JP2017019981A - Rubber composition and pneumatic tire - Google Patents
Rubber composition and pneumatic tire Download PDFInfo
- Publication number
- JP2017019981A JP2017019981A JP2015141340A JP2015141340A JP2017019981A JP 2017019981 A JP2017019981 A JP 2017019981A JP 2015141340 A JP2015141340 A JP 2015141340A JP 2015141340 A JP2015141340 A JP 2015141340A JP 2017019981 A JP2017019981 A JP 2017019981A
- Authority
- JP
- Japan
- Prior art keywords
- rubber composition
- rubber
- mass
- parts
- general formula
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 84
- 239000005060 rubber Substances 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 229920003244 diene elastomer Polymers 0.000 claims description 24
- 229910000831 Steel Inorganic materials 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000010959 steel Substances 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims description 8
- 229920003049 isoprene rubber Polymers 0.000 claims description 8
- 229920003052 natural elastomer Polymers 0.000 claims description 8
- 229920001194 natural rubber Polymers 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 abstract 1
- 238000003878 thermal aging Methods 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000004073 vulcanization Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000011324 bead Substances 0.000 description 9
- 230000003712 anti-aging effect Effects 0.000 description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 7
- 239000004636 vulcanized rubber Substances 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000012763 reinforcing filler Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- GNVXPFBEZCSHQZ-UHFFFAOYSA-N iron(2+);sulfide Chemical compound [S-2].[Fe+2] GNVXPFBEZCSHQZ-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920005683 SIBR Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 organic acid cobalt salt Chemical class 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- YJEUJARPQSLENW-UHFFFAOYSA-M B([O-])([O-])[O-].C(CCCCCC(C)(C)C)(=O)[O-].[Co+4] Chemical compound B([O-])([O-])[O-].C(CCCCCC(C)(C)C)(=O)[O-].[Co+4] YJEUJARPQSLENW-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-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
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ゴム組成物および空気入りタイヤに関する。 The present invention relates to a rubber composition and a pneumatic tire.
空気入りタイヤには強い衝撃や大きな荷重がかかるため、通常、空気入りタイヤは、スチールコードからなるベルトをゴム組成物で被覆したベルト層を有する。
このようなスチールコードを被覆するためのゴム組成物（スチールコード被覆用ゴム組成物）として、例えば特許文献１には、「天然ゴムを含むジエン系ゴム１００質量部に対し、有機酸コバルト塩を０．１〜１０質量部、窒素吸着比表面積（Ｎ２ＳＡ）が１００ｍ２／ｇ以下であるカーボンブラックを４０〜８０質量部、下記の樹脂溶液を、ノボラック型フェノール系樹脂の質量として０．１〜２０質量部、および硬化剤を０．１〜２０質量部配合してなることを特徴とするスチールコード被覆用ゴム組成物。」が開示されている（請求項１）。
Since a strong impact and a large load are applied to the pneumatic tire, the pneumatic tire usually has a belt layer in which a belt made of a steel cord is covered with a rubber composition.
As a rubber composition for coating such a steel cord (steel cord covering rubber composition), for example, in Patent Document 1, “100 parts by mass of diene rubber containing natural rubber is coated with an organic acid cobalt salt. 0.1 to 10 parts by mass, 40 to 80 parts by mass of carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 100 m 2 / g or less, and the following resin solution as a mass of the novolac-type phenol resin: A rubber composition for coating a steel cord, comprising 1 to 20 parts by mass and 0.1 to 20 parts by mass of a curing agent "is disclosed (Claim 1).
近年の空気入りタイヤのさらなる性能向上の要求に応じるべく、スチールコード被覆用ゴム組成物の一層の性能向上が求められている。
具体的には、要求される性能の一つとして、上述のスチールコード被覆用ゴム組成物の製造時におけるブルームの抑制が挙げられる。ゴム組成物の表面にブルームが発生すると、ゴム組成物の再混練などが必要となり、生産性の低下を招いてしまうためである。
また、スチールコードの変形に追従できるように、破断伸びに優れていることが求められる。
さらに、上記の空気入りタイヤは、使用状態や使用時の環境によっては、走行中に内部発熱することがある。そのため、上述のスチールコード被覆用ゴム組成物には、走行中に内部発熱する場合であっても、破断伸びや破断強度に優れていること（耐熱老化性に優れること）が求められる。
また、上記スチールコード被覆用ゴム組成物は、スチールコードとの密着性に優れていることが求められており、特に多様な環境下での使用に対応すべく、湿熱後の接着性（密着性）に優れていることが要求される。
In order to meet the demand for further improvement in performance of pneumatic tires in recent years, further improvement in performance of rubber compositions for coating steel cords is required.
Specifically, as one of the required performances, suppression of bloom at the time of producing the above rubber composition for coating a steel cord can be mentioned. This is because when bloom occurs on the surface of the rubber composition, re-kneading of the rubber composition is required, leading to a decrease in productivity.
Moreover, it is calculated | required that it is excellent in elongation at break so that the deformation | transformation of a steel cord can be tracked.
Furthermore, the above pneumatic tire may generate internal heat during running depending on the use state and the environment during use. Therefore, the rubber composition for coating a steel cord described above is required to have excellent elongation at break and strength at break (excellent in heat aging resistance) even when internally generating heat during running.
Further, the rubber composition for coating a steel cord is required to have excellent adhesion to a steel cord. Adhesion after wet heat (adhesion) is particularly suitable for use in various environments. ) Is required to be excellent.
このようななか、本発明者が、特許文献１に記載の組成を参考にジエン系ゴムおよび有機酸コバルトを含有する系について検討したところ、上述したスチールコード被覆用ゴム組成物に求められる特性を必ずしも満たすものではなく、さらなる改良が必要であることが分かった。 Under such circumstances, the present inventor examined a system containing a diene rubber and an organic acid cobalt with reference to the composition described in Patent Document 1, and the properties required for the steel cord coating rubber composition described above were not necessarily obtained. It turns out that it does not satisfy and needs further improvement.
そこで、本発明は、ブルームの発生が抑制され、破断伸び、耐熱老化性および湿熱後の接着性に優れたゴム組成物、およびこれが適用された空気入りタイヤを提供することを目的とする。 Accordingly, an object of the present invention is to provide a rubber composition in which the occurrence of bloom is suppressed and which has excellent elongation at break, heat aging resistance and adhesion after wet heat, and a pneumatic tire to which the rubber composition is applied.
本発明者は、上記課題について鋭意検討した結果、特定の金属硫化物を特定範囲で含有するゴム組成物を用いることにより、上記課題が解決できることを見出し、本発明に至った。
すなわち、本発明者は、以下の構成により上記課題が解決できることを見出した。
As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a rubber composition containing a specific metal sulfide in a specific range, and have reached the present invention.
That is, the present inventor has found that the above problem can be solved by the following configuration.
［１］
ジエン系ゴムを１００質量部と、
下記一般式（１）で表される金属硫化物を０．２〜１０質量部と、
を含有する、ゴム組成物。
ＭＳ ・・・一般式（１）
（前記一般式（１）中、Ｍは、周期表における第８族〜第１１族の２価の遷移金属元素を表し、Ｓは、２価の硫黄原子を表す。）
［２］
上記ジエン系ゴムが、天然ゴム、イソプレンゴムおよびブタジエンゴムから選択される少なくとも１種のゴムを含む、上記［１］に記載のゴム組成物。
［３］
さらに、硫黄を含む加硫成分を含有し、
上記硫黄の含有量が、上記ジエン系ゴム１００質量部に対して４〜１０質量部である、上記［１］または［２］に記載のゴム組成物。
［４］
さらに、酸化亜鉛を含有し、
酸化亜鉛の含有量が、上記ジエン系ゴム１００質量部に対して４〜１５質量部である、上記［１］〜［３］のいずれか１つに記載のゴム組成物。
［５］
上記［１］〜［４］のいずれか１つに記載のゴム組成物で被覆されたスチールコードを有する、空気入りタイヤ。
[1]
100 parts by weight of diene rubber,
0.2 to 10 parts by mass of a metal sulfide represented by the following general formula (1),
A rubber composition comprising:
MS: General formula (1)
(In the general formula (1), M represents a divalent transition metal element of Group 8 to Group 11 in the periodic table, and S represents a divalent sulfur atom.)
[2]
The rubber composition according to [1], wherein the diene rubber includes at least one rubber selected from natural rubber, isoprene rubber, and butadiene rubber.
[3]
Furthermore, it contains a vulcanized component containing sulfur,
The rubber composition according to [1] or [2], wherein the sulfur content is 4 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
[4]
In addition, it contains zinc oxide,
The rubber composition according to any one of [1] to [3], wherein the content of zinc oxide is 4 to 15 parts by mass with respect to 100 parts by mass of the diene rubber.
[5]
A pneumatic tire having a steel cord coated with the rubber composition according to any one of [1] to [4].
以下に示すように、本発明によれば、ブルームの発生が抑制され、破断伸び、耐熱老化性および湿熱後の接着性に優れたゴム組成物、およびこれが適用された空気入りタイヤを提供することができる。 As shown below, according to the present invention, it is possible to provide a rubber composition in which occurrence of bloom is suppressed and excellent in elongation at break, heat aging resistance and adhesion after wet heat, and a pneumatic tire to which the rubber composition is applied. Can do.
以下に、本発明のゴム組成物について説明する。
なお、本発明において「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
Below, the rubber composition of this invention is demonstrated.
In the present invention, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
［ゴム組成物］
本発明のゴム組成物は、ジエン系ゴムを１００質量部と、後述する一般式（１）で表される金属硫化物（以下、「特定金属硫化物」ともいう。）を０．２〜１０質量部と、を含有する。
本発明のゴム組成物はこのような構成をとるため、上述した効果が得られるものと考えらえる。
[Rubber composition]
In the rubber composition of the present invention, 100 parts by mass of diene rubber and 0.2 to 10 of metal sulfide represented by the following general formula (1) (hereinafter also referred to as “specific metal sulfide”). Part by mass.
Since the rubber composition of the present invention has such a configuration, it can be considered that the above-described effects can be obtained.
その理由は明らかではないが、およそ以下のとおりと推測される。
ゴム組成物を加硫する場合、通常、ゴム組成物を高温（例えば１３０〜１９０℃程度）で加熱する。このとき、上記特定金属硫化物を構成する硫黄原子と金属元素とが解離して、解離した金属元素が錯体を形成することで、ゴム組成物の加硫を活性化させると考えられる。これにより、破断伸びおよび耐熱老化性が優れたものになると推測される。
また、ゴム組成物に含まれる成分とスチールコードの金属元素との相互作用を、上記特定金属硫化物が安定化させることにより、湿熱後の接着性が優れたものになると推測される。このことは、後述する実施例欄において、上記特定金属硫化物を含有する場合（各実施例参照）には、その他の金属硫化物（比較例３および４参照）と比較して、湿熱後の接着性（ワイヤ引抜力）が向上していることからも推測できる。
さらに、特定量の特定金属硫化物を用いることにより、ブルームの発生が抑制されるものと推測される。このことは、後述する実施例欄において、特定量の上記特定金属硫化物を含有する場合（各実施例参照）には、有機酸金属塩を含有する場合（比較例１参照）と比較して、ブルームの発生が抑制されていることからも推測できる。
The reason is not clear, but it is presumed that it is as follows.
When vulcanizing a rubber composition, the rubber composition is usually heated at a high temperature (for example, about 130 to 190 ° C.). At this time, it is considered that the sulfur atom and the metal element constituting the specific metal sulfide are dissociated, and the dissociated metal element forms a complex, thereby activating the vulcanization of the rubber composition. Thereby, it is estimated that breaking elongation and heat aging resistance are excellent.
Moreover, it is estimated that the adhesiveness after wet heat will become excellent because the said specific metal sulfide stabilizes the interaction of the component contained in a rubber composition, and the metal element of a steel cord. This is because, in the example column described later, when the above-mentioned specific metal sulfide is contained (see each example), compared with other metal sulfides (see comparative examples 3 and 4), after wet heat It can also be inferred from the fact that the adhesion (wire pulling force) is improved.
Furthermore, it is presumed that the occurrence of bloom is suppressed by using a specific amount of the specific metal sulfide. This is because, in the example column described later, when a specific amount of the specific metal sulfide is contained (see each example), compared with a case where an organic acid metal salt is contained (see comparative example 1). It can also be estimated from the fact that the occurrence of bloom is suppressed.
＜ジエン系ゴム＞
本発明のゴム組成物は、ジエン系ゴムを含有する。
ジエン系ゴムとしては、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、芳香族ビニル−共役ジエン共重合ゴム〔例えば、スチレン−イソプレンゴム、スチレン−ブタジエン−イソプレンゴム（ＳＢＩＲ）、スチレン−ブタジエンゴム（ＳＢＲ）〕、スチレン−イソプレンゴム（ＳＩＲ）、スチレン−イソプレン−ブタジエンゴム（ＳＩＢＲ）等が挙げられる。これらは、１種単独で用いてもよく、２種以上を併用してもよい。
上記ジエン系ゴムの中でも、天然ゴム、イソプレンゴムおよびブタジエンゴムから選択される少なくとも１種のゴムを含むことが好ましい。
<Diene rubber>
The rubber composition of the present invention contains a diene rubber.
Examples of the diene rubber include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), and aromatic vinyl-conjugated diene copolymer rubber [for example, styrene-isoprene rubber, styrene. -Butadiene-isoprene rubber (SBIR), styrene-butadiene rubber (SBR)], styrene-isoprene rubber (SIR), styrene-isoprene-butadiene rubber (SIBR), and the like. These may be used alone or in combination of two or more.
Among the diene rubbers, it is preferable to include at least one rubber selected from natural rubber, isoprene rubber and butadiene rubber.
＜金属硫化物＞
本発明のゴム組成物は、特定金属硫化物を含有する。特定金属硫化物は、下記一般式（１）で表される金属硫化物である。
<Metal sulfide>
The rubber composition of the present invention contains a specific metal sulfide. The specific metal sulfide is a metal sulfide represented by the following general formula (1).
ＭＳ ・・・一般式（１） MS: General formula (1)
上記一般式（１）中、Ｍは、周期表における第８族〜第１１族の２価の遷移金属元素を表し、Ｓは、２価の硫黄原子を表す。
このような第８族〜第１１族の２価の遷移金属元素の中でも、ゴム中での硫化反応を促進して湿熱後の接着性をより向上できるという観点から、鉄（Ｆｅ）、コバルト（Ｃｕ）、ニッケル（Ｎｉ）、銅（Ｃｕ）であることが好ましい。
In the general formula (1), M represents a divalent transition metal element of Group 8 to Group 11 in the periodic table, and S represents a divalent sulfur atom.
Among these Group 8 to Group 11 divalent transition metal elements, iron (Fe), cobalt (from the viewpoint that the adhesion after wet heat can be further improved by promoting the sulfurization reaction in rubber. Cu), nickel (Ni), and copper (Cu) are preferable.
特定金属硫化物としては、例えば、硫化鉄（ＦｅＳ）、硫化コバルト（ＣｏＳ）、硫化ニッケル（ＮｉＳ）、硫化銅（ＣｕＳ）が挙げられ、入手が容易であるという観点から、硫化鉄（ＦｅＳ）、硫化銅（ＣｕＳ）であることが好ましい。
また、硫化鉄（ＦｅＳ）および硫化銅（ＣｕＳ）のうち、ゴム組成物中での分散性に優れるという観点から、硫化銅であることが好ましい。
特定金属硫化物は、１種単独で使用してもよいし、２種以上併用してもよい。
Examples of the specific metal sulfide include iron sulfide (FeS), cobalt sulfide (CoS), nickel sulfide (NiS), and copper sulfide (CuS). From the viewpoint of easy availability, iron sulfide (FeS). Copper sulfide (CuS) is preferable.
Of iron sulfide (FeS) and copper sulfide (CuS), copper sulfide is preferable from the viewpoint of excellent dispersibility in the rubber composition.
A specific metal sulfide may be used individually by 1 type, and may be used together 2 or more types.
特定金属硫化物の含有量は、ジエン系ゴム１００質量部に対して０．２〜１０質量部であり、０．２〜６質量部が好ましく、０．５〜３質量部がより好ましい。特定金属硫化物の含有量が上記範囲内であることで、破断伸び、耐熱老化性および湿熱後の接着性が優れたものとなる。
一方、特定金属硫化物の含有量が０．２質量部未満であると、湿熱後の接着性が低下する。また、特定金属硫化物の含有量が１０質量部を超えると、耐熱老化性および湿熱後の接着性が低下する。
Content of a specific metal sulfide is 0.2-10 mass parts with respect to 100 mass parts of diene rubber, 0.2-6 mass parts is preferable, and 0.5-3 mass parts is more preferable. When the content of the specific metal sulfide is within the above range, the elongation at break, the heat aging resistance, and the adhesiveness after wet heat become excellent.
On the other hand, if the content of the specific metal sulfide is less than 0.2 parts by mass, the adhesiveness after wet heat decreases. Moreover, when content of a specific metal sulfide exceeds 10 mass parts, the heat aging resistance and the adhesiveness after wet heat will fall.
＜加硫成分＞
本発明のゴム組成物は、硫黄を含む加硫成分を含有することが好ましい。
硫黄を含有する場合の含有量は、金属に対する接着性がより優れたものになるという観点から、ジエン系ゴム１００質量部に対して４〜１０質量部が好ましく、５〜８質量部がより好ましい。
<Vulcanization component>
The rubber composition of the present invention preferably contains a vulcanizing component containing sulfur.
The content in the case of containing sulfur is preferably 4 to 10 parts by mass and more preferably 5 to 8 parts by mass with respect to 100 parts by mass of the diene rubber from the viewpoint that the adhesion to metal is more excellent. .
加硫成分としては、硫黄以外の加硫剤や、スルフェンアミド系、グアニジン系、チアゾール系、チオウレア系、チウラム系等の加硫促進剤などを含有していてもよい。
加硫促進剤の含有量としては、金属に対する接着性がより優れたものになるという観点から、ジエン系ゴム１００質量部に対して０．１〜３質量部が好ましく、０．３〜１質量部がより好ましい。
The vulcanizing component may contain a vulcanizing agent other than sulfur, a sulfenamide-based, guanidine-based, thiazole-based, thiourea-based, thiuram-based vulcanization accelerator, and the like.
The content of the vulcanization accelerator is preferably 0.1 to 3 parts by mass, and 0.3 to 1 part by mass with respect to 100 parts by mass of the diene rubber from the viewpoint that the adhesion to metal is more excellent. Part is more preferred.
＜酸化亜鉛＞
本発明のゴム組成物は、加硫を促進させるという観点から、酸化亜鉛を含有することが好ましい。
酸化亜鉛を含有する場合の含有量は、加硫を促進させる効果がより向上するという観点から、ジエン系ゴム１００質量部に対して４〜１５質量部が好ましく、５〜１０質量部がより好ましい。
<Zinc oxide>
The rubber composition of the present invention preferably contains zinc oxide from the viewpoint of promoting vulcanization.
The content in the case of containing zinc oxide is preferably 4 to 15 parts by mass and more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the diene rubber from the viewpoint that the effect of promoting vulcanization is further improved. .
＜補強性充填材＞
本発明のゴム組成物は、補強性充填材を含有することが好ましい。
補強性充填材としては、特に限定されず、例えば、カーボンブラック、無機充填材などが挙げられる。補強性充填材は、１種単独で用いてもよく、２種以上を併用してもよい。
無機充填材としては、例えば、シリカ、水酸化アルミニウム、クレー、アルミナ、タルク、マイカ、カオリン、ガラスバルーン、ガラスビーズ、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、炭酸カルシウム、酸化マグネシウム、酸化チタン、チタン酸カリウム、硫酸バリウム等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。なお、無機充填材を用いる場合は、適宜、シランカップリング剤を使用してもよい。
無機充填材は、目的に応じて適宜選択できるが、ゴム組成物の補強効果に優れるという理由から、シリカが好ましい。
補強性充填材を含有する場合の含有量は、ゴム組成物の補強効果と加工性とを両立させるという理由から、ジエン系ゴム１００質量部に対して３０〜１００質量部が好ましく、４０〜９０質量部がより好ましく、５０〜８０質量部がさらに好ましい。
<Reinforcing filler>
The rubber composition of the present invention preferably contains a reinforcing filler.
The reinforcing filler is not particularly limited, and examples thereof include carbon black and inorganic filler. The reinforcing filler may be used alone or in combination of two or more.
Examples of the inorganic filler include silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, and titanium. Examples thereof include potassium acid and barium sulfate, and these may be used alone or in combination of two or more. In addition, when using an inorganic filler, you may use a silane coupling agent suitably.
The inorganic filler can be appropriately selected according to the purpose, but silica is preferable because it is excellent in the reinforcing effect of the rubber composition.
The content in the case of containing the reinforcing filler is preferably 30 to 100 parts by mass, and preferably 40 to 90 parts per 100 parts by mass of the diene rubber, because the reinforcing effect and processability of the rubber composition are compatible. A mass part is more preferable and 50-80 mass parts is further more preferable.
＜老化防止剤＞
本発明のゴム組成物は、老化防止剤を含有することが好ましい。
このような老化防止剤としては、特に限定されないが、例えば、芳香族アミン系の老化防止剤や、フェノール系の老化防止剤などを用いることができる。
老化防止剤を含有する場合の含有量は、耐熱老化性をより向上させるという理由から、ジエン系ゴム１００質量部に対して０．２〜１０質量部が好ましく、１〜５質量部がより好ましい。
<Anti-aging agent>
The rubber composition of the present invention preferably contains an antiaging agent.
Such an anti-aging agent is not particularly limited, and for example, an aromatic amine-based anti-aging agent, a phenol-based anti-aging agent and the like can be used.
In the case of containing an anti-aging agent, the content is preferably 0.2 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the diene rubber because the heat aging resistance is further improved. .
＜その他の成分＞
上記添加剤としては、例えば、シランカップリング剤、ステアリン酸、加工助剤、プロセスオイル、液状ポリマー、テルペン樹脂、熱硬化性樹脂、モノマー、硬化剤などのゴム組成物に一般的に使用される各種添加剤が挙げられる。
また、本発明のゴム組成物は、上述した本発明の効果が十分に発揮される範囲内で、さらに有機酸金属塩を含有してもよい。このような有機酸金属塩としては、有機酸コバルト塩（例えば、ナフテン酸コバルト、ステアリン酸コバルト、ホウ酸ネオデカン酸コバルト等）などが挙げられる。
<Other ingredients>
Examples of the additive are generally used in rubber compositions such as silane coupling agents, stearic acid, processing aids, process oils, liquid polymers, terpene resins, thermosetting resins, monomers, and curing agents. Various additives are mentioned.
Moreover, the rubber composition of the present invention may further contain an organic acid metal salt within a range in which the above-described effects of the present invention are sufficiently exhibited. Examples of such organic acid metal salts include organic acid cobalt salts (for example, cobalt naphthenate, cobalt stearate, cobalt borate neodecanoate, etc.).
＜ゴム組成物の製造方法＞
本発明のゴム組成物の製造方法は特に限定されず、その具体例としては、例えば、上述した各成分を、公知の方法、装置（例えば、バンバリーミキサー、ニーダー、ロールなど）を用いて、混練する方法などが挙げられる。本発明のゴム組成物が加硫成分を含有する場合は、加硫成分以外の成分を先に高温（好ましくは１３０〜１９０℃）で混合し、冷却してから、加硫成分を混合するのが好ましい。
また、本発明のゴム組成物は、従来公知の加硫または架橋条件で加硫または架橋することができる。
<Method for producing rubber composition>
The method for producing the rubber composition of the present invention is not particularly limited, and specific examples thereof include, for example, kneading the above-described components using a known method and apparatus (for example, a Banbury mixer, a kneader, a roll, etc.). The method of doing is mentioned. When the rubber composition of the present invention contains a vulcanized component, the components other than the vulcanized component are first mixed at a high temperature (preferably 130 to 190 ° C.), cooled, and then mixed with the vulcanized component. Is preferred.
The rubber composition of the present invention can be vulcanized or crosslinked under conventionally known vulcanization or crosslinking conditions.
＜用途＞
本発明のゴム組成物は、スチールコードを被覆するためのゴム組成物（スチールコード被覆用ゴム組成物）として好適に使用される。
<Application>
The rubber composition of the present invention is suitably used as a rubber composition for coating a steel cord (rubber composition for coating a steel cord).
［空気入りタイヤ］
本発明の空気入りタイヤは、上述した本発明のゴム組成物で被覆されたスチールコードを有する空気入りタイヤである。
図１に、本発明の空気入りタイヤの実施態様の一例を表すタイヤの部分断面概略図を示すが、本発明の空気入りタイヤは図１に示す態様に限定されるものではない。
[Pneumatic tire]
The pneumatic tire of the present invention is a pneumatic tire having a steel cord coated with the rubber composition of the present invention described above.
FIG. 1 shows a schematic partial sectional view of a tire representing an example of an embodiment of the pneumatic tire of the present invention, but the pneumatic tire of the present invention is not limited to the embodiment shown in FIG.
図１において、符号１はビード部を表し、符号２はサイドウォール部を表し、符号３はタイヤトレッド部を表す。
また、左右一対のビード部１間においては、繊維コードが埋設されたカーカス層４が装架されており、このカーカス層４の端部はビードコア５およびビードフィラー６の廻りにタイヤ内側から外側に折り返されて巻き上げられている。
また、タイヤトレッド部３においては、カーカス層４の外側に、ベルト層７がタイヤ１周に亘って配置されている。ここで、ベルト層７はスチールコードからなるベルトを上述した本発明のゴム組成物で被覆したものである。
また、ビード部１においては、リムに接する部分にリムクッション８が配置されている。
In FIG. 1, reference numeral 1 represents a bead portion, reference numeral 2 represents a sidewall portion, and reference numeral 3 represents a tire tread portion.
Further, a carcass layer 4 in which fiber cords are embedded is mounted between the pair of left and right bead portions 1, and the end of the carcass layer 4 extends from the inside of the tire to the outside around the bead core 5 and the bead filler 6. Wrapped and rolled up.
Further, in the tire tread portion 3, a belt layer 7 is disposed over the circumference of the tire on the outside of the carcass layer 4. Here, the belt layer 7 is obtained by coating a belt made of steel cord with the above-described rubber composition of the present invention.
Moreover, in the bead part 1, the rim cushion 8 is arrange | positioned in the part which touches a rim | limb.
本発明の空気入りタイヤは、例えば、従来公知の方法に従って製造することができる。また、タイヤに充填する気体としては、通常のまたは酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウムなどの不活性ガスを用いることができる。 The pneumatic tire of the present invention can be manufactured, for example, according to a conventionally known method. Moreover, as gas with which a tire is filled, inert gas, such as nitrogen, argon, helium other than the air which adjusted normal or oxygen partial pressure, can be used.
以下、実施例を用いて、本発明のゴム組成物について詳細に説明する。ただし、本発明はこれに限定されるものではない。 Hereinafter, the rubber composition of the present invention will be described in detail using examples. However, the present invention is not limited to this.
＜ゴム組成物の調製＞
下記第１表に示す成分を、同表に示す割合（質量部）で配合した。
具体的には、まず、下記第１表に示す成分のうち硫黄および加硫促進剤を除く成分を、１．７リットルの密閉式バンバリーミキサーを用いて５分間混合して、１６０℃程度で放出し、室温まで冷却してマスターバッチを得た。さらに、上記バンバリーミキサーを用いて、得られたマスターバッチに硫黄および加硫促進剤を１１０℃以下で３分混合し、ゴム組成物を得た。
<Preparation of rubber composition>
The components shown in Table 1 below were blended in the proportions (parts by mass) shown in the same table.
Specifically, first, among the components shown in Table 1 below, the components excluding sulfur and the vulcanization accelerator are mixed for 5 minutes using a 1.7 liter closed Banbury mixer and released at about 160 ° C. And cooled to room temperature to obtain a master batch. Furthermore, using the Banbury mixer, sulfur and a vulcanization accelerator were mixed for 3 minutes at 110 ° C. or less to the obtained master batch to obtain a rubber composition.
＜評価試験＞
上記のようにして得られたゴム組成物について、以下の各種評価試験を行った。
<Evaluation test>
The rubber composition obtained as described above was subjected to the following various evaluation tests.
（ブルーム）
調製したゴム組成物（未加硫）を室温（２５℃）で２週間放置して、ゴム組成物（未加硫）の表面のブルームの有無を目視にて観察した。評価基準は次の通りである。
「○」：ゴム組成物の表面全体にブルームの発生が無い。
「△」：ゴム組成物の表面の一部にブルームが発生した。
「×」：ゴム組成物の表面全体にブルームが発生した。
(Bloom)
The prepared rubber composition (unvulcanized) was allowed to stand at room temperature (25 ° C.) for 2 weeks, and the presence or absence of bloom on the surface of the rubber composition (unvulcanized) was visually observed. The evaluation criteria are as follows.
“◯”: Bloom does not occur on the entire surface of the rubber composition.
“Δ”: Bloom was generated on a part of the surface of the rubber composition.
“X”: Bloom was generated on the entire surface of the rubber composition.
（破断伸び）
調製したゴム組成物（未加硫）を、金型（１５ｃｍ×１５ｃｍ×０．２ｃｍ）中、１６０℃で２０分間プレス加硫して、加硫ゴム試験片を作製した。
作製した加硫ゴム試験片について、ＪＩＳ Ｋ６２５１：２０１０に準拠し、ＪＩＳ３号ダンベル型試験片（厚さ２ｍｍ）を打ち抜き、温度２０℃、引張り速度５００ｍｍ／分の条件で破断伸び（＝破断時の伸び率）を測定した。
評価結果は、比較例１を１００とする指数で表した。指数が大きいほど破断伸びが大きく、破断伸びに優れる。
(Elongation at break)
The prepared rubber composition (unvulcanized) was press vulcanized at 160 ° C. for 20 minutes in a mold (15 cm × 15 cm × 0.2 cm) to prepare a vulcanized rubber test piece.
About the produced vulcanized rubber test piece, in accordance with JIS K6251: 2010, a JIS No. 3 dumbbell-type test piece (thickness 2 mm) was punched, and the elongation at break (= at the time of breakage at a temperature of 20 ° C. and a pulling speed of 500 mm / min. (Elongation rate) was measured.
The evaluation results were expressed as an index with Comparative Example 1 as 100. The greater the index, the greater the elongation at break and the better the elongation at break.
（耐熱老化性）
・老化後の２０℃での破断伸び
上記の破断伸びの評価と同様にして得られた加硫ゴム試験片を、７０℃条件下で９６時間放置した。
放置後の加硫ゴム試験片について、ＪＩＳ Ｋ６２５１：２０１０に準拠し、ＪＩＳ３号ダンベル型試験片（厚さ２ｍｍ）を打ち抜き、温度２０℃、引張り速度５００ｍｍ／分の条件で破断伸び（＝破断時の伸び率）を測定した。
評価結果は、比較例１を１００とする指数で表した。指数が大きいほど破断伸びが大きく、室温時の耐熱老化性に優れる。
(Heat aging resistance)
-Breaking elongation at 20 ° C after aging A vulcanized rubber test piece obtained in the same manner as in the above-described evaluation of breaking elongation was allowed to stand at 70 ° C for 96 hours.
Regarding the vulcanized rubber test piece after standing, in accordance with JIS K6251: 2010, a JIS No. 3 dumbbell-type test piece (thickness 2 mm) is punched, and the elongation at break is obtained under the conditions of a temperature of 20 ° C. and a pulling speed of 500 mm / min. Of elongation).
The evaluation results were expressed as an index with Comparative Example 1 as 100. The greater the index, the greater the elongation at break and the better the heat aging resistance at room temperature.
・老化後の７０℃での破断伸び、老化後の７０℃での破断強度
上記の破断伸びの評価と同様にして得られた加硫ゴム試験片を、７０℃条件下で９６時間放置した。
放置後の加硫ゴム試験片について、ＪＩＳ Ｋ６２５１：２０１０に準拠し、ＪＩＳ３号ダンベル型試験片（厚さ２ｍｍ）を打ち抜き、温度７０℃、引張り速度５００ｍｍ／分の条件で破断伸び（＝破断時の伸び率）、破断強度（＝破断時の強度）を測定した。
評価結果は、比較例１を１００とする指数で表した。指数が大きいほど破断伸びおよび破断強度が大きく、高温時の耐熱老化性に優れる。
-Breaking elongation at 70 ° C after aging, breaking strength at 70 ° C after aging A vulcanized rubber test piece obtained in the same manner as in the above evaluation of breaking elongation was allowed to stand for 96 hours at 70 ° C.
About the vulcanized rubber specimen after standing, in accordance with JIS K6251: 2010, a JIS No. 3 dumbbell-shaped specimen (thickness 2 mm) is punched out, and the elongation at break is obtained under the conditions of a temperature of 70 ° C. and a pulling speed of 500 mm / min. Elongation rate) and breaking strength (= strength at break).
The evaluation results were expressed as an index with Comparative Example 1 as 100. The larger the index, the greater the breaking elongation and breaking strength, and the better the heat aging resistance at high temperatures.
（湿熱後の接着性（湿熱後のワイヤ引抜力））
得られたゴム組成物について、ＡＳＴＭ−Ｄ−２に準拠してコードの引抜力を測定した（加硫後のゴムを使用）。なお、引抜力の測定は、湿度９６％ＲＨ・温度７０℃の条件下で２週間、試験サンプルを放置した後に行った。
結果は比較例１の引抜力を１００とする指数で表した。指数が大きいほど引抜力が大きく、湿熱後の接着性に優れる。
(Adhesiveness after wet heat (wire pulling force after wet heat))
With respect to the obtained rubber composition, the pulling force of the cord was measured according to ASTM-D-2 (using rubber after vulcanization). The pulling force was measured after leaving the test sample for 2 weeks under the conditions of humidity 96% RH and temperature 70 ° C.
The results were expressed as an index with the pulling force of Comparative Example 1 as 100. The larger the index, the greater the pulling force and the better the adhesion after wet heat.
＜評価結果＞
以上の評価試験の結果を下記第１表にあわせて示す。
<Evaluation results>
The results of the above evaluation tests are also shown in Table 1 below.
上記第１表に示されている各成分の詳細は以下のとおりである。また、第１表中の各成分の含有量は、質量部である。
・ＮＲ：天然ゴム（ＲＳＳ＃３）
・有機酸金属塩：ステアリン酸コバルト（ＤＩＣ社製）
・硫化銅：関東化学社製
・硫化鉄：和光純薬工業製
・硫化カルシウム７水和物：純正化学株式会社製
・硫化マグネシウム：米山薬品工業社製
・硫酸銅５水和物：関東化学社製
・ＣＢ：シーストＫＨ（カーボンブラック、東海カーボン社製）
・酸化亜鉛：亜鉛華 酸化亜鉛３種（正同化学工業社製）
・老化防止剤：サントフレックス６ＰＰＤ（フレキシス社製）
・硫黄：クリステックスＨＳ ＯＴ ２０（アクゾノーベル社製）
・加硫促進剤：ノクセラーＤＺ（大内新興化学工業社製）
Details of each component shown in Table 1 are as follows. Moreover, content of each component in Table 1 is a mass part.
・ NR: Natural rubber (RSS # 3)
-Organic acid metal salt: Cobalt stearate (manufactured by DIC)
-Copper sulfide: manufactured by Kanto Chemical Co., Ltd.-Iron sulfide: manufactured by Wako Pure Chemical Industries, Ltd.-Calcium sulfide heptahydrate: manufactured by Junsei Chemical Co., Ltd.-Magnesium sulfide: manufactured by Yoneyama Pharmaceutical Co., Ltd.-Copper sulfate pentahydrate: Kanto Chemical Co., Ltd. Made by CB: Seast KH (Carbon Black, Tokai Carbon Co., Ltd.)
・ Zinc oxide: Zinc flower 3 types of zinc oxide (manufactured by Shodo Chemical Industry Co., Ltd.)
Anti-aging agent: Santoflex 6PPD (manufactured by Flexis)
・ Sulfur: Cristex HS OT 20 (manufactured by Akzo Nobel)
・ Vulcanization accelerator: Noxeller DZ (made by Ouchi Shinsei Chemical Co., Ltd.)
第１表から分かるように、本実施例のゴム組成物はいずれも、ブルームの発生が抑制され、破断伸び、耐熱老化性および湿熱後の接着性に優れていることが示された。
実施例１〜４の対比から、特定金属硫化物の含有量がジエン系ゴム１００質量部に対して１〜３質量部の範囲にある実施例２〜３のゴム組成物は、破断伸び、耐熱老化性および湿熱後の接着性により優れていることが示された。同様に、実施例５〜８の対比から、実施例６〜７のゴム組成物は、破断伸び、耐熱老化性および湿熱後の接着性により優れていることが示された。
As can be seen from Table 1, all of the rubber compositions of this example were suppressed in blooming and were found to be excellent in elongation at break, heat aging resistance and adhesiveness after wet heat.
From the comparison of Examples 1 to 4, the rubber composition of Examples 2 to 3 in which the content of the specific metal sulfide is in the range of 1 to 3 parts by mass with respect to 100 parts by mass of the diene rubber, It was shown to be superior to aging and adhesion after wet heat. Similarly, from the comparison of Examples 5 to 8, it was shown that the rubber compositions of Examples 6 to 7 were superior in breaking elongation, heat aging resistance, and adhesion after wet heat.
一方、特定金属硫化物（上記一般式（１）で表される金属硫化物）を含有せず、有機酸金属塩を含有する比較例１のゴム組成物は、ブルームの発生を抑制できず、また、破断伸び、耐熱老化性および湿熱後の接着性が不十分であった。
また、特定金属硫化物を含有しない比較例２のゴム組成物は、湿熱後の密着性が不十分であった。
また、金属硫化物を含有するものの、特定金属硫化物を含有しない比較例３〜４のゴム組成物は、破断伸びと湿熱後の接着性が不十分であった。比較例３および４で使用した金属硫化物を構成する金属元素は、特定金属硫化物を構成する金属元素よりもイオン化傾向が高く、このことが性能低下に影響したものと考えられる。
また、特定金属硫化物の含有量がジエン系ゴム１００質量部に対して０．２質量部未満の比較例５のゴム組成物は、湿熱後の接着性が不十分であった。
また、特定金属硫化物の含有量がジエン系ゴム１００質量部に対して１０質量部超の比較例６のゴム組成物は、耐熱老化性（特に７０℃における破断伸び）と湿熱後の接着性が不十分であった。
また、特定金属硫化物に代えて、硫酸銅を用いた比較例７のゴム組成物は、破断伸びと耐熱老化性（特に７０℃における破断伸び、破断強度）と湿熱後の接着性が不十分であった。
On the other hand, the rubber composition of Comparative Example 1 that does not contain the specific metal sulfide (metal sulfide represented by the above general formula (1)) and contains the organic acid metal salt cannot suppress the occurrence of bloom, Moreover, elongation at break, heat aging resistance and adhesion after wet heat were insufficient.
Moreover, the rubber composition of Comparative Example 2 containing no specific metal sulfide had insufficient adhesion after wet heat.
Moreover, although the rubber composition of Comparative Examples 3-4 which contains a metal sulfide but does not contain a specific metal sulfide, the elongation at break and the adhesiveness after wet heat were insufficient. The metal element constituting the metal sulfide used in Comparative Examples 3 and 4 has a higher ionization tendency than the metal element constituting the specific metal sulfide, which is considered to have affected the performance degradation.
Further, the rubber composition of Comparative Example 5 in which the content of the specific metal sulfide was less than 0.2 parts by mass with respect to 100 parts by mass of the diene rubber had insufficient adhesion after wet heat.
Further, the rubber composition of Comparative Example 6 having a specific metal sulfide content of more than 10 parts by mass with respect to 100 parts by mass of the diene rubber has heat aging resistance (particularly, elongation at break at 70 ° C.) and adhesiveness after wet heat. Was insufficient.
In addition, the rubber composition of Comparative Example 7 using copper sulfate instead of the specific metal sulfide has insufficient elongation at break, heat aging resistance (particularly, elongation at break at 70 ° C., strength at break) and adhesiveness after wet heat. Met.
１ ビード部
２ サイドウォール部
３ タイヤトレッド部
４ カーカス層
５ ビードコア
６ ビードフィラー
７ ベルト層
８ リムクッション
1 Bead part 2 Side wall part 3 Tire tread part 4 Carcass layer 5 Bead core 6 Bead filler 7 Belt layer 8 Rim cushion
Claims (5)
下記一般式（１）で表される金属硫化物を０．２〜１０質量部と、
を含有する、ゴム組成物。
ＭＳ ・・・一般式（１）
（前記一般式（１）中、Ｍは、周期表における第８族〜第１１族の２価の遷移金属元素を表し、Ｓは、２価の硫黄原子を表す。） 100 parts by weight of diene rubber,
0.2 to 10 parts by mass of a metal sulfide represented by the following general formula (1),
A rubber composition comprising:
MS: General formula (1)
(In the general formula (1), M represents a divalent transition metal element of Group 8 to Group 11 in the periodic table, and S represents a divalent sulfur atom.)
前記硫黄の含有量が、前記ジエン系ゴム１００質量部に対して４〜１０質量部である、請求項１または２に記載のゴム組成物。 Furthermore, it contains a vulcanized component containing sulfur,
The rubber composition according to claim 1 or 2, wherein the sulfur content is 4 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
酸化亜鉛の含有量が、前記ジエン系ゴム１００質量部に対して４〜１５質量部である、請求項１〜３のいずれか１項に記載のゴム組成物。 In addition, it contains zinc oxide,
The rubber composition according to any one of claims 1 to 3, wherein a content of zinc oxide is 4 to 15 parts by mass with respect to 100 parts by mass of the diene rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015141340A JP6623589B2 (en) | 2015-07-15 | 2015-07-15 | Pneumatic tire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015141340A JP6623589B2 (en) | 2015-07-15 | 2015-07-15 | Pneumatic tire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017019981A true JP2017019981A (en) | 2017-01-26 |
| JP6623589B2 JP6623589B2 (en) | 2019-12-25 |
Family
ID=57887762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015141340A Active JP6623589B2 (en) | 2015-07-15 | 2015-07-15 | Pneumatic tire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6623589B2 (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55151054A (en) * | 1979-05-15 | 1980-11-25 | Bridgestone Corp | Novel rubber composition |
| JPS56118643A (en) * | 1980-02-26 | 1981-09-17 | Yokohama Rubber Co Ltd:The | Evaluation method for adhesion of brass-plated steel cord to rubber |
| JPS5785992A (en) * | 1980-11-17 | 1982-05-28 | Sumitomo Bakelite Co Ltd | Resin composition for plating |
| JP2003529622A (en) * | 1998-12-24 | 2003-10-07 | アクシュネット カンパニー | Low compressibility, rebound resilience golf ball containing inorganic sulfide catalyst and method for producing the same |
| JP2006219530A (en) * | 2005-02-08 | 2006-08-24 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| JP2006249361A (en) * | 2005-03-14 | 2006-09-21 | Bridgestone Corp | Rubber composition for tread and tire |
| JP2009029945A (en) * | 2007-07-27 | 2009-02-12 | Panasonic Corp | Flame-retardant resin composition, production method thereof and molding method thereof |
| JP2013503266A (en) * | 2009-08-25 | 2013-01-31 | エヌ・ジー・エフ ヨーロッパ リミテッド | Reinforcing structure for rubber article and manufacturing method |
| WO2013051689A1 (en) * | 2011-10-07 | 2013-04-11 | ダイソー株式会社 | Semi-conductive rubber composition |
-
2015
- 2015-07-15 JP JP2015141340A patent/JP6623589B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55151054A (en) * | 1979-05-15 | 1980-11-25 | Bridgestone Corp | Novel rubber composition |
| JPS56118643A (en) * | 1980-02-26 | 1981-09-17 | Yokohama Rubber Co Ltd:The | Evaluation method for adhesion of brass-plated steel cord to rubber |
| JPS5785992A (en) * | 1980-11-17 | 1982-05-28 | Sumitomo Bakelite Co Ltd | Resin composition for plating |
| JP2003529622A (en) * | 1998-12-24 | 2003-10-07 | アクシュネット カンパニー | Low compressibility, rebound resilience golf ball containing inorganic sulfide catalyst and method for producing the same |
| JP2006219530A (en) * | 2005-02-08 | 2006-08-24 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| JP2006249361A (en) * | 2005-03-14 | 2006-09-21 | Bridgestone Corp | Rubber composition for tread and tire |
| JP2009029945A (en) * | 2007-07-27 | 2009-02-12 | Panasonic Corp | Flame-retardant resin composition, production method thereof and molding method thereof |
| JP2013503266A (en) * | 2009-08-25 | 2013-01-31 | エヌ・ジー・エフ ヨーロッパ リミテッド | Reinforcing structure for rubber article and manufacturing method |
| WO2013051689A1 (en) * | 2011-10-07 | 2013-04-11 | ダイソー株式会社 | Semi-conductive rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6623589B2 (en) | 2019-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9109102B2 (en) | Rubber composition for use in tire side walls and pneumatic tire using the same | |
| JP2011246563A (en) | Rubber composition for tire and pneumatic tire using the same | |
| JP5168458B2 (en) | Rubber composition and pneumatic tire | |
| JP4472596B2 (en) | Rubber composition for tire tread | |
| WO2012114667A1 (en) | Rubber-metal wire composite body and tire using same | |
| WO2016084892A1 (en) | Rubber composition for tire bead insulation, and pneumatic tire using same | |
| JP6623589B2 (en) | Pneumatic tire | |
| JP2009057535A (en) | Pneumatic tire | |
| WO2019230350A1 (en) | Rubber composition and pneumatic tire | |
| JP2016029118A (en) | Rubber composition and pneumatic tire using the same | |
| JP6135259B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP2017075265A (en) | Tire rubber composition | |
| US20170182843A1 (en) | Rubber Composition and Pneumatic Tire Using Same | |
| JP2011157495A (en) | Rubber composition for tire rim cushion and pneumatic tire using the same | |
| JP2017082122A (en) | Rubber composition for tire for heavy load | |
| JP6701671B2 (en) | Rubber composition for tires | |
| JP6645782B2 (en) | Rubber composition for hose and hydraulic hose | |
| JP2007169429A (en) | Rubber composition for chafer and tire having chafer comprising the same | |
| JP2005187825A (en) | Pneumatic tire | |
| JP2005015638A (en) | Rubber composition for tire | |
| CN104292529A (en) | Bicycle tire tread slab base | |
| JP7167595B2 (en) | Rubber composition for metal adhesion and pneumatic tire using the same | |
| JP7215186B2 (en) | Rubber composition for metal adhesion and pneumatic tire using the same | |
| JP7035570B2 (en) | Rubber composition and pneumatic tires using it | |
| JP2017082121A (en) | Rubber composition for tire for heavy load |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180711 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190716 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190717 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190913 |
|
| 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: 20191029 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20191111 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6623589 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| 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 |