an epoxy group, an amino group, and a hydroxyl group.
  • a rubber containing 20% or more of a gel component is dispersed and mixed.
  • thermoplastic polyester elastomer into a rubber which may contain at least one kind of functional group selected from a carboxyl group, an epoxy group, an amino group and a hydroxyl group
  • a method of dynamically cross-linking a thermoplastic polyester elastomer into a rubber which may contain at least one kind of functional group selected from a carboxyl group, an epoxy group, an amino group and a hydroxyl group
  • Japanese Patent Laid-Open No. No. 5—1 2 5 2 6 3 3 Japanese Patent Laid-Open No. No. 5—1 2 5 2 6
  • the present invention uses a modified olefin-based elastomer having improved compatibility with a polyester-based elastomer to provide a stable structure that could not be achieved by the prior art, and to provide flexibility and rubber elasticity.
  • the purpose of the present invention is to provide a thermoplastic elastomer material which has excellent (compression elongation), good oil resistance, heat resistance and impact resistance.
  • the present inventors have found that a specific hydroxyl-modified olefin-based elastomer exhibits extremely good affinity with a polyester-based elastomer, and have made the present invention iij.
  • thermoplastic elastomer yarn comprising the following components (A) and (B).
  • thermoplastic elastomer comprising the following components (A), (B) and (E): Offer one thing.
  • the thermoplastic elastomer yarn of the present invention has a flexural modulus according to JIS-K7203 of 1000 MPa or less, preferably 500 MPa or less, and particularly preferably in the range of 1 to 500 MPa, according to JIS-K7203.
  • Hardness is 30 or more, preferably 40a, particularly preferably 50 to 100. If the flexural modulus exceeds the noted range, impact resistance is When the JIS-A hardness is less than the above range, the property (3 ⁇ 4I property) is inferior.
  • the polyester-based elastomer of the present invention is a thermoplastic polyester block copolymer, and has a flexural modulus according to JIS-K7203, which is less than or equal to l OOOMPa, preferably 0 to 600 ⁇ 1-3, and particularly preferably. Use 10-60 OMPa.
  • polyester-based elastomers include a polyester-polyether block copolymer using a high-melting-point hard component as an aromatic polyester, a low-melting-point soft component as a fatty polyether, and a high-melting-point hard component.
  • a polyester polyester block copolymer using an aromatic polyester, a low melting point soft component and a fatty polyester is exemplified.
  • the polyester polyether block copolymer is composed of 1 aliphatic C ⁇ 2 and Z or alicyclic diol with 2 to 12 carbon atoms, 2 aromatic dicarboxylic acid or its alkyl ester, and 3 polyalkylene with MS average molecular weight of 400 to 6000. Ether glycol And polycondensation of oligomers obtained by esterification or esterification.
  • C 2 - ⁇ 2 aliphatic radiol Z or alicyclic diol used in the present invention those known as raw materials for polyesters, in particular, raw materials for polyester elastomers can be used.
  • raw materials for polyester elastomers include ethylene glycol and propylene glycol. , Trimethylene glycol, tetramethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, hexanediol, decanediol, etc.
  • 1,4-butanediol, ethylene glycol, and particularly preferably 1,4-butanediol are used as a component, and one or two kinds of R: can be used.
  • aromatic dicarboxylic acid examples include those known as raw materials for polyesters, especially polyester elastomers, and include terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid.
  • terephthalic acid and 2,6-naphthalenedicarboxylic acid, particularly preferably terephthalic acid are used, and these two kinds may be used in combination.
  • a small amount of a fatty acid such as adipic acid, sebacic acid, cyclohexane-1,4-dicarboxylic acid, or dimeric acid can be used in combination.
  • alkyl ester of an aromatic dicarboxylic acid examples include dimethyl esters such as dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate and 2,6-dimethyl naphthalate, and preferably dimethyl terephthalate,
  • 2,6-dimethyl naphthalate particularly preferably dimethyl terephthalate, which can be used in combination of two kinds of i :.
  • trifunctional triols, other diols and other dicarboxylic acids and esters thereof may be copolymerized in a small amount, and further, a fatty dicarboxylic acid such as adipic acid or an alicyclic dicarboxylic acid.
  • Carboxylic acid or its alkyl ester may be used in combination with the copolymer component.
  • the polyalkylene ether glycol generally has a weight average weight of 400 to 600, and is preferably used in a force of preferably 500 to 4000, particularly preferably 600 to 3 , 0 0 0. If the weight average molecular weight is less than 400, the block properties of the copolymer will be insufficient, and if the SS average: ⁇ amount exceeds 600, the physical properties of the polymer will decrease due to phase separation in the system.
  • the polyalkylene ether glycol includes polyethylene ether glycol, poly (1,2 and 1,3 propylene ether) glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, ethylene oxide and propylene oxide.
  • Block or random copolymer ethylene oxide and tetrahydrofuran block or random copolymer, polyethylene ether glycol-propylene ether glycol block copolymer, and the like. You can also Preferred is polytetramethylene ether glycol.
  • the content of the polyalkylene ether dalicol is preferably 5 to 95 SS%, more preferably 10 to 85 wt%, and particularly preferably 20 to 8 SS%, based on the block copolymer. 0S »%. If the content exceeds 95 SS%, it is difficult to obtain a polymer by condensation polymerization.
  • polyester polyester block copolymer of the present invention may be obtained by replacing the above-mentioned (3) polyalkylene ether glycol having a weight average molecular weight of 400 to 600 with fat or alicyclic dicarboxylic acid and fat JK3 ⁇ 4 diene.
  • Examples of 4 include fatty acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-1,4'-dicarboxylic acid; dicarboxylic acid or succinic acid, oxalic acid Fatty acids such as adipic acid, sebacic acid, and decanedicarboxylic acid! ⁇ One or more dicarboxylic acids and 2 to 2 carbon atoms; L2 glycol such as ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, etc.
  • Polyol oligomers having a structure in which one or more of the above diols are condensed are exemplified.
  • Examples of 5 include polycaprolactone-based polyester oligomers synthesized from ⁇ -force prolactone, ⁇ -oxocaproic acid, and the like.
  • alicyclic dicarboxylic acids fatty acids and dicarboxylic acids
  • aromatic dicarboxylic acids such as isophthalic acid
  • the lower limit of the melting point of the hard component having a high melting point is not particularly set, but generally, it is 150 ° C., preferably 170 ° C. or higher, and more preferably 190 ° C. or more. C or more.
  • the upper limit of It of the low melting point software of the present invention is not particularly limited, and “ ⁇ is 130 ° C. or less, preferably 100 ° C. or less.
  • the esterification, transesterification, and combination reaction in the present invention can be performed according to a conventional method.
  • one or two of known ⁇ 4 ⁇ ⁇ such as alcoholates such as tin, titanium, zinc and manganese, chlorides and oxides can be used, respectively.
  • tetrabutyl titanate is preferred.
  • Phosphoric acid, phosphorous acid, phosphoric acid, or a metal salt thereof may be added as an auxiliary agent.
  • Addition of 8 is preferable because the content of the terminal carboxyl group is slightly improved and the decomposition resistance is improved.
  • metal salts of aluminum phosphate include sodium phosphate, potassium phosphate, lithium phosphate, and the like. Particularly preferred is sodium phosphate.
  • the amount of the metal salt of the aluminum phosphate is 1 to 1% with respect to the polymer to be produced; LOO Oppm, preferably 3 to 200 ppm, more preferably 5 to 80 ppm, and less than 1 ppm.
  • LOO Oppm preferably 3 to 200 ppm, more preferably 5 to 80 ppm, and less than 1 ppm.
  • the effect of addition is not sufficiently obtained, and addition of more than 1000 ppm is not preferable because the effect is not changed and the coupling reaction is inhibited.
  • the alkali metal phosphate may be added to the molten polymer in any state of a solution, a slurry, and a solid.
  • the addition timing is preferably at least before the completion of the combined reaction. In other words, it may be added at any time between the esterification or ester exchange gSiS i and before the end of the fi synthesis reaction. In particular, it is preferable to add in a slurry form immediately before the start of the polycondensation, because the addition of the slurry is small. In the reaction step, other additives may be present.
  • hindered phenol-based oxides ij hindered phenol-based oxides ij, hindered amine-based oxides ⁇ , phosphorus-based oxidization stabilizers, sulfur-based oxidized oxides ⁇ ⁇ and triazole-based light stabilizers, and other known additives can be used.
  • the addition of hindered phenol-based ammonium oxide Pj to the polymer in an amount of 0.01 to LSS% is more preferable.
  • the esterification or ester exchange is usually carried out at 120 to 250 ° C, preferably 150 to 230 ° C, and the melt polycondensation reaction is usually carried out at 200 to 280 under a pressure of 10 t0 rr or less. ⁇ 6 hours.
  • the polymer obtained by melt polymerization is kept at a temperature higher than the melting point, and is discharged from the reaction vessel and pelletized.
  • the pellets obtained here are necessary May be further subjected to solid-phase polymerization.
  • the weaving ratio of the high melting point hard component and the low melting point soft component in the polyester elastomer (A) is preferably from 80Z20 to heavy SJt; L0Z90, more preferably 60/4 0 to 15 Z85.
  • Polyester elastomers which are particularly preferably used include polytetramethylene terephthalate or polytrimethylene terephthalate 1,2,6-naphthalate as a hard component and polytetramethylene ether glycol as a soft component. Is what is done.
  • polyester polyether copolymers examples include commercially available polymers such as “Perprene P” (trade name of Toyo! ⁇ ), “Hytrel” (trade name of Toray DuPont), and “Low Mod” (Japan). G-Plastic Co., Ltd.), “Nichigo Polyester” (Nippon Synthetic Chemical Industry Co., Ltd .: fc3 ⁇ 4 ⁇ trade name), “Teijin Polyester Elastomer” (trade name, manufactured by Teijin Limited), etc. As a copolymer, a commercially available polymer "Perprene S" (Toyo Boseki: h ⁇
  • the modified olefin elastomer of the present invention is obtained by subjecting the olefin elastomer to a specific amount of an ⁇ , ⁇ -unsaturated carboxylic acid ester having a hydroxyl group and other vinyl monomers in a graft copolymerization step.
  • the olefin elastomer has a flexural modulus at room temperature of 500 MPa or less, preferably 300 MPa or less, and particularly preferably 1 MPa or less at room temperature.
  • the glass transition temperature is preferably not more than 0 OMPa and not more than 10 ° C. 7/1740
  • olefin-based elastomer examples include homopolymers of olefins such as polybutadiene, polyisoprene, and polyisobutylene, and a random polymer that is polymerized from 12 to 65% by weight of ethylene and 88 to 35 tt% of an olefin other than ethylene.
  • Rubber, such as block, graft, etc., or tertiary rubbery polymer which is polymerized from ethylene, lignified resin other than ethylene, and non-conjugated gen, and measured by JIS K7203 Those having a flexural modulus of 200 kg / cm 2 or less are preferred.
  • tertiary rubbery polymer which is polymerized from ethylene, ⁇ -refining other than ethylene and non-conjugated gen
  • examples of the tertiary rubbery polymer which is polymerized from ethylene, ⁇ -refining other than ethylene and non-conjugated gen are the above ⁇ - Olefin and non-conjugated gens such as 5-ethylidene norbornene, 5-methylnorbornene, 5-vinylnorbornene, Ethylene-propylene-non-using such Ntajen ⁇ 3 ⁇ 4 Jefferies down copolymer rubber (EPDM) Hitoshiryoku, 'and the like.
  • EPDM Jefferies down copolymer rubber
  • olefin elastomers include ethylene-butadiene copolymers, ethylene-isoprene copolymers, ethylene-chloroprene copolymers, and other copolymers of ethylene and gen; ethylene-vinyl benzoate copolymers, Copolymers of ethylene and an organic ester, such as an ethylene-ethyl acrylate copolymer and an ethylene-methyl acrylate copolymer, may be mentioned.
  • copolymers or copolymer rubbers may be any of a random copolymer, a block copolymer, a graft copolymer, and a copolymer.
  • These elastic polymers may be used alone or in combination.
  • EPM ethylene-propylene copolymer rubber
  • non-conjugated gen such as copolymer gen copolymer rubber (EPDM), ethylene / butene copolymer rubber (EBM), ethylene / propylene / butene copolymer rubber, ethylene / hexene copolymer, and ethylene / octene copolymer
  • EPDM copolymer gen copolymer rubber
  • EBM ethylene / butene copolymer rubber
  • ethylene / propylene / butene copolymer rubber ethylene / hexene copolymer
  • ethylene / octene copolymer A copolymer of ethylene and an organic acid ester such as an ethylene copolymer, ethylene monovinyl acetate copolymer, ethylene monoethyl acrylate copolymer, and ethylene methyl acrylate copolymer is preferable.
  • EPM Ethylene 'propylene copolymer rubber
  • EPDM ethylene-butene copolymer rubber
  • EBM ethylene-propylene-butene copolymer rubber
  • ethylene'hexene copolymer ethylene-octene copolymer, etc.
  • the Mooney viscosity at 100 ° C. (ML 1 +4 (100 ° C.)) of the above olefin copolymer rubber is 10 to 400, preferably 15 to 350 in “ ⁇ ”. If the viscosity exceeds the above range, the appearance of the molded product is poor, and if the viscosity is less than the above range, the rubber elasticity is inferior.
  • ⁇ -Unsaturated rubonic esters include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2, 3-dihydroxypropyl (meth) acrylate, 2-hydroxymethyl-3-hydroxypropyl (meth) acrylate, 2,2-dihydroxymethyl-1,3-hydroxypropyl (meth) acrylate, ⁇ number 4 to 40 of ethylene (Meth) acrylates such as (meth) acrylates of glycol or propylene glycol oligomers, bis (2-hydroxyethyl) malate, bis (2-hydroquinethyl) fumarate, bis (2-hydroxy) Propyl) malate, bis (2-hydroxypropyl) Malate, bis (2,3-dihydroxypropyl) maleate, bis (2,3-dihydroxypropyl) fumarate, bis (2-hydroxymethyl-3-hydroxypropyl)
  • maleic acid ester or fumaric acid ester has two Not only one in which both carboxylic acid groups are esterified with a hydroxyalkyl group, but also one in which only one is esterified can be exemplified as similar monomers.
  • (meth) acrylamides such as N-methylol (meth) acrylamide can be used.
  • (meth) acrylate described here means acrylate and methacrylate
  • (meth) acrylic acid means acrylic and methacrylic acid
  • (meth) acrylamide means acrylamide and methacrylic. It means amide.
  • the a, -unsaturated carboxylic acid ester having a hydroxyl group may be used alone or in combination of two or more. Among them, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, ethylene glycol having 4 to 40 carbon atoms or propylene glycol And the like. Olefin methacrylate or acrylate esters of oligomers are preferred.
  • vinyl monomers examples include styrene, ⁇ -methylstyrene, ⁇ -methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, and nitrostyrene.
  • styrene-based monomers such as styrene, ⁇ -methylstyrene, ⁇ -methoxystyrene, and methylstyrene are preferred.
  • the graft polymerization of an ⁇ , 3-unsaturated carboxylic acid ester having a hydroxyl group and another vinyl monomer onto the olefinic rubbery polymer in order to obtain a modified olefinic rubbery polymer is carried out in a solution state, Either a melted state or a suspended state may be employed.
  • a solution state Either a melted state or a suspended state
  • a reaction in the presence or absence of a radical generator such as an organic peroxide, a method of irradiating ultraviolet rays or radiation, or a method of contacting with oxygen or ozone.
  • the graft polymerization usually takes 30 to 350. C, preferably in the range of 50 to 300 ° C., and the reaction time of the graft polymerization is 50 hours or less,
  • Radical generators include t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-1,2,5-dihydroperoxide, benzoyl peroxide, dicumyl peroxide, 1,3-bis (T-butyl peroxy isopropyl) Organic and non-oxides such as benzene, t-butyl peroxybenzoate, dibutyl peroxide, methyl ethyl ketone peroxide, peroxidized rhodium, peroxy acid hTK element, etc.
  • An azo compound such as t-butane and a carbon radical such as dicumyl can be used.
  • These radical generators can be selected in the context of denaturing agents and reaction forms. Also 2 More than one species can be used in combination. -The amount of the radical generator used is in the range of 0 to 30 SS parts, preferably 0 to 1 O fifi parts, based on 100 parts by weight of the above-mentioned olefin elastomer.
  • ⁇ In the graft copolymerization is generally in the range of 30 to 350 ° C, preferably 50 to 300 ° C, and the modification reaction time is 50 hours or less, preferably 0.5 minutes to 24 hours. Range.
  • the graft copolymerization reaction may be in any of a solution state, a melt state, and a suspension state.
  • * R-dependent components are removed by, for example, adding or removing an organic ⁇ j such as xylene or a transfer agent. Can also.
  • organic ⁇ j such as xylene or a ⁇ i cliff transfer agent or the like is added, or reactive components are removed. You can also do it below to do so.
  • the S-unsaturated carboxylic acid ester having water introduced into the olefinic elastomer is represented by the following formula: 0.0 1 to 20 SS section, preferably
  • ⁇ Ft of the other vinyl monomer to be introduced into the olefin-based elastomer is:
  • the compatibility may be improved, and the compatibility is further improved by using together.
  • the amount exceeds 50 parts by weight, the appearance of the product may be degraded, or the likeness may be reduced, which is not preferable.
  • the olefin-based elastomer ⁇ S of the ⁇ , -unsaturated carboxylic acid ester having a hydroxyl group is in the range of 0.01 to 10% by weight, preferably 0.05 to 8MS%, more preferably 0.1 to 5ftl%. If the ⁇ , ⁇ -unsaturated carboxylate ester having less than 0.01% by weight has less than 0.01% by weight, the compatibility is small, and if it exceeds 10% by weight, gelling and other problems occur, causing problems in processability. Unfavorable because the appearance of the product may be worsened.
  • the aromatic vinyl monomer in the olefin elastomer is 0.0 l to 20 m »%, preferably 0.05 to : L 0% by weight, more preferably
  • ⁇ B of the aromatic vinyl monomer is less than 0.0 i myk, the compatibility is poorly improved, and when it exceeds 20 fiS%, there is a problem in processability due to gelation etc. The strength may deteriorate, which is not preferable.
  • the thermoplastic elastomer composition of the present invention may contain other components other than the component (A) and component (B) m.
  • the modified olefin-based elastomer in ( ⁇ ) may be replaced with an unmodified olefin-based elastomer.
  • the unmodified olefin elastomer can be selected from those exemplified as used for obtaining the above-mentioned modified olefin elastomer, and the olefin elastomer is an organic peroxide; 3 ⁇ 4 Heat treatment underneath and crosslinking mainly by radicals may be used.
  • the mixing ratio of the modified olefin rubbery polymer obtained by the above graft polymerization step and the unmodified olefin rubbery polymer is preferably a modified olefin rubber obtained by the graft polymerization step. 5 to 100% by weight, more preferably 10 to 95% by weight, particularly preferably 20 to 90% by weight, unmodified rubber-based polymer 95 to 0 fiS%, more preferably 90 to 5% by weight, Particularly preferred is 80 to 1%. Further, polycarbonate ", polyphenylene ether, polyamide and the like can be contained in the resin material within a range not to impair the object of the present invention.
  • Various additives such as a cross-linking agent, a cross-linking auxiliary agent, a »fe agent, a flame retardant, a component, and an antistatic agent can be added.
  • an antioxidant it is particularly important to add an antioxidant, and specifically, commercially available products such as phenol-based, phosphite-based, thioether-based, hindered amine-based Mitsuyasu, and triazole-based Mitsuyasu-RJ are available.
  • Antioxidants can be mentioned.
  • a bisphosphazoline compound a difunctional compound of a diepoxy compound or other multifunctional compound, or a monophosphodibis (2,6-diene) such as triphenylphosphite is used.
  • phosphites exemplified by diphosphites such as tert-butyl 4-methylphenyl) pentaerythritol diphosphite is ⁇ 3 ⁇ 4, and ⁇ is an alkali metal salt such as anhydrous potassium carbonate. Can also be added.
  • thermoplastic resins various types of thermoplastic resins, various elastomer-crosslinking agents, various plasticizers, etc. can be blended.
  • thermoplastic resins examples include propylene polymers such as propylene copolymer, propylene / ethylene block copolymer, and propylene / ethylene random copolymer, low-density polyethylene (branched ethylene polymer), medium-density and high-density polyethylene ( Ethylene polymers such as linear ethylene polymers, ethylene and unsaturated compounds such as ethylene 'unsaturated carboxylic acid copolymers or their anhydrides (acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itacone) Acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid, and Olefin resins such as copolymers of these anhydrides); styrene homopolymers; acryl; styrene resins such as tolyl styrene resin, acrylonitrile butadiene styrene
  • the softening agent for carbon Tk rubber used as a target in the thermoplastic elastomer of the present invention has a fi * average ⁇ F amount of 300 to 2,000, preferably 500 to 1,500. Can be mentioned.
  • Such a softening agent for carbon bT-based rubber is a mixture of an aromatic ring, a naphthene R and a paraffin ring, and one in which the number of paraffins is 50% by weight JL in the total carbon. It is called paraffinic oil, and naphthenes with a prime number of 30-45fi *% are called naphthenic oils, and fragrances; ⁇ those with a prime number of more than 30% are classified as power ⁇ fragrance oils. Among them, it is preferable to use paraffinic oil from the viewpoint of weatherability.
  • the paraffinic oil used in the present invention has a kinematic viscosity at 40 ° C of 20 to 800 cSt (centistokes), preferably 50 to 600 cSt, and an ugly point of 0 to -40 ° C, preferably 0. ⁇ One 30. C and flash (COC) 200-400 ° C, preferably 250-350. C oil power is preferred.
  • Charcoal is a softening agent for a base rubber, and is preferably 0 to 200 £ S parts, preferably 0.1 to 100 parts by weight, and 100 parts by weight of L, and particularly preferably Is strongly preferred to be compounded at 1 to 50 parts by weight.
  • the hydrocarbon rubber softener is important for controlling the physical condition and the melt fluidity during molding.
  • the elastic polymer referred to in the present invention is a polymer having a rubber elasticity other than the "olefin elastomer" described in the component (B), and specifically, a hydrogenated product of styrene butadiene rubber (SBR); Styrene ⁇ ethylene ⁇ butylene ⁇ styrene copolymer
  • SEBS styrene-ethylene-propylene-styrene copolymer
  • SEPS styrene-gen block copolymer
  • a compound having a main chain of a styrene-gen block copolymer such as a 7-nitrogen additive of a styrene-isoprene-butylene-styrene block copolymer
  • the above-mentioned olefin-based copolymer rubber Commercially available thermoplastic elastomers, including Mitsubishi Chemicals ⁇ tS!
  • the hydrate of the styrene gen block copolymer is important in addition to the above for adjusting the melt fluidity during molding.
  • the hydrogenated product of the diene block copolymer is a polymer block consisting of butadiene alone, isoprene alone, or a mixture of isoprene and butadiene, specifically, styrene-butadiene.
  • Hydrogen of styrene block copolymer (hereinafter sometimes abbreviated simply as “hydrogenated S—B—S”), styrene 'isoprene ⁇ Hydrogen of styrene block copolymer (hereinafter simply referred to as “It may be abbreviated as hydrogenated S-I-SJ.) Or a styrene.isoprene 'butadiene' styrene block copolymer hydrate (hereinafter simply abbreviated as” hydrogenated S-BI-S "). ) Can be mentioned.
  • These styrene-conjugated diene block copolymer hydrates have an SS average liver volume of 50,000 to 500,000, preferably 60,000 to 400,000, particularly preferably 70,000 to 300,000, Styrene content of 5 to 5% Ofil%, preferably 8 to 45 fiS%, particularly preferably 10 to 40% 1%, 1,2-microstructure less than 20%, preferably less than 15%, hydrogenation rate 95% It is important to use a block copolymer of R ⁇ , preferably 97% or more.
  • average ⁇ 1 amount is the average amount of fiS in terms of polystyrene measured by gel permeation chromatography (GPC) under the following conditions.
  • Equipment 150C ALC / GPC (MILLI PORE)
  • Weight average of the hydrogenated product of the above styrene / gen block copolymer ⁇ If it exceeds 500,000, it is inferior in property, and if it is less than 50,000, it is inferior in rubber elasticity and strength is there.
  • Examples of the method for producing the hydrate of these styrene gen block copolymers include, for example, a method described in Japanese Patent Publication No. 23798/1971 using lithium or styrene in an inert solvent. Then, the copolymer is synthesized by the method described in, for example, JP-B-42-8704, JP-B-43-6636, JP-A-59-133203, and JP-A-60-79005. Add water in an inert solvent! Water added in the presence of ⁇ ; 4 ⁇ can be mentioned.
  • the hydrogenated S—I—S is prepared, for example, by the method described in JP-A-2-102212, and the hydrogenated S—BI—S is prepared, for example, by the method described in JP-A-3-188114.
  • the elastic polymer is blended in an amount of 0 to 200 MS parts, preferably 0.1 to 100 parts by weight, particularly preferably 1 to 50 parts by weight, based on 100 SS parts of fi ⁇ (A) and ⁇ (B) in total. That force is preferred.
  • the cross-linking agent referred to in the present invention can be an organic cross-linking agent, an inorganic cross-linking agent, or a resin cross-linking agent commonly used for rubber and resin.
  • Organic crosslinking agents include organic peroxides, azo compounds, oxime compounds, and nitroso compounds. Substances and organic sulfur compounds. -For the organic ill compounds, specifically, compounds having a half-life of 1 minute and S ⁇ in the range of 120 to 280 ° C are used for ⁇ I, for example, acetylperoxide.
  • Succinic peroxide benzoylperoxide, m-toluoyl peroxide, t-butylperoxide 2-ethylhexanoate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) Cyclohexane, t-butylperoxyisopropyl carbonate, 2,2-bis (t-butylperoxy) octane, t-butylperoxyacetate, 2,5-dimethyl-2,5-di (benzoylper Hexane) hexane, t-butylperoxylaurate, di-t-butylperoxyisophthalate, t-butylperoxybenzene, dicumylperoxide, ⁇ , a'- (T-butylperoxy-m-isopropyl) benzene, t-butylcumylperoxide, 2,5-dimethyl-2,
  • azo compound examples include diazoaminobenzene, bisazoester, N-phenylcarbamoylazoformate, and bis (dioxotriazoline) derivative.
  • Examples of the oxime compound include p-quinone dioxime and p-quinone dioxime benzoate.
  • nitroso compound examples include poly-p-dinitrosobenzene, N- (2-methyl-12-ditrosopropyl) -14,2-trosoaniline and the like.
  • Organic sulfur compounds include 4,4 'dithiodimorpholine, N, Examples thereof include monobis (hexahydro-1H-azepinone-12), alkylpuenol disulfide, phosphorus-containing polysulfide, and highly polysulfur compounds.
  • the non-bridging agent include sulfur, sulfur chloride, sulfur disulfide, selenium, peroxy acid bSI6, peroxide, and tellurium.
  • the resin crosslinking agent examples include a phenol resin and an amine resin.
  • the phenol tree is a di- or polymethylol phenol tree flum
  • the amino resin is a resin obtained by combining formaldehyde with an amino compound such as melamine, benzoguanamine and urea.
  • crosslinking agents can be mixed and mixed. Further, a crosslinking assistant and a crosslinking (St agent) can be used in combination as a target component.
  • crosslinking assistant when an organic peroxide is used as a crosslinking agent, it is preferable to use a crosslinking assistant together.
  • the crosslinking aid include divinylbenzene, metaphenylene bismaleimide, quinone dioxime, 1,2-polybutadiene, triaryl cyanurate, diaryl phthalate, ethylene glycol dimethacrylate, trimethylol propane trimethacrylate, triethylene dalicol dimethacrylate, and tritriethyl methacrylate. Allyl isocyanurate and the like can be mentioned.
  • thermoplastic elastomer yarn Composition ratio of thermoplastic elastomer yarn
  • thermoplastic elastomer yarn of the invention according to the first aspect!
  • the composition ratio of each component is 5 to 9 smm%, preferably 30 to 98 £ ft% of the combination of component (A) and strong (A) and ⁇ (B). It is preferably from 35 to 95 Sfi%, particularly preferably from 40 to 90%.
  • thermoplastic elastomer has poor oil resistance, heat resistance, andmony, and those exceeding the above range have poor flexibility and rubber elasticity.
  • each component constituting the thermoplastic elastomer of the present invention according to the second aspect.
  • the proportion of the component is 100 parts by weight of the component (B) modified olefin elastomer.
  • the polyester elastomer is 5 to 400 parts by weight, preferably 40 to 300 parts by weight
  • the crosslinking agent is 0.01 to 20 parts by weight, preferably 0.05 to 5 parts by weight.
  • ingredient (A) If the strength is less than 5 SS part, the thigh properties such as tensile strength at break and elongation at tensile strength are deteriorated, which is a problem. Is a problem. Also, if the crosslinking agent (E) is less than 0.0 I MS part, the crosslinking MS of the oligomeric rubbery polymer is low and the compression length of the elastomer-elastomer becomes large, which is a problem. This is a problem of poor properties due to cross-linking of the plastic polyester elastomer.
  • the method for obtaining the thermoplastic elastomer product of the present invention is not particularly limited, but is practically a melting method, a solution method, or a suspension method.
  • a concrete melting method powder is granular (A) and
  • (B) was uniformly mixed with the additives described in the section of additional compounding materials, if necessary, using a Henschel mixer, ribbon blender, V-type blender, etc. After that, there is a method of blending with an ordinary machine such as a Banbury mixer, a kneader, a roll, a multi-screw extruder such as a single-screw or twin-screw extruder.
  • each component ⁇ is 100. (: Up to 400 ° C., preferably 150 ° C. to 300 ° C., particularly preferably 180 ° C. to 280 ° C.
  • the method and the method are not particularly limited. For example, a method in which a modified oil-based elastomer and a polyester-based elastomer and f3 ⁇ 4] -like compounding material components are collectively M according to ' ⁇ , After modifying the modified olefin and polyester elastomers, the remaining components, including additional ingredients, are added.
  • kneading the olefinic elastomer, ⁇ -unsaturated carboxylic acid ester having hydroxyl group, other vinyl monomer, radical initiator, polyester elastomer and additional components at once.
  • a method such as a method of kneading under reduced pressure may be employed.
  • an organic solvent such as chlorobenzene, trichlorobenzene, or xylene, or ⁇ ) such as tetrakis (2-ethylhexoxy) titan or dibutyltin oxide can be added.
  • the method for producing a 6 ⁇ body from the thermoplastic elastomer of the present invention includes a film method (such as a T-die laminating method), a calender, a (co) extrusion molding method, a blow method, a rotation, a press injection method (an insert injection method).
  • Method a two-color injection male method, a core-back injection method, a sandwich injection method, and an injection press molding method.
  • Injection method is particularly preferable. In doing so, it is important to use the material that has been dried, and drying is preferably performed at a temperature of 20 to 150 ° C, preferably 50 to L; In C, the time is from 1 to 24 hours, preferably from 1 to 10 hours, and more preferably from 1 to 5 hours. Furthermore, it is more effective to perform ⁇ under reduced pressure, and drying under ⁇ reduces 3 ⁇ 4i3 ⁇ 4 and shortens the time. If the material is not used, the surface of the molded product may be roughened or its physical properties may be reduced.
  • ⁇ is 100 to 300 ° C., preferably 150 to 280 °, particularly preferably 200 to 260 ° (: expansion of 50 to 1, 0 0 0 k gZ cm 2, is J3 ⁇ 43 ⁇ 4 preferably 1 OOSOO k injection pressure of gZ cm 2. also, runners, also be used in recycling the non ⁇ portion Ya not Hinto products such spool such it can.
  • thermoplastic elastomer of the present invention can be used as various industrial parts.
  • Various industrial parts with packing for the purpose of sealing, waterproofing, soundproofing, etc., electric cords m 3 ⁇ 43 ⁇ 4 s, belts, hoses, tubes, noise reduction gears, etc., electrical and electronic parts, sports goods, etc. be able to.
  • the measurement samples of (1) to (6) were performed using an in-line screw type injection fig machine (Toshiba machine 3 ⁇ 4 3 ⁇ 4 ⁇ small injection molding machine; IS90B), injection pressure 500 kg / cm 2 , injection ⁇ 3 ⁇ 4 240 ° C, 0 It was obtained by punching a 120 mm x 120 mm x 3 mm sheet at ⁇ C in the ⁇ direction.
  • IS90B In-line screw type injection fig machine
  • JIS-A storage [1] Conforms to JIS-K-6301
  • the ester exchange reaction was performed at 150 to 230 ° C for 3.5 hours, and then the hindered phenol-based oxidizing stabilizer [Ciba Geigy Co., Ltd. Name: Irganoxl 010] 230-245 under reduced pressure of 3 t0 rr or less, adding 0.18 parts by weight.
  • polyester-based elastomer polyester polyether block copolymer: density 1.19 gZcm 3 , Shoichi D, 52, melt flow rate (MFR: 245; C, 2 (16 kg load) 34 gZl 0 min, Flexural modulus 215MPa).
  • EP 01 hereinafter referred to as “EPR”; propylene 2% by weight, Mooney viscosity ML 1 + 4 (100.C) 19. MFR at 230 ° C 3.6 g / 10 ⁇ , JIS-A hardness 73) 40 g, 2-hydroxyethyl methacrylate 2 g, styrene 2 g and bis (t- After mixing 0.06 g of butyl peroxyisopropyl) benzene, the mixture was mixed with a twin-screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd., trade name: Laboplastomill) at 180 ° C and a screw rotation speed of 180 rpm to obtain a mixture. This was melted for 5 minutes, and the material was pulverized to obtain a pellet.
  • EPR propylene 2% by weight, Mooney viscosity ML 1 + 4 (100.C) 19. MFR at 230 ° C 3.6 g / 10
  • the obtained modified modified elastomer-based pellet Petratka et al., Found that the structural unit based on 2-hydroxyethyl methacrylate ⁇ S determined by the IR method was 1.13SS%, and the structural unit ⁇ ft of styrene was 0.86fifi%. Met.
  • the MFR of the pellet at 230 ° C measured according to JIS-K-7210 was 0.44 g / 10 minutes.
  • EPR manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: EP01
  • 252 was completely dissolved in 500 ml of benzene with 110 parts, and 7.5 g of 2-hydroxyethyl methacrylate and 7.5 g of styrene were added.
  • 2 g of benzoyl peroxide was added dropwise to a radical initiator solution in which 25 ml of benzene was dissolved, and reacted for 3 hours.
  • the reaction system is poured into 4 L of methanol to obtain a modified olefin elastomer as a precipitate.
  • the resulting modified olefin elastomer is filtered off and washed with methanol. After that, the mixture was purified under reduced pressure at room temperature.
  • ⁇ of the structural unit based on 2-hydroxypropyl methacrylate is 0.43%
  • structural unit of styrene ⁇ S is 0.36% by weight
  • 1 && is 1.67 gZl0. Minutes.
  • B-1 was prepared in the same manner as B-1 except that styrene was not used and t-butylperoxybenzoate was used instead of bis (t-butylperoxyisopropyl) benzene.
  • ⁇ based on 2-hydroxyethyl methacrylate was 0.67 fiS%, and MFR was 0.73 gZlO.
  • the phenol-based antioxidant was added to the tmi 0 oms part of B-7, component (C) and other component (F-1) of the component (B) having the composition shown in Table 5 (Ciba Geigy 3 ⁇ 4S3 ⁇ 4 brand name “Ilganox 1010”) 200 with the addition of 0.05 parts by weight.
  • the mixture was further treated with 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-1 3 (trade name “Cahexa ADJ”) as a peroxide.
  • a partially cross-linked pellet was obtained, and the remaining components of components (A) and (B) in Table 1 were B-1 and a phenolic antioxidant (Ciba-Geigine ⁇ S3 ⁇ 4 trade name “Ilganox 1010 0.2 llfcfi part, thioether-based antioxidant (calcium shiraishi: t3 ⁇ 4 trade name: “Seanox 412 S”) 0.2 Part B is added, LZD-33, twin screw extruder with a cylinder diameter of 45 mm At a temperature of 240 ° C. to obtain a thermoplastic elastomer pellet of the present invention. This was injected as described above into a sheet, and the above evaluation was performed. Table 5 shows the results.
  • the phenolic antioxidant is prevented for the total t—Ml 00SS part of B-7, component (C) and other (F-1) of the component (B) in the platform composition shown in Table 1.
  • Ingredients (Ciba Geigine ⁇ 3 ⁇ 4 trade name “Ilganox 1010”) I set it to ⁇ of C and made it at Banbari to get pellets. This pellet and the remaining ⁇ in Table 1-6, component B, are B-1 and phenol-based antioxidants.
  • Stopping agent (Cilibaox Corporation's product name "Ilganox 101/10") "0.2 fi3 ⁇ 4 part and thioether-based antioxidant (Shiraishi calcium ⁇ trade name” Seanox 4 12 S ”) 0.2 SS part was added, and the pellet was set to 240 mm with a twin-screw extruder having an L / D of 33 and a cylinder diameter of 45 mm to obtain a thermoplastic elastomer pellet of the present invention. This was injected ⁇ ⁇ as described above to obtain a sheet, and the above evaluation was performed. Table 6 shows the results.
  • Reference Example 1 Ethylene-propylene rubbery polymer (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: EP 01) 10 OS * part, 2-hydroxyethyl methyl acrylate 3SJI part, styrene 33 ⁇ 4 ⁇ part, And ⁇ , a'-bis (t-butylperoxy-1-m-isopropyl) benzene (manufactured by NOF CORPORATION, trade name: Perbutyl-P) 0.
  • ⁇ S of 2-hydroxyethyl methacrylate structural unit (hereinafter, referred to as HEMA unit) is 1.6 MM%, and styrene structural unit (hereinafter, referred to as St unit) is 1.55% by weight. Met.
  • HEMA-g-EPR 2-hydroxyethyl methacrylate graft copolymerized ethylene-propylene rubbery polymer
  • Oil-extended ethylene-propylene-ethylidene norbornene rubbery polymer EP 98 Japanese synthetic rubber: fcia trade name, a mixture of 100SS part of rubber and 75 parts by weight of process oil (PW380)] 8 Ofi * part and paraffin-based process oil PW- 380 (Idemitsu Kosan 3 ⁇ 4 ⁇ trade name) 2 Rubber part obtained by 4 minutes M processing with Toyo Seiki Nippon Lapoplast mill set to 100 ° C and 80 rpm at 45.7 £ 3 ⁇ 4 Oil-extended olefin rubbery polymer whose oil part is 54.3fiS% (hereinafter abbreviated as oil-extended EPDM.
  • the rubber part is (A) and the oil part is target.
  • thermoplastic elastomer fiber is melt-injected with a minimax machine at 200 mm and then melt-injected to produce a piece, which is tensile-rupture point 3 ⁇ 4J3 ⁇ 4 (unit: kgfZcm 2 ) and tensile elongation at break in accordance with JIS K7113. (Unit is%) was measured.
  • a test piece was prepared by press-molding the thermoplastic elastomer at 230 ° C, and the compression set (unit was measured after compression at 70 ° C for 22 hours and 25% in accordance with JISK6301. In this case, the smaller the compression set i, the better the rubber elasticity.
  • Hardness ⁇ ⁇ A test piece was prepared by pressing the thermoplastic elastomer at 230 ° C, and the hardness was determined by performing an A-type spring-type hardness test SIH according to JIS K6301.
  • thermoplastic elastomer Hfl ⁇ product was prepared and evaluated in the same manner as in Example 1. Table 7 shows the results.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition à base d'élastomère thermoplastique comprenant les constituants (A) et (B) ci-après: (A) élastomère en polyester: de 5 à 98 % en poids; et (B) élastomère à oléfine modifiée obtenu en soumettant à une copolymérisation greffée 100 parties, en poids, d'un élastomère d'oléfine, de 0,01 à 20 parties, en poids, d'un carboxylate hydroxylé, α,β-insaturés, et de 0 à 50 parties, en poids, d'un autre monomère vinylique, étant entendu, que pour ce constituant (B), on a entre 95 et 2 % en poids. L'invention concerne aussi une composition à base d'élastomère thermoplastique comprenant les constituants (A), (B) et (E) ci-après: (A) un élastomère de polyester: de 5 à 400 parties en poids; (B) un élastomère d'oléfine modifiée obtenue en soumettant à une copolymérisation greffée un élastomère d'oléfine, un carboxylate hydroxylé α,β-insaturé et un monomère vinylique aromatique, ce constituant étant éventuellement mélangé avec un élastomère d'oléfine, étant entendu que le contenu des unités de carboxylate α,β-insaturé oscille entre 0,01 et 10 % en poids, et que le contenu des unités de monomère vinylique aromatique oscille entre 0,01 et 20 % en poids; la proportion dudit constituant est de 100 parties, en poids; et (E) un agent de réticulation: de 0,01 à 20 parties en poids.
PCT/JP1996/003269 1995-11-07 1996-11-07 Compositions a base d'elastomere thermoplastique WO1997017402A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP7/288463 1995-11-07
JP28846395A JPH09132700A (ja) 1995-11-07 1995-11-07 熱可塑性組成物及びその成形体
JP29518195A JPH09137034A (ja) 1995-11-14 1995-11-14 熱可塑性エラストマー組成物
JP7/295181 1995-11-14

Publications (1)

Publication Number Publication Date
WO1997017402A1 true WO1997017402A1 (fr) 1997-05-15

Family

ID=26557190

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1996/003269 WO1997017402A1 (fr) 1995-11-07 1996-11-07 Compositions a base d'elastomere thermoplastique

Country Status (1)

Country Link
WO (1) WO1997017402A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56143235A (en) * 1980-04-11 1981-11-07 Sumitomo Naugatuck Co Ltd Elastomer composition
JPS57102945A (en) * 1980-12-18 1982-06-26 Japan Synthetic Rubber Co Ltd Softened thermoplastic resin composition
JPS60177039A (ja) * 1984-02-23 1985-09-11 Sumitomo Naugatuck Co Ltd 耐落球衝撃性に優れる樹脂組成物
JPS62205149A (ja) * 1986-03-04 1987-09-09 Sumitomo Naugatuck Co Ltd 耐衝撃性、リブ強度に優れる耐候性樹脂組成物
JPS63142056A (ja) * 1986-12-03 1988-06-14 Japan Synthetic Rubber Co Ltd 熱可塑性エラストマ−組成物
JPH05125263A (ja) * 1991-03-27 1993-05-21 Japan Synthetic Rubber Co Ltd 熱可塑性エラストマー組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56143235A (en) * 1980-04-11 1981-11-07 Sumitomo Naugatuck Co Ltd Elastomer composition
JPS57102945A (en) * 1980-12-18 1982-06-26 Japan Synthetic Rubber Co Ltd Softened thermoplastic resin composition
JPS60177039A (ja) * 1984-02-23 1985-09-11 Sumitomo Naugatuck Co Ltd 耐落球衝撃性に優れる樹脂組成物
JPS62205149A (ja) * 1986-03-04 1987-09-09 Sumitomo Naugatuck Co Ltd 耐衝撃性、リブ強度に優れる耐候性樹脂組成物
JPS63142056A (ja) * 1986-12-03 1988-06-14 Japan Synthetic Rubber Co Ltd 熱可塑性エラストマ−組成物
JPH05125263A (ja) * 1991-03-27 1993-05-21 Japan Synthetic Rubber Co Ltd 熱可塑性エラストマー組成物

Similar Documents

Publication Publication Date Title
US6653401B2 (en) Thermoplastic elastomer composition
WO2002090433A1 (fr) Composition elastomere thermoplastique
JP2001146533A (ja) 高耐衝撃性熱可塑性樹脂組成物
JP3101230B2 (ja) 熱可塑性エラストマー組成物及びその製造法
JPH01213361A (ja) 熱可塑性樹脂組成物
JPS59131613A (ja) エラストマー状成形体の製造方法
JP2002201333A (ja) ブロック共重合体組成物
WO2000061662A1 (fr) Procédé de production d'une composition à base de caoutchouc
WO2000061681A1 (fr) Composition à base de caoutchouc
JP2008291100A (ja) 架橋型熱可塑性エラストマー組成物
JP2008226850A (ja) 難燃性熱可塑性エラストマー樹脂組成物およびその製造方法
WO1997017402A1 (fr) Compositions a base d'elastomere thermoplastique
JP2001323172A (ja) 低臭気熱可塑性重合体組成物
JPH01213360A (ja) 樹脂組成物
JP3505897B2 (ja) 熱可塑性エラストマー組成物
JP3938850B2 (ja) 熱可塑性エラストマー組成物
JP4758588B2 (ja) 架橋オレフィン系ゴム組成物
JP3402421B2 (ja) 熱可塑性組成物及びその成形体
JP2002284944A (ja) 熱可塑性軟質樹脂組成物
JP2004067944A (ja) 極性熱可塑性エラストマー組成物
JP3755325B2 (ja) ポリエステル系エラストマー組成物
JPH09132700A (ja) 熱可塑性組成物及びその成形体
JP2004243544A (ja) 熱可塑性エラストマーを基材とした積層体及び積層管状体
JP2000072892A (ja) 耐摩耗性に優れた熱可塑性エラストマー組成物
JP3387647B2 (ja) 熱可塑性樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase