JP4711710B2 - Rubber composition - Google Patents
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- JP4711710B2 JP4711710B2 JP2005082693A JP2005082693A JP4711710B2 JP 4711710 B2 JP4711710 B2 JP 4711710B2 JP 2005082693 A JP2005082693 A JP 2005082693A JP 2005082693 A JP2005082693 A JP 2005082693A JP 4711710 B2 JP4711710 B2 JP 4711710B2
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- tocopherol
- secondary amine
- rubber
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- rubber composition
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- 229920001971 elastomer Polymers 0.000 title claims description 25
- 239000005060 rubber Substances 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 title claims description 20
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011732 tocopherol Substances 0.000 claims description 24
- 229930003799 tocopherol Natural products 0.000 claims description 23
- 229960001295 tocopherol Drugs 0.000 claims description 21
- 235000010384 tocopherol Nutrition 0.000 claims description 20
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims description 20
- -1 aromatic secondary amine Chemical class 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 230000003712 anti-aging effect Effects 0.000 description 27
- 239000003795 chemical substances by application Substances 0.000 description 21
- 235000006708 antioxidants Nutrition 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 229930003427 Vitamin E Natural products 0.000 description 6
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 6
- 239000011709 vitamin E Substances 0.000 description 6
- 235000019165 vitamin E Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229940046009 vitamin E Drugs 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000019149 tocopherols Nutrition 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 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
- 244000055346 Paulownia Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 239000004615 ingredient Substances 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
- 239000004014 plasticizer Substances 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
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明はゴム組成物に関し、更に詳しくは芳香族第２級アミン系老化防止剤、特に老化防止剤６Ｃ（Ｎ−（１，３−ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレンジアミン）の配合量を減した場合でも高い老化防止効果と優れた耐摩耗性が得られる老化防止剤系を配合したゴム組成物に関する。 The present invention relates to a rubber composition, and more particularly, an aromatic secondary amine-based anti-aging agent, particularly an anti-aging agent 6C (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine). The present invention relates to a rubber composition containing an anti-aging agent system that can provide a high anti-aging effect and excellent wear resistance even when the amount is reduced.
ゴムの典型的な老化防止剤として、芳香族第２級アミン系老化防止剤、特に老化防止剤６Ｃがゴム組成物用として一般的に用いられているが、近年の環境に優しいエコタイヤの開発の観点から、その使用量を削減したり、ビタミンＣやＥなどといった天然型酸化防止剤への置き換えが望まれている。本発明に関連する先行技術文献情報として特許文献１があげられる。 As a typical anti-aging agent for rubber, an aromatic secondary amine anti-aging agent, particularly anti-aging agent 6C, is generally used for rubber compositions. From the viewpoint, it is desired to reduce the amount used or to replace it with natural antioxidants such as vitamin C and E. Patent Document 1 is given as information on prior art documents related to the present invention.
従って、本発明は近年の環境保全のニーズに対応して、しかもゴムの老化防止効果と耐摩耗性が改良された老化防止剤系シリカ配合ゴム組成物を提供することを目的とする。 Accordingly, it is an object of the present invention to provide an anti-aging silica compounded rubber composition which has improved anti-aging effect and abrasion resistance of rubber in response to recent environmental conservation needs.
本発明に従えば、ジエン系ゴム１００重量部、シリカ２〜１００重量部、芳香族第２級アミン系老化防止剤０．５〜３．５重量部及びトコフェロールを含んでなり、芳香族第２級アミン系老化防止剤とトコフェロールとの配合比率（重量比）が０．２５≦トコフェロール／（トコフェロール＋芳香族第２級アミン系老化防止剤）≦０．６７であるゴム組成物が提供される。 According to the present invention, it comprises 100 parts by weight of a diene rubber, 2 to 100 parts by weight of silica , 0.5 to 3.5 parts by weight of an aromatic secondary amine antioxidant, and a tocopherol. Provided is a rubber composition in which the blending ratio (weight ratio) of the secondary amine-based antioxidant and tocopherol is 0.25 ≦ tocopherol / (tocopherol + aromatic secondary amine-based antioxidant) ≦ 0.67. .
本発明によれば、以下の実施例にも示すように、天然ゴムなどのジエン系ゴム／シリカ配合系において芳香族第２級アミン系老化防止剤とトコフェロール（ビタミンＥ）を特定の比率で配合することにより、相乗効果が生じ各々単独で使用した場合よりも高い老化防止効果と優れた耐摩耗性が得られる。 According to the present invention, as shown in the following examples, an aromatic secondary amine antioxidant and tocopherol (vitamin E) are blended at a specific ratio in a diene rubber / silica blend system such as natural rubber. By doing so, a synergistic effect is produced, and a higher anti-aging effect and superior wear resistance are obtained than when used alone.
本発明に従えば、ジエン系ゴム／シリカ配合系ゴム組成物において、老化防止剤として芳香族第２級アミン系老化防止剤（好ましくは老化防止剤６Ｃ）と天然型酸化防止剤のトコフェロール（ビタミンＥ）を、ジエン系ゴム１００重量部当り芳香族第２級アミン系老化防止剤０．５〜３．５重量部、好ましくは０．５〜２．０重量部配合し、そしてトコフェロールを、芳香族第２級アミン系老化防止剤とトコフェロールとの配合比率（重量比）が式：
０．２５≦トコフェロール／（トコフェロール＋芳香族第２級アミン系老化防止剤）≦０．６７
を満足するように配合する。
According to the present invention, the di-ene-based rubber / silica-containing rubber composition, the aromatic secondary amine-based anti-aging agent (preferably the antioxidant 6C) and natural antioxidants as antioxidant tocopherols ( Vitamin E) is blended in an amount of 0.5 to 3.5 parts by weight, preferably 0.5 to 2.0 parts by weight of aromatic secondary amine anti-aging agent per 100 parts by weight of diene rubber, and tocopherol The blending ratio (weight ratio) of the aromatic secondary amine anti-aging agent and tocopherol is represented by the formula:
0.25 ≦ tocopherol / (tocopherol + aromatic secondary amine type antioxidant) ≦ 0.67
Is blended to satisfy
本発明に従ったゴム組成物に配合されるジエン系ゴム成分としては、タイヤ用、その他として一般に使用することができる任意のジエン系ゴム、例えば各種天然ゴム（ＮＲ）、各種ポリイソプレンゴム（ＩＲ）、各種スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、各種ポリブタジエンゴム（ＢＲ）、各種アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）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として使用することができる。 Examples of the diene rubber component blended in the rubber composition according to the present invention include any diene rubber that can be generally used for tires and others, such as various natural rubbers (NR) and various polyisoprene rubbers (IR ), Various styrene-butadiene copolymer rubbers (SBR), various polybutadiene rubbers (BR), various acrylonitrile-butadiene copolymer rubbers (NBR), etc., and these can be used alone or in any blend. Can do.
本発明に従ったゴム組成物には補強剤としてシリカ（又はシリカ及びカーボンブラック）を配合するのが好ましいが、かかるシリカ及びカーボンブラックとしてはタイヤ用その他として一般的にゴム組成物中に配合することができる任意のものを使用することができる。またその配合量も従前通りで特に限定はないが、シリカは、ジエン系ゴム１００重量部に対し、好ましくは２〜１００重量部、更に好ましくは１０〜８０重量部配合する。 Silica (or silica and carbon black) is preferably blended as a reinforcing agent in the rubber composition according to the present invention, and such silica and carbon black are generally blended in a rubber composition for tires and others. Any that can be used. Moreover, the compounding quantity is as usual and is not particularly limited, but the silica is preferably blended in an amount of 2 to 100 parts by weight, more preferably 10 to 80 parts by weight, per 100 parts by weight of the diene rubber.
シリカの配合に際しては、シリカと一緒に配合することができるシランカップリング剤を用いることができ、そのようなシランカップリング剤の種類には特に限定はない。シランカップリング剤の配合量にも特に限定はないが、配合シリカの重量に対し８〜１２重量％配合するのが一般的である。 In blending silica, a silane coupling agent that can be blended together with silica can be used, and the type of such silane coupling agent is not particularly limited. The amount of the silane coupling agent is not particularly limited, but it is generally 8 to 12% by weight based on the weight of the compounded silica.
本発明において老化防止剤の一成分として使用する芳香族第２級アミン系老化防止剤、特に老化防止剤６Ｃは従来から汎用、市販されている任意のものを用いることができる。この配合量が少な過ぎると老化防止効果が低くなるので好ましく、逆に多過ぎるとトコフェロールとの併用効果が見られないので好ましくない。 In the present invention, any aromatic secondary amine-based anti-aging agent used as a component of the anti-aging agent, in particular, the anti-aging agent 6C, can be any conventional and commercially available one. If the blending amount is too small, the effect of preventing aging is lowered, and conversely, if too large, the combined effect with tocopherol is not seen, which is not preferred.
本発明において、前記芳香族第２級アミン系老化防止剤と併用するトコフェロールはα，β，δ，ζ１，η，ε，ζ２，−トコフェロールなどの公知の天然トコフェロール及び化学合成トコフェロールを用いることができる。これらは理研ビタミン（株）などから市販されており、本発明に従えばそのような市販品を使用することができる。 In the present invention, known tocopherols such as α, β, δ, ζ1, η, ε, ζ2, and -tocopherol and chemically synthesized tocopherols may be used as the tocopherol used in combination with the aromatic secondary amine-based antioxidant. it can. These are commercially available from Riken Vitamin Co., Ltd., and such commercially available products can be used according to the present invention.
芳香族第２級アミン系老化防止剤とトコフェロールとは前記式（Ｉ）を満足するような重量比で配合しなければならない。トコフェロールがこの式（Ｉ）の値を満足しないと芳香族第２級アミン系老化防止剤との併用効果（芳香族第２級アミン系老化防止剤単体よりも老化防止効果が高く、耐摩耗性が優れること）が見られない。 The aromatic secondary amine anti-aging agent and tocopherol must be blended in a weight ratio that satisfies the formula (I). If the tocopherol does not satisfy the value of the formula (I), the combined use effect with the aromatic secondary amine anti-aging agent (the anti-aging effect is higher than the aromatic secondary amine anti-aging agent alone, and the wear resistance is high. Is not seen).
本発明に係るゴム組成物には、前記した必須成分及び任意成分に加えて、その他の補強剤（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、他の老化防止剤、可塑剤などのタイヤ用、その他一般ゴム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、加硫して組成物とし、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。 The rubber composition according to the present invention includes other reinforcing agents (fillers), vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, and other anti-aging agents, in addition to the above-described essential and optional components. Various additives generally blended for tires such as plasticizers and other general rubbers can be blended, and these additives are kneaded and vulcanized by a general method to obtain a composition. It can be used for sulfurization or crosslinking. The blending amounts of these additives may be conventional conventional blending amounts as long as the object of the present invention is not adversely affected.
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１〜３及び比較例１〜５
サンプルの調製
表Ｉに示す配合（重量部）において、加硫促進剤と硫黄を除く成分を１．８リットルの密閉型ミキサーで４．５分間混練し、１５５±５℃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。
Examples 1-3 and Comparative Examples 1-5
Sample preparation In the formulation (parts by weight) shown in Table I, the ingredients other than the vulcanization accelerator and sulfur were kneaded for 4.5 minutes with a 1.8 liter closed mixer and released when the temperature reached 155 ± 5 ° C. To obtain a master batch. A vulcanization accelerator and sulfur were kneaded with this master batch with an open roll to obtain a rubber composition.
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１５０℃で３０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 resulting rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 150 ° C. for 30 minutes to prepare a vulcanized rubber sheet, and 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
引張り試験：ＪＩＳ Ｋ−６２５７に準拠して、上で得たサンプルの老化前後の引張り強度（破断強度）及び破断伸びを測定した。なお、老化試験はギヤーオーブン中で１００℃×４８時間熱老化させて行なった。
Rubber physical property evaluation test method Tensile test: Based on JIS K-6257, the tensile strength (breaking strength) and elongation at break of the sample obtained above were measured. The aging test was conducted by heat aging in a gear oven at 100 ° C. for 48 hours.
耐摩耗性：ＪＩＳ Ｋ−６２６４の７で規定されるランボーン摩耗試験を用い、同７．４．１で規定される標準試験条件にて測定を行った。測定結果は、比較例１の値を１００として指数表示した。この値が大きいほど耐摩耗性が良好であることを示す。 Abrasion resistance: Using a Lambourne abrasion test specified in 7 of JIS K-6264, measurement was performed under the standard test conditions specified in 7.4.1. The measurement results are displayed as an index with the value of Comparative Example 1 being 100. It shows that abrasion resistance is so favorable that this value is large.
表Ｉ脚注
＊１：天然ゴム
＊２：日本シリカ（株）製 ニップシールＡＱ
＊３：デクサ社製 Ｓｉ６９
＊４：正同化学工業（株）製 酸化亜鉛 ３種
＊５：日本油脂（株）製 ビーズステアリン酸 桐
＊６：住友化学工業（株）製 アンチゲン６Ｃ
＊７：理研ビタミン（株）製 理研Ｅオイル ７１０（総ビタミンＥ含量６７．１％以上、Ｅ−α含量６７．１％以上）
＊８：理研ビタミン（株）製 理研Ｅオイル スーパー８０（総ビタミンＥ含量６４％以上、Ｅ−α含量３％以下、Ｅ−δ含量３０〜３５％）
＊９：武田薬品工業（株）製 アスコルビン酸
＊１１：鶴見化学工業（株）製 金華印油入微粉硫黄
＊１２：三新化学工業（株）製 サンセラーＣＭ−Ｇ
＊１３：ＦＬＥＸＳＹＳ社製 ＰＥＲＫＡＣＩＴ ＤＰＧ
Table I Footnote * 1: Natural rubber * 2: Nippon Silica Co., Ltd. nip seal AQ
* 3: Dexa Si69
* 4: Zinc Oxide, manufactured by Shodo Chemical Industry Co., Ltd. 3 types * 5: Beads stearic acid paulownia made by Nippon Oil & Fats Co., Ltd.
* 7: Riken E Oil 710, manufactured by Riken Vitamin Co., Ltd. (total vitamin E content 67.1% or higher, E-α content 67.1% or higher)
* 8: Riken E Oil Super 80 manufactured by Riken Vitamin Co., Ltd. (total vitamin E content 64% or more, E-α content 3% or less, E-δ content 30 to 35%)
* 9: Ascorbic acid manufactured by Takeda Pharmaceutical Co., Ltd. * 11: Fine powdered sulfur with Jinhua seal oil manufactured by Tsurumi Chemical Industry Co., Ltd. * 12: Sunseller CM-G manufactured by Sanshin Chemical Industry Co., Ltd.
* 13: PERKACIT DPG manufactured by FLEXSYS
表Ｉの結果から明らかなように、シリカ配合系ゴム組成物において、老化防止剤が単独の比較例１〜３に比較して、実施例１〜３では引張り強度を維持しながら、伸び及び耐摩耗性が改良され、老化防止剤を併用したがトコフェロール量の多い比較例４では本発明の所望の効果は認められなかった。比較例５は、トコフェロール（ビタミンＥ）に代えてビタミンＣを老化防止剤６Ｃと併用した系であるが、実施例のような併用による改善効果は認められない。 As is apparent from the results of Table I, in the silica compounded rubber composition, the anti-aging agent is higher in elongation and resistance while maintaining tensile strength in Examples 1 to 3 than in Comparative Examples 1 to 3 alone. Although the wear resistance was improved and an anti-aging agent was used in combination, the desired effect of the present invention was not observed in Comparative Example 4 having a large amount of tocopherol. Comparative Example 5 is a system in which vitamin C is used in combination with anti-aging agent 6C instead of tocopherol (vitamin E), but the improvement effect by the combined use as in Examples is not recognized.
本発明によれば従来の芳香族第２級アミン系老化防止剤、特に老化防止剤６Ｃの一部を天然型酸化防止剤であるトコフェロールに置き換えることによって、環境に優しいエコタイヤ化を実現できると共に、老化防止効果と耐摩耗性も改善されるので時代のニーズに合致したタイヤ、その他のゴム製品に用いることができる。 According to the present invention, by replacing a part of the conventional aromatic secondary amine anti-aging agent, particularly anti-aging agent 6C, with tocopherol which is a natural type antioxidant, an eco-friendly eco-tire can be realized, The anti-aging effect and wear resistance are also improved, so it can be used for tires and other rubber products that meet the needs of the times.
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| JPH09296078A (en) * | 1996-03-04 | 1997-11-18 | Yokohama Rubber Co Ltd:The | Tire rubber composition |
| JP2002194141A (en) * | 2000-12-22 | 2002-07-10 | Sumitomo Chem Co Ltd | Method of manufacturing butadiene polymer molded article |
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| JPH09296078A (en) * | 1996-03-04 | 1997-11-18 | Yokohama Rubber Co Ltd:The | Tire rubber composition |
| JP2002194141A (en) * | 2000-12-22 | 2002-07-10 | Sumitomo Chem Co Ltd | Method of manufacturing butadiene polymer molded article |
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| JP2021008558A (en) * | 2019-07-01 | 2021-01-28 | 横浜ゴム株式会社 | Rubber composition |
| JP7343757B2 (en) | 2019-07-01 | 2023-09-13 | 横浜ゴム株式会社 | rubber composition |
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