CN114437462B - Rubber composition for shoe sole and application thereof, vulcanized rubber and preparation method and application thereof - Google Patents
Rubber composition for shoe sole and application thereof, vulcanized rubber and preparation method and application thereof Download PDFInfo
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- CN114437462B CN114437462B CN202011202227.6A CN202011202227A CN114437462B CN 114437462 B CN114437462 B CN 114437462B CN 202011202227 A CN202011202227 A CN 202011202227A CN 114437462 B CN114437462 B CN 114437462B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 129
- 239000005060 rubber Substances 0.000 title claims abstract description 129
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 44
- 239000006229 carbon black Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 claims description 26
- 239000000654 additive Substances 0.000 claims description 26
- 230000000996 additive effect Effects 0.000 claims description 25
- 239000003607 modifier Substances 0.000 claims description 22
- 230000003712 anti-aging effect Effects 0.000 claims description 21
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 150000003505 terpenes Chemical class 0.000 claims description 16
- 235000007586 terpenes Nutrition 0.000 claims description 16
- 229910052925 anhydrite Inorganic materials 0.000 claims description 14
- 229920002943 EPDM rubber Polymers 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 239000004902 Softening Agent Substances 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- -1 alcohol compound Chemical class 0.000 claims description 5
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 150000002978 peroxides Chemical group 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000010692 aromatic oil Substances 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 claims description 2
- 238000011056 performance test Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000010077 mastication Methods 0.000 description 3
- 230000018984 mastication Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UUXFJUNKKOMDPE-UHFFFAOYSA-N 2-octadecanoyloxycarbonylbenzoic acid Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(=O)C1=CC=CC=C1C(O)=O UUXFJUNKKOMDPE-UHFFFAOYSA-N 0.000 description 1
- PKNDIQVRBKYDMC-UHFFFAOYSA-N CC(C)CCCCC(OC(C1=CC=CC=C1C(O)=O)=O)=O Chemical compound CC(C)CCCCC(OC(C1=CC=CC=C1C(O)=O)=O)=O PKNDIQVRBKYDMC-UHFFFAOYSA-N 0.000 description 1
- MFEBHRWBEJMBLR-UHFFFAOYSA-N CCCCCCCCCCCCC1=CC=CC=C1S(=O)(=O)OC(=O)C2=CC=CC=C2C(=O)O Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(=O)(=O)OC(=O)C2=CC=CC=C2C(=O)O MFEBHRWBEJMBLR-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of rubber, and discloses a rubber composition for soles and application thereof, vulcanized rubber and a preparation method and application thereof. The vulcanized rubber prepared from the rubber composition provided by the invention has higher tensile strength, wear resistance and flexing resistance.
Description
Technical Field
The invention relates to the field of rubber, in particular to a rubber composition for soles and application thereof, a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in the soles.
Background
The shoe is a necessity of life of people, and the sole is an important factor influencing the quality of the shoe. Currently, the main materials of the sole material mainly include TPR, EVA, rubber, polyurethane, and the like.
In the prior art, a large amount of white filler is applied to shoe products, particularly light-colored or colored products, so that good wear resistance, skid resistance and vamp adhesion performance can be endowed to soles, wherein white carbon black is most widely applied, but the surface of the white carbon black contains polar groups, so that the white carbon black is poor in compatibility with rubber base materials and has adverse effects on the performance of the products.
CN109929155A discloses a rubber composition and vulcanized rubber for shoe soles, and a preparation method and application thereof, and the technology is to improve the dispersion of white carbon black in a rubber matrix by adding a rubber modifier to modify the rubber matrix, but the rubber matrix is only limited to ethylene propylene diene monomer, and the application range is limited.
Moreover, when other rubbers are used as the rubber base, the rubbers thus obtained have the disadvantages of not high strength and poor wear resistance and flex resistance when used for the production of shoe soles.
Disclosure of Invention
The invention aims to overcome the defects of low rubber strength, poor wear resistance and poor flex resistance of the rubber composition provided by the prior art when the rubber composition is used for preparing soles.
In order to achieve the above object, a first aspect of the present invention provides a rubber composition for shoe soles, which comprises the following components stored independently of each other or in a mixture of two or more of them: the rubber composition comprises main body rubber, white carbon black, zinc methacrylate, a surface modifier, hydrogenated terpene resin, an activating agent, a softening agent, a vulcanizing agent, an auxiliary crosslinking agent, an anti-aging agent and an additive, wherein the main body rubber is the combination of styrene butadiene rubber and ethylene propylene diene monomer, the additive is calcium sulfate whisker or anhydrite, and the vulcanizing agent is a peroxide vulcanizing agent;
in the main rubber, the mass ratio of the styrene-butadiene rubber to the ethylene propylene diene monomer is 10:90 to 40:60, adding a solvent to the mixture;
relative to 100 parts by weight of the main rubber, the white carbon black content is 20-30 parts by weight, the zinc methacrylate content is 5-15 parts by weight, the surface modifier content is 3-7 parts by weight, the hydrogenated terpene resin content is 10-15 parts by weight, the activator content is 3-6 parts by weight, the softener content is 5-8 parts by weight, the vulcanizing agent content is 1-5 parts by weight, the co-crosslinking agent content is 1-5 parts by weight, the anti-aging agent content is 1-3 parts by weight, and the additive content is 5-15 parts by weight; and the total amount of the white carbon black, the zinc methacrylate and the additive is 30-60 parts by weight.
A second aspect of the present invention provides a method for preparing a vulcanized rubber, the method comprising: the respective components in the rubber composition of the aforementioned first aspect are kneaded to form a final batch, and the final batch is subjected to a vulcanization treatment.
A third aspect of the present invention provides a vulcanized rubber prepared by the above-described method.
A fourth aspect of the invention provides the use of the above-described vulcanized rubber in shoe soles.
The fifth aspect of the present invention provides the use of the above rubber composition for the preparation of a rubber for shoe soles.
The rubber composition provided by the invention has the advantages of high rubber strength, good wear resistance and good flex resistance when being used for preparing soles.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a rubber composition for shoe soles, which contains the following components stored independently of each other or in a mixture of two or more of them: the rubber composition comprises main rubber, white carbon black, zinc methacrylate, a surface modifier, hydrogenated terpene resin, an activating agent, a softening agent, a vulcanizing agent, an auxiliary crosslinking agent, an anti-aging agent and an additive, wherein the main rubber is a combination of styrene butadiene rubber and ethylene propylene diene monomer, the additive is calcium sulfate whisker or anhydrite, and the vulcanizing agent is a peroxide vulcanizing agent;
in the main rubber, the mass ratio of the styrene-butadiene rubber to the ethylene propylene diene monomer rubber is 10:90 to 40:60, adding a solvent to the mixture;
relative to 100 parts by weight of the main rubber, the white carbon black content is 20-30 parts by weight, the zinc methacrylate content is 5-15 parts by weight, the surface modifier content is 3-7 parts by weight, the hydrogenated terpene resin content is 10-15 parts by weight, the activator content is 3-6 parts by weight, the softener content is 5-8 parts by weight, the vulcanizing agent content is 1-5 parts by weight, the co-crosslinking agent content is 1-5 parts by weight, the anti-aging agent content is 1-3 parts by weight, and the additive content is 5-15 parts by weight; and the total amount of the white carbon black, the zinc methacrylate and the additive is 30-60 parts by weight.
The inventors have found that the strength, wear resistance and flex resistance of a vulcanized rubber prepared from the rubber composition can be improved by adding a specific amount of zinc methacrylate, white carbon black and calcium sulfate whisker or anhydrite as additives to the rubber composition together as a filler and simultaneously compounding the filler with a specific amount of a hydrogenated terpene resin.
Preferably, in the main body rubber, the mass ratio of the styrene-butadiene rubber to the ethylene propylene diene monomer is 20:80 to 30:70;
relative to 100 parts by weight of the main rubber, the white carbon black content is 23-27 parts by weight, the zinc methacrylate content is 8-12 parts by weight, the surface modifier content is 5-6 parts by weight, the hydrogenated terpene resin content is 11-14 parts by weight, the activator content is 4-5 parts by weight, the softener content is 5-7 parts by weight, the vulcanizing agent content is 2-4 parts by weight, the co-crosslinking agent content is 2-4 parts by weight, the anti-aging agent content is 2-3 parts by weight, and the additive content is 8-12 parts by weight; and the total amount of the white carbon black, the zinc methacrylate and the additive is 39-51 parts by weight.
According to a preferred embodiment, the additive is calcium sulfate whisker, and the total amount of the white carbon black, the zinc methacrylate and the calcium sulfate whisker is 40 to 51 parts by weight with respect to 100 parts by weight of the main rubber.
According to another preferred embodiment, the additive is anhydrite, and the total amount of the white carbon, the zinc methacrylate and the anhydrite is 39 to 49 parts by weight with respect to 100 parts by weight of the body rubber.
Preferably, the styrene-butadiene rubber is emulsion polymerized styrene-butadiene rubber and/or solution polymerized styrene-butadiene rubber.
Preferably, the ethylene-propylene-diene monomer rubber contains 50-60 wt% of ethylene structural units, 30-41 wt% of propylene structural units and the third monomer is ethylidene norbornene.
Preferably, the white carbon black is fumed silica and/or precipitated silica, and preferably precipitated silica.
Preferably, the nitrogen adsorption specific surface area of the white carbon black is 80-220m 2 Per g, preferably from 110 to 190m 2 /g。
Preferably, the average aspect ratio of the calcium sulfate whiskers is 30-80, preferably 30-50.
Preferably, the calcium sulfate whiskers have an average diameter of 1 to 6 μm, preferably 1 to 3 μm.
Preferably, the mean diameter of the anhydrite is from 10 to 35 μm, preferably from 10 to 15 μm.
Preferably, the surface modifier is at least one of a silane coupling agent, a zirconate coupling agent, a phthalate coupling agent and an alcohol compound. More preferably, the surface modifier is a silane coupling agent.
Preferably, the surface modifier is at least one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide (Si 69), bis- [3- (triethoxysilyl) propyl ] disulfide (Si 75), and gamma-methacryloxypropyltrimethoxysilane (KH 570).
In the present invention, the zirconate coupling agent may be, for example, diethyl dicitrate dipropoxy zirconate, and the phthalate coupling agent may be, for example, at least one of isopropyl tris (stearoyl) phthalate, isopropyl tris (isooctanoyl) phthalate, and isopropyl tris (dodecylbenzenesulfonyl) phthalate. The alcohol compound used as the surface modifier is polyethylene glycol and isopropanol.
Preferably, the activator is a combination of a metal oxide and a fatty acid.
Preferably, in the activator, the metal oxide is zinc oxide and/or magnesium oxide and the fatty acid is stearic acid.
Preferably, the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, and white mineral oil.
Preferably, the sulfurizing agent is at least one of dicumyl peroxide, di-tert-butylperoxydiisopropylbenzene, and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane.
Preferably, the auxiliary crosslinking agent is at least one of triallyl isocyanurate, triallyl cyanurate, trimethylolpropane trimethacrylate and N, N' -m-phenylene bismaleimide.
Preferably, the anti-aging agent is at least one of amine anti-aging agents, quinoline anti-aging agents, benzimidazole anti-aging agents and phenol anti-aging agents. More preferably, the antioxidant is at least one of antioxidant 264, antioxidant RD, antioxidant 4010NA, antioxidant D and antioxidant MB.
As previously mentioned, a second aspect of the present invention provides a process for preparing a vulcanized rubber, the process comprising: the respective components in the rubber composition of the aforementioned first aspect are kneaded to form a final batch, and the final batch is subjected to a vulcanization treatment.
In the present invention, the kneading method is not particularly limited as long as the raw materials of the components of the rubber composition can be uniformly mixed. For example, the components of the rubber composition may be simultaneously kneaded, or several of the components may be kneaded first, and then the remaining components may be added to continue kneading.
However, in order to obtain higher strength, better abrasion resistance and better flex resistance, according to a preferred embodiment, the step of subjecting the components of the rubber composition of the aforementioned first aspect to said compounding comprises:
(1) Carrying out first mixing on main rubber, white carbon black, an additive and a surface modifier to obtain first mixed rubber;
(2) Carrying out second mixing on zinc methacrylate, hydrogenated terpene resin, an activating agent, an anti-aging agent and a softening agent with the first mixed rubber to obtain second mixed rubber;
(3) And carrying out third mixing on a vulcanizing agent, an auxiliary crosslinking agent and the second mixed rubber to obtain a final rubber.
According to another preferred embodiment, the step of subjecting the respective components of the rubber composition of the first aspect to the kneading comprises:
(1) Firstly plasticating the main rubber to obtain plasticated rubber, and then carrying out first mixing on the plasticated rubber, white carbon black, an additive and a surface modifier to obtain first mixed rubber;
(2) Carrying out second mixing on zinc methacrylate, hydrogenated terpene resin, an activating agent, an anti-aging agent and a softening agent with the first mixed rubber to obtain second mixed rubber;
(3) And carrying out third mixing on a vulcanizing agent, an auxiliary crosslinking agent and the second mixed rubber to obtain a final rubber.
Preferably, the conditions of the mastication at least satisfy: the plasticating temperature is 70-90 ℃, and the plasticating time is 0.5-1min.
Preferably, said first mixing, said second mixing, said third mixing and said masticating are each independently carried out in an internal mixer and/or an open mill.
The inventors have found that the strength, abrasion resistance and flex resistance of the vulcanizate can be improved with this preferred embodiment.
Preferably, in step (1), the conditions of the first mixing are at least satisfied: the mixing temperature is 100-160 ℃, the mixing time is 2-8min, and more preferably, the first mixing condition at least satisfies the following conditions: the mixing temperature is 140-150 ℃; the mixing time is 2-4min. When the mastication process is included, the time during the mastication process is not counted in the time of the first mixing.
Preferably, in step (2), the conditions of the second mixing are at least satisfied: the mixing temperature is 120-170 ℃, the mixing time is 3-8min, more preferably, the second mixing conditions at least satisfy: the mixing temperature is 145-165 ℃; the mixing time is 5-7min.
Preferably, in step (3), the conditions of the third mixing are at least satisfied: the mixing temperature is not higher than 120 ℃, the mixing time is 4-6min, and more preferably, the third mixing condition at least satisfies the following conditions: the mixing temperature is 90-110 ℃, and the mixing time is 4-5min.
Preferably, the conditions of the vulcanization treatment at least satisfy: the vulcanizing time is 10-45min, the vulcanizing temperature is 150-180 ℃, the vulcanizing pressure is 3.5-40MPa, and more preferably, the vulcanizing treatment conditions at least meet the following conditions: the vulcanizing time is 10-25min, the vulcanizing temperature is 165-180 ℃, and the vulcanizing pressure is 10-20MPa. The inventors found that the final rubber compound is subjected to the above-mentioned vulcanization treatment, and the finally obtained vulcanized rubber has better mechanical properties (improved strength and better wear resistance) and better flex resistance.
In the present invention, the pressures are gauge pressures unless otherwise specified.
As previously mentioned, a third aspect of the present invention provides a vulcanizate prepared by the above-described method.
As previously mentioned, a fourth aspect of the invention provides the use of a vulcanized rubber as described above in a shoe sole.
As described above, the fifth aspect of the present invention provides the use of the above-mentioned rubber composition for the production of a rubber for shoe soles.
The present invention will be described in detail below by way of examples. In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
The equipment involved in the following examples is shown in table 1 and the test methods are shown in table 2.
The chemicals used in the examples are commercially available and are specified below:
styrene-butadiene rubber I: the PR1205 brand, solution polymerized styrene butadiene rubber, produced by Taiwan Qimei industries GmbH.
Styrene-butadiene rubber II: the product is 1502, emulsion polymerized styrene butadiene rubber, produced by the company of Qilu petrochemical division, china.
Ethylene propylene diene monomer I: 4045, the content of ethylene structural units is 52 wt%, the content of propylene structural units is 40 wt%, the third monomer is ethylidene norbornene, produced by Jilin petrochemical company.
Ethylene propylene diene monomer II: 4070, the ethylene structural unit content is 58.5 wt%, the propylene structural unit content is 31 wt%, the third monomer is ethylidene norbornene, manufactured by Jilin petrochemical company.
White carbon black: 165GR, nitrogen adsorption specific surface area of 165. + -.15 m 2 G, produced by Rodiya, france.
Zinc methacrylate: manufactured by chemical technology, inc., of Ke chemical engineering (Beijing).
Calcium sulfate whisker: average aspect ratio of 45, average diameter of 4 μm, produced by Shenyang Dongdong mineral materials research & development Co.
Anhydrite: average diameter of 13 μm, manufactured by Hengtai new building materials, inc., anhui.
Surface modifier: bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide (Si 69), manufactured by Nanjing eosin chemical Co., ltd.
Hydrogenated terpene resin: manufactured by Nochi chemical technology, inc., guangzhou.
Softening agent: white mineral oil No. 10 (10 # white oil for short), produced by Shandong Taichang petrochemical science and technology Limited.
Activating agent: zinc oxide, stearic acid, weifang Heng Feng chemical company.
An anti-aging agent I: 2,6-di-tert-butyl-p-cresol (anti-aging agent 264), manufactured by Panzhihua chemical (Shanghai) Co., ltd.
And (3) an anti-aging agent II: 2-mercaptobenzimidazole (antioxidant MB), manufactured by Gaoyi county Li and chemical Co., ltd.
Vulcanizing agent: DCP, shanghai Fang Rui, manufactured by Chemicals, inc.
Auxiliary crosslinking agent: TAIC, manufactured by petrochemical technology development corporation of jingling, south beijing.
TABLE 1
| Serial number | Device name | Model number | Manufacturer of the product |
| 1 | Internal mixer | BR1600 | Rall of American Farad |
| 2 | Open mill | XK-160 | Qingdao Xincheng Yiming mechanical Co Ltd |
| 3 | Flat vulcanizing machine | XLB-D400*400*2 | Shanghai first rubber machinery plant |
| 1 | Universal tensile machine | SHIMADZU，AG-20KNG | JapaneseShimadzu corporation |
| 2 | Rubber bending tester | GT-7011-GLH | Taiwan high speed railway, china |
| 3 | Akron abrasion machine | GT-7012-A | Taiwan high speed railway, china |
TABLE 2
Unless otherwise specified, 10g is represented per part by weight (or per part) in the following examples; the temperature ranges in the following examples represent the actual temperature changes as indicated by the temperature monitors during the mixing process.
Preparation example 1: preparation of vulcanized rubber
First mixing:
and adding the main rubber into an internal mixer, setting the rotating speed of the internal mixer to be 80rpm, and setting the plastication temperature of the internal mixer for plastication to obtain plasticated rubber. And then adding the white carbon black, the additive and the surface modifier into an internal mixer, setting the mixing temperature of the internal mixer, and carrying out first mixing with the plasticated rubber to obtain a first mixed rubber.
And (3) second mixing:
and lifting the upper top bolt of the internal mixer of the first mixing, mixing the zinc methacrylate, the hydrogenated terpene resin, the activating agent, the anti-aging agent and the softening agent with the first mixed rubber for the second mixing, discharging rubber, and standing for 4 hours to obtain a second mixed rubber.
And (3) third mixing:
and plasticating the second rubber compound in an internal mixer at the rotation speed of 80rpm and the initial plastication temperature of 40 ℃ for 1min, and adding a vulcanizing agent and an auxiliary crosslinking agent for third mixing to obtain the final rubber compound.
The final rubber batch was passed through an open mill with a roller gap of 5mm three times and the final rubber batch obtained was left for 24 hours.
The final rubber compound was vulcanized on a press vulcanizer having a temperature and a pressure set to obtain a vulcanized rubber, which was designated as Z1, and subjected to a performance test, and the results are shown in Table 6. Information on the necessary process conditions and the like in the present production examples are shown in tables 3 and 4.
Preparation example 12
And (3) second mixing:
and adding the main rubber into an internal mixer, setting the rotating speed of the internal mixer to be 80rpm, and setting the plastication temperature of the internal mixer for plastication to obtain plasticated rubber. And then adding the white carbon black, the additive, the surface modifier, the zinc methacrylate, the hydrogenated terpene resin, the activator, the anti-aging agent and the softener into an internal mixer, setting the mixing temperature of the internal mixer, and carrying out second mixing with the plasticated rubber to obtain a second mixed rubber.
And (3) third mixing:
and plasticating the second rubber compound in an internal mixer at the rotation speed of 80rpm and the initial plastication temperature of 40 ℃ for 1min, and adding a vulcanizing agent and an auxiliary crosslinking agent for third mixing to obtain the final rubber compound.
The final rubber is passed through an open mill with the roller spacing of 5mm for three times, and the obtained open mill rubber is parked for 24 hours.
The final rubber was vulcanized on a press vulcanizer having a temperature and a pressure set to obtain a vulcanized rubber, which was designated as Z12, and subjected to a performance test, and the results are shown in Table 6. Information on the necessary process conditions and the like in the present production examples are shown in tables 3 and 4.
Unless otherwise specified, the same procedures as in preparation example 1 were followed for the other preparation examples, except that the process conditions and the component formulations were as shown in Table 3, the component formulations were as shown in Table 4, and the results of the performance tests were as shown in Table 6.
TABLE 3
TABLE 4
Table 4 (continuation watch)
Comparative example 1
A vulcanizate was prepared according to the formulation and method of preparation example 1, except that: the zinc methacrylate was replaced with an equal weight portion of white carbon black, and the final vulcanized rubber was designated as D1, specifically as shown in table 5, and the results of the performance tests are shown in table 6.
Comparative example 2
A vulcanized rubber was prepared according to the formulation and method of preparation example 2, except that: the calcium sulfate whiskers are replaced by equal parts by weight of white carbon black, the finally prepared vulcanized rubber is recorded as D2, specifically shown in Table 5, and the performance test results are shown in Table 6.
Comparative example 3
A vulcanizate was prepared according to the formulation and method of preparation example 3, except that: the white carbon black was replaced with an equal weight part of zinc methacrylate, and the finally obtained vulcanized rubber was recorded as D3, specifically shown in table 5, and the results of the performance tests are shown in table 6.
Comparative example 4
A vulcanized rubber was prepared according to the formulation and method of preparation example 4, except that: white carbon black was replaced with equal parts by weight of anhydrite, and the finally obtained vulcanized rubber was recorded as D4, specifically as shown in table 5, and the results of the performance tests are shown in table 6.
Comparative example 5
A vulcanized rubber was prepared by following the procedure of preparation example 5, except that: the anhydrite was replaced with equal parts by weight of white carbon black, and the finally obtained vulcanized rubber was recorded as D5, specifically as shown in table 5, and the results of the performance tests are shown in table 6.
Comparative example 6
A vulcanized rubber was prepared by following the procedure of preparation example 6, except that: the final vulcanizate was identified as D6 without the use of hydrogenated terpene resin, as shown in Table 5, and the results of the performance testing are shown in Table 6.
TABLE 5
TABLE 6
| Sample numbering | High tensile strengthDegree (MPa) | Akron abrasion (cm) 3 ) | Fatigue life (thousands times) |
| Z1 | 10.8 | 0.31 | 4.8 |
| Z2 | 11.9 | 0.34 | 4.6 |
| Z3 | 11.1 | 0.33 | 4.4 |
| Z4 | 11.2 | 0.33 | 4.7 |
| Z5 | 12.1 | 0.32 | 4.6 |
| Z6 | 11.6 | 0.34 | 4.4 |
| Z7 | 9.4 | 0.48 | 3.4 |
| Z8 | 10.4 | 0.45 | 3.8 |
| Z9 | 10.5 | 0.44 | 3.6 |
| Z10 | 9.8 | 0.49 | 3.4 |
| Z11 | 9.3 | 0.49 | 3.7 |
| Z12 | 9.2 | 0.46 | 3.5 |
| D1 | 7.4 | 0.71 | 2.7 |
| D2 | 8.1 | 0.61 | 2.2 |
| D3 | 7.5 | 0.63 | 2.4 |
| D4 | 7.0 | 0.64 | 2.5 |
| D5 | 8.2 | 0.63 | 2.4 |
| D6 | 6.6 | 0.69 | 2.3 |
As can be seen from the results in Table 6, the vulcanizates produced from the improved rubber compositions of the present invention are capable of improving the strength, abrasion resistance and flex resistance of the vulcanized rubber products.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (26)
1. A rubber composition for shoe soles, characterized in that the composition contains the following components stored independently or in a mixture of two or more of them: the rubber composition comprises main body rubber, white carbon black, zinc methacrylate, a surface modifier, hydrogenated terpene resin, an activating agent, a softening agent, a vulcanizing agent, an auxiliary crosslinking agent, an anti-aging agent and an additive, wherein the main body rubber is the combination of styrene butadiene rubber and ethylene propylene diene monomer, the additive is calcium sulfate whisker or anhydrite, and the vulcanizing agent is a peroxide vulcanizing agent;
the nitrogen adsorption specific surface area of the white carbon black is 80-220m 2 (ii)/g; the average length-diameter ratio of the calcium sulfate whisker is 30-80, and the average diameter is 1-6 mu m; the average diameter of the anhydrite is 10-35 mu m;
in the main rubber, the mass ratio of the styrene-butadiene rubber to the ethylene propylene diene monomer is 10:90 to 40:60;
relative to 100 parts by weight of the main rubber, the white carbon black content is 20-30 parts by weight, the zinc methacrylate content is 5-15 parts by weight, the surface modifier content is 3-7 parts by weight, the hydrogenated terpene resin content is 10-15 parts by weight, the activator content is 3-6 parts by weight, the softener content is 5-8 parts by weight, the vulcanizing agent content is 1-5 parts by weight, the co-crosslinking agent content is 1-5 parts by weight, the anti-aging agent content is 1-3 parts by weight, and the additive content is 5-15 parts by weight; and the total amount of the white carbon black, the zinc methacrylate and the additive is 30-60 parts by weight.
2. The rubber composition according to claim 1, wherein the content mass ratio of the styrene-butadiene rubber to the ethylene-propylene-diene monomer in the main rubber is 20:80 to 30:70;
relative to 100 parts by weight of the main rubber, the white carbon black content is 23-27 parts by weight, the zinc methacrylate content is 8-12 parts by weight, the surface modifier content is 5-6 parts by weight, the hydrogenated terpene resin content is 11-14 parts by weight, the activator content is 4-5 parts by weight, the softener content is 5-7 parts by weight, the vulcanizing agent content is 2-4 parts by weight, the co-crosslinking agent content is 2-4 parts by weight, the anti-aging agent content is 2-3 parts by weight, and the additive content is 8-12 parts by weight; and the total amount of the white carbon black, the zinc methacrylate and the additive is 39-51 parts by weight.
3. The rubber composition according to claim 1 or 2, wherein the additive is calcium sulfate whiskers, and the total amount of the white carbon, the zinc methacrylate, and the calcium sulfate whiskers is 40 to 51 parts by weight relative to 100 parts by weight of the main rubber; or
The additive is anhydrite, and the total amount of the white carbon black, the zinc methacrylate and the anhydrite is 39-49 parts by weight relative to 100 parts by weight of the main rubber.
4. The rubber composition according to claim 1 or 2, wherein the styrene-butadiene rubber is emulsion-polymerized styrene-butadiene rubber and/or solution-polymerized styrene-butadiene rubber.
5. The rubber composition according to claim 1 or 2, wherein the ethylene-propylene-diene monomer has an ethylene structural unit content of 50 to 60 wt%, a propylene structural unit content of 30 to 41 wt%, and the third monomer is ethylidene norbornene.
6. The rubber composition according to claim 1 or 2, wherein the white carbon is fumed silica and/or precipitated silica.
7. The rubber composition according to claim 1 or 2, wherein the white carbon is precipitated white carbon.
8. The rubber composition according to claim 1 or 2, wherein the silica has a nitrogen adsorption specific surface area of 110 to 190m 2 (ii)/g; the average length-diameter ratio of the calcium sulfate whisker is 30-50; the average diameter of the calcium sulfate whisker is 1-3 μm; the average diameter of the anhydrite is 10-15 mu m.
9. The rubber composition according to claim 1 or 2, wherein the surface modifier is at least one of a silane coupling agent, a zirconate coupling agent, a phthalate coupling agent, and an alcohol compound, and the alcohol compound is at least one of polyethylene glycol and isopropyl alcohol.
10. The rubber composition according to claim 1 or 2, wherein the surface modifier is a silane coupling agent.
11. The rubber composition according to claim 1 or 2, wherein the surface modifier is at least one of bis- [ γ - (triethoxysilyl) propyl ] tetrasulfide, bis- [3- (triethoxysilyl) propyl ] disulfide, and γ -methacryloxypropyltrimethoxysilane.
12. The rubber composition according to claim 1 or 2, wherein the activator is a combination of a metal oxide and a fatty acid.
13. The rubber composition according to claim 1 or 2, wherein in the activator, the metal oxide is zinc oxide and/or magnesium oxide, and the fatty acid is stearic acid.
14. The rubber composition according to claim 1 or 2, wherein the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, and white mineral oil.
15. The rubber composition of claim 1 or 2, wherein the vulcanizing agent is at least one of dicumyl peroxide, di-tert-butylperoxydiisopropylbenzene, and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane.
16. The rubber composition according to claim 1 or 2, wherein the auxiliary crosslinking agent is at least one of triallyl isocyanurate, triallyl cyanurate, trimethylolpropane trimethacrylate, and N, N' -m-phenylene bismaleimide.
17. The rubber composition according to claim 1 or 2, wherein the antioxidant is at least one of an amine antioxidant, a quinoline antioxidant, a benzimidazole antioxidant, and a phenol antioxidant.
18. The rubber composition according to claim 1 or 2, wherein the antioxidant is at least one of antioxidant 264, antioxidant RD, antioxidant 4010NA, antioxidant D and antioxidant MB.
19. A method of preparing a vulcanizate, the method comprising: mixing the components of the rubber composition of any one of claims 1 to 18 to form a final batch, and subjecting the final batch to a vulcanization treatment.
20. The method of claim 19, wherein said mixing the components comprises the steps of:
(1) Carrying out first mixing on main rubber, white carbon black, an additive and a surface modifier to obtain first mixed rubber;
(2) Carrying out second mixing on zinc methacrylate, hydrogenated terpene resin, an activating agent, an anti-aging agent and a softening agent with the first mixed rubber to obtain second mixed rubber;
(3) And carrying out third mixing on a vulcanizing agent, an auxiliary crosslinking agent and the second mixed rubber to obtain a final rubber.
21. The method of claim 19 or 20, wherein the method further comprises: firstly plasticating the main rubber to obtain plasticated rubber, and then carrying out the mixing on the plasticated rubber and the rest components in the rubber composition;
the plastication conditions at least satisfy: the plasticating temperature is 70-90 ℃, and the plasticating time is 0.5-1min.
22. A method according to any one of claims 20, wherein in step (1), the conditions of the first mixing are at least such that: the mixing temperature is 100-160 ℃, and the mixing time is 2-8min;
in the step (2), the conditions of the second mixing at least satisfy: the mixing temperature is 120-170 ℃, and the mixing time is 3-8min;
in the step (3), the third mixing conditions at least satisfy: the mixing temperature is not higher than 120 ℃, and the mixing time is 4-6min;
the conditions of the vulcanization treatment at least satisfy: the vulcanizing time is 10-45min, the vulcanizing temperature is 150-180 ℃, and the vulcanizing pressure is 3.5-40MPa.
23. A method according to any one of claims 20, wherein in step (1), the conditions of the first mixing are at least such that: the mixing temperature is 140-150 ℃, and the mixing time is 2-4min;
in the step (2), the second mixing conditions at least satisfy: the mixing temperature is 145-165 ℃, and the mixing time is 5-7min;
in the step (3), the third mixing conditions at least satisfy: the mixing temperature is 90-110 ℃, and the mixing time is 4-5min;
the vulcanization time at least satisfies the following conditions: the vulcanizing time is 10-25min, the vulcanizing temperature is 165-180 ℃, and the vulcanizing pressure is 10-20MPa.
24. A vulcanized rubber produced by the process of any one of claims 19-23.
25. Use of the vulcanizate of claim 24 for the preparation of shoe soles.
26. Use of the rubber composition according to any one of claims 1 to 18 for the preparation of rubber for shoe soles.
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| WO2009110562A1 (en) * | 2008-03-07 | 2009-09-11 | Jsr株式会社 | Thermoplastic elastomer composition |
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| EP0930337A2 (en) * | 1998-01-20 | 1999-07-21 | JSR Corporation | Thermoplastic elastomer composition |
| CN1747999A (en) * | 2003-02-05 | 2006-03-15 | Jsr株式会社 | Flame-retardant rubber composition, rubber articles and wire covering materials |
| CN1637065A (en) * | 2003-11-28 | 2005-07-13 | Jsr株式会社 | Oil-resistant and weather-resistant rubber composition and molded article using the same |
| WO2009110562A1 (en) * | 2008-03-07 | 2009-09-11 | Jsr株式会社 | Thermoplastic elastomer composition |
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