JP5470742B2 - Rubber composition - Google Patents
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- JP5470742B2 JP5470742B2 JP2008129949A JP2008129949A JP5470742B2 JP 5470742 B2 JP5470742 B2 JP 5470742B2 JP 2008129949 A JP2008129949 A JP 2008129949A JP 2008129949 A JP2008129949 A JP 2008129949A JP 5470742 B2 JP5470742 B2 JP 5470742B2
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- 229920001971 elastomer Polymers 0.000 title claims description 48
- 239000005060 rubber Substances 0.000 title claims description 48
- 239000000203 mixture Substances 0.000 title claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 238000004073 vulcanization Methods 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims description 13
- 229960003067 cystine Drugs 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- -1 organic acid cobalt salt Chemical class 0.000 claims description 8
- 229920003244 diene elastomer Polymers 0.000 claims description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 235000019393 L-cystine Nutrition 0.000 claims description 4
- 239000004158 L-cystine Substances 0.000 claims description 4
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 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 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YRVRZDIWEXCJSX-UHFFFAOYSA-N 2-methyl-3-(3-triethoxysilylpropyl)thiirane-2-carboxylic acid Chemical compound CCO[Si](OCC)(OCC)CCCC1SC1(C)C(O)=O YRVRZDIWEXCJSX-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- MFNWUMRYUYUAAV-UHFFFAOYSA-N 4-(3-trimethoxysilylpropyl)-3H-1,3-benzothiazole-2-thione Chemical compound CO[Si](OC)(OC)CCCC1=CC=CC2=C1N=C(S2)S MFNWUMRYUYUAAV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 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
- ZZOXWBGGPBLVNQ-UHFFFAOYSA-N CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC Chemical compound CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC ZZOXWBGGPBLVNQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HBACTRZJLWXFBM-UHFFFAOYSA-N s-[[methyl(4-trimethoxysilylbutyl)carbamoyl]trisulfanyl] n-methyl-n-(4-trimethoxysilylbutyl)carbamothioate Chemical compound CO[Si](OC)(OC)CCCCN(C)C(=O)SSSSC(=O)N(C)CCCC[Si](OC)(OC)OC HBACTRZJLWXFBM-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はゴム組成物に関し、更に詳しくは金属との接着性に優れたゴム組成物に関する。 The present invention relates to a rubber composition, and more particularly to a rubber composition having excellent adhesion to a metal.
ゴムと金属との接着のために各種コンパウンドが使用されており、例えば空気入りタイヤにおいてはベルトコードやカーカスコードなどの補強用スチールコードとの接着を目的としたコンパウンドが多用されている。このようなゴム組成物としては例えば特許文献１に記載されているように、ゴム成分に、カーボンブラック及び／又はシリカ、有機酸コバルト塩、加硫促進剤、硫黄などが配合されている。
加硫促進剤としては例えば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）は金属接着用ゴムに配合すると非常に接着に有効な配合剤として使用されているが、代替技術の開発が必要である。
Various compounds are used for bonding rubber and metal. For example, in a pneumatic tire, a compound for bonding with a reinforcing steel cord such as a belt cord or a carcass cord is often used. As such a rubber composition, as described in Patent Document 1, for example, carbon black and / or silica, an organic acid cobalt salt, a vulcanization accelerator, sulfur and the like are blended in the rubber component.
As a vulcanization accelerator, for example, DZ (N, N′-dicyclohexyl-2-benzothiazolylsulfenamide) is used as a compounding agent that is very effective for adhesion when blended with rubber for metal bonding. Development is necessary.
従って、本発明の目的は前記従前の典型的な金属接着用加硫促進剤であるＤＺに代えて、金属接着用ゴム組成物に配合するのに適した加硫促進剤を提供することにある。 Accordingly, an object of the present invention is to provide a vulcanization accelerator suitable for blending into a metal bonding rubber composition in place of DZ, which is the conventional typical metal bonding vulcanization accelerator. .
本発明に従えば、ジエン系ゴム１００重量部、カーボンブラック及び／又はシリカ２０〜１２０重量部、シスチン０．０５〜１０重量部、有機酸コバルト塩０．０５〜５重量部並びに硫黄５〜１０重量部を含んでなるゴム組成物が提供される。 According to the present invention, 100 parts by weight of diene rubber, 20 to 120 parts by weight of carbon black and / or silica, 0.05 to 10 parts by weight of cystine, 0.05 to 5 parts by weight of organic acid cobalt salt, and 5 to 10 parts of sulfur. A rubber composition comprising parts by weight is provided.
本発明によれば、ジエン系ゴム１００重量部に対し、カーボンブラック及び／又はシリカ２０〜１２０重量部、シスチン０．０５〜１０重量部、有機酸コバルト塩０．０５〜５重量部並びに硫黄５〜１０重量部を配合することにより、金属との接着性に優れたゴム組成物を得ることができる。 According to the present invention, carbon black and / or silica 20 to 120 parts by weight, cystine 0.05 to 10 parts by weight, organic acid cobalt salt 0.05 to 5 parts by weight and sulfur 5 with respect to 100 parts by weight of the diene rubber. By blending 10 parts by weight to 10 parts by weight, a rubber composition having excellent adhesion to metal can be obtained.
本発明者らは前記課題を解決すべく研究を進めた結果、ジエン系ゴム１００重量部に対し、カーボンブラック及び／又はシリカ２０〜１２０重量部（好ましくは５０〜８０重量部）、シスチン（好ましくはＬ−シスチン）０．０５〜１０重量部（好ましくは０．２〜５重量部、更に好ましくは０．２〜１．５重量部）、有機酸コバルト塩０．０５〜５重量部（好ましくは０．２〜２重量部）並びに硫黄５〜１０重量部（好ましくは６〜８重量部）を配合することにより、好ましくは、加硫促進剤ＮＳ（Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド）０．０５〜５重量部（好ましくは０．２〜１重量部）を更に配合することにより、金属との接着性に優れたゴム組成物を得ることに成功し、本発明を完成した。前記ジエン系ゴムの８０重量％以上が天然ゴムであるのが接着強度保持の観点から好ましい。 As a result of researches to solve the above problems, the present inventors have found that carbon black and / or silica 20 to 120 parts by weight (preferably 50 to 80 parts by weight), cystine (preferably 100 parts by weight of diene rubber). Is L-cystine) 0.05 to 10 parts by weight (preferably 0.2 to 5 parts by weight, more preferably 0.2 to 1.5 parts by weight), and 0.05 to 5 parts by weight of organic acid cobalt salt (preferably Is preferably 0.2 to 2 parts by weight) and 5 to 10 parts by weight (preferably 6 to 8 parts by weight) of sulfur, preferably NS (N-tert-butyl-2-benzothia (Zolylsulfenamide) 0.05 to 5 parts by weight (preferably 0.2 to 1 part by weight) was further blended to successfully obtain a rubber composition having excellent adhesion to metal, and the present invention. Was completed. It is preferable from the viewpoint of maintaining adhesive strength that 80% by weight or more of the diene rubber is natural rubber.
本発明のゴム組成物に使用するジエン系ゴムとしては、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリルブタジエンゴム、エチレン−プロピレン−ジエン共重合体ゴム、スチレン−イソプレン共重合体ゴム、イソプレン−ブタジエン共重合体ゴムなどをあげることができ、これらは単独又は任意のブレンドで使用することができる。 Examples of the diene rubber used in the rubber composition of the present invention include natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber, ethylene. -Propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, isoprene-butadiene copolymer rubber and the like can be mentioned, and these can be used alone or in any blend.
本発明のゴム組成物に使用するカーボンブラックとしては、従来から接着用ゴム組成物に一般的に配合されている任意のカーボンブラックを用いることができる。具体的にはＩＳＡＦ、ＨＡＦ等が好ましく使用できるが、特に限定されるものではない。カーボンブラックの配合量が少ないと補強性が十分でなくなるおそれがあり、逆に多いと硬く、破断伸びが小さくなり、ゴムがもろくなるので好ましくない。 As the carbon black used in the rubber composition of the present invention, any carbon black conventionally blended in an adhesive rubber composition can be used. Specifically, ISAF, HAF, and the like can be preferably used, but are not particularly limited. If the blending amount of carbon black is small, the reinforcing property may not be sufficient. On the other hand, if the blending amount is large, it will be hard, the elongation at break will be small, and the rubber will be brittle.
本発明のゴム組成物に使用するシリカとしては、従来からタイヤその他用のゴム組成物として配合されている任意のシリカとすることができる。カーボンブラックと共にシリカを配合すると発熱性低下の効果が発現するので好ましい。シリカの配合量が多いと混合加工性の低下や破断強度やモジュラスが低下するので好ましくない。本発明において、カーボンブラックとシリカとの配合量には特に制限はないが、カーボンブラックとシリカの比（カーボンブラック／シリカ）（重量比）が１００〜０／０〜１００、好ましくは１００〜６０／０〜４０、更に好ましくは、１００〜８０／０〜２０である。 The silica used in the rubber composition of the present invention can be any silica conventionally blended as a tire or other rubber composition. It is preferable to add silica together with carbon black because the effect of reducing exothermicity is exhibited. A large amount of silica is not preferable because the mixing processability, breaking strength, and modulus decrease. In the present invention, the blending amount of carbon black and silica is not particularly limited, but the ratio of carbon black to silica (carbon black / silica) (weight ratio) is 100 to 0/0 to 100, preferably 100 to 60. / 0 to 40, more preferably 100 to 80/0 to 20.
本発明のゴム組成物にシリカを使用する場合にはシランカップリング剤を使用するのが好ましい。そのようなシランカップリング剤としては従来からシリカと共に配合されるもののうち、好ましくは分子中に硫黄原子を含有する任意のものとすることができ、例えば３−トリメトキシシリルプロピル−Ｎ，Ｎ−ジメチルカルバモイル−テトラスルフィド、トリメトキシシリルプロピル−メルカプトベンゾチアゾールテトラスルフィド、トリエトキシシリルプロピル−メタクリレート−モノスルフィド、ジメトキシメチルシリルプロピル−Ｎ，Ｎ−ジメチルチオカルバモイル−テトラスルフィド、ビス−〔３−（トリエトキシシリル）−プロピル〕テトラスルフィド、ビス−〔３−（トリエトキシシリル）−プロピル〕ジスルフィド、３−メルカプトプロピルトリメトキシシランなどを用いることができる。これらは公知の化合物であり、数多くの市販品が利用できる。シランカップリング剤の配合量はシリカ重量当り１〜１０重量％であるのが好ましく、この配合量が少ないと、シリカの補強性不足によるゴム強度の低下が起こるおそれがあるので好ましくなく、逆に多いと加工中のヤケが発生するおそれがあるので好ましくない。 When silica is used in the rubber composition of the present invention, it is preferable to use a silane coupling agent. As such a silane coupling agent, among those conventionally blended with silica, any one containing a sulfur atom in the molecule can be preferably used. For example, 3-trimethoxysilylpropyl-N, N- Dimethylcarbamoyl-tetrasulfide, trimethoxysilylpropyl-mercaptobenzothiazole tetrasulfide, triethoxysilylpropyl-methacrylate-monosulfide, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl-tetrasulfide, bis- [3- (tri Ethoxysilyl) -propyl] tetrasulfide, bis- [3- (triethoxysilyl) -propyl] disulfide, 3-mercaptopropyltrimethoxysilane and the like can be used. These are known compounds, and many commercially available products can be used. The blending amount of the silane coupling agent is preferably 1 to 10% by weight based on the weight of the silica. If the blending amount is small, the rubber strength may be lowered due to insufficient silica reinforcement. If the amount is too large, there is a risk of burning during processing, which is not preferable.
本発明において使用するシスチン、好ましくはＬ−シスチンは天然に産するアミノ酸で市販品を配合して使用することができる。シスチンの配合量が少ないと金属へのゴム付きが悪くなるので好ましくなく、逆に多いと加硫が速くなり、スコーチしやすくなったり接着耐久性が低下するので好ましくない。 The cystine used in the present invention, preferably L-cystine, is a naturally occurring amino acid that can be used in combination with a commercially available product. If the amount of cystine is too small, it is not preferable because the rubber is poorly attached to the metal. On the other hand, if the amount is too large, vulcanization is accelerated, and scorching is likely to occur or adhesion durability is reduced.
本発明において使用する有機酸コバルト塩は金属などとの接着用ゴム組成物に一般に配合されている任意の有機酸コバルト塩とすることができ、具体的にはナフテン酸コバルト、ステアリン酸コバルト、オルトホウ酸コバルト、ネオデカン酸コバルト、酢酸コバルト、ネオデカン酸オルトホウ酸コバルト、コバルトアセチルアセトナートなどをあげることができ、これらは広く市販されており、本発明においてもこれらの市販品を用いることができる。本発明において、有機酸コバルト塩の配合量が少ないと金属への接着ゴム付や接着耐久性が低下するので好ましくなく、逆に多いとゴムの劣化を促進するので好ましくない。 The organic acid cobalt salt used in the present invention can be any organic acid cobalt salt generally blended in a rubber composition for adhesion to metals and the like, specifically, cobalt naphthenate, cobalt stearate, orthoboron. Examples thereof include cobalt acid, cobalt neodecanoate, cobalt acetate, cobalt neodecanoate orthoborate, and cobalt acetylacetonate, and these are widely commercially available, and these commercial products can also be used in the present invention. In the present invention, if the amount of the organic acid cobalt salt is small, it is not preferable because adhesion to metal or adhesion durability is lowered, and conversely if it is too large, deterioration of the rubber is promoted.
本発明において使用する硫黄は従来からゴム組成物に一般に使用されている市販の硫黄を用いることができ、この配合量が少ないと接着力が低下するので好ましくなく、逆に多いと破断伸びが低下してゴムがもろくなるので好ましくない。 As the sulfur used in the present invention, commercially available sulfur that has been generally used in rubber compositions can be used, and if this amount is small, the adhesive strength is lowered, which is not preferable. This is not preferable because the rubber becomes brittle.
本発明に係るゴム組成物には、前記した成分に加えて、カーボンブラックやシリカ以外の補強剤（フィラー）、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用、その他のゴム組成物用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the components described above, the rubber composition according to the present invention includes reinforcing agents (fillers) other than carbon black and silica, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, plastics Various additives that are generally blended for tires such as additives and other rubber compositions can be blended, and these additives are kneaded into a composition by a general method to be vulcanized or crosslinked. Can be used to do. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例１〜１１及び比較例１〜２
サンプルの調製
表Ｉに示す配合において、加硫促進剤と硫黄を除く成分を２リットルの密閉型ミキサーで５分間混練し、１５０℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄をオープンロールで混練し、ゴム組成物を得た。このゴム組成物を用いて以下に示す試験法で未加硫物性を評価した。結果は表Ｉに示す。
Examples 1-11 and Comparative Examples 1-2
Sample preparation In the formulation shown in Table I, the components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes with a 2 liter closed mixer, and when the temperature reached 150 ° C, a master batch was obtained. A vulcanization accelerator and sulfur were kneaded with this master batch with an open roll to obtain a rubber composition. Using this rubber composition, unvulcanized physical properties were evaluated by the following test methods. The results are shown in Table I.
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１４８℃で５０分間加硫して加硫ゴムシートを調製し、以下に示す試験法で加硫ゴムの物性を測定した。結果は表Ｉに示す。 Next, the obtained rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 148 ° C. for 50 minutes to prepare a vulcanized rubber sheet. The physical properties of the vulcanized rubber were measured by the following test methods. It was measured. The results are shown in Table I.
ゴム物性評価試験法
Ｔ９５（９５％加硫度）：ＪＩＳＫ６３００に準拠して１４８℃で測定した。
Rubber physical property evaluation test method T95 (95% vulcanization degree): Measured at 148 ° C. according to JISK6300.
Ｍ１００（伸び１００％時の引張応力）、ＴＢ（引張強さ）及びＥＢ（破断伸び）：ＪＩＳＫ６２５１に準拠して加硫試験サンプルからＪＩＳ３号形ダンベルにて２ｍｍゴムシートを打抜き、５００ｍｍ／分の引張速度の条件下で伸び１００％時の引張応力（Ｍ１００）、引張強さ（ＴＢ）、破断伸び（ＥＢ）を測定した。 M100 (tensile stress at 100% elongation), TB (tensile strength) and EB (elongation at break): according to JIS K6251, a 2 mm rubber sheet was punched out from a vulcanized test sample with a JIS No. 3 dumbbell, and 500 mm / min. Tensile stress (M100), tensile strength (TB), and elongation at break (EB) at 100% elongation were measured under the conditions of tensile speed.
接着試験
引抜力、ゴム付
黄銅メッキスチールコード（１×５構造）の複数本を１２．５ｍｍ間隔で互いに平行に並べて長尺状物とし、この長尺状物の表裏両側からゴム組成物を該長尺状物にコーティングして、該長尺状物を該ゴム組成物に埋め込み、１４８℃×４５分加硫して、試験サンプルを得た。この試験サンプルからＡＳＴＭ−Ｄ−２に準拠してコードを引き抜き、その引き抜き時の力とワイヤー（スチールコード）へのゴム被覆率（％）を評価した。数値の大きい方がよい。
Adhesion test pulling force, rubber-coated brass-plated steel cords (1 × 5 structure) are arranged in parallel at 12.5 mm intervals to form a long product, and the rubber composition is applied to both sides of the long product from both sides A long sample was coated, the long product was embedded in the rubber composition, and vulcanized at 148 ° C. for 45 minutes to obtain a test sample. A cord was pulled out from this test sample according to ASTM-D-2, and the force at the time of pulling out and the rubber coverage (%) on the wire (steel cord) were evaluated. A larger number is better.
表Ｉ脚注
ＮＲ：天然ゴム ＲＳＳ＃３
ＳＢＲ：日本ゼオン（株）製 Ｎｉｐｏｌ １５０２
ＣＢ：東海カーボン（株）製 カーボンブラック シーストＫＨ（よう素吸着量９０cm3／１００g、ＤＢＰ吸収量１１９×１０−５m3／kg）
シリカ：東ソー・シリカ（株）製 ニップシールＡＱ
カップリング剤：エポニックデッグサジャパン製 Ｓｉ６９
Ｌ−シスチン：関東化学製：特級（下記式参照）
加硫促進剤ＤＺ：大内新興化学工業（株）製 ノクセラーＤＺ−Ｇ
加硫促進剤ＮＳ：大内新興化学工業（株）製 ノクセラーＮＳ
Table I Footnote NR: Natural rubber RSS # 3
SBR: Nipol 1502 manufactured by Nippon Zeon Co., Ltd.
CB: Tokai Carbon Co., Ltd. Carbon black SEAST KH (iodine adsorption 90cm 3 / 100g, DBP absorption 119 × 10-5m 3 / kg)
Silica: NIPSEAL AQ manufactured by Tosoh Silica Corporation
Coupling agent: Si69 made by Eponic Degussa Japan
L-cystine: manufactured by Kanto Chemical Co., Ltd .: special grade (see formula below)
Vulcanization accelerator DZ: Nouchira DZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator NS: Nouchira NS manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
なお、表Ｉに示した実施例１〜１１及び比較例１〜２の配合には以下の成分を共通に配合した。
亜鉛華（正同化学工業（株）製 酸化亜鉛 ３種）７重量部
ステアリン酸（日本油脂（株）製 ビーズステアリン酸）１重量部
老化防止剤（６ＰＰＤ）（フレキシス社製 サントフレックス ６ＰＰＤ）１重量部
老化防止剤（ＲＤ）（大内新興化学工業（株）製 ノクラック２２４）１重量部
ナフテン酸コバルト（日鋼金属（株）製、ナフテン酸コバルト（Ｃｏ含有率１０％））０．５重量部
硫黄（アクゾノーベル（株）製 クリステックスＨＳ ＯＴ ２０）６．５重量部
In addition, the following components were mix | blended in common with the mixing | blending of Examples 1-11 shown in Table I, and Comparative Examples 1-2.
7 parts by weight of zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.) 1 part by weight of stearic acid (bead stearic acid manufactured by Nippon Oil & Fats Co., Ltd.) Anti-aging agent (6PPD) (Santflex 6PPD manufactured by Flexis) 1 Part by weight Anti-aging agent (RD) (Nocrack 224, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 1 part by weight Cobalt naphthenate (Nikko Steel Co., Ltd., cobalt naphthenate (Co content 10%)) 0.5 Part by weight Sulfur (Akzo Nobel Kristex HS OT 20) 6.5 parts by weight
本発明では、加硫促進剤ＤＺの代替品として、天然物であるシスチンを加硫促進剤として使用することにより、ゴム組成物の接着性、接着耐久性が向上し、かつＤＺの使用量を削減することができ、また、シスチンは非石油資源原料であるため環境の観点からも好ましい。得られたゴム組成物は良好な接着性のために接着用ゴム組成物、特にタイヤのベルトコード被覆ゴムとして有用である。 In the present invention, as an alternative to the vulcanization accelerator DZ, by using cystine as a natural product as a vulcanization accelerator, the adhesion and durability of the rubber composition are improved, and the amount of DZ used is reduced. Moreover, since cystine is a non-petroleum resource raw material, it is preferable also from an environmental viewpoint. The obtained rubber composition is useful as a rubber composition for adhesion, particularly as a belt cord covering rubber of a tire because of good adhesion.
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| EP2517898A1 (en) * | 2011-04-29 | 2012-10-31 | Lanxess Deutschland GmbH | Rubber mixtures containing silicic acids with additives containing sulphur |
| US20130245199A1 (en) * | 2012-03-14 | 2013-09-19 | Ralf Mruk | Functionalized elastomer |
| US20130245198A1 (en) * | 2012-03-14 | 2013-09-19 | Ralf Mruk | Pneumatic tire |
| EP2671727A1 (en) * | 2012-06-06 | 2013-12-11 | LANXESS Deutschland GmbH | Rubber mixtures containing silicic acids with additives containing sulphur |
| JP6535351B2 (en) | 2014-05-21 | 2019-06-26 | 株式会社ブリヂストン | Rubber compound for manufacturing tires |
| JPWO2016009776A1 (en) * | 2014-07-15 | 2017-04-27 | 住友ゴム工業株式会社 | Manufacturing method of rubber composition for tire and pneumatic tire |
| CN106355238A (en) * | 2016-08-29 | 2017-01-25 | 江苏通用科技股份有限公司 | Intelligent tire with built-in RFID |
| CN112048108A (en) * | 2020-09-17 | 2020-12-08 | 山东玲珑轮胎股份有限公司 | Low-odor belt rubber composition of novel bonding system |
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| JPS61221242A (en) * | 1985-03-27 | 1986-10-01 | Bridgestone Corp | Low heat generating rubber composition |
| US6780925B2 (en) * | 2001-12-21 | 2004-08-24 | The Goodyear Tire & Rubber Company | Rubber composition with silica reinforcement obtained with an amino acid or amino acid-containing protein based activator and use thereof in tires |
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