JP6359411B2 - Rubber composition for covering steel cord and pneumatic tire - Google Patents
Rubber composition for covering steel cord and pneumatic tire Download PDFInfo
- Publication number
- JP6359411B2 JP6359411B2 JP2014203742A JP2014203742A JP6359411B2 JP 6359411 B2 JP6359411 B2 JP 6359411B2 JP 2014203742 A JP2014203742 A JP 2014203742A JP 2014203742 A JP2014203742 A JP 2014203742A JP 6359411 B2 JP6359411 B2 JP 6359411B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- mass
- rubber composition
- vulcanization accelerator
- steel cord
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001971 elastomer Polymers 0.000 title claims description 42
- 239000005060 rubber Substances 0.000 title claims description 42
- 239000000203 mixture Substances 0.000 title claims description 34
- 229910000831 Steel Inorganic materials 0.000 title claims description 21
- 239000010959 steel Substances 0.000 title claims description 21
- 238000004073 vulcanization Methods 0.000 claims description 47
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 15
- 229920003244 diene elastomer Polymers 0.000 claims description 13
- CAXJFBOSFXRPOJ-UHFFFAOYSA-N n-phenyl-n-(trichloromethylsulfanyl)benzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)N(SC(Cl)(Cl)Cl)C1=CC=CC=C1 CAXJFBOSFXRPOJ-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 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 5
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 claims description 2
- JLKZUNOWPPEBPX-UHFFFAOYSA-N zinc;3h-1,3-benzothiazole-2-thione Chemical compound [Zn+2].C1=CC=C2SC(=S)NC2=C1 JLKZUNOWPPEBPX-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 13
- 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 13
- 238000002156 mixing Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 2
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- -1 steel Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 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
- 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 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 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 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、タイヤのスチールコード被覆用ゴム組成物及びこれを用いた空気入りタイヤに関するものである。 The present invention relates to a rubber composition for covering a steel cord of a tire and a pneumatic tire using the same.
タイヤ用等のゴム組成物は、ジエン系ゴムに対して硫黄や加硫促進剤等の加硫系配合剤を含まない配合剤を混合する工程と、その加硫系配合剤を含まない配合剤を混合する工程で得た混合物に加硫系配合剤を添加して混合する工程とを有する製造方法により製造される。加硫促進剤には数多くの種類があるが、代表的なものとして、チアゾール系加硫促進剤やスルフェンアミド系加硫促進剤が広く用いられている。 A rubber composition for tires, etc. includes a step of mixing a diene rubber with a compounding agent not containing a vulcanizing compound such as sulfur or a vulcanization accelerator, and a compounding agent not containing the vulcanizing compounding agent. And a step of adding a vulcanizing compound to the mixture obtained in the step of mixing and mixing the mixture. Although there are many types of vulcanization accelerators, as typical ones, thiazole vulcanization accelerators and sulfenamide vulcanization accelerators are widely used.
しかし、これらの加硫促進剤を用いて得られたゴム組成物は、スチール等の金属に対する接着性が不足する傾向があり、スチールコード被覆用として用いた場合に得られるタイヤの耐久性が未だ十分ではなく、より優れた接着力が長期間持続するゴム組成物が望まれている。 However, rubber compositions obtained using these vulcanization accelerators tend to have insufficient adhesion to metals such as steel, and the durability of tires obtained when used for coating steel cords is still unsatisfactory. There is a demand for a rubber composition that is not sufficient and has a superior adhesive strength that lasts for a long period of time.
本発明者は、チアゾール系加硫促進剤又はスルフェンアミド系加硫促進剤とＮ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドとを所定の割合で併用することにより、上記課題を解決しうることを見出した。 The inventor has solved the above-mentioned problems by using a thiazole vulcanization accelerator or a sulfenamide vulcanization accelerator and N-phenyl-N- (trichloromethylthio) benzenesulfonamide in a predetermined ratio. I found out.
このＮ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドを使用したゴム組成物に関しては、例えば特許文献１及び２に、チアゾール系加硫促進剤と本化合物とを含有し、引張り物性や耐スコーチ性等が向上した防振ゴム組成物がそれぞれ開示されている。 With regard to the rubber composition using this N-phenyl-N- (trichloromethylthio) benzenesulfonamide, for example, Patent Documents 1 and 2 contain a thiazole vulcanization accelerator and the present compound, and have tensile properties and scorch resistance. Anti-vibration rubber compositions having improved properties and the like are disclosed.
しかし、これらの文献に記載されたゴム組成物はタイヤ用ではなく、スルホンアミド系化合物は主として耐スコーチ性の向上のために使用されており、金属に対する接着力の向上については何ら記載されず、示唆すらされていない。 However, the rubber compositions described in these documents are not for tires, and sulfonamide compounds are mainly used to improve scorch resistance, and nothing is described about improvement of adhesion to metals. Not even suggested.
本発明は、上記に鑑みてなされたものであり、スチールコードへの接着性がより向上したスチールコード被覆用ゴム組成物、及びこのゴム組成物を用いたことにより耐久性が向上した空気入りタイヤを提供することを目的とする。 The present invention has been made in view of the above, and a rubber composition for coating a steel cord with improved adhesion to a steel cord, and a pneumatic tire with improved durability by using this rubber composition The purpose is to provide.
本発明に係るゴム組成物は、ジエン系ゴムと、２−メルカプトベンゾチアゾール、２−ベンゾチアゾリルジスルフィド、２−メルカプトベンゾチアゾールのナトリウム塩、２−メルカプトベンゾチアゾールの亜鉛塩、Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド、Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド、及びＮ，Ｎ−ジシクロヘキシル−２−ベンゾチアゾリルスルフェンアミドの中から選択された加硫促進剤１種又は２種以上とを含有するものであって、上記の課題を解決するために、Ｎ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドをジエン系ゴム１００質量部に対して０．１〜１質量部含有し、このＮ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドの含有量が上記加硫促進剤の合計量１質量部当たり０．１〜０．５質量部であるものとする。
The rubber composition according to the present invention comprises a diene rubber, 2-mercaptobenzothiazole , 2-benzothiazolyl disulfide, sodium salt of 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole, N-cyclohexyl- Vulcanization accelerator 1 selected from 2-benzothiazolylsulfenamide, Nt-butyl-2-benzothiazolylsulfenamide, and N, N-dicyclohexyl-2-benzothiazolylsulfenamide 1 In order to solve the above-described problems, N-phenyl-N- (trichloromethylthio) benzenesulfonamide is added in an amount of 0.1 to 100 parts by mass of diene rubber. Contains 1 part by mass of this N-phenyl-N- (trichloromethylthio) benzenesulfonamide An amount shall be 0.1-0.5 mass part per 1 mass part of total amounts of the said vulcanization accelerator.
本発明に係る空気入りタイヤは、上記スチールコード被覆用ゴム組成物を用いて得られるものとする。 The pneumatic tire according to the present invention is obtained using the steel cord covering rubber composition.
本発明に係るスチールコード被覆用ゴム組成物によれば、上記の通りチアゾール系加硫促進剤及び／又はスルフェンアミド系加硫促進剤と、Ｎ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドとを所定の割合で併用することにより、スチールコードに対する接着性及びその耐老化性を大きく向上させることが可能となる。よってこのゴム組成物を用いることにより、スチールコードによる補強効果がより高く、耐久性が向上した空気入りタイヤを得ることができる。 According to the rubber composition for coating a steel cord according to the present invention, as described above, a thiazole vulcanization accelerator and / or a sulfenamide vulcanization accelerator, and N-phenyl-N- (trichloromethylthio) benzenesulfonamide In combination at a predetermined ratio can greatly improve the adhesion to steel cord and its aging resistance. Therefore, by using this rubber composition, it is possible to obtain a pneumatic tire having a higher reinforcing effect by the steel cord and improved durability.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本実施形態のゴム組成物に用いるジエン系ゴムは特に限定されないが、例としては、天然ゴム（ＮＲ）、合成イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、ニトリルゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、ブチルゴム（ＩＩＲ）、スチレン−イソプレン共重合体ゴム、ブタジエン−イソプレン共重合体ゴム、スチレン−イソプレン−ブタジエン共重合体ゴム等が挙げられ、これらはいずれか１種単独で用いることも、２種以上組み合わせて用いることもできる。これらの中でも、ＮＲ、ＢＲ及びＳＢＲからなる群から選択された少なくとも１種であることが好ましい。 The diene rubber used in the rubber composition of the present embodiment is not particularly limited. Examples thereof include natural rubber (NR), synthetic isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), and nitrile rubber. (NBR), chloroprene rubber (CR), butyl rubber (IIR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, and the like. One species can be used alone, or two or more species can be used in combination. Among these, at least one selected from the group consisting of NR, BR and SBR is preferable.
ジエン系ゴムとしては、主鎖中又は末端が変性された変性ジエン系ゴムを必要に応じて使用することもできる。変性ジエン系ゴムの具体例としては、ＮＲ、ＩＲ、ＢＲ、ＳＢＲの主鎖又は末端が、アミノ基、水酸基、カルボキシル基、アルコキシ基、アルコキシシリル基、チオール基などの少なくとも１種の官能基で変性されたものが挙げられる。 As the diene rubber, a modified diene rubber whose main chain or terminal is modified may be used as necessary. As specific examples of the modified diene rubber, the main chain or terminal of NR, IR, BR, and SBR is at least one functional group such as amino group, hydroxyl group, carboxyl group, alkoxy group, alkoxysilyl group, and thiol group. A modified one is mentioned.
本実施形態のゴム組成物には、チアゾール系加硫促進剤及びスルフェンアミド系加硫促進剤から選択された少なくとも１種を含有し、その加硫促進剤とＮ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドゴムとの併用により、本発明の目的とするスチールコードに対する接着性向上効果が得られる。 The rubber composition of this embodiment contains at least one selected from a thiazole vulcanization accelerator and a sulfenamide vulcanization accelerator, and the vulcanization accelerator and N-phenyl-N- (trichloro By the combined use with methylthio) benzenesulfonamide rubber, the effect of improving the adhesiveness to the steel cord intended by the present invention can be obtained.
チアゾール系加硫促進剤の具体例としては、２−メルカプトベンゾチアゾール（略号：Ｍ又はＭＢＴ）、２−ベンゾチアゾリルジスルフィド（略号：ＤＭ又はＭＢＴＳ）、２−メルカプトベンゾチアゾールのナトリウム塩（略号：ＮａＭＢＴ）、２−メルカプトベンゾチアゾールの亜鉛塩（略号：ＭＺ又はＺｎＭＢＴ）が挙げられる。これらのチアゾール系加硫促進剤の中では、２−ベンゾチアゾリルジスルフィド及び２−メルカプトベンゾチアゾール亜鉛塩が特に好ましい。 Specific examples of thiazole vulcanization accelerators include 2-mercaptobenzothiazole (abbreviation: M or MBT), 2-benzothiazolyl disulfide (abbreviation: DM or MBTS), sodium salt of 2-mercaptobenzothiazole (abbreviation). : NaMBT), zinc salt of 2-mercaptobenzothiazole (abbreviation: MZ or ZnMBT). Among these thiazole vulcanization accelerators, 2-benzothiazolyl disulfide and 2-mercaptobenzothiazole zinc salt are particularly preferable.
また、スルフェンアミド系加硫促進剤の例としては、Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド（略号：ＣＺ）、Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド（略号：ＮＳ）、Ｎ，Ｎ−ジシクロヘキシル−２−ベンゾチアゾリルスルフェンアミド（略号：ＤＺ）が挙げられる。 Examples of the sulfenamide-based vulcanization accelerator include N-cyclohexyl-2-benzothiazolylsulfenamide (abbreviation: CZ), Nt-butyl-2-benzothiazolylsulfenamide (abbreviation: NS), N, N-dicyclohexyl-2-benzothiazolylsulfenamide (abbreviation: DZ).
これらチアゾール系加硫促進剤及び／又はスルフェンアミド系加硫促進剤は、１種を単独で使用することもでき、２種以上の混合物を使用することもできる。 These thiazole vulcanization accelerators and / or sulfenamide vulcanization accelerators can be used alone or in a mixture of two or more.
上記チアゾール系加硫促進剤及び／又はスルフェンアミド系加硫促進剤のゴム組成物中の含有量は、上記接着性の向上効果の点から、ジエン系ゴム１００質量部に対して０．３〜５質量部が好ましく、０．５〜３質量部がより好ましい。 The content of the thiazole vulcanization accelerator and / or the sulfenamide vulcanization accelerator in the rubber composition is 0.3 with respect to 100 parts by mass of the diene rubber from the viewpoint of the effect of improving the adhesiveness. -5 mass parts is preferable, and 0.5-3 mass parts is more preferable.
本実施形態では、上記チアゾール系加硫促進剤及び／又はスルフェンアミド系加硫促進剤以外の加硫促進剤も使用することができる。それら加硫促進剤の例としては、グアニジン系、チウラム系、ジチオカルバミン酸塩系等が挙げられる。このうちグアニジン系加硫促進剤の例としては、１，３−ジフェニルグアニジン（略号：ＤＰＧ又はＤ）、１，３−ジ−ｏ−トリルグアニジン（略号：ＤＯＴＧ）、１−ｏ−トリルビグアニド（略号：ＯＴＢＧ）等が挙げられる。但し、加硫促進剤全体中でベンゾチアゾール系加硫促進剤及び／又はスルフェンアミド系加硫促進剤が占める割合が５０質量％以上であることが好ましく、６５質量％以上であることがより好ましい。 In the present embodiment, a vulcanization accelerator other than the thiazole vulcanization accelerator and / or the sulfenamide vulcanization accelerator can also be used. Examples of these vulcanization accelerators include guanidine, thiuram, and dithiocarbamate. Among them, examples of guanidine vulcanization accelerators include 1,3-diphenylguanidine (abbreviation: DPG or D), 1,3-di-o-tolylguanidine (abbreviation: DOTG), 1-o-tolylbiguanide ( (Abbreviation: OTBG). However, the proportion of benzothiazole vulcanization accelerator and / or sulfenamide vulcanization accelerator in the entire vulcanization accelerator is preferably 50% by mass or more, and more preferably 65% by mass or more. preferable.
本実施形態のゴム組成物において用いる、Ｎ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドは、従来はスコーチ防止剤として使用されてきたが、本発明では、チアゾール系加硫促進剤及び／又はスルフェンアミド系加硫促進剤との併用により、スチールコードに対する接着性向上効果に寄与する。この効果の観点から、本化合物の含有量は、上記ベンゾチアゾール系加硫促進剤及び／又はスルフェンアミド系加硫促進剤の合計量１質量部当たり０．１〜０．５質量部が好ましく、０．１〜０．３質量部がより好ましい。また、ジエン系ゴム１００質量部に対する含有量では０．１〜１質量部が好ましく、０．３〜０．５質量部がより好ましい。 N-phenyl-N- (trichloromethylthio) benzenesulfonamide used in the rubber composition of the present embodiment has been conventionally used as a scorch inhibitor, but in the present invention, a thiazole vulcanization accelerator and / or Concomitant use with sulfenamide vulcanization accelerators contributes to improved adhesion to steel cords. From the viewpoint of this effect, the content of the present compound is preferably 0.1 to 0.5 parts by mass per 1 part by mass of the total amount of the benzothiazole vulcanization accelerator and / or sulfenamide vulcanization accelerator. 0.1 to 0.3 parts by mass is more preferable. Moreover, 0.1-1 mass part is preferable in content with respect to 100 mass parts of diene rubbers, and 0.3-0.5 mass part is more preferable.
本実施形態のゴム組成物には、ゴム分野で通常使用されている補強性充填剤を使用することができる。補強性充填剤の例としては、ゴム分野で通常使用されているカーボンブラック、シリカ、タルク、クレイ、水酸化アルミニウム、酸化チタン等が例示され、通常はカーボンブラック又はシリカが好ましく用いられる。 In the rubber composition of the present embodiment, a reinforcing filler usually used in the rubber field can be used. Examples of reinforcing fillers include carbon black, silica, talc, clay, aluminum hydroxide, titanium oxide and the like that are commonly used in the rubber field, and carbon black or silica is usually preferably used.
カーボンブラックは、特に限定されず、公知の種々の品種を用いることができ、例えば、ＳＡＦ級（Ｎ１００番台）、ＩＳＡＦ級（Ｎ２００番台）、ＨＡＦ級（Ｎ３００番台）、ＦＥＦ級（Ｎ５００番台）、ＧＰＦ級（Ｎ６００番台）（ともにＡＳＴＭグレード）のものが好ましく用いられる。 Carbon black is not particularly limited, and various known varieties can be used. For example, SAF class (N100 series), ISAF class (N200 series), HAF class (N300 series), FEF class (N500 series), GPF grades (N600 range) (both ASTM grades) are preferably used.
シリカも特に限定されず、乾式法シリカ（無水ケイ酸）、湿式法シリカ（含水ケイ酸）等のいずれも使用できる。シリカのチッ素吸着比表面積（Ｎ2ＳＡ）は、１２０〜２４０ｍ2／ｇの範囲が好ましい。 Silica is not particularly limited, and any of dry process silica (anhydrous silicic acid), wet process silica (hydrous silicic acid) and the like can be used. The nitrogen adsorption specific surface area (N 2 SA) of silica is preferably in the range of 120 to 240 m 2 / g.
上記補強性充填剤の配合量は特に限定されず、カーボンブラックのみを使用する場合は、通常はゴム成分１００質量部あたり３０〜８０質量部の範囲が好ましく、シリカを配合する場合は、通常はゴム成分１００質量部あたり１０〜１２０質量部の範囲が好ましい。またシリカを配合する場合、ゴム成分１００質量部あたりカーボンブラックを５〜５０質量部配合することが好ましく、シリカ／カーボンブラックの配合比率は１／２０〜１／０．１が特に好ましい。 The compounding amount of the reinforcing filler is not particularly limited. When only carbon black is used, the range of 30 to 80 parts by mass is usually preferable per 100 parts by mass of the rubber component. A range of 10 to 120 parts by mass per 100 parts by mass of the rubber component is preferable. When silica is blended, it is preferable to blend 5 to 50 parts by mass of carbon black per 100 parts by mass of the rubber component, and the blending ratio of silica / carbon black is particularly preferably 1/20 to 1 / 0.1.
上記補強性充填剤としてシリカを使用する場合は、シランカップリング剤を併用するのが好ましい。シランカップリング剤の種類は特に限定されず、タイヤ用ゴム組成物において一般に使用されるものを使用することができ、例としてはスルフィドシラン、メルカプトシラン等が挙げられる。シランカップリング剤の含有量はシリカに対して５〜１５質量％が好ましい。 When silica is used as the reinforcing filler, it is preferable to use a silane coupling agent in combination. The kind of silane coupling agent is not particularly limited, and those generally used in rubber compositions for tires can be used. Examples thereof include sulfide silane and mercaptosilane. The content of the silane coupling agent is preferably 5 to 15% by mass with respect to silica.
本実施形態に係るゴム組成物には、上記の各成分の他に、オイル、亜鉛華、ステアリン酸、老化防止剤、ワックス、加硫剤など、ゴム組成物において一般に使用される各種添加剤を配合することができる。上記加硫剤としては、粉末硫黄、沈降硫黄、コロイド硫黄、不溶性硫黄、高分散性硫黄などの硫黄成分が挙げられ、特に限定するものではないが、その配合量は、ジエン系ゴム１００質量部に対して０．１〜１０質量部であることが好ましく、より好ましくは０．５〜５質量部である。 The rubber composition according to the present embodiment includes various additives generally used in rubber compositions such as oil, zinc white, stearic acid, anti-aging agent, wax, and vulcanizing agent in addition to the above components. Can be blended. Examples of the vulcanizing agent include sulfur components such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Although not particularly limited, the blending amount thereof is 100 parts by mass of diene rubber. It is preferable that it is 0.1-10 mass parts with respect to it, More preferably, it is 0.5-5 mass parts.
実施形態に係るゴム組成物は、通常に用いられるバンバリーミキサーやニーダー、ロール等の混合機を用いて、常法に従い混練し作製することができる。すなわち、第一混合段階で、ゴム成分に対し、加硫剤及び加硫促進剤を除く他の添加剤を添加混合し、次いで、得られた混合物に、最終混合段階で加硫剤及び加硫促進剤を添加混合してゴム組成物を調製することができる。 The rubber composition according to the embodiment can be prepared by kneading according to a conventional method using a commonly used Banbury mixer, kneader, roll, or other mixer. That is, in the first mixing stage, other additives excluding the vulcanizing agent and vulcanization accelerator are added to and mixed with the rubber component, and then the resulting mixture is mixed with the vulcanizing agent and vulcanizing in the final mixing stage. A rubber composition can be prepared by adding and mixing an accelerator.
本発明の空気入りタイヤは、例えば次の工程によって得ることができる。まず、スチールコードを上記ゴム組成物で被覆してから、ベルト等の部材の所望の形状に成形する。次に、成形した部材を他のタイヤ部材と貼りあわせることにより、未加硫タイヤを調製する。その後、未加硫タイヤを加硫することにより、本発明の空気入りタイヤを得ることができる。 The pneumatic tire of the present invention can be obtained, for example, by the following process. First, a steel cord is coated with the rubber composition, and then formed into a desired shape of a member such as a belt. Next, an unvulcanized tire is prepared by pasting the molded member with another tire member. Thereafter, the pneumatic tire of the present invention can be obtained by vulcanizing the unvulcanized tire.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。また、以下において「部」又は「％」というときは、特にことわらない限り質量基準とする。 Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “part” or “%” is based on mass unless otherwise specified.
バンバリーミキサーを使用し、下記表１に示す配合（質量部）に従って、まず、第一混合段階で、ジエン系ゴム成分に対し、硫黄及び加硫促進剤を除く他の配合剤を添加し、混練し（排出温度＝１６０℃）、次いで、得られた混練物に、最終混合段階で、硫黄と加硫促進剤を添加し混練して（排出温度＝９０℃）、ゴム組成物を調製した。表１中の各成分の詳細は、以下の通りである。 Using a Banbury mixer, according to the blending (parts by mass) shown in Table 1 below, first, in the first mixing stage, other blending agents except for sulfur and vulcanization accelerator are added to the diene rubber component and kneaded. Then, in the final mixing stage, sulfur and a vulcanization accelerator were added and kneaded (discharge temperature = 90 ° C.) to prepare the rubber composition. The details of each component in Table 1 are as follows.
・加硫促進剤ＣＺ：Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド（住友化学株式会社製「ソクシノールＣＺ」）
・加硫促進剤ＤＭ：ジベンゾチアジルジスルフィド（大内新興化学株式会社製「ノクセラーＤＭ」）
・加硫促進剤ＮＳ：Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド（大内新興化学株式会社製「ノクセラーＭＺ」）
・加硫促進剤ＤＺ：Ｎ，Ｎ−ジシクロヘキシル−２−ベンゾチアゾリルスルフェンアミド（大内新興化学株式会社製「ノクセラーＤＺ」）
・Ｎ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミド：ＬＡＮＸＥＳＳ社製「Ｖｕｌｋａｌｅｎｔ Ｅ／Ｃ」
・ＮＲ：ＲＳＳ３号
・カーボンブラック（ＨＡＦ−ＬＳ）：東海カーボン株式会社製「シースト３００」
・亜鉛華：三井金属鉱業株式会社製「亜鉛華３号」
・老化防止剤１：大内新興化学株式会社製「ノクラック６Ｃ」
・老化防止剤１：松原産業株式会社製「アンチオキシダントＦＲ」
・レゾルシン：住友化学工業株式会社製「レゾルシン」
・ヘキサメトキシメチルメラミン：三井サイテック株式会社製「サイレッツ９６３Ｌ」
・代替アロマ：ＪＸ日鉱日石エネルギー株式会社製「プロセスＮＣ１４０」
・ステアリン酸：花王株式会社製「ルナックＳ−２０」
・ステアリン酸コバルト：ＪＸ日鉱日石エネルギー株式会社製「ステアリン酸コバルト」
・不溶性硫黄：四国化成株式会社製「ミュークロンＯＴ−２０」
Vulcanization accelerator CZ: N-cyclohexyl-2-benzothiazolylsulfenamide (“Soccinol CZ” manufactured by Sumitomo Chemical Co., Ltd.)
・ Vulcanization accelerator DM: Dibenzothiazyl disulfide ("Noxeller DM" manufactured by Ouchi Shinsei Chemical Co., Ltd.)
・ Vulcanization accelerator NS: Nt-butyl-2-benzothiazolylsulfenamide (“Noxeller MZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.)
・ Vulcanization accelerator DZ: N, N-dicyclohexyl-2-benzothiazolylsulfenamide ("Noxeller DZ" manufactured by Ouchi Shinsei Chemical Co., Ltd.)
N-phenyl-N- (trichloromethylthio) benzenesulfonamide: “Vulkalent E / C” manufactured by LANXESS
NR: RSS No. 3 Carbon black (HAF-LS): “Seast 300” manufactured by Tokai Carbon Co., Ltd.
・ Zinc flower: “Zinc flower 3” manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Aging inhibitor 1: “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
Anti-aging agent 1: “Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.
・ Resorcin: “Resorcin” manufactured by Sumitomo Chemical Co., Ltd.
・ Hexamethoxymethylmelamine: “CYRETS 963L” manufactured by Mitsui Cytec Co., Ltd.
・ Alternative aroma: “Process NC140” manufactured by JX Nippon Oil & Energy Corporation
・ Stearic acid: “Lunac S-20” manufactured by Kao Corporation
・ Cobalt stearate: “Cobalt stearate” manufactured by JX Nippon Oil & Energy Corporation
Insoluble sulfur: “Muclon OT-20” manufactured by Shikoku Kasei Co., Ltd.
得られた各ゴム組成物を用いて、１６０℃×３０分の条件で加硫して、厚さ１ｍｍのシート状試験片を作製し、スチールコードに対する接着性を評価した。評価方法は以下の通りである。結果を表１に示す。 Each rubber composition obtained was vulcanized under conditions of 160 ° C. × 30 minutes to produce a sheet-like test piece having a thickness of 1 mm, and the adhesion to the steel cord was evaluated. The evaluation method is as follows. The results are shown in Table 1.
接着性：黄銅メッキスチールコードを１７本／２５ｍｍの間隔で並べ、評価用ゴムシートで挟み込んだものを２枚重ね、１６０℃×３０分で加硫してサンプルを作成した。これらサンプルにつき、２層のスチールコード間の剥離試験を、オートグラフ（島津製作所株式会社製「ＤＣＳ５００」）を用いて５００ｍｍ／ｍｉｎの引張り速度で行った。接着性の指標として、剥離後のスチールコードのゴム被覆率を目視にて確認し、比較例１の結果を１００として指数表示した。数値が大きいほど接着性が良好であることを示す。 Adhesiveness: Brass-plated steel cords were arranged at intervals of 17 pieces / 25 mm, two pieces sandwiched between evaluation rubber sheets were stacked, and vulcanized at 160 ° C. for 30 minutes to prepare a sample. For these samples, a peel test between two steel cords was performed at a pulling speed of 500 mm / min using an autograph (“DCS500” manufactured by Shimadzu Corporation). As an index of adhesiveness, the rubber coverage of the steel cord after peeling was visually confirmed, and the result of Comparative Example 1 was indicated as 100 as an index. It shows that adhesiveness is so favorable that a numerical value is large.
老化試験後の接着性：恒温恒湿槽（佐竹化学機械工業株式会社製「ＫＶ４０」）にて、上記サンプルを、温度７０℃、湿度９５％の環境下に２０日間保持し、そのサンプルにつき上記評価方法にて接着性を評価した。
Adhesion after aging test: The above sample is kept in a constant temperature and humidity chamber ("KV40" manufactured by Satake Chemical Machinery Co., Ltd.) for 20 days in an environment of temperature 70 ° C and humidity 95%. Adhesiveness was evaluated by an evaluation method.
表１に示す結果から、チアゾール系加硫促進剤又はスルフェンアミド系加硫促進剤と共にＮ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドを所定の割合で使用した実施例１〜１０は、Ｎ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドを使用しないか、使用してもチアゾール系加硫促進剤又はスルフェンアミド系加硫促進剤との割合が本発明で規定した範囲外である各比較例と比較して、スチールコードに対する接着性及びその耐老化性が顕著に向上していることが分かる。 From the results shown in Table 1, Examples 1 to 10 using N-phenyl-N- (trichloromethylthio) benzenesulfonamide in a predetermined ratio together with a thiazole vulcanization accelerator or a sulfenamide vulcanization accelerator are as follows: N-phenyl-N- (trichloromethylthio) benzenesulfonamide is not used, or even if it is used, the ratio with the thiazole vulcanization accelerator or sulfenamide vulcanization accelerator is outside the range defined in the present invention. Compared with each comparative example, it turns out that the adhesiveness with respect to a steel cord and its aging resistance are remarkably improved.
Claims (2)
２−メルカプトベンゾチアゾール、２−ベンゾチアゾリルジスルフィド、２−メルカプトベンゾチアゾールのナトリウム塩、２−メルカプトベンゾチアゾールの亜鉛塩、Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド、Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド、及びＮ，Ｎ−ジシクロヘキシル−２−ベンゾチアゾリルスルフェンアミドの中から選択された加硫促進剤１種又は２種以上とを含有するスチールコード被覆用ゴム組成物であって、
Ｎ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドを前記ジエン系ゴム１００質量部に対して０．１〜１質量部含有し、
このＮ−フェニル−Ｎ−（トリクロロメチルチオ）ベンゼンスルホンアミドの含有量が前記加硫促進剤の合計量１質量部当たり０．１〜０．５質量部である
ことを特徴とするスチールコード被覆用ゴム組成物。 Diene rubber,
2-mercaptobenzothiazole, 2-benzothiazolyl disulfide, sodium salt of 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazolylsulfenamide, Nt-butyl Steel cord coating rubber containing one or more vulcanization accelerators selected from 2-benzothiazolylsulfenamide and N, N-dicyclohexyl-2-benzothiazolylsulfenamide A composition comprising:
Containing 0.1 to 1 part by mass of N-phenyl-N- (trichloromethylthio) benzenesulfonamide with respect to 100 parts by mass of the diene rubber;
For steel cord coating, wherein the content of N-phenyl-N- (trichloromethylthio) benzenesulfonamide is 0.1 to 0.5 parts by mass per 1 part by mass of the total amount of the vulcanization accelerator Rubber composition.
A pneumatic tire comprising the rubber composition for covering a steel cord according to claim 1 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014203742A JP6359411B2 (en) | 2014-10-02 | 2014-10-02 | Rubber composition for covering steel cord and pneumatic tire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014203742A JP6359411B2 (en) | 2014-10-02 | 2014-10-02 | Rubber composition for covering steel cord and pneumatic tire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016069608A JP2016069608A (en) | 2016-05-09 |
| JP6359411B2 true JP6359411B2 (en) | 2018-07-18 |
Family
ID=55864118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014203742A Active JP6359411B2 (en) | 2014-10-02 | 2014-10-02 | Rubber composition for covering steel cord and pneumatic tire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6359411B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023018578A (en) * | 2021-07-27 | 2023-02-08 | 株式会社ブリヂストン | Hose inner tube rubber composition, laminate, and hose |
| JP2023018576A (en) * | 2021-07-27 | 2023-02-08 | 株式会社ブリヂストン | Hose inner tube rubber composition, laminate, and hose |
| JP2024050070A (en) * | 2022-09-29 | 2024-04-10 | 住友理工株式会社 | Industrial Hose |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE758927A (en) * | 1969-11-15 | 1971-05-13 | Bayer Ag | NEW VULCANIZATION DELAYERS BASED ON SUBSTITUTE SULFONAMIDES |
| US4107332A (en) * | 1977-01-17 | 1978-08-15 | Chevron Research Company | Mite and mite-ovicidal compositions |
| JPS58160331A (en) * | 1982-03-18 | 1983-09-22 | Sumitomo Chem Co Ltd | Sulfonamide-containing rubber composition |
| JP2008156433A (en) * | 2006-12-22 | 2008-07-10 | Bando Chem Ind Ltd | Rubber composition and conveyer belt |
| JP2010196030A (en) * | 2009-01-27 | 2010-09-09 | Shikoku Chem Corp | Rubber composition |
| DE102009023915A1 (en) * | 2009-05-27 | 2010-12-02 | Rhein-Chemie Rheinau Gmbh | Mixtures of functionalized diene rubbers with trimethylolpropane and fatty acid, a process for their preparation and their use |
| JP2011178922A (en) * | 2010-03-02 | 2011-09-15 | Bridgestone Corp | Rubber composition, and tire using the same |
| JP6112755B2 (en) * | 2011-04-26 | 2017-04-12 | 株式会社ブリヂストン | Anti-vibration rubber composition and anti-vibration rubber |
| JP5855931B2 (en) * | 2011-12-26 | 2016-02-09 | 株式会社ブリヂストン | Rubber composition for conveyor belt and conveyor belt |
| JP5893937B2 (en) * | 2012-01-30 | 2016-03-23 | 株式会社ブリヂストン | Anti-vibration rubber composition, crosslinked anti-vibration rubber composition and anti-vibration rubber |
| JP6013175B2 (en) * | 2012-03-29 | 2016-10-25 | 住友理工株式会社 | Conductive roll for electrophotographic equipment |
| JP5928273B2 (en) * | 2012-09-20 | 2016-06-01 | 株式会社ブリヂストン | Method for producing rubber composition |
| JP5949493B2 (en) * | 2012-11-22 | 2016-07-06 | 株式会社ブリヂストン | Anti-vibration rubber composition and anti-vibration rubber |
| EP2774924A1 (en) * | 2013-01-29 | 2014-09-10 | Rhein Chemie Rheinau GmbH | New compositions, cross-linkable rubber mixtures containing these compositions, process for their production and their use |
-
2014
- 2014-10-02 JP JP2014203742A patent/JP6359411B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016069608A (en) | 2016-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2009155637A (en) | Rubber composition for tire | |
| JP2013147581A (en) | Rubber composition and tire using the same | |
| JP2015021111A (en) | Method of producing rubber composition | |
| JP6359411B2 (en) | Rubber composition for covering steel cord and pneumatic tire | |
| JP6116439B2 (en) | Method for producing rubber composition | |
| JP6420196B2 (en) | Method for producing rubber composition | |
| JP5631761B2 (en) | Method for producing rubber composition for tire | |
| JP5563233B2 (en) | Steel cord bonding rubber composition and pneumatic tire | |
| JP2012153758A (en) | Production method for rubber composition for tire | |
| JP2010013504A (en) | Rubber composition for air spring, and air spring | |
| JP6326334B2 (en) | Rubber composition and pneumatic tire | |
| US10472504B2 (en) | Rubber composition | |
| JP4910416B2 (en) | Rubber composition for tire | |
| JP5501812B2 (en) | Rubber composition and pneumatic tire | |
| AU2018327183A1 (en) | Rubber composition, inner peripheral cover rubber, conveyor belt, and belt conveyor | |
| JP2010254857A (en) | Rubber composition for wing or rubber chafer and pneumatic tire | |
| JP2017031281A (en) | Rubber composition and pneumatic tire | |
| JP6196872B2 (en) | Method for producing rubber composition | |
| WO2018139165A1 (en) | Tire | |
| JP4680234B2 (en) | Rubber composition for covering carcass cord and tire having carcass using the same | |
| JP2011001463A (en) | Rubber composition for bead apex or insulation, and pneumatic tire | |
| JP2010285511A (en) | Rubber composition for covering carcass cord and pneumatic tire | |
| JP6456778B2 (en) | Rubber composition for covering steel cord and pneumatic tire | |
| JP5415790B2 (en) | Rubber composition and pneumatic tire | |
| JP2001279026A (en) | Rubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170619 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180319 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180327 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180523 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180612 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180620 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6359411 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |