JP2016524030A - ゴムタイヤ配合物の製造方法 - Google Patents
ゴムタイヤ配合物の製造方法 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 17
- 229920001971 elastomer Polymers 0.000 title claims abstract description 16
- 239000005060 rubber Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 238000009472 formulation Methods 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 239000002861 polymer material Substances 0.000 claims abstract description 23
- 239000012038 nucleophile Substances 0.000 claims abstract description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 239000008117 stearic acid Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000002203 pretreatment Methods 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 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 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- FGKIZAATMHLTKO-UHFFFAOYSA-N 1-(diaminomethylideneamino)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1NC(=N)NNC(N)=N FGKIZAATMHLTKO-UHFFFAOYSA-N 0.000 claims description 2
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 claims description 2
- GIUBHMDTOCBOPA-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2SC(S)=NC2=C1 GIUBHMDTOCBOPA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000012990 dithiocarbamate Substances 0.000 claims description 2
- -1 dithiophosphate Chemical compound 0.000 claims description 2
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000012991 xanthate Substances 0.000 claims description 2
- PGNWIWKMXVDXHP-UHFFFAOYSA-L zinc;1,3-benzothiazole-2-thiolate Chemical compound [Zn+2].C1=CC=C2SC([S-])=NC2=C1.C1=CC=C2SC([S-])=NC2=C1 PGNWIWKMXVDXHP-UHFFFAOYSA-L 0.000 claims description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 2
- 238000007781 pre-processing Methods 0.000 claims 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims 1
- 238000010058 rubber compounding Methods 0.000 claims 1
- 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 claims 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims 1
- 229960002447 thiram Drugs 0.000 claims 1
- 238000005096 rolling process Methods 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- 101100184147 Caenorhabditis elegans mix-1 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
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
-
- 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
-
- 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
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
(第1の混合ステップ)
混合に先だって、230〜270リットルの接線式ローターミキサーに表Iの成分を充填比66〜72%で投入した。
ミキサーを40〜60rpmの速度で作動させ、温度が140〜160℃に達した時点で、得られた配合物をミキサーから取り出した。
表Iに示す成分を、先の混合ステップの配合物に充填比63〜67%で添加した。
ミキサーを20〜40rpmの速度で作動させ、温度が100〜110℃に達した時点で、得られた配合物をミキサーから取り出した。
(ポリマーベースのTg−50℃超部分及びTg−50℃未満部分の前処理)
混合に先だって、230〜270リットルの接線式ローターミキサーに表I〜IIIの成分を充填比66〜72%で投入した。
ミキサーを40〜60rpmの速度で作動させ、温度が140〜160℃に達した時点で、得られた配合物をミキサーから取り出した。
混合に先だって、230〜270リットルの接線式ローターミキサーに表I〜IIIの成分を充填比66〜72%で投入した。
ミキサーを40〜60rpmの速度で作動させ、温度が140〜160℃に達した時点で、得られた配合物をミキサーから取り出した。
表I〜IIIに示す成分を、先の混合ステップの配合物に充填比63〜67%で添加した。
ミキサーを20〜40rpmの速度で作動させ、温度が100〜110℃に達した時点で、得られた配合物をミキサーから取り出した。
Claims (10)
- ポリマーベースが、ガラス転移温度−50℃超の第1のポリマー材料から部分的に構成され、かつ、ガラス転移温度−50℃未満の第2のポリマー材料から部分的に構成されてなる、シリカを充填剤として含むゴム配合物の製造方法であって、
前記第1のポリマー材料と、表面積80〜135m2/gのシリカと、シラン結合剤と、少なくとも1つの求核剤とを混合する前記第1のポリマー材料の前処理ステップと;
前記第2のポリマー材料と、表面積150〜220m2/gのシリカと、シラン結合剤と、少なくとも1つの求核剤とを混合する前記第2のポリマー材料の前処理ステップと;
前記第1のポリマー材料の前処理ステップ及び前記第2のポリマー材料の前処理ステップから生じたそれぞれの配合物を混合して1つの配合物とする混合ステップと;
ステアリン酸及び硬化システムを製造された配合物に添加し、混合する最終ステップと、を含む、ゴム配合物の製造方法。 - 前記求核剤は硬化促進剤類のものである、請求項1に記載のゴム配合物の製造方法。
- 硬化促進剤類の前記求核剤は、アミン、ジスルフィド、グアニジン及びその誘導体、チオ尿素及びその誘導体、チアゾール、チウラム、スルフェンアミド及びその誘導体、ジチオカルバメート、ジチオホスフェート、及び、キサンテートからなる群から選択され、
より好ましくは、前記硬化促進剤は、ベンゾチアジル−シクロヘキシル−スルフェンアミド(CBS)、N−tert−ブチル−2−ベンゾチアジルスルフェンアミド(TBBS)、2−メルカプトベンゾチアゾール(MBT)、2−メルカプトベンゾチアゾールの亜鉛塩(ZMBT)、ベンゾチアジル−2−ジシクロヘキシルスルフェンアミド(DCBS)、ジフェニルグアニジン(DPG)、トリフェニルグアニジン(TPG)、ジオルトトリルグアニジン(DOTG)、o−トリルビグアニジン(OTBG)、ジフェニルチオ尿素(DPTU)、ベンゾチアゾールジスルフィド(MBTS)、ヘキサメチレンテトラミン(HMT)、テトラベンジルチウラムジスルフィド(TBzTD)、および、それらの混合物からなる群のものである、請求項2に記載のゴム配合物の製造方法。 - 各前記前処理ステップにおいて、シリカの量は当該前処理ステップに存在するゴムに対して10〜80phrである、請求項1〜3のいずれか一項に記載のゴム配合物の製造方法。
- 使用される前記ポリマーベースは、前記第1のポリマー材料を80〜20phr含み、前記第2のポリマー材料を20〜80phr含む、請求項1〜4のいずれか一項に記載のゴム配合物の製造方法。
- 前記第1のポリマー材料はスチレン−ブタジエン共重合体(SBR)である、請求項1〜5のいずれか一項に記載のゴム配合物の製造方法。
- 前記第2のポリマー材料はポリブタジエン(BR)又は天然ゴム(NR)である、請求項1〜6のいずれか一項に記載のゴム配合物の製造方法。
- 請求項1〜7のいずれか一項に記載のゴム配合物の製造方法により製造された、ゴム配合物。
- 請求項8のゴム配合物により作製されてなる、タイヤの部分。
- 少なくとも一部が本発明の方法により製造された配合物から作製されてなる、タイヤ。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT000398A ITRM20130398A1 (it) | 2013-07-08 | 2013-07-08 | Metodo per la preparazione di una mescola in gomma per pneumatici |
ITRM2013A000398 | 2013-07-08 | ||
PCT/IB2014/062952 WO2015004605A1 (en) | 2013-07-08 | 2014-07-08 | Rubber tyre compound production method |
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JP2016524030A true JP2016524030A (ja) | 2016-08-12 |
JP6466431B2 JP6466431B2 (ja) | 2019-02-06 |
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JP2016524929A Active JP6466431B2 (ja) | 2013-07-08 | 2014-07-08 | ゴムタイヤ配合物の製造方法 |
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Country | Link |
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US (1) | US9644085B2 (ja) |
EP (1) | EP3019341B1 (ja) |
JP (1) | JP6466431B2 (ja) |
CN (1) | CN105377576B (ja) |
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JP6570551B2 (ja) * | 2014-06-13 | 2019-09-04 | 株式会社ブリヂストン | 二酸化ケイ素を含むタイヤ製造用ゴムコンパウンド |
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JP2012036370A (ja) * | 2010-07-16 | 2012-02-23 | Sumitomo Rubber Ind Ltd | トレッド用ゴム組成物及び空気入りタイヤ |
WO2012043858A1 (ja) * | 2010-10-01 | 2012-04-05 | 株式会社ブリヂストン | ゴム組成物の製造方法 |
JP2015000933A (ja) * | 2013-06-14 | 2015-01-05 | 住友ゴム工業株式会社 | トラック・バスタイヤのキャップトレッド用ゴム組成物及びトラック・バスタイヤ |
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JP4835769B2 (ja) * | 2010-05-26 | 2011-12-14 | 横浜ゴム株式会社 | タイヤトレッド用ゴム組成物 |
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JP2012036370A (ja) * | 2010-07-16 | 2012-02-23 | Sumitomo Rubber Ind Ltd | トレッド用ゴム組成物及び空気入りタイヤ |
WO2012043858A1 (ja) * | 2010-10-01 | 2012-04-05 | 株式会社ブリヂストン | ゴム組成物の製造方法 |
JP2015000933A (ja) * | 2013-06-14 | 2015-01-05 | 住友ゴム工業株式会社 | トラック・バスタイヤのキャップトレッド用ゴム組成物及びトラック・バスタイヤ |
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US20160145424A1 (en) | 2016-05-26 |
JP6466431B2 (ja) | 2019-02-06 |
EP3019341A1 (en) | 2016-05-18 |
CN105377576A (zh) | 2016-03-02 |
ITRM20130398A1 (it) | 2015-01-09 |
WO2015004605A1 (en) | 2015-01-15 |
EP3019341B1 (en) | 2019-03-27 |
US9644085B2 (en) | 2017-05-09 |
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