JP2016060837A - Rubber composition and pneumatic tire - Google Patents
Rubber composition and pneumatic tire Download PDFInfo
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- JP2016060837A JP2016060837A JP2014190095A JP2014190095A JP2016060837A JP 2016060837 A JP2016060837 A JP 2016060837A JP 2014190095 A JP2014190095 A JP 2014190095A JP 2014190095 A JP2014190095 A JP 2014190095A JP 2016060837 A JP2016060837 A JP 2016060837A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 54
- 239000005060 rubber Substances 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000004073 vulcanization Methods 0.000 claims abstract description 56
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 15
- 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 abstract description 15
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 7
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 6
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000002156 mixing Methods 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 7
- 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
- 239000005062 Polybutadiene Substances 0.000 description 4
- 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 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- -1 sulfonamide compound Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 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
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-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
- 235000021355 Stearic acid Nutrition 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
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000005065 mining Methods 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
- 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
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 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 description 2
- 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
- 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
- 239000011324 bead Substances 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 238000012545 processing Methods 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
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 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 description 1
- 150000003456 sulfonamides Chemical class 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
- 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
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- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
Description
本発明は、チアゾール系加硫促進剤を用いたゴム組成物及びこれから得られる空気入りタイヤに関するものである。 The present invention relates to a rubber composition using a thiazole vulcanization accelerator and a pneumatic tire obtained therefrom.
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、代表的なものの一つとして、２−メルカプトベンゾチアゾール等のチアゾール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 one representative one, thiazole vulcanization accelerators such as 2-mercaptobenzothiazole are widely used.
しかしチアゾール系加硫促進剤を用いて得られたゴムは、一般に耐摩耗性に優れる一方で、引裂強さ（耐引裂性）が十分ではない傾向があり、優れた耐摩耗性を維持しつつ、引裂強さをより向上させるゴム組成物が望まれている。 However, rubbers obtained using thiazole vulcanization accelerators generally have excellent wear resistance, but tend to have insufficient tear strength (tear resistance), while maintaining excellent wear resistance. Therefore, a rubber composition that further improves the tear strength is desired.
本発明者は、チアゾール系加硫促進剤と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 present inventor has found that the above-described problems can be solved by using a thiazole-based vulcanization accelerator and N-phenyl-N- (trichloromethylthio) benzenesulfonamide in a predetermined ratio.
チアゾール系加硫促進剤とスルホンアミド系化合物とを併用したゴム組成物としては、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。 As a rubber composition using a thiazole vulcanization accelerator and a sulfonamide compound in combination, for example, in Patent Documents 1 and 2, a thiazole vulcanization accelerator, N-phenyl-N- (trichloromethylthio) benzenesulfonamide, And anti-vibration rubber compositions with improved tensile properties and scorch resistance are disclosed.
また、特許文献３には、チウラム系加硫促進剤とスルホンアミド系化合物とを含有し、ブルーム性と耐ヘタリ性が向上した電子写真機器用導電性ロールを得るためのゴム組成物が開示されている。 Patent Document 3 discloses a rubber composition that contains a thiuram vulcanization accelerator and a sulfonamide compound, and that is used to obtain a conductive roll for electrophotographic equipment with improved blooming and sag resistance. ing.
さらに特許文献４には、チウラム系加硫促進剤とスルホンアミド系スコーチ防止剤を配合した給紙・搬送用ゴムロール用ゴム組成物が開示されている。 Furthermore, Patent Document 4 discloses a rubber composition for a rubber roll for paper feeding / conveying in which a thiuram vulcanization accelerator and a sulfonamide scorch inhibitor are blended.
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、耐摩耗性や引裂強さ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 for improving the scorch resistance, and nothing is described about the improvement of wear resistance and tear strength. Not even suggested.
本発明は、上記に鑑みてなされたものであり、チアゾール系加硫促進剤の配合による優れた耐摩耗性を維持しつつ、引裂強さをより向上させたゴムが得られるゴム組成物、これを用い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 from which a rubber with improved tear strength can be obtained while maintaining excellent wear resistance by blending a thiazole vulcanization accelerator, An object of the present invention is to provide a pneumatic tire using the tire.
本発明に係るゴム組成物は、ジエン系ゴムと、下記化学式（１）又は（２）で表されるベンゾチアゾール系加硫促進剤から選択された加硫促進剤１種又は２種以上を５０質量％以上含有する加硫促進剤と、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含有するものとする。 The rubber composition according to the present invention includes 50 or more diene rubbers and one or more vulcanization accelerators selected from benzothiazole vulcanization accelerators represented by the following chemical formula (1) or (2). It contains a vulcanization accelerator containing at least mass% and N-phenyl-N- (trichloromethylthio) benzenesulfonamide.
上記ゴム組成物は、ベンゾチアゾール系以外の加硫促進剤としてグアニジン系加硫促進剤を含有することが好ましい。 The rubber composition preferably contains a guanidine vulcanization accelerator as a vulcanization accelerator other than benzothiazole.
また、上記ゴム組成物は、ジエン系ゴム１００質量部に対して、上記ベンゾチアゾール系加硫促進剤を０．５〜１０質量部含有し、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０．１〜５質量部含有することが好ましい。 Further, the rubber composition contains 0.5 to 10 parts by mass of the benzothiazole vulcanization accelerator with respect to 100 parts by mass of the diene rubber, and N-phenyl-N- (trichloromethylthio) benzenesulfonamide. It is preferable to contain 0.1-5 mass parts.
本発明に係る空気入りタイヤは上記ゴム組成物を用いて得られるものとし、例えばベーストレッドに用いたものとする。 The pneumatic tire according to the present invention is obtained using the rubber composition, and is used for, for example, a base tread.
本発明に係るゴム組成物によれば、上記の通りベンゾチアゾール系加硫促進剤を５０質量％以上含む加硫促進剤と、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併用したことによる相乗効果として、ゴムの耐摩耗性と引裂強さを共に向上させることが可能となる。 According to the rubber composition according to the present invention, as described above, a vulcanization accelerator containing 50% by mass or more of a benzothiazole vulcanization accelerator and N-phenyl-N- (trichloromethylthio) benzenesulfonamide are used in combination. As a synergistic effect, it is possible to improve both the wear resistance and tear strength of the rubber.
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の主鎖中又は末端が、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, at least one functional group such as an amino group, a hydroxyl group, a carboxyl group, an alkoxy group, an alkoxysilyl group, or a thiol group is present in the main chain or terminal of NR, IR, BR, or SBR. And those modified with.
本実施形態のゴム組成物で用いる加硫促進剤は、上記化学式（１）又は（２）で表されるベンゾチアゾール系加硫促進剤を５０質量％以上含有することが好ましく、６５質量％以上含有することがより好ましい。これらベンゾチアゾール系加硫促進剤を５０質量％以上含有する加硫促進剤を使用することにより、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の併用により、耐摩耗性と引裂強さを共に向上させる上記相乗効果が得られる。 The vulcanization accelerator used in the rubber composition of the present embodiment preferably contains 50% by mass or more of the benzothiazole vulcanization accelerator represented by the chemical formula (1) or (2), and 65% by mass or more. It is more preferable to contain. By using a vulcanization accelerator containing 50% by mass or more of these benzothiazole-based vulcanization accelerators, wear resistance and tear strength can be obtained in combination with N-phenyl-N- (trichloromethylthio) benzenesulfonamide. The above-mentioned synergistic effect that improves both can be obtained.
化学式（１）及び（２）中、Ｒがアルコキシ基又はアルキル基の場合、炭素数は３以下が好ましい。 In the chemical formulas (1) and (2), when R is an alkoxy group or an alkyl group, the number of carbon atoms is preferably 3 or less.
化学式（１）で表されるベンゾ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）、化学式（２）で表されるベンゾ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の亜鉛塩（略号：ＭＺ又はＺｎＭＢＴ）が挙げられる。これらのベンゾ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 the benzothiazole vulcanization accelerator represented by the chemical formula (1) include 2-mercaptobenzothiazole (abbreviation: M or MBT), 2-benzothiazolyl disulfide (abbreviation: DM or MBTS), 2 -Sodium salt of mercaptobenzothiazole (abbreviation: NaMBT), specific examples of the benzothiazole vulcanization accelerator represented by chemical formula (2) include zinc salt of 2-mercaptobenzothiazole (abbreviation: MZ or ZnMBT). Can be mentioned. Among these benzothiazole vulcanization accelerators, 2-benzothiazolyl disulfide and 2-mercaptobenzothiazole zinc salt are particularly preferable.
これらベンゾチアゾール系加硫促進剤は、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 benzothiazole vulcanization accelerators can be used alone or in a mixture of two or more.
上記ベンゾチアゾール系加硫促進剤のゴム組成物中の含有量は、上記耐摩耗性と引裂強さの向上効果の点から、ジエン系ゴム１００質量部に対して０．５〜１０質量部が好ましく、１〜５質量部がより好ましい。 The content of the benzothiazole vulcanization accelerator in the rubber composition is 0.5 to 10 parts by mass with respect to 100 parts by mass of the diene rubber from the viewpoint of the effect of improving the abrasion resistance and tear strength. Preferably, 1 to 5 parts by mass is more preferable.
上記ベンゾチアゾール系加硫促進剤以外の加硫促進剤としては、グアニジン系、スルフェンアミド系、チウラム系、ジチオカルバミン酸塩系等の公知の加硫促進剤の１種又は２種以上を適宜使用することができる。 As the vulcanization accelerator other than the benzothiazole vulcanization accelerator, one or more known vulcanization accelerators such as guanidine, sulfenamide, thiuram, and dithiocarbamate are appropriately used. can do.
中でも、加硫速度の制御が容易である点からグアニジン系加硫促進剤を併用することが好ましい。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。グアニジン系加硫促進剤の使用量はジエン系ゴム１００質量部に対して０．１〜５質量部が好ましく、０．２〜２．５質量部がより好ましい。 Among them, it is preferable to use a guanidine vulcanization accelerator in combination because the vulcanization rate can be easily controlled. 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) and the like. 0.1-5 mass parts is preferable with respect to 100 mass parts of diene rubbers, and, as for the usage-amount of a guanidine type vulcanization accelerator, 0.2-2.5 mass parts is more preferable.
次に、本実施形態のゴム組成物において、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は、ジエン系ゴム１００質量部に対して０．１〜５質量部含有することが好ましく、０．２〜３質量部含有することがより好ましい。本化合物は、従来スコーチ防止剤として使用されているが、本発明では上記化学式（１）又は（２）で表されるベンゾチアゾール系加硫促進剤と併用することにより、耐摩耗性を損なうことなく引裂強さを向上させる効果に寄与する。 Next, in the rubber composition of the present embodiment, N-phenyl-N- (trichloromethylthio) benzenesulfonamide is preferably contained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the diene rubber. It is more preferable to contain 2-3 mass parts. This compound is conventionally used as a scorch inhibitor, but in the present invention, wear resistance is impaired by using it together with a benzothiazole vulcanization accelerator represented by the above chemical formula (1) or (2). Contributes to the effect of improving tear strength.
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.
カーボンブラックとしては、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。 The 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 class (N600 series) (both ASTM grade) 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、タイヤ部材の用途等によって適宜調整されるものであるが、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 blending amount of the reinforcing filler is not particularly limited, and is appropriately adjusted depending on the use of the tire member. However, when only carbon black is used, usually 30 to 80 mass per 100 mass parts of the rubber component. The range is preferably 10 parts by weight to 120 parts by weight per 100 parts by weight of the rubber component. 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.
このようにして得られたゴム組成物は、タイヤ用、防振ゴム用、コンベアベルト用などの各種ゴム部材に用いることができる。中でもタイヤ用として用いるのが好ましく、乗用車用、トラックやバスの大型タイヤなど各種用途、サイズの空気入りタイヤのトレッド部、サイドウォール部、ビード部、タイヤコード被覆用ゴムなどタイヤの各部位に適用することができる。すなわち、このゴム組成物は、常法に従い、例えば、押出加工によって所定の形状に成形され、他の部品と組み合わせた後、例えば１４０〜１８０℃で加硫成形することにより、空気入りタイヤを製造することができる。上記の中でも、タイヤのトレッド用として好適に用いることができる。 The rubber composition thus obtained can be used for various rubber members for tires, vibration-proof rubbers, conveyor belts and the like. Among them, it is preferable to use it for tires, and it is applied to various parts of tires such as tread parts, sidewall parts, bead parts, tire cord covering rubbers for various uses such as passenger car, truck and bus large tires, size pneumatic tires. can do. That is, this rubber composition is molded into a predetermined shape by, for example, extrusion processing according to a conventional method, and combined with other parts, and then vulcanized at, for example, 140 to 180 ° C. to produce a pneumatic tire. can do. Among the above, it can be suitably used for tire treads.
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.
・ＳＢＲ：ＪＳＲ株式会社製「ＳＢＲ１５０２」
・ＮＲ：ＲＳＳ３号
・カーボンブラック：東海カーボン株式会社製「シースト３」
・オイル：ＪＸ日鉱日石金属株式会社製「プロセスＮＣ１４０」
・亜鉛華：三井金属鉱業株式会社製「亜鉛華３号」
・ステアリン酸：花王株式会社製「ルナックＳ−２０」
・老化防止剤：大内新興化学株式会社製「ノクラック６Ｃ」
・硫黄：鶴見化学工業株式会社製「粉末硫黄」
・加硫促進剤１：２−ベンゾチアゾリルジスルフィド（大内新興化学株式会社製「ノクセラーＤＭ」）
・加硫促進剤２：２−メルカプトベンゾチアゾール亜鉛塩（大内新興化学株式会社製「ノクセラーＭＺ」）
・加硫促進剤３：１，３−ジフェニルグアニジン（大内新興化学株式会社製「ノクセラーＤ」）
・加硫促進剤４：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」）
・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」
・ SBR: “SBR1502” manufactured by JSR Corporation
・ NR: RSS 3 ・ Carbon black: “Seast 3” manufactured by Tokai Carbon Co., Ltd.
・ Oil: “Process NC140” manufactured by JX Nippon Mining & Metals
・ Zinc flower: “Zinc flower 3” manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Stearic acid: “Lunac S-20” manufactured by Kao Corporation
・ Anti-aging agent: “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
・ Sulfur: “Sulfur Powder” manufactured by Tsurumi Chemical Co., Ltd.
・ Vulcanization accelerator 1: 2-benzothiazolyl disulfide ("Noxeller DM" manufactured by Ouchi Shinsei Chemical Co., Ltd.)
・ Vulcanization accelerator 2: 2-mercaptobenzothiazole zinc salt (“Noxeller MZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.)
・ Vulcanization accelerator 3: 1,3-diphenylguanidine ("Noxeller D" manufactured by Ouchi Shinsei Chemical Co., Ltd.)
Vulcanization accelerator 4: N-cyclohexyl-2-benzothiazolylsulfenamide (“Soccinol CZ” manufactured by Sumitomo Chemical Co., Ltd.)
N-phenyl-N- (trichloromethylthio) benzenesulfonamide: “Vulkalent E / C” manufactured by LANXESS
得られた各ゴム組成物について、１６０℃×２０分で加硫して所定形状の試験片を作製し、引裂強さと耐摩耗性を評価した。各評価方法は以下の通りである。結果を表１に示す。 About each obtained rubber composition, it vulcanized | cured at 160 degreeC * 20 minutes, the test piece of a predetermined shape was produced, and tear strength and abrasion resistance were evaluated. Each evaluation method is as follows. The results are shown in Table 1.
引裂強さ：ＪＩＳ Ｋ６２５２に準拠して測定した。すなわち、規定のクレセント形で打ち抜き、くぼみ中央に０．５０±０．０８ｍｍの切れ込みを入れたサンプルを用い、（株）島津製作所製の引張試験機によって５００ｍｍ／ｍｉｎの引張り速度で試験を行い、試験片が切断に至るまでの引き裂く力の最大値を読み取り、比較例１の結果を１００として指数表示した。値が大きいほど引裂強さ（耐引裂性）が優れることを示す。
耐摩耗性：ＪＩＳ Ｋ６２６４に準拠して、岩本製作所（株）製のランボーン摩耗試験機を用いて、荷重３ｋｇ、スリップ率２０％、温度２３℃で摩耗量を測定し、比較例１の値を１００とした指数で表示した。値が小さいほど耐摩耗性に優れることを示す。
Tear strength: measured in accordance with JIS K6252. That is, using a sample punched out with a specified crescent shape and having a notch of 0.50 ± 0.08 mm in the center of the indentation, a test was performed at a tensile speed of 500 mm / min with a tensile tester manufactured by Shimadzu Corporation. The maximum value of the tearing force until the test piece was cut was read, and the result of Comparative Example 1 was taken as 100 and displayed as an index. Larger values indicate better tear strength (tear resistance).
Abrasion resistance: In accordance with JIS K6264, the amount of wear was measured at a load of 3 kg, a slip rate of 20%, and a temperature of 23 ° C. using a lambone wear tester manufactured by Iwamoto Seisakusho Co., Ltd. Expressed with an index of 100. It shows that it is excellent in abrasion resistance, so that a value is small.
表１に示す結果から分かるように、ベンゾチアゾール系加硫促進剤を５０質量％以上含有する加硫促進剤と、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それぞれ所定量使用した実施例１〜１１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比較例１及び３と比較して、耐摩耗性と引裂強さが共に優れたものとなった。 As can be seen from the results shown in Table 1, a predetermined amount of each of a vulcanization accelerator containing 50% by mass or more of a benzothiazole vulcanization accelerator and N-phenyl-N- (trichloromethylthio) benzenesulfonamide was used. In Examples 1 to 11, both abrasion resistance and tear strength were excellent as compared with Comparative Examples 1 and 3 in which N-phenyl-N- (trichloromethylthio) benzenesulfonamide was not used.
ベンゾチアゾール系加硫促進剤と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併用しても、加硫促進剤中のベンゾチアゾール系加硫促進剤の含有量が少ない比較例２及び４では、耐摩耗性と引裂強さが共に劣る結果となった。 Comparative Example 2 in which the content of the benzothiazole vulcanization accelerator in the vulcanization accelerator is small even when the benzothiazole vulcanization accelerator and N-phenyl-N- (trichloromethylthio) benzenesulfonamide are used in combination. In No. 4, both wear resistance and tear strength were inferior.
Claims (5)
化学式（１）又は（２）で表されるベンゾチアゾール系加硫促進剤から選択された加硫促進剤１種又は２種以上を５０質量％以上含有する加硫促進剤と、
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含有する
ことを特徴とするゴム組成物。
A vulcanization accelerator containing 50% by mass or more of one or more vulcanization accelerators selected from benzothiazole vulcanization accelerators represented by chemical formula (1) or (2);
A rubber composition comprising N-phenyl-N- (trichloromethylthio) benzenesulfonamide.
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| US11312842B2 (en) * | 2017-11-30 | 2022-04-26 | Bridgestone Corporation | Rubber composition, rubber composition for tires, and tire |
| WO2023112393A1 (en) * | 2021-12-15 | 2023-06-22 | 株式会社ブリヂストン | Tire rubber composition, and tire |
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| AU2018377346B2 (en) * | 2017-11-30 | 2023-10-19 | Bridgestone Corporation | Rubber composition, rubber composition for tires, and tire |
| WO2023112393A1 (en) * | 2021-12-15 | 2023-06-22 | 株式会社ブリヂストン | Tire rubber composition, and tire |
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