KR102620795B1 - Rubber composition for tire tread and Tire comprising the rubber composition - Google Patents
Rubber composition for tire tread and Tire comprising the rubber composition Download PDFInfo
- Publication number
- KR102620795B1 KR102620795B1 KR1020210150854A KR20210150854A KR102620795B1 KR 102620795 B1 KR102620795 B1 KR 102620795B1 KR 1020210150854 A KR1020210150854 A KR 1020210150854A KR 20210150854 A KR20210150854 A KR 20210150854A KR 102620795 B1 KR102620795 B1 KR 102620795B1
- Authority
- KR
- South Korea
- Prior art keywords
- rubber composition
- tire
- rubber
- earth metal
- alkaline earth
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 92
- 239000005060 rubber Substances 0.000 title claims abstract description 92
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 20
- 239000005011 phenolic resin Substances 0.000 claims abstract description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 10
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910019440 Mg(OH) Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 18
- -1 bromobutyl Chemical group 0.000 description 17
- 244000043261 Hevea brasiliensis Species 0.000 description 16
- 229920003052 natural elastomer Polymers 0.000 description 16
- 229920001194 natural rubber Polymers 0.000 description 16
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011324 bead Substances 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 9
- 150000004756 silanes Chemical class 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 230000003712 anti-aging effect Effects 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 7
- 229960002447 thiram Drugs 0.000 description 7
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000010692 aromatic oil Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012991 xanthate Substances 0.000 description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- 239000000446 fuel Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 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 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
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- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- GPRYVSOUOYKCHJ-UHFFFAOYSA-N 1-[chloro(fluoro)methoxy]-1,1,2,3,3,3-hexafluoropropane Chemical compound FC(Cl)OC(F)(F)C(F)C(F)(F)F GPRYVSOUOYKCHJ-UHFFFAOYSA-N 0.000 description 1
- MINNIIWBFAPUKJ-UHFFFAOYSA-N 1-n-octyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NCCCCCCCC)=CC=C1NC1=CC=CC=C1 MINNIIWBFAPUKJ-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
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- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
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- YBKBEKGVHFHCRI-UHFFFAOYSA-L zinc;piperidine-1-carbodithioate Chemical compound [Zn+2].[S-]C(=S)N1CCCCC1.[S-]C(=S)N1CCCCC1 YBKBEKGVHFHCRI-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
원료 고무로서 스티렌부타디엔 고무; 필러로서 실리카; 페놀계 레진; 및 알칼리토금속 이온 함유 화합물;을 포함하는, 타이어 트레드 고무 조성물이 개시된다.Styrene butadiene rubber as a raw material rubber; Silica as filler; Phenolic resin; A tire tread rubber composition comprising a compound containing alkaline earth metal ions is disclosed.
Description
타이어 트레드 고무 조성물 및 이를 포함하는 타이어에 관한 것이다.It relates to a tire tread rubber composition and a tire containing the same.
자동차의 타이어는 무거운 하중을 지탱하며, 고속 회전하는 물체이다. 타이어의 내구성에 가장 큰 영향을 미치는 트레드는 지면과의 맞닿아 있어 타이어의 주행 성능에 많은 영향을 미치게 된다.Car tires are objects that support heavy loads and rotate at high speeds. The tread, which has the greatest impact on the durability of a tire, is in contact with the ground and has a great impact on the driving performance of the tire.
타이어 트레드 고무가 가져야 할 특성으로서 조정 안정성, 승차감, 연비성능, 스노우 성능, 내마모 성능, 제동 성능, 내구력 등이 있다.The characteristics that tire tread rubber must have include steering stability, ride comfort, fuel efficiency, snow performance, abrasion resistance, braking performance, and durability.
한 측면은 히스테리시스 증가 없이 그립력을 향상시켜 습윤 제동력을 향상시킨 트레드 고무 조성물을 제공하는 것이다.One aspect is to provide a tread rubber composition that improves wet braking by improving grip without increasing hysteresis.
다른 한 측면은 상기 고무 조성물로 제조된 타이어를 제공하는 것이다.Another aspect is to provide a tire made from the rubber composition.
한 측면에 따라,According to one aspect,
원료 고무로서 스티렌부타디엔 고무; Styrene butadiene rubber as a raw material rubber;
필러로서 실리카; Silica as filler;
페놀계 레진; 및 Phenolic resin; and
알칼리토금속 이온 함유 화합물;을 Compounds containing alkaline earth metal ions;
포함하는, 타이어 트레드 고무 조성물이 제공된다. A tire tread rubber composition is provided, comprising:
다른 한 측면에 따라,According to one other aspect,
상기 타이어 트레드 고무 조성물로 제조된 타이어가 제공된다.A tire made from the tire tread rubber composition is provided.
본 발명의 일 구현예에 따른 타이어 트레드 고무 조성물을 사용한 타이어는 실리카 및 레진 함량은 유지하여 히스테리시스 증가를 유발하지 않고도, 그립력을 향상시켜 습윤 제동력을 향상시켰다.Tires using the tire tread rubber composition according to one embodiment of the present invention maintained the silica and resin contents and improved wet braking power by improving grip without causing an increase in hysteresis.
도 1은 일 구현예에 따른 타이어의 구조를 개략적으로 나타낸 도면이다.
도 2는 페놀계 레진 및 알칼리토금속 이온 함유 화합물이 결합하여 complex를 형성하는 것을 모식적으로 나타낸 그림이다.
도 3은 일 구현예에 따른 트레드 고무 조성물에서 고무, 페놀계 레진 및 알칼리토금속 이온 함유 화합물이 3차원적으로 작용하여 거대 complex를 형성하는 것을 모식적으로 나타낸 그림이다.Figure 1 is a diagram schematically showing the structure of a tire according to an embodiment.
Figure 2 is a diagram schematically showing the combination of a phenol-based resin and an alkaline earth metal ion-containing compound to form a complex.
Figure 3 is a diagram schematically showing the three-dimensional action of rubber, phenolic resin, and an alkaline earth metal ion-containing compound to form a large complex in a tread rubber composition according to an embodiment.
이하에서 예시적인 일 구현예에 타이어 트레드 고무 조성물 및 타이어에 관하여 더욱 상세히 설명한다.Hereinafter, the tire tread rubber composition and tire in one exemplary embodiment will be described in more detail.
본 명세서에 개시된 창의적 사상은 다양한 변환을 가할 수 있고 여러 가지 구현예를 가질 수 있는 바, 특정 구현예들을 상세한 설명에 상세하게 설명하고 필요한 경우 특정 구현예들을 도면에 예시한다. 본 명세서의 창의적 사상의 효과 및 특징, 그리고 그것들을 달성하는 방법은 도면과 함께 상세하게 후술되어 있는 구현예들을 참조하면 명확해질 것이다. 그러나 본 명세서의 창의적 사상은 이하에서 개시되는 구현예들에 한정되는 것이 아니라 다양한 형태로 구현될 수 있다. The creative idea disclosed in this specification can be subjected to various transformations and can have various implementation examples, and specific implementation examples are described in detail in the detailed description and, if necessary, specific implementation examples are illustrated in the drawings. The effects and features of the creative ideas of this specification and methods for achieving them will become clear by referring to the implementation examples described in detail below along with the drawings. However, the creative ideas of the present specification are not limited to the implementation examples disclosed below and may be implemented in various forms.
이하의 구현예에서, 제1, 제2 등의 용어는 한정적인 의미가 아니라 하나의 구성 요소를 다른 구성 요소와 구별하는 목적으로 사용되었다. In the following implementation examples, terms such as first and second are used not in a limiting sense but for the purpose of distinguishing one component from another component.
이하의 구현예에서, 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다.In the following embodiments, singular terms include plural terms unless the context clearly dictates otherwise.
이하의 구현예에서, 포함하다 또는 가지다 등의 용어는 명세서상에 기재된 특징, 또는 구성요소가 존재함을 의미하는 것이고, 하나 이상의 다른 특징들 또는 구성요소가 부가될 가능성을 미리 배제하는 것은 아니다. In the following implementation examples, terms such as include or have mean that the features or components described in the specification exist, and do not preclude the possibility of adding one or more other features or components.
일 구현예가 달리 구현 가능한 경우에 특정한 공정 순서는 설명되는 순서와 다르게 수행될 수도 있다. 예를 들어, 연속하여 설명되는 두 공정이 실질적으로 동시에 수행될 수도 있고, 설명되는 순서와 반대의 순서로 진행될 수 있다. In cases where an embodiment can be implemented differently, a specific process sequence may be performed differently from the described sequence. For example, two processes described in succession may be performed substantially at the same time, or may be performed in an order opposite to that in which they are described.
이하, 필요한 경우에, 첨부된 도면을 참조하여 본 발명의 구현예들을 상세히 설명하며, 도면을 참조하여 설명할 때 동일하거나 대응하는 구성 요소는 동일한 도면부호를 부여하고 이에 대한 중복되는 설명은 생략하기로 한다. Hereinafter, when necessary, embodiments of the present invention will be described in detail with reference to the accompanying drawings. When describing with reference to the drawings, identical or corresponding components will be assigned the same reference numerals and redundant description thereof will be omitted. Do this.
도면에서는 설명의 편의를 위하여 구성 요소들이 그 크기가 과장 또는 축소될 수 있다. 예컨대, 도면에서 나타난 각 구성의 크기 및 두께는 설명의 편의를 위해 임의로 나타내었으므로, 본 명세서에 개시된 창의적 사상이 반드시 도시된 바에 한정되지 않는다. In the drawings, the sizes of components may be exaggerated or reduced for convenience of explanation. For example, the size and thickness of each component shown in the drawings are shown arbitrarily for convenience of explanation, so the creative ideas disclosed in this specification are not necessarily limited to what is shown.
타이어의 습윤 제동 성능은 트레드 고무 조성물의 특성 및 노면 거칠기 특성에 영향을 받는다. 트레드 고무 조성물에 실리카와 같은 친수성 보강제를 적용하여 물과의 친화성을 높이거나 그립 레진과 같은 첨가제를 적용하여 그립력을 증가시켜 습윤 제동 성능을 향상시킬 수 있다.The wet braking performance of a tire is affected by the properties of the tread rubber composition and the road surface roughness characteristics. Wet braking performance can be improved by applying a hydrophilic reinforcing agent such as silica to the tread rubber composition to increase affinity for water, or by increasing grip strength by applying additives such as grip resin.
그런데, 습윤 제동 성능 향상을 위해 실리카 함량 및 그립 레진의 함량을 증가시킬 경우 고무의 히스테리시스 증가로 인해 에너지 손실이 커져 타이어의 회전 저항이 높아지는 단점을 초래한다.However, when the silica content and the grip resin content are increased to improve wet braking performance, energy loss increases due to increased hysteresis of the rubber, resulting in a disadvantage in that the rolling resistance of the tire increases.
따라서, 고무의 에너지 손실 증가를 최소화하고 습윤 제동 성능을 향상시키기 위해서는 실리카 및 그립 레진의 함량은 유지한 채 그립력만을 높이는 배합 설계 기술이 요구된다.Therefore, in order to minimize the increase in energy loss of rubber and improve wet braking performance, a mixing design technology that increases grip strength while maintaining the content of silica and grip resin is required.
일 구현예에 따른 타이어 트레드 고무 조성물은 원료 고무로서 스티렌부타디엔 고무; 필러로서 실리카; 페놀계 레진; 및 알칼리토금속 이온 함유 화합물;을 포함할 수 있다. A tire tread rubber composition according to one embodiment includes styrenebutadiene rubber as a raw rubber; Silica as filler; Phenolic resin; and alkaline earth metal ion-containing compounds.
상기 페놀계 레진은 예를 들어, 일반적인 페놀 레진 이외에 변성(modified) 테르펜 페놀 레진, 테르펜 페놀 레진, 또는 이들의 임의의 조합을 포함할 수 있다.For example, the phenolic resin may include modified terpene phenol resin, terpene phenol resin, or any combination thereof in addition to general phenol resin.
예를 들어, 페놀 레진은 하기 화학식 1로 표시되는 반복 단위를 포함할 수 있다:For example, the phenolic resin may include a repeating unit represented by Formula 1:
<화학식 1><Formula 1>
상기 화학식 1 중, n은 5 내지 70일 수 있다.In Formula 1, n may be 5 to 70.
예를 들어, 상기 변성(modified) 테르펜 페놀 수지는 테르펜과 페놀의 중합체로서 하기 화학식 2로 표시되는 반복 단위를 포함할 수 있다:For example, the modified terpene phenol resin is a polymer of terpene and phenol and may include a repeating unit represented by the following formula (2):
<화학식 2><Formula 2>
상기 화학식 2 중, m은 7 내지 30일 수 있다.In Formula 2, m may be 7 to 30.
본 발명의 일 구현예에 따르면, 상기 알칼리토금속 이온 함유 화합물이 알칼리토금속의 산화물, 알칼리토금속의 수산화물, 또는 이들의 임의의 조합을 포함할 수 있다. According to one embodiment of the present invention, the alkaline earth metal ion-containing compound may include an oxide of an alkaline earth metal, a hydroxide of an alkaline earth metal, or any combination thereof.
상기 알칼리토금속은 예를 들어, 베릴륨, 마그네슘, 칼슘, 스트론튬, 바륨, 라듐 등일 수 있다.The alkaline earth metal may be, for example, beryllium, magnesium, calcium, strontium, barium, radium, etc.
본 발명의 일 구현예에 따르면, 상기 알칼리토금속 이온 함유 화합물이 MgO, Mg(OH)2, CaO, Ca(OH)2 또는 이들의 임의의 조합을 포함할 수 있다. According to one embodiment of the present invention, the alkaline earth metal ion-containing compound may include MgO, Mg(OH) 2 , CaO, Ca(OH) 2 or any combination thereof.
본 발명의 일 구현예에 따른 타이어 트레드 고무 조성물에서, 실리카 및 페놀계 레진의 함량은 유지한 채 습윤 제동 성능을 향상시키기 위해 알칼리토금속 이온 함유 화합물을 첨가하였고, 첨가된 알칼리토금속 이온 함유 화합물의 알칼리토금속 이온은 상기 페놀계 레진의 OH기와 결합을 형성할 수 있다.In the tire tread rubber composition according to one embodiment of the present invention, an alkaline earth metal ion-containing compound was added to improve wet braking performance while maintaining the content of silica and phenolic resin, and the alkali of the added alkaline earth metal ion-containing compound was added. Earth metal ions can form a bond with the OH group of the phenolic resin.
도 2는 페놀계 레진 및 알칼리토금속 이온 함유 화합물이 농화 반응 (thickening reaction)으로 결합하여 complex를 형성하는 것을 모식적으로 나타낸 그림이다.Figure 2 is a diagram schematically showing how a phenol-based resin and an alkaline earth metal ion-containing compound combine through a thickening reaction to form a complex.
이렇게 형성된 complex는 고무와의 혼합 및 가교 과정에서 3차원적으로 작용하여 더욱 거대한 complex를 형성할 수 있다. 이를 도 3에 도식적으로 나타내었다. 도 3은 일 구현예에 따른 트레드 고무 조성물에서 고무, 페놀계 레진 및 알칼리토금속 이온 함유 화합물이 3차원적으로 작용하여 거대 complex를 형성하는 것을 모식적으로 나타낸 그림이다.The complex formed in this way can act three-dimensionally during the mixing and crosslinking process with rubber to form an even larger complex. This is schematically shown in Figure 3. Figure 3 is a diagram schematically showing the three-dimensional action of rubber, phenolic resin, and an alkaline earth metal ion-containing compound to form a large complex in a tread rubber composition according to an embodiment.
이러한 거대 complex는 노면과의 마찰을 증가시키고 결과적으로 습윤 제동력이 향상되는 결과를 가져온다. This large complex increases friction with the road surface, resulting in improved wet braking power.
본 발명의 일 구현예에 따르면, 상기 알칼리토금속 이온 함유 화합물의 함량은 원료 고무 100 중량부를 기준으로 0.1 내지 3.0 중량부일 수 있다.According to one embodiment of the present invention, the content of the alkaline earth metal ion-containing compound may be 0.1 to 3.0 parts by weight based on 100 parts by weight of raw rubber.
상기 알칼리토금속 이온 함유 화합물의 함량이 상기 범위일 때, 습윤 제동력이 최적이 된다.When the content of the alkaline earth metal ion-containing compound is within the above range, the wet braking force is optimal.
본 발명의 일 구현예에 따르면, 상기 페놀계 레진의 연화점은 80 내지 150℃일 수 있다. 본 명세서 중 "연화점"은 레진에 일정한 하중을 가하고 일정한 승온 속도로 가열할 때 변형하기 시작하는 온도를 의미한다.According to one embodiment of the present invention, the softening point of the phenol-based resin may be 80 to 150°C. In this specification, “softening point” refers to the temperature at which the resin begins to deform when a certain load is applied to the resin and heated at a certain temperature increase rate.
본 발명의 일 구현예에 따르면, 상기 페놀계 레진의 함량이 원료 고무 100 중량부를 기준으로 8.0 내지 12 중량부일 수 있다.According to one embodiment of the present invention, the content of the phenolic resin may be 8.0 to 12 parts by weight based on 100 parts by weight of raw rubber.
상기 페놀계 레진의 연화점 및 함량이 상기 범위일 때, 습윤 제동력이 최적이 된다.When the softening point and content of the phenolic resin are within the above range, wet braking power is optimal.
본 발명의 일 구현예에 따르면, 상기 타이어 트레드 고무 조성물은 원료 고무로서 스티렌부타디엔 고무만을 포함할 수 있다. According to one embodiment of the present invention, the tire tread rubber composition may include only styrenebutadiene rubber as the raw rubber.
한편, 상기 타이어 트레드 조성물은 원료 고무로서 예를 들어, 부타디엔 고무, 이소프렌-함유 스티렌 부타디엔 고무, 니트릴 함유 스티렌 부타디엔 고무, 네오프렌 고무, 클로로부틸 고무, 브로모부틸 고무 중에서 선택된 적어도 1종을 더 포함할 수도 있다. Meanwhile, the tire tread composition may further include at least one raw rubber selected from, for example, butadiene rubber, isoprene-containing styrene butadiene rubber, nitrile-containing styrene butadiene rubber, neoprene rubber, chlorobutyl rubber, and bromobutyl rubber. It may be possible.
또한, 상기 고무 조성물은 원료 고무로서 합성 고무 이외에 천연 고무를 더 포함할 수도 있다. 상기 천연고무는 일반적인 천연고무 또는 변성 천연고무일 수 있다.Additionally, the rubber composition may further include natural rubber in addition to synthetic rubber as the raw rubber. The natural rubber may be general natural rubber or modified natural rubber.
상기 일반적인 천연고무는 천연고무로서 알려진 것이면 어느 것이라도 사용될 수 있고, 원산지 등이 한정되지 않는다. 상기 천연고무는 시스-1,4-폴리이소프렌을 주체로서 포함하지만, 요구 특성에 따라서 트랜스-1,4-폴리이소프렌을 포함할 수도 있다. 따라서, 상기 천연고무에는 시스-1,4-폴리이소프렌을 주체로서 포함하는 천연고무 외에, 예컨대 남미산 사포타과의 고무의 일종인 발라타 등, 트랜스-1,4-이소프렌을 주체로서 포함하는 천연고무도 포함할 수 있다.The general natural rubber can be used as long as it is known as natural rubber, and its place of origin is not limited. The natural rubber mainly contains cis-1,4-polyisoprene, but may also contain trans-1,4-polyisoprene depending on required properties. Accordingly, the above-mentioned natural rubber includes, in addition to natural rubber containing cis-1,4-polyisoprene as a main body, natural rubber containing trans-1,4-isoprene as a main body, such as balata, a type of rubber of the Sapotaceae family from South America. It may also contain rubber.
상기 변성 천연고무는, 상기 일반적인 천연고무를 변성 또는 정제한 것을 의미한다. 예컨대, 상기 변성 천연고무로는 에폭시화 천연고무(ENR), 탈단백 천연고무(DPNR), 수소화 천연고무 등을 들 수 있다.The modified natural rubber refers to the general natural rubber that has been modified or refined. For example, the modified natural rubber includes epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber.
본 발명의 일 구현예에 따르면, 상기 고무 조성물은 필러를 포함할 수 있고, 예를 들어, 실리카 및/또는 카본 블랙을 포함할 수 있다. 바람직하게는 상기 고무 조성물은 필러로서 실리카만을 포함할 수 있다.According to one embodiment of the present invention, the rubber composition may include a filler, for example, silica and/or carbon black. Preferably, the rubber composition may contain only silica as a filler.
상기 실리카는 일반적으로 알려진 것이면 어느 것이라도 사용될 수 있으며, 예를 들면 상업적으로 판매되고 있는 Z-175, HD-165GR, US7000GR 또는 9000GR 등을 사용할 수 있다.Any commonly known silica can be used, for example, commercially available Z-175, HD-165GR, US7000GR or 9000GR.
본 발명의 일 구현예에 따르면, 상기 실리카의 함량은 상기 원료고무 100 중량부에 대하여 60 내지 100 중량부, 예를 들어, 70 내지 90 중량부일 수 있다. 실리카의 함량이 상기 범위인 경우 트레드 고무의 물성이 최적이 된다.According to one embodiment of the present invention, the content of silica may be 60 to 100 parts by weight, for example, 70 to 90 parts by weight, based on 100 parts by weight of the raw rubber. When the silica content is within the above range, the physical properties of the tread rubber are optimal.
상기 실리카는 질소흡착 비표면적(nitrogen surface area per gram, N2SA)이 100 내지 180 m2/g이고, CTAB(cetyl trimethyl ammonium bromide)흡착 비표면적이 110 내지 170 m2/g일 수 있으나, 본 발명이 이에 한정되는 것은 아니다.The silica may have a nitrogen surface area per gram (N 2 SA) of 100 to 180 m 2 /g and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 110 to 170 m 2 /g. The present invention is not limited to this.
상기 실리카의 질소흡착 비표면적이 100m2/g 미만이면 충진제인 실리카에 의한 보강성능이 불리해질 수 있고, 180m2/g을 초과하면 고무 조성물의 가공성이 불리해질 수 있다. 또한, 상기 실리카의 CTAB흡착 비표면적이 110m2/g 미만이면 충진제인 실리카에 의한 보강성능이 불리해질 수 있고, 170m2/g을 초과하면 고무 조성물의 가공성이 불리해질 수 있다.If the nitrogen adsorption specific surface area of the silica is less than 100 m 2 /g, the reinforcement performance by silica as a filler may be disadvantageous, and if it exceeds 180 m 2 /g, the processability of the rubber composition may be disadvantageous. In addition, if the CTAB adsorption specific surface area of the silica is less than 110 m 2 /g, the reinforcement performance by silica as a filler may be disadvantageous, and if it exceeds 170 m 2 /g, the processability of the rubber composition may be disadvantageous.
본 발명의 일 구현예에 따르면, 상기 트레드 고무 조성물은 실리카 및 커플링제를 포함할 수 있다. 커플링제는 실리카의 분산을 향상시키기 위한 것일 수 있다. 한편, 실리카의 함량에 따라 커플링제를 포함하지 않을 수도 있다.According to one embodiment of the present invention, the tread rubber composition may include silica and a coupling agent. The coupling agent may be used to improve dispersion of silica. Meanwhile, depending on the silica content, a coupling agent may not be included.
상기 커플링제는 예를 들어, 실란 커플링제일 수 있다. 실란 커플링제는 Si를 포함하는 커플링제로서, 실란 커플링제는 실리카의 OH에 결합하는 방식으로 실리카의 극성을 감소시켜 고무와 잘 혼합되도록 한다. 실란 커플링제는 본 발명이 속하는 분야에서 통상적으로 사용되는 것이라면 어느 것이나 사용할 수 있다.The coupling agent may be, for example, a silane coupling agent. The silane coupling agent is a coupling agent containing Si, and the silane coupling agent binds to the OH of silica to reduce the polarity of silica so that it mixes well with rubber. Any silane coupling agent can be used as long as it is commonly used in the field to which the present invention pertains.
상기 실란 커플링제는 설파이드계 실란 화합물, 머캅토계 실란 화합물, 비닐계 실란 화합물, 아미노계 실란 화합물, 글리시독시계 실란 화합물, 니트로계 실란 화합물, 클로로계 실란 화합물, 메타크릴계 실란 화합물 및 이들의 혼합물 중에서 선택될 수 있다.The silane coupling agent includes sulfide-based silane compounds, mercapto-based silane compounds, vinyl-based silane compounds, amino-based silane compounds, glycidoxy-based silane compounds, nitro-based silane compounds, chloro-based silane compounds, methacrylic silane compounds, and mixtures thereof. can be selected from among.
상기 설파이드계 실란 화합물은 비스(3-트리에톡시실릴프로필)테트라설파이드, 비스(2-트리에톡시실릴에틸)테트라설파이드, 비스(4-트리에톡시실릴부틸)테트라설파이드, 비스(3-트리메톡시실릴프로필)테트라설파이드, 비스(2-트리메톡시실릴에틸)테트라설파이드, 비스(4-트리메톡시실릴부틸)테트라설파이드, 비스(3-트리에톡시실릴프로필)트리설파이드, 비스(2-트리에톡시실릴에틸)트리설파이드, 비스(4-트리에톡시실릴부틸)트리설파이드, 비스(3-트리메톡시실릴프로필)트리설파이드, 비스(2-트리메톡시실릴에틸)트리설파이드, 비스(4-트리메톡시실릴부틸)트리설파이드, 비스(3-트리에톡시실릴프로필)디설파이드, 비스(2-트리에톡시실릴에틸)디설파이드, 비스(4-트리에톡시실릴부틸)디설파이드, 비스(3-트리메톡시실릴프로필)디설파이드, 비스(2-트리메톡시실릴에틸)디설파이드, 비스(4-트리메톡시실릴부틸)디설파이드, 3-트리메톡시실릴프로필-N,N-디메틸티오카바모일테트라설파이드, 3-트리에톡시실릴프로필-N,N-디메틸티오카바모일테트라설파이드, 2-트리에톡시실릴에틸-N,N-디메틸티오카바모일테트라설파이드, 2-트리메톡시실릴에틸-N,N-디메틸티오카바모일테트라설파이드, 3-트리메톡시실릴프로필벤조티아졸릴테트라설파이드, 3-트리에톡시실릴프로필벤조티아졸테트라설파이드, 3-트리메톡시실릴프로필메타크릴레이트모노설파이드, 3-트리메톡시실릴프로필메타크릴레이트모노설파이드 및 이들의 혼합물 중에서 선택될 수 있다.The sulfide-based silane compounds include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, and bis(3-tri). Methoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(4-trimethoxysilylbutyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(2) -Triethoxysilylethyl)trisulfide, bis(4-triethoxysilylbutyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(2-trimethoxysilylethyl)trisulfide, bis (4-trimethoxysilylbutyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(4-triethoxysilylbutyl)disulfide, bis( 3-trimethoxysilylpropyl)disulfide, bis(2-trimethoxysilylethyl)disulfide, bis(4-trimethoxysilylbutyl)disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl Tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-trimethoxysilylethyl-N ,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzothiazoletetrasulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, 3 -Trimethoxysilylpropyl methacrylate monosulfide and mixtures thereof.
상기 머캅토 실란 화합물은 3-머캅토프로필트리메톡시실란, 3-머캅토프로필트리에톡시실란, 2-머캅토에틸트리메톡시실란, 2-머캅토에틸트리에톡시실란 및 이들의 혼합물 중에서 선택될 수 있다. 상기 비닐계 실란 화합물은 에톡시실란, 비닐트리메톡시실란 및 이들의 혼합물 중에서 선택될 수 있다. 상기 아미노계 실란 화합물은 3-아미노프로필트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-(2-아미노에틸)아미노프로필트리에톡시실란, 3-(2-아미노에틸)아미노프로필트리메톡시실란 및 혼합물 중에서 선택될 수 있다. 상기 글리시독시계 실란 화합물은 γ-글리시독시프로필트리에톡시실란, γ-글리시독시프로필트리메톡시실란, γ-글리시독시프로필메틸디에톡시실란, γ-글리시독시프로필메틸디메톡시실란 및 이들의 혼합물 중에서 선택될 수 있다. 상기 니트로계 실란 화합물은 3-니트로프로필트리메톡시실란, 3-니트로프로필트리에톡시실란 및 이들의 혼합물 중에서 선택될 수 있다. 상기 클로로계 실란 화합물은 3-클로로프로필트리메톡시실란, 3-클로로프로필트리에톡시실란, 2-클로로에틸트리메톡시실란, 2-클로로에틸트리에톡시실란 및 이들의 혼합물 중에서 선택될 수 있다. 상기 메타크릴계 실란 화합물은 γ-메타크릴록시프로필 트리메톡시실란, γ-메타크릴록시프로필 메틸디메톡시실란, γ-메타크릴록시프로필 디메틸메톡시실란 및 이들의 혼합물 중에서 선택될 수 있다.The mercapto silane compound is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and mixtures thereof. can be selected The vinyl-based silane compound may be selected from ethoxysilane, vinyltrimethoxysilane, and mixtures thereof. The amino silane compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, and 3-(2-aminoethyl)aminopropyltri. It may be selected from methoxysilanes and mixtures. The glycidoxy-based silane compounds include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane. and mixtures thereof. The nitro-based silane compound may be selected from 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane, and mixtures thereof. The chloro-based silane compound may be selected from 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, and mixtures thereof. . The methacryloxypropyl silane compound may be selected from γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl methyldimethoxysilane, γ-methacryloxypropyl dimethylmethoxysilane, and mixtures thereof.
본 발명의 일 구현예에 따르면, 상기 커플링제의 함량은 원료 고무 100 중량부에 대하여 5 내지 11 중량부일 수 있다. 원료 고무의 함량 및 실리카의 함량을 고려할 때, 커플링제의 함량이 상기 범위인 경우 고무 조성물의 가공이 무난하고 가교된 고무의 물성이 최적이 된다.According to one embodiment of the present invention, the content of the coupling agent may be 5 to 11 parts by weight based on 100 parts by weight of raw rubber. Considering the content of the raw rubber and the content of silica, when the content of the coupling agent is within the above range, the processing of the rubber composition is smooth and the physical properties of the crosslinked rubber are optimal.
상기 카본블랙은 질소흡착 비표면적(nitrogen surface area per gram, N2SA)이 30 내지 300m2/g일 수 있고, DBP(n-dibutyl phthalate) 흡유량이 60 내지 180cc/100g 일 수 있으나, 본 발명이 이에 한정되는 것은 아니다.The carbon black may have a nitrogen adsorption specific surface area per gram (N 2 SA) of 30 to 300 m 2 /g and a DBP (n-dibutyl phthalate) oil absorption of 60 to 180 cc/100 g, but according to the present invention This is not limited to this.
상기 카본블랙의 질소흡착 비표면적이 300m2/g을 초과하면 타이어용 고무 조성물의 가공성이 불리해질 수 있고, 30m2/g미만이면 충진제인 카본블랙에 의한 보강 성능이 불리해질 수 있다. 또한, 상기 카본블랙의 DBP 흡유량이 180cc/100g을 초과하면 고무 조성물의 가공성이 저하될 수 있고, 60cc/100g 미만이면 충진제인 카본블랙에 의한 보강 성능이 불리해질 수 있다.If the nitrogen adsorption specific surface area of the carbon black exceeds 300 m 2 /g, the processability of the rubber composition for tires may be disadvantageous, and if it is less than 30 m 2 /g, the reinforcement performance by carbon black as a filler may be disadvantageous. In addition, if the DBP oil absorption of the carbon black exceeds 180cc/100g, the processability of the rubber composition may be reduced, and if it is less than 60cc/100g, the reinforcement performance by the carbon black as a filler may be disadvantageous.
상기 카본블랙의 대표적인 예로는 N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 또는 N991 등을 들 수 있다.Representative examples of the carbon black include N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582 , N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 or N991.
상기 카본블랙은 상기 원료고무 100 중량부에 대하여 예를 들어 3 내지 20 중량부로 포함될 수 있고, 예를 들어 5 내지 15 중량부로 포함될 수 있다.The carbon black may be included in an amount of, for example, 3 to 20 parts by weight, for example, 5 to 15 parts by weight, based on 100 parts by weight of the raw rubber.
상기 타이어 트레드 고무 조성물은 선택적으로 추가적인 가류제, 가류촉진제, 가류촉진조제, 노화방지제, 산화 방지제, 또는 연화제 등의 각종의 첨가제를 더 포함할 수 있다. 상기 각종의 첨가제는 본 발명이 속하는 분야에서 통상적으로 사용되는 것이라면 어느 것이나 사용할 수 있으며, 이들의 함량은 통상적인 타이어 트레드 고무 조성물에서 사용되는 배합비에 따르는 바, 특별히 한정되지 않는다.The tire tread rubber composition may optionally further include various additives such as additional vulcanizing agent, vulcanization accelerator, vulcanization accelerator aid, anti-aging agent, antioxidant, or softener. Any of the above various additives can be used as long as they are commonly used in the field to which the present invention pertains, and their content is not particularly limited as it depends on the mixing ratio used in a typical tire tread rubber composition.
상기 가류제로는 유황계 가류제를 바람직하게 사용할 수 있다. 상기 유황계 가류제는 분말 황(S), 불용성 황(S), 침강 황(S), 콜로이드(colloid) 황 등의 무기 가류제와, 테트라메틸티우람 디설파이드(tetramethylthiuram disulfide, TMTD), 테트라에틸티우람 디설파이드(tetraethyltriuram disulfide, TETD), 디티오디모르폴린(dithiodimorpholine) 등의 유기 가류제를 사용할 수 있다. 상기 유황 가류제로는 구체적으로 원소 유황 또는 유황을 만들어 내는 가황제, 예를 들면 아민 디설파이드(amine disulfide), 고분자 유황 등을 사용할 수 있다. As the vulcanizing agent, a sulfur-based vulcanizing agent can be preferably used. The sulfur-based vulcanizing agent includes inorganic vulcanizing agents such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S), and colloidal sulfur, tetramethylthiuram disulfide (TMTD), and tetraethyl Organic curing agents such as tetraethyltriuram disulfide (TETD) and dithiodimorpholine can be used. As the sulfur vulcanizing agent, elemental sulfur or a vulcanizing agent that produces sulfur, for example, amine disulfide, polymer sulfur, etc. may be used.
상기 가류제는 상기 원료고무 100 중량부에 대하여 0.5 내지 10.0 중량부로 포함되는 것이 적절한 가황 효과로서 원료고무가 열에 덜 민감하고 화학적으로 안정하게 해준다는 점에서 바람직하다.The vulcanizing agent is preferably included in an amount of 0.5 to 10.0 parts by weight based on 100 parts by weight of the raw rubber in order to achieve an appropriate vulcanization effect and makes the raw rubber less sensitive to heat and chemically stable.
상기 가류촉진제는 가황 속도를 촉진하거나 초기 가황 단계에서 지연작용을 촉진하는 촉진제(accelerator)를 의미한다.The vulcanization accelerator refers to an accelerator that accelerates the speed of vulcanization or promotes a delay in the initial vulcanization stage.
상기 가류촉진제로는 술펜아미드계, 티아졸계, 티우람계, 티오우레아계, 구아니딘계, 디티오카르밤산계, 알데히드-아민계, 알데히드-암모니아계, 이미다졸린계, 크산테이트계 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있다.The vulcanization accelerators include sulfenamide-based, thiazole-based, thiuram-based, thiourea-based, guanidine-based, dithiocarbamic acid-based, aldehyde-amine-based, aldehyde-ammonia-based, imidazoline-based, xanthate-based and these. Any one selected from the group consisting of combinations may be used.
상기 술펜아미드계 가류촉진제로는, 예컨대 N-시클로헥실-2-벤조티아질술펜아미드(CBS), N-tert-부틸-2-벤조티아질술펜아미드(TBBS), N,N-디시클로헥실-2-벤조티아질술펜아미드, N-옥시디에틸렌-2-벤조티아질술펜아미드, N,N-디이소프로필-2-벤조티아졸술펜아미드 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나의 술펜아미드계 화합물을 사용할 수 있다.The sulfenamide-based vulcanization accelerators include, for example, N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and N,N-dicyclohexyl. -2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, and any one selected from the group consisting of combinations thereof. Sulfenamide-based compounds can be used.
상기 티아졸계 가류촉진제로는, 예컨대 2-머캅토벤조티아졸(MBT), 디벤조티아질디설파이드(MBTS), 2-머캅토벤조티아졸의 나트륨염, 2-머캅토벤조티아졸의 아연염, 2-머캅토벤조티아졸의 구리염, 2-머캅토벤조티아졸의 시클로헥실아민염, 2-(2,4-디니트로페닐)머캅토벤조티아졸, 2-(2,6-디에틸4-모르폴리노티오)벤조티아졸 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나의 티아졸계 화합물을 사용할 수 있다. The thiazole-based vulcanization accelerator includes, for example, 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), sodium salt of 2-mercaptobenzothiazole, and zinc salt of 2-mercaptobenzothiazole. , copper salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-di Any one thiazole-based compound selected from the group consisting of ethyl4-morpholinothio)benzothiazole and combinations thereof can be used.
상기 티우람계 가류촉진제로는, 예컨대 테트라메틸티우람디설파이드(TMTD), 테트라에틸티우람디설파이드, 테트라메틸티우람모노설파이드, 디펜타메틸렌티우람디설파이드, 디펜타메틸렌티우람모노설파이드, 디펜타메틸렌티우람테트라설파이드, 디펜타메틸렌티우람헥사설파이드, 테트라부틸티우람디설파이드, 펜타메틸렌티우람테트라설파이드 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나의 티우람계 화합물을 사용할 수 있다.The thiuram-based vulcanization accelerator includes, for example, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram monosulfide, and dipentamethylene. Any one thiuram-based compound selected from the group consisting of thiuram tetrasulfide, dipentamethylenethiuramhexasulfide, tetrabutylthiuram disulfide, pentamethylenethiuramtetrasulfide, and combinations thereof can be used.
상기 티오우레아계 가류촉진제로는, 예컨대 티아카르바미드, 디에틸티오요소, 디부틸티오요소, 트리메틸티오요소, 디오르토톨릴티오요소 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나의 티오우레아계 화합물을 사용할 수 있다. The thiourea-based vulcanization accelerator includes, for example, any thiourea-based agent selected from the group consisting of thiacarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, and combinations thereof. Compounds can be used.
상기 구아니딘계 가류촉진제로는, 예컨대 디페닐구아니딘, 디오르토톨릴구아니딘, 트리페닐구아니딘, 오르토톨릴비구아니드, 디페닐구아니딘프탈레이트 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나의 구아니딘계 화합물을 사용할 수 있다.As the guanidine-based vulcanization accelerator, for example, any guanidine-based compound selected from the group consisting of diphenylguanidine, diorthotolylguanidine, triphenylguanidine, orthotolylbiguanide, diphenylguanidine phthalate, and combinations thereof may be used. You can.
상기 디티오카르밤산계 가류촉진제로는, 예컨대 에틸페닐디티오카르밤산아연, 부틸페닐디티오카르밤산아연, 디메틸디티오카르밤산나트륨, 디메틸디티오카르밤산아연, 디에틸디티오카르밤산아연, 디부틸디티오카르밤산아연, 디아밀디티오카르밤산아연, 디프로필디티오카르밤산아연, 펜타메틸렌디티오카르밤산아연과 피페리딘의 착염, 헥사데실이소프로필디티오카르밤산아연, 옥타데실이소프로필디티오카르밤산아연 디벤질디티오카르밤산아연, 디에틸디티오카르밤산나트륨, 펜타메틸렌디티오카르밤산피페리딘, 디메틸디티오카르밤산셀레늄, 디에틸디티오카르밤산텔루늄, 디아밀디티오카르밤산카드뮴 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나의 디티오카르밤산계 화합물을 사용할 수 있다.The dithiocarbamate-based vulcanization accelerators include, for example, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, complex salt of zinc pentamethylenedithiocarbamate and piperidine, zinc hexadecylisopropyldithiocarbamate, octadecyl Zinc isopropyldithiocarbamate, Zinc dibenzyldithiocarbamate, Sodium diethyldithiocarbamate, Piperidine pentamethylenedithiocarbamate, Selenium dimethyldithiocarbamate, Tellurium diethyldithiocarbamate, Dia. Any dithiocarbamate-based compound selected from the group consisting of cadmium milddithiocarbamate and combinations thereof can be used.
상기 알데히드-아민계 또는 알데히드-암모니아계 가류촉진제로는, 예컨대 아세트알데히드-아닐린 반응물, 부틸알데히드-아닐린 축합물, 헥사메틸렌테트라민, 아세트알데히드-암모니아 반응물 및 이들의 조합으로 이루어진 군에서 선택되는 알데히드-아민계 또는 알데히드-암모니아계 화합물을 사용할 수 있다. The aldehyde-amine or aldehyde-ammonia vulcanization accelerator includes, for example, an aldehyde selected from the group consisting of acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant, and combinations thereof. -Amine-based or aldehyde-ammonia-based compounds can be used.
상기 이미다졸린계 가류촉진제로는, 예컨대 2-머캅토이미다졸린 등의 이미다졸린계 화합물을 사용할 수 있고, 상기 크산테이트계 가류촉진제로는, 예컨대 디부틸크산토겐산아연 등의 크산테이트계 화합물을 사용할 수 있다.As the imidazoline-based vulcanization accelerator, for example, imidazoline-based compounds such as 2-mercaptoimidazoline can be used, and as the xanthate-based vulcanization accelerator, for example, xanthate-based compounds such as zinc dibutylxanthogenate. Compounds can be used.
상기 가류촉진제는 가류 속도 촉진을 통한 생산성 증진 및 고무 물성의 증진을 극대화시키기 위하여 상기 원료고무 100 중량부에 대하여 0.5 내지 4.0 중량부로 포함될 수 있다.The vulcanization accelerator may be included in an amount of 0.5 to 4.0 parts by weight based on 100 parts by weight of the raw rubber in order to maximize productivity and rubber physical properties through acceleration of vulcanization speed.
상기 가류촉진조제는 상기 가류촉진제와 병용하여 그 촉진 효과를 완전하게 하기 위해서 사용되는 배합제로서, 무기계 가류촉진조제, 유기계 가류촉진조제 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있다. The vulcanization accelerator is a compounding agent used in combination with the vulcanization accelerator to completely enhance its accelerating effect. Any one selected from the group consisting of inorganic vulcanization accelerator, organic vulcanization accelerator, and combinations thereof may be used. .
상기 무기계 가류촉진조제로는 산화아연(ZnO), 탄산아연(zinc carbonate), 산화납(lead oxide), 수산화 칼륨 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있다. 상기 유기계 가류촉진조제로는 스테아르산, 스테아르산 아연, 팔미트산, 리놀레산, 올레산, 라우르산, 디부틸 암모늄-올레이트(dibutyl ammonium oleate), 이들의 유도체 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있다.The inorganic vulcanization accelerator may be any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, lead oxide, potassium hydroxide, and combinations thereof. The organic vulcanization accelerator is selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof, and combinations thereof. You can use any one that works.
특히, 상기 가류촉진조제로서 상기 산화아연과 상기 스테아르산을 함께 사용할 수 있으며, 이 경우 상기 산화아연이 상기 스테아르산에 녹아 상기 가류촉진제와 유효한 복합체(complex)를 형성하여, 가황 반응 중 유리한 황을 만들어냄으로써 고무의 가교 반응을 용이하게 한다.In particular, the zinc oxide and the stearic acid can be used together as the vulcanization accelerator. In this case, the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator, thereby producing sulfur, which is beneficial during the vulcanization reaction. This facilitates the crosslinking reaction of rubber.
상기 산화아연과 상기 스테아르산을 함께 사용하는 경우 적절한 가류촉진조제로서의 역할을 위하여 각각 상기 원료고무 100 중량부에 대하여 1 내지 10 중량부 및 0.5 내지 3 중량부로 사용할 수 있다. 상기 산화아연과 상기 스테아르산의 함량이 상기 범위 미만인 경우 가황 속도가 느려 생산성이 저하될 수 있으며, 상기 범위를 초과하는 경우 스코치 현상이 발생하여 물성이 저하될 수 있다.When the zinc oxide and the stearic acid are used together, they can be used in an amount of 1 to 10 parts by weight and 0.5 to 3 parts by weight, respectively, based on 100 parts by weight of the raw rubber to serve as an appropriate vulcanization accelerator. If the content of zinc oxide and stearic acid is less than the above range, the vulcanization speed may be slow and productivity may be reduced, and if it exceeds the above range, a scorch phenomenon may occur and physical properties may be reduced.
상기 연화제는 고무에 가소성을 부여시켜 가공을 용이하게 하기 위하여 또는 가황 고무의 경도를 저하시키기 위하여 고무 조성물에 첨가되는 것으로, 고무 배합시나 고무 제조시에 사용되는 오일류 기타 재료를 의미한다. 상기 연화제는 가공오일(Process oil) 또는 기타 고무 조성물에 포함되는 오일류를 의미한다. 상기 연화제로는 석유계 오일, 식물유지 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있으나, 본 발명이 이에 한정되는 것은 아니다.The softener is added to the rubber composition to provide plasticity to the rubber to facilitate processing or to reduce the hardness of vulcanized rubber, and refers to oils and other materials used when mixing rubber or manufacturing rubber. The softener refers to process oil or other oils included in the rubber composition. The softener may be any one selected from the group consisting of petroleum oil, vegetable oil, and combinations thereof, but the present invention is not limited thereto.
상기 석유계 오일로는 파라핀계 오일, 나프텐계 오일, 방향족계 오일 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있다.The petroleum oil may be any one selected from the group consisting of paraffin oil, naphthenic oil, aromatic oil, and combinations thereof.
상기 파라핀계 오일의 대표적인 예로 미창 오일 주식회사의 P-1, P-2, P-3, P-4, P-5, P-6 등을 들 수 있고, 상기 나프텐계 오일의 대표적인 예로는 미창 오일 주식회사의 N-1, N-2, N-3 등을 들 수 있으며, 상기 방향족계 오일의 대표적인 예로는 미창 오일 주식회사의 A-2, A-3 등을 들 수 있다.Representative examples of the paraffinic oil include P-1, P-2, P-3, P-4, P-5, and P-6 of Michang Oil Co., Ltd., and representative examples of the naphthenic oil include Michang Oil. Examples include N-1, N-2, N-3, etc. from Co., Ltd., and representative examples of the aromatic oil include A-2, A-3, etc. from Michang Oil Co., Ltd.
그러나, 최근 환경 의식의 고조와 함께 상기 방향족계 오일에 포함된 폴리사이클릭 아로마틱 탄화수소(Polycyclic Aromatic Hydrocarbons, 이하 PAHs라 한다)의 함량이 3 중량% 이상일 때는 암 유발 가능성이 높은 것으로 알려진바, TDAE(treated distillate aromatic extract) 오일, MES(mild extraction solvate) 오일, RAE(residual aromatic extract) 오일 또는 중질 나프텐성 오일을 바람직하게 사용할 수 있다.However, with the recent increase in environmental awareness, it is known that when the content of polycyclic aromatic hydrocarbons (PAHs) contained in the aromatic oil is more than 3% by weight, there is a high possibility of causing cancer, and TDAE ( Treated distillate aromatic extract) oil, MES (mild extraction solvate) oil, RAE (residual aromatic extract) oil, or heavy naphthenic oil can be preferably used.
특히, 상기 연화제로서 사용하는 오일은 상기 오일 전체에 대하여 PAHs 성분의 총 함량이 3중량% 이하이고, 동점도가 95 이상(210μ연화제 내의 방향족 성분이 15 내지 25중량%, 나프텐계 성분이 27 내지 37중량% 및 파라핀계 성분이 38 내지 58중량%인 TDAE 오일을 바람직하게 사용할 수 있다. In particular, the oil used as the softener has a total content of PAHs of 3% by weight or less and a kinematic viscosity of 95 or more (15 to 25% by weight of aromatic components in the 210μ softener and 27 to 37% by weight of naphthenic components). TDAE oil with a weight percent and a paraffinic component of 38 to 58 weight percent can be preferably used.
상기 TDAE 오일은 상기 TDAE 오일을 포함한 타이어의 저온 특성, 연비 성능을 우수하게 하면서도 PAHs의 암 유발 가능성 등의 환경적 요인에 대해서도 유리한 특성을 갖는다.The TDAE oil has excellent low-temperature characteristics and fuel efficiency performance of tires containing the TDAE oil, and also has advantageous properties against environmental factors such as the possibility of PAHs causing cancer.
상기 식물유지로는 피마자유, 면실유, 아마인유, 카놀라유, 대두유, 팜유, 야자유, 낙화생유, 파인유, 파인타르, 톨유, 콘유, 쌀겨기름, 홍화유, 참기름, 올리브유, 해바라기유, 팜핵유, 동백유, 호호바유, 마카다미아너트유, 사플라워 오일, 동유 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있다.The above vegetable oils include castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, pine tar, tall oil, corn oil, rice bran oil, safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, and camellia oil. , jojoba oil, macadamia nut oil, safflower oil, tung oil, and combinations thereof can be used.
상기 연화제는 상기 원료고무 100 중량부에 대하여 0 내지 40 중량부로 사용하는 것이 원료고무의 가공성을 좋게 한다는 점에서 바람직하다.The softener is preferably used in an amount of 0 to 40 parts by weight based on 100 parts by weight of the raw rubber in that it improves the processability of the raw rubber.
상기 노화방지제는 산소에 의해서 타이어가 자동 산화되는 연쇄반응을 정지시키기 위하여 사용되는 첨가제이다. 상기 노화방지제로는 아민계, 페놀계, 퀴놀린계, 이미다졸계, 카르밤산 금속염, 왁스 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나를 적절하게 선택하여 사용할 수 있다.The anti-aging agent is an additive used to stop the chain reaction in which tires are automatically oxidized by oxygen. The anti-aging agent may be appropriately selected from the group consisting of amine-based, phenol-based, quinoline-based, imidazole-based, carbamate metal salts, waxes, and combinations thereof.
상기 아민계 노화방지제로는 N-페닐-N'-(1,3-디메틸)-p-페닐렌디아민, N-(1,3-디메틸부틸)-N'-페닐-p-페닐렌디아민, N-페닐-N'-이소프로필-p-페닐렌디아민, N,N'-디페닐-p-페닐렌디아민, N,N'-디아릴-p-페닐렌디아민, N-페닐-N'-사이클로헥실 p-페닐렌디아민, N-페닐-N'-옥틸-p-페닐렌디아민 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나를 사용할 수 있다. 상기 페놀계 노화방지제로는 페놀계인 2,2'-메틸렌-비스(4-메틸-6-tert-부틸페놀), 2,2'-이소부틸리덴-비스(4,6-디메틸페놀), 2,6-디-t-부틸-p-크레졸 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나를 사용할 수 있다. 상기 퀴놀린계 노화방지제로는 2,2,4-트리메틸-1,2-디하이드로퀴놀린 및 그 유도체를 사용할 수 있고, 구체적으로 6-에톡시-2,2,4-트리메틸-1,2-디하이드로퀴놀린, 6-아닐리노-2,2,4-트리메틸-1,2-디하이드로퀴놀린, 6-도데실-2,2,4-트리메틸-1,2-디하이드로퀴놀린 및 이들의 조합으로 이루어진 군에서 선택된 어느 하나를 사용할 수 있다. 상기 왁스로는 바람직하게 왁시 하이드로카본을 사용할 수 있다.The amine-based anti-aging agent includes N-phenyl-N'-(1,3-dimethyl)-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-diaryl-p-phenylenediamine, N-phenyl-N' -Any one selected from the group consisting of cyclohexyl p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof may be used. The phenol-based anti-aging agents include phenol-based 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2 , 6-di-t-butyl-p-cresol, and any one selected from the group consisting of combinations thereof can be used. As the quinoline-based anti-aging agent, 2,2,4-trimethyl-1,2-dihydroquinoline and its derivatives can be used, specifically 6-ethoxy-2,2,4-trimethyl-1,2-di. Hydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, and combinations thereof Any one selected from the group can be used. As the wax, waxy hydrocarbon can be preferably used.
상기 노화방지제는 노화 방지 작용 이외에 고무에 대한 용해도가 커야 하고, 휘발성이 작고 고무에 대하여 비활성이어야 하며, 가황을 저해하지 않아야 한다는 등의 조건을 고려할 때, 상기 원료고무 100 중량부에 대하여 1 내지 10 중량부로 포함될 수 있다.Considering the conditions that the anti-aging agent must have a high solubility in rubber in addition to anti-aging effect, must be low in volatility and inert to rubber, and must not inhibit vulcanization, it must be used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the raw rubber. It may be included by weight.
상기 산화방지제의 전형적 양은, 예를 들면, 약 1 내지 약 5 중량부로 포함될 수 있다. 대표적 산화방지제는, 예를 들면, 다이페닐-p-페닐렌다이아민 및 다른 것들이나, 이에 제한되지는 않는다.A typical amount of the antioxidant may be, for example, about 1 to about 5 parts by weight. Representative antioxidants include, but are not limited to, diphenyl-p-phenylenediamine and others.
도 1을 참조하면, 타이어(10)는 트레드부(100), 사이드월부(200) 및 비드부(300)를 포함한다.Referring to FIG. 1, the
트레드부(100)는 단면상 지면과 접하는 부분으로, 노면 등으로부터의 충격, 외상으로부터 타이어를 보호하는 역할을 한다. 상기와 같은 트레드부의 표면에는 타이어의 배수성 향성을 위해 그루브(groove)에 의해 구획되는 다수 개의 블록들이 형성될 수 있다.The
상기 트레드에 본 발명의 일 구현예에 따른 고무 조성물이 포함된다. The tread includes a rubber composition according to an embodiment of the present invention.
트레드부를 중심으로 타이어의 폭 방향을 따라 양측으로 사이드월(200) 및 비드부(300)가 순차적으로 위치한다.The
사이드월(200)은 트레드의 양 단부로부터 연장되어 타이어의 측면을 형성하는 부분으로, 주행 중 지속적으로 반복되는 수축 및 팽창작용을 견디며, 내측면에 위치하는 카카스층(400)을 보호하는 역할을 한다.The
비드부(300)는 사이드월(200)의 양단에 구비되어 코드지의 끝부분을 감싸고 있으며 상기 비드부(300)는 링 형태의 강선재를 포함하는 비드 코어(500)를 포함한다.The
좌우 한 쌍의 비드부(300) 사이에는 카카스층(400)이 위치하며 타이어 내부에 타이어 고무 시트와 접합되어 타이어의 골격을 형성하는 역할을 하고 상기 카카스층(400)이 비드 코어(500) 주위를 타이어 내측에서 외측으로 감아 올라가고 있다. A
카카스층(400)의 내측의 일면상에는 이너라이너(700)가 위치하며 타이어 내부의 공기가 밖으로 빠져나가지 않도록 하는 역할을 한다.The
트레드부(100)에 위치하는 카카스층(400)의 외측면에는 트레드의 탄성을 높이고, 조종성 및 안정성을 갖도록 하는 보강층으로서 벨트층(600)이 위치한다. A
벨트층 고무는 코발트 화합물을 포함할 수 있으며, 상기 코발트 화합물은 코발트 염, 코발트-붕소 에스테르, 유기산 코발트염, 무기산 코발트염, 비코발트 염 등이 사용되고 있으며, 접착 시스템으로써는 코발트 염 단독, 코발트-RH, 코발트-HRH 외에도 수지[예를 들면, 메틸렌 수용체: 페놀계, 레조시놀계, 크레졸계 등, 또는 공여체: 헥사메틸렌테트라아민(HMT), 헥사메톡시메틸멜라민(HMMA), 펜타메톡시메틸멜라민(PMMA)]을 개질한 접착 시스템 등이 있다. The belt layer rubber may contain a cobalt compound, and the cobalt compound includes cobalt salt, cobalt-boron ester, organic acid cobalt salt, inorganic acid cobalt salt, and non-cobalt salt. As an adhesive system, cobalt salt alone, cobalt- In addition to RH and cobalt-HRH, resins [e.g., methylene acceptor: phenolic, resorcinol, cresol, etc., or donor: hexamethylenetetraamine (HMT), hexamethoxymethylmelamine (HMMA), pentamethoxymethyl There is an adhesive system modified with melamine (PMMA).
일반적으로 접착력 향상을 위해서 접착 배합 고무의 접착계 개선(코발트-RH, 코발트-HRH, 이들의 변성 시스템), 접착조제로 사용되는 수지의 개선과 성능 향상, 접착 조제로 사용되는 코발트 염 개선, 접착 고무의 가류 시스템 개선, 새로운 배합 조성물 사용(보강제, 카본블랙, 실리카, 폴리머, 약품 류) 등을 사용하고 있다. In general, to improve adhesion, improvement of the adhesive system of adhesive compound rubber (cobalt-RH, cobalt-HRH, their modified system), improvement of resin used as an adhesive aid and improved performance, improvement of cobalt salt used as an adhesive aid, and adhesion Improvements to the rubber vulcanization system and use of new compounding compositions (reinforcers, carbon black, silica, polymers, chemicals) are being used.
상기 코발트 화합물의 함량은 원료 고무 100 중량부에 대해서 0.2 내지 5.0 중량부 포함할 수 있으나, 이에 제한되지는 않는다.The content of the cobalt compound may include 0.2 to 5.0 parts by weight based on 100 parts by weight of raw rubber, but is not limited thereto.
상기 벨트층(600)과 트레드부(100) 사이에 하이브리드 코드를 포함하는 캡플라이(800)가 배치될 수 있다. 캡플라이(800)는 주행시 벨트층(600)의 유동을 억제하여 타이어의 성능을 유지시켜 줄 수 있다.A cap ply 800 including a hybrid cord may be disposed between the
상기 타이어 트레드 고무 조성물은 통상적인 2단계의 연속 제조 공정을 통하여 제조될 수 있다. 즉, 110 내지 190
본 발명의 또 다른 일 구현예에 따른 타이어는 그린 타이어 성형시 상기 타이어 트레드 고무 조성물을 이용하는 단계를 포함한다. 상기 타이어 트레드 고무 조성물을 이용하여 그린 타이어를 성형하는 방법 등은 종래에 타이어의 제조에 이용되는 방법이면 어느 것이든 적용이 가능한 바, 본 명세서에서 상세한 설명은 생략한다.A tire according to another embodiment of the present invention includes the step of using the tire tread rubber composition when forming a green tire. Any method conventionally used for manufacturing tires can be applied to the method of forming a green tire using the tire tread rubber composition, and detailed description thereof will be omitted in this specification.
도 1에서는 승용차용 타이어에 대해서 예시하고 있으나, 이에 한정되지 않고, 승용차용 타이어, 경주용 타이어, 비행기 타이어, 농기계용 타이어, 오프로드(off-the-road) 타이어, 트럭 타이어 또는 버스 타이어 등일 수 있다. 또한, 상기 타이어는 레디얼(radial) 타이어 또는 바이어스(bias) 타이어일 수 있으며, 바람직하게는 레디얼 타이어이다.In Figure 1, tires for passenger cars are illustrated, but the tire is not limited thereto, and may be tires for passenger cars, racing tires, airplane tires, tires for agricultural machinery, off-the-road tires, truck tires, or bus tires. there is. Additionally, the tire may be a radial tire or a bias tire, and is preferably a radial tire.
이하의 실시예 및 비교예를 통하여 본 발명이 더욱 상세하게 설명된다. 단, 실시예는 본 발명을 예시하기 위한 것으로서 이들만으로 본 발명의 범위가 한정되는 것이 아니다.The present invention is explained in more detail through the following examples and comparative examples. However, the examples are for illustrating the present invention and are not intended to limit the scope of the present invention.
비교예 및 실시예Comparative Examples and Examples
하기 표 1의 각 성분들을 기재된 비율(단위: 중량부)로 밴버리 믹서에 투입하고 혼합하였다. 탄젠셜 타입(Tangential type)의 밴버리 믹서(Banbury mixer)에 모든 성분이 투입된 후 1.65L 용량의 충전율(fill factor)이 0.65에서 0.70이 되도록 각 성분의 비율을 조절하였다.Each component in Table 1 below was added to a Banbury mixer in the ratio indicated (unit: parts by weight) and mixed. After all ingredients were added to the Tangential type Banbury mixer, the ratio of each ingredient was adjusted so that the fill factor of 1.65L capacity was from 0.65 to 0.70.
1) EVONIK社, HD-165GR1) EVONIK, HD-165GR
2) 비스(3-트리에톡시실릴프로필)테트라설파이드2) Bis(3-triethoxysilylpropyl)tetrasulfide
3) Koresin: 연화점 130~150℃3) Koresin: softening point 130~150℃
4) RAE4) R.A.E.
5) N,N-Dicyclohexyl-2-benzothiazolesulfenamide5) N,N-Dicyclohexyl-2-benzothiazolesulfenamide
평가예Evaluation example
가류 고무 물성 평가Evaluation of vulcanized rubber properties
비교예 1, 2 및 실시예 1 내지 3의 고무 조성물로 제조된 고무 시트를 가류기에서 165℃에서 10분 동안 가류하여 시편을 제작하였다. 각각의 시편에 대하여 경도, 인장 강도 등의 물성을 평가하였다. 그 결과를 하기 표 2에 나타내었다.Rubber sheets prepared from the rubber compositions of Comparative Examples 1 and 2 and Examples 1 to 3 were vulcanized in a vulcanizer at 165°C for 10 minutes to prepare specimens. Physical properties such as hardness and tensile strength were evaluated for each specimen. The results are shown in Table 2 below.
HD(hardness)HD(hardness)
Shore A형 경도계를 이용하여 ASTM D2240-97 따라 두께 6mm 이상, 지름 10mm이상의 평활한 면에서 하나의 시편을 총 5회 측정하여 그 평균값으로 정하였다.Using a Shore A type hardness tester, one specimen was measured a total of 5 times on a smooth surface with a thickness of 6 mm or more and a diameter of 10 mm or more according to ASTM D2240-97, and the average value was determined.
인장 강도(Tensile properties)Tensile properties
가교된 시편의 인장강도 측정은 인장시험기(INSTRON)를 이용하여 ASTM D412에 따라 진행하였다. 측정용 시편의 제조는 유압 프레스를 이용해 시트형태로 제작하고 시편절단기를 이용하여 덤벨형으로 제작하였다. 시험조건은 상온에서 인장속도를 500 mm/min로 측정하였다. 인장강도(T/S)는 인장시험기에서 시험편이 끊어질 때까지의 스트레스 값을 나타낸 값으로 단위면적당 받는 힘을 측정하였다.The tensile strength of the cross-linked specimen was measured according to ASTM D412 using a tensile tester (INSTRON). The specimen for measurement was manufactured in a sheet form using a hydraulic press and in a dumbbell form using a specimen cutter. The test conditions were measured at room temperature and the tensile speed was 500 mm/min. Tensile strength (T/S) is a value representing the stress value until the test piece breaks in a tensile tester, and is measured as the force received per unit area.
신율elongation
신율을 인장 시험기에서 시험편이 끊어질 때까지의 스트레인 값을 %로 나타내는 방법으로 측정하였다.Elongation was measured in a tensile tester by expressing the strain value as a percentage until the test piece breaks.
동특성Dynamic characteristics
동특성으로서 점탄성은 가보 비스코미터(Gabo viscometer) 측정기를 사용하여 0.2% 변형에 10Hz Frequency 하에서 -70℃에서 70℃까지의 Tanδ 값을 측정하였다. 60℃에서의 Tan δ는 값이 작을수록 주행 중 발열이 적어 회전 저항이 우수함을 나타낸다.As a dynamic property, viscoelasticity was measured using a Gabo viscometer measuring Tanδ value from -70℃ to 70℃ at 0.2% strain and 10Hz frequency. The smaller the value of Tan δ at 60℃, the less heat is generated during driving, indicating excellent rolling resistance.
습윤마찰계수Wet friction coefficient
Ueshima사의 RTMS 장비를 이용하여 고무의 wet 상태에서의 friction 값을 측정하였음. 일정 속도로 회전하는 노면과 샘플 사이에 slip을 주었을 때 발생하는 힘을 측정하여 peak friction 값을 도출함. 값이 클수록 friction 특성이 우수함. The friction value in the wet state of rubber was measured using Ueshima's RTMS equipment. The peak friction value is derived by measuring the force generated when slip is applied between a road surface rotating at a constant speed and a sample. The larger the value, the better the friction characteristics.
평가 결과를 하기 표 2에 나타내었다The evaluation results are shown in Table 2 below.
표 1, 2의 결과로부터, 실리카 및 페놀계 레진의 함량을 증가시키지 않고, 알칼리토금속 이온 함유 화합물, 예를 들어, MgO를 첨가시킴으로써 트레드 고무의 습윤 마찰력이 증가한다는 것을 알 수 있다. From the results in Tables 1 and 2, it can be seen that the wet friction of the tread rubber is increased by adding an alkaline earth metal ion-containing compound, such as MgO, without increasing the content of silica and phenolic resin.
또한, 비교예 및 실시예 모두 60℃ tanδ 값에는 크게 변화가 없다는 것을 확인하였다. 따라서, 실시예의 경우 회전 저항이 높아지지 않았고, 비교예 및 실시예 모두 회전 저항은 유사하다는 것을 알 수 있다. In addition, it was confirmed that there was no significant change in the tan δ value at 60°C in both comparative examples and examples. Therefore, it can be seen that the rotation resistance did not increase in the Example, and the rotation resistance was similar in both the Comparative Example and the Example.
MgO 대신, Al2O3을 사용한 비교예 2의 경우 물성이 소폭 저하되는 경향이며, 트레드 고무의 습윤 마찰력 증가가 미미함을 확인할 수 있다. In Comparative Example 2, where Al 2 O 3 was used instead of MgO, the physical properties tended to decrease slightly, and it could be confirmed that the increase in wet friction of the tread rubber was slight.
이상에서는 실시예들을 참조하여 설명하였지만, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although the above has been described with reference to the embodiments, those skilled in the art may modify and modify the present invention in various ways without departing from the spirit and scope of the present invention as set forth in the claims of the present invention. You will understand that you can change it.
10: 타이어
100: 트레드부
200: 사이드월부
300: 비드부
400: 카카스층
500: 비드 코어
600: 벨트층
700: 이너라이너
800: 캡플라이10: tires
100: Tread part
200: Side wall part
300: Bead part
400: Carcass layer
500: bead core
600: Belt layer
700: Innerliner
800: Capfly
Claims (10)
실리카로 이루어진 필러;
페놀계 레진; 및
알칼리토금속 이온 함유 화합물;을
포함하며,
상기 실리카의 함량이 원료 고무 100 중량부를 기준으로 70 내지 90 중량부이고,
상기 실리카는 질소흡착 비표면적(nitrogen surface area per gram, N2SA)이 100 내지 180 m2/g이고, CTAB(cetyl trimethyl ammonium bromide)흡착 비표면적이 110 내지 170 m2/g이며,
상기 페놀계 레진의 함량이 원료 고무 100 중량부를 기준으로 8.0 내지 12 중량부인, 타이어 트레드 고무 조성물.Raw rubber made of styrene butadiene rubber;
Filler made of silica;
Phenolic resin; and
Compounds containing alkaline earth metal ions;
Includes,
The content of the silica is 70 to 90 parts by weight based on 100 parts by weight of raw rubber,
The silica has a nitrogen surface area per gram (N 2 SA) of 100 to 180 m 2 /g and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 110 to 170 m 2 /g,
A tire tread rubber composition wherein the content of the phenolic resin is 8.0 to 12 parts by weight based on 100 parts by weight of raw rubber.
상기 알칼리토금속 이온 함유 화합물이 알칼리토금속의 산화물, 알칼리토금속의 수산화물, 또는 이들의 임의의 조합을 포함하는, 타이어 트레드 고무 조성물.According to paragraph 1,
A tire tread rubber composition, wherein the alkaline earth metal ion-containing compound comprises an oxide of an alkaline earth metal, a hydroxide of an alkaline earth metal, or any combination thereof.
상기 알칼리토금속 이온 함유 화합물이 MgO, Mg(OH)2, CaO, Ca(OH)2 또는 이들의 임의의 조합을 포함하는, 타이어 트레드 고무 조성물. According to paragraph 1,
A tire tread rubber composition, wherein the alkaline earth metal ion-containing compound includes MgO, Mg(OH) 2 , CaO, Ca(OH) 2 or any combination thereof.
상기 알칼리토금속 이온 함유 화합물의 함량이 원료 고무 100 중량부를 기준으로 0.1 내지 3.0 중량부인, 타이어 트레드 고무 조성물.According to paragraph 1,
A tire tread rubber composition wherein the content of the alkaline earth metal ion-containing compound is 0.1 to 3.0 parts by weight based on 100 parts by weight of raw rubber.
상기 페놀계 레진의 연화점이 80 내지 150℃인, 타이어 트레드 고무 조성물.According to paragraph 1,
A tire tread rubber composition wherein the phenolic resin has a softening point of 80 to 150°C.
상기 페놀계 레진의 OH기는 알칼리토금속 이온 함유 화합물의 알칼리토금속 이온과 결합을 형성하는, 타이어 트레드 고무 조성물.According to paragraph 1,
A tire tread rubber composition, wherein the OH group of the phenolic resin forms a bond with the alkaline earth metal ion of the alkaline earth metal ion-containing compound.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3366453B2 (en) | 1994-08-19 | 2003-01-14 | 株式会社ブリヂストン | Rubber composition for tire tread |
| JP5253706B2 (en) * | 2004-12-21 | 2013-07-31 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
| JP6329003B2 (en) | 2014-06-02 | 2018-05-23 | 株式会社ブリヂストン | Rubber composition and tire using the same |
| JP2021088676A (en) | 2019-12-05 | 2021-06-10 | 住友ゴム工業株式会社 | Tire rubber composition and tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS575907A (en) * | 1980-06-14 | 1982-01-12 | Oishi Kinzoku Kogyo Kk | Apparatus for feeding male or female member of hook |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3366453B2 (en) | 1994-08-19 | 2003-01-14 | 株式会社ブリヂストン | Rubber composition for tire tread |
| JP5253706B2 (en) * | 2004-12-21 | 2013-07-31 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
| JP6329003B2 (en) | 2014-06-02 | 2018-05-23 | 株式会社ブリヂストン | Rubber composition and tire using the same |
| JP2021088676A (en) | 2019-12-05 | 2021-06-10 | 住友ゴム工業株式会社 | Tire rubber composition and tire |
Non-Patent Citations (1)
| Title |
|---|
| A. Gardziella et al.. Phenolic Resins. Springer. 2000년(제2판), p.407. 1부.* |
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