JP2009040902A - Rubber composition and pneumatic tire produced by using the same - Google Patents
Rubber composition and pneumatic tire produced by using the same Download PDFInfo
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- JP2009040902A JP2009040902A JP2007207876A JP2007207876A JP2009040902A JP 2009040902 A JP2009040902 A JP 2009040902A JP 2007207876 A JP2007207876 A JP 2007207876A JP 2007207876 A JP2007207876 A JP 2007207876A JP 2009040902 A JP2009040902 A JP 2009040902A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 91
- 239000005060 rubber Substances 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 82
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011787 zinc oxide Substances 0.000 claims abstract description 58
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 24
- 239000000945 filler Substances 0.000 claims abstract description 10
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 8
- 235000014692 zinc oxide Nutrition 0.000 claims description 56
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 229920003049 isoprene rubber Polymers 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000032683 aging Effects 0.000 abstract description 13
- 238000005299 abrasion Methods 0.000 abstract description 10
- 230000000704 physical effect Effects 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 abstract description 4
- 239000000306 component Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 silica compound Chemical class 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XZGAWWYLROUDTH-UHFFFAOYSA-N 1,1,1-triethoxy-3-(3,3,3-triethoxypropyltetrasulfanyl)propane Chemical compound CCOC(OCC)(OCC)CCSSSSCCC(OCC)(OCC)OCC XZGAWWYLROUDTH-UHFFFAOYSA-N 0.000 description 1
- YKBYBYAFEAREKR-UHFFFAOYSA-N 4-(3-dimethoxysilylbutyltetrasulfanyl)butan-2-yl-dimethoxysilane Chemical compound CO[SiH](OC)C(C)CCSSSSCCC(C)[SiH](OC)OC YKBYBYAFEAREKR-UHFFFAOYSA-N 0.000 description 1
- 241000254043 Melolonthinae Species 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 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
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 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
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、シリカ配合系のゴム組成物において、熱老化による物性変化が少なく耐摩耗性に優れたゴム組成物及びそれを用いた空気入りタイヤに関する。 TECHNICAL FIELD The present invention relates to a rubber composition having excellent wear resistance with little change in physical properties due to heat aging, and a pneumatic tire using the same, in a silica compound rubber composition.
従来より、シリカ配合ゴム組成物においては、高い耐摩耗性を得るためにシランカップリング剤を添加したシリカとエラストマーを化学的に結合させることが必要である。このような目的で配合されるシランカップリング剤としては、一般的にビス（トリエトキシプロピル）テトラスルフィドが用いられているが、これ以外のシランカップリング剤についても数多くのものが知られている。 Conventionally, in a silica-containing rubber composition, it is necessary to chemically bond a silica to which a silane coupling agent is added and an elastomer in order to obtain high wear resistance. Bis (triethoxypropyl) tetrasulfide is generally used as a silane coupling agent to be blended for such purposes, but many other silane coupling agents are known. .
また、有機リチウム化合物を開始剤としてジエン系単量体を（共）重合した後、重合活性末端を特定のアルコキシシラン系化合物と反応させて得られる変性（共）重合体をゴム重量分率で２０重量％以上含んでなるゴム成分１００重量部に対してシリカ充填剤を１０重量部から１００重量部含有する耐摩耗性を向上させたタイヤ用ゴム組成物が知られている（例えば、特許文献１参照）。 In addition, a modified (co) polymer obtained by (co) polymerizing a diene monomer with an organolithium compound as an initiator and then reacting the polymerization active terminal with a specific alkoxysilane compound is obtained by weight fraction of rubber. 2. Description of the Related Art A tire rubber composition with improved wear resistance containing 10 to 100 parts by weight of a silica filler with respect to 100 parts by weight of a rubber component containing 20% by weight or more is known (for example, patent document) 1).
しかしながら、上記各種シランカップリング剤から耐摩耗性の向上が検討されているが、未だ不十分であり、耐摩耗性の更なる改良が必要であるのが現状である。
また、上記特許文献１の変性（共）重合体を用いて耐摩耗性の向上を図る手法においては、使用できるポリマーが溶液重合ポリマーに限定されてしまう点に課題があり、また、熱老化による物性変化が大きく、耐摩耗性においても不十分である点に課題がある。
However, although improvement of wear resistance has been studied from the various silane coupling agents, it is still insufficient and the current situation is that further improvement of wear resistance is necessary.
Moreover, in the method of aiming at an improvement in abrasion resistance using the modified (co) polymer of Patent Document 1, there is a problem in that the usable polymer is limited to the solution polymerization polymer, and also due to heat aging. There is a problem in that the physical property change is large and the wear resistance is insufficient.
一方、複合亜鉛華は、ゴムの加硫促進助剤として知られており、炭酸カルシウムなどの表面に亜鉛華を複合させ、亜鉛華自身の加硫促進助剤としての効果を失わず、形状と比表面積を自由に変化させることにより、より反応しやすくなるために開発されたものであり（例えば、特許文献２参照）、カーボンブラック配合のゴム組成物に使用されている（例えば、特許文献３及び４参照）。
しかしながら、シリカ、シランカップリング剤配合のゴム組成物において、複合亜鉛華を配合すること、並びに、複合亜鉛華の特異的作用については全く知られていないものである。
However, in a rubber composition containing silica and a silane coupling agent, it is not known at all about blending composite zinc white and specific action of composite zinc white.
本発明は、上記従来の課題及び現状等に鑑み、これを解消しようとするものであり、シリカ配合系のゴム組成物において、熱老化による物性変化が少なく耐摩耗性に優れたゴム組成物及びそれを用いた空気入りタイヤを提供することを目的とする。 In view of the above-described conventional problems and current situation, the present invention intends to solve this problem, and in a rubber composition based on silica, there is little change in physical properties due to heat aging, and a rubber composition excellent in wear resistance and An object is to provide a pneumatic tire using the same.
本発明者は、上記従来の課題等について鋭意検討した結果、少なくとも一種のジエン系ゴムからなるゴム成分に対し、充填剤として少なくともシリカを特定量含有すると共に、シランカップリング剤をシリカに対して特定の割合で含有せしめ、酸化亜鉛成分として特定量となる複合亜鉛華を含有することにより、上記目的のゴム組成物及びそれを用いた空気入りタイヤが得られることを見い出し、本発明を完成するに至ったのである。 As a result of intensive studies on the above-described conventional problems, the present inventor has at least a specific amount of silica as a filler for a rubber component composed of at least one diene rubber, and a silane coupling agent for silica. It is found that a rubber composition of the above purpose and a pneumatic tire using the same can be obtained by containing a composite zinc white having a specific amount as a zinc oxide component. It came to.
すなわち、本発明は、次の（１）〜（６）に存する。
（１） 少なくとも一種のジエン系ゴムからなるゴム成分１００質量部に対し、充填剤として少なくともシリカを１０〜１５０質量部、シランカップリング剤をシリカに対して１〜２０質量％、酸化亜鉛成分として０．５質量部以上２．０質量部未満を含み、酸化亜鉛として複合亜鉛華を含有することを特徴とするゴム組成物。
（２） 複合亜鉛華が、表面に酸化亜鉛の層を有する上記（１）に記載のゴム組成物。
（３） 複合亜鉛華が、内部に無機金属塩を含有する上記（２）に記載のゴム組成物。
（４） ゴム成分１００質量部のうち、天然ゴム及び／又は合成イソプレンゴムが３０質量部以下である上記（１）〜（３）の何れか一つに記載のゴム組成物。
（５） 上記（１）〜（４）の何れか一つに記載のゴム組成物を用いたことを特徴とする空気入りタイヤ。
（６） 上記（１）〜（４）の何れか一つに記載のゴム組成物をトレッドに用いたことを特徴とする空気入りタイヤ。
That is, the present invention resides in the following (1) to (6).
(1) At least 10 to 150 parts by mass of silica as a filler and 1 to 20% by mass of a silane coupling agent with respect to silica as a zinc oxide component with respect to 100 parts by mass of a rubber component composed of at least one diene rubber. A rubber composition comprising 0.5 parts by mass or more and less than 2.0 parts by mass and containing composite zinc white as zinc oxide.
(2) The rubber composition according to (1), wherein the composite zinc white has a zinc oxide layer on the surface.
(3) The rubber composition according to (2), wherein the composite zinc white contains an inorganic metal salt inside.
(4) The rubber composition according to any one of the above (1) to (3), wherein 100 parts by mass of the rubber component is 30 parts by mass or less of natural rubber and / or synthetic isoprene rubber.
(5) A pneumatic tire using the rubber composition according to any one of (1) to (4) above.
(6) A pneumatic tire characterized by using the rubber composition according to any one of (1) to (4) in a tread.
本発明によれば、従来のシリカ配合ゴム組成物よりも、熱老化による物性変化が少なく耐摩耗性に優れたゴム組成物及びそれを用いた空気入りタイヤが提供される。 ADVANTAGE OF THE INVENTION According to this invention, the rubber composition excellent in abrasion resistance with few physical property changes by heat aging compared with the conventional silica compounded rubber composition, and a pneumatic tire using the same are provided.
以下に、本発明の実施形態を詳しく説明する。
本発明のゴム組成物は、少なくとも一種のジエン系ゴムからなるゴム成分１００質量部に対し、充填剤として少なくともシリカを１０〜１５０質量部、シランカップリング剤をシリカに対して１〜２０質量％、酸化亜鉛成分として０．５質量部以上２．０質量部未満を含み、酸化亜鉛として複合亜鉛華を含有することを特徴とするものである。
Hereinafter, embodiments of the present invention will be described in detail.
In the rubber composition of the present invention, at least 10 to 150 parts by mass of silica as a filler and 1 to 20% by mass of a silane coupling agent with respect to silica with respect to 100 parts by mass of a rubber component composed of at least one diene rubber. The zinc oxide component contains 0.5 parts by mass or more and less than 2.0 parts by mass, and zinc oxide contains composite zinc white.
本発明に用いるゴム成分としては、少なくとも一種のジエン系ゴムが挙げられる。
ジエン系ゴムとしては、例えば、天然ゴム、及び、イソプレンゴム、ブタジエンゴム、スチレン−ブタジエンゴム、クロロプレンゴム、ニトリルゴム等の合成ゴムが挙げられ、これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
これらのゴム成分１００質量部のうち、天然ゴム及び／又は合成イソプレンゴムが３０質量部以下、好ましくは、０〜２０質量部であることが好ましい。
特に、ゴム成分としては、スチレン−ブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）が好ましい。
Examples of the rubber component used in the present invention include at least one diene rubber.
Examples of the diene rubber include natural rubber and synthetic rubbers such as isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, and nitrile rubber, and these may be used alone. Two or more kinds may be used in combination.
Among 100 parts by mass of these rubber components, natural rubber and / or synthetic isoprene rubber is 30 parts by mass or less, preferably 0 to 20 parts by mass.
In particular, the rubber component is preferably styrene-butadiene rubber (SBR) or butadiene rubber (BR).
本発明に用いる充填剤としては、少なくともシリカをゴム成分１００質量部に対し、１０〜１５０質量部、好ましくは、３０〜１５０質量部含有することが望ましい。
用いるシリカは、耐摩耗性の向上、ウェットブレーキ性能を向上させるために用いられるものであり、シリカの範疇に入るものであれば、特に限定されず、例えば、シリカ、シリカが固定化されたカーボンブラック等を用いることができる。好ましくは、沈降法によるシリカが好ましく用いられる。シリカは、特にＢＥＴ比表面積が４０〜３５０ｍ２／ｇ、７０〜３００ｍ２／ｇであるものが望ましい。このようなシリカとしては、市販では東ソーシリカ社製の「ニップシールＡＱ」、デグザ社製の「Ultrasil ＶＮ３」などを挙げることができるが、これらに限定されるものではない。
これらのシリカの含有量は、１０質量部未満であると、シリカを含有せしめる効果がなく、補強性が著しく低下し、一方、１５０質量部を越えると、シリカ同士の凝集が激しくなり、分散が極度に悪化することとなる。
As a filler used in the present invention, at least silica is contained in an amount of 10 to 150 parts by mass, preferably 30 to 150 parts by mass with respect to 100 parts by mass of the rubber component.
Silica to be used is used to improve wear resistance and wet brake performance, and is not particularly limited as long as it falls within the category of silica. For example, silica and carbon on which silica is immobilized are used. Black or the like can be used. Preferably, silica by precipitation is preferably used. Silica, especially BET specific surface area of 40~350m 2 / g, it it is desirable in 70~300m 2 / g. Examples of such silica include “Nip Seal AQ” manufactured by Tosoh Silica Co., “Ultrasil VN3” manufactured by Degussa Co., and the like, but are not limited thereto.
When the content of these silicas is less than 10 parts by mass, there is no effect of containing silica, and the reinforcing property is remarkably reduced. On the other hand, when the content exceeds 150 parts by mass, the aggregation of silicas becomes severe and dispersion occurs. It will be extremely worse.
本発明に用いるシランカップリング剤は、タイヤなどのゴム部材の耐摩耗性を更に向上させることができ、例えば、従来公知のシランカップリング剤の中から任意のものを用いることができる。
具体的に用いることができるシランカップリング剤としては、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−トリメトキシシリルプロピル）テトラスルフィド、ビス（３−メチルジメ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チル）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、ビス（３−トリメトキシシリルプロピル）ジスルフィド、ビス（３−トリエトキシシリルプロピル）トリスルフィド、３−オクタノイルチオ−１−プロピルトリエトキシシラン、３−（２−メチル−１，３−プロパンジアルコキシエトキシシリル）−１−プロピルチオオクタノエート等が挙げられ、これらの市販品を用いることができる。これらのシランカップリング剤は、１種単独で使用してもよいし、２種以上を併用してもよい。
用いることができるシランカップリング剤として、市販ではＳｉ６９、Ｓｉ７５（以上、デグサ社製）、ＮＸＴシラン、ＮＸＴ Ｌｏｗ Ｖ（モメンティブパフォーマンスマテリアルズ社製）などを挙げることができるが、これらに限定されるものではない。
The silane coupling agent used in the present invention can further improve the wear resistance of a rubber member such as a tire. For example, any conventionally known silane coupling agent can be used.
Specific examples of silane coupling agents that can be used include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-methyldimethoxysilylpropyl) tetrasulfide, Bis (3-triethoxysilyltyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) trisulfide, 3-octanoylthio- Examples thereof include 1-propyltriethoxysilane, 3- (2-methyl-1,3-propanedialkoxyethoxysilyl) -1-propylthiooctanoate, and these commercial products can be used. These silane coupling agents may be used alone or in combination of two or more.
Examples of the silane coupling agent that can be used include Si69, Si75 (manufactured by Degussa), NXT silane, NXT Low V (manufactured by Momentive Performance Materials), and the like. It is not a thing.
これらのシランカップリング剤の含有量は、用いるシリカに対して、１〜２０質量％、好ましくは、５〜１５質量％であることが望ましい。
このシランカップリング剤の含有量がシリカに対して１質量％未満では、シランカップリング剤を含有せしめる効果が十分に発揮されないことがあり、一方、２０質量％を越えると、効果が更に向上せず、コスト増につながることとなる。
The content of these silane coupling agents is 1 to 20% by mass, preferably 5 to 15% by mass, based on the silica used.
When the content of the silane coupling agent is less than 1% by mass with respect to silica, the effect of containing the silane coupling agent may not be sufficiently exhibited. On the other hand, when the content exceeds 20% by mass, the effect is further improved. It will lead to cost increase.
本発明に用いる複合亜鉛華は、酸化亜鉛成分としてゴム成分１００質量部に対し、０．５質量部以上２．０質量部未満を含むものであり、ゴム組成物に配合乃至加硫時に微細化し、ゴム組成物中に広く分散し得る形態を有するものであれば特に制限はなく、目的に応じて適宜選択することができ、例えば、表面に酸化亜鉛の層を有するものなどが好適に挙げられる。
用いることができる複合亜鉛華としては、例えば、特開昭４９−１３０８９３号公報、特開昭４９−２９３００号公報、特開昭６０−２６４３２４号公報等に記載されたものなどが好適に挙げられる。
The composite zinc white used in the present invention contains 0.5 parts by mass or more and less than 2.0 parts by mass with respect to 100 parts by mass of the rubber component as a zinc oxide component, and is refined during compounding or vulcanization in the rubber composition. There is no particular limitation as long as it has a form that can be widely dispersed in the rubber composition, and it can be appropriately selected according to the purpose. For example, those having a zinc oxide layer on the surface are preferred. .
Preferred examples of the composite zinc white that can be used include those described in JP-A-49-130893, JP-A-49-29300, JP-A-60-264324, and the like. .
用いる複合亜鉛華は、表面に酸化亜鉛（亜鉛華）の層を有し、コア成分として内部に無機金属塩を含有するのが好ましい。前記無機金属塩としては、例えば、ゴム業界で無機充填材として公知のものの中から適宜選択することができ、例えば、炭酸カルシウム、硫酸カルシウムと炭酸カルシウムとの併用などが挙げられるが、本発明においては何らこれらに限定されるものではない。
この複合亜鉛華における亜鉛華と他の成分との比率、前記複合体亜鉛華における前記表面の亜鉛華の層の厚みなどは、目的に応じて適宜選択することができ、これらを適宜選択することにより、該複合亜鉛華の特性を任意に制御することができる。
また、複合亜鉛華の粒径としては、特に制限はなく目的に応じて適宜選択することができるが、大きくなると該ゴム組成物における耐摩耗性等が劣化することことがあるので、小さい方が好ましい。
市販品では、井上石灰工業社製のＭＥＴＡ−Ｚシリーズ（Ｌ４０，Ｌ５０，Ｌ６０，Ｚ１０２等）を用いることができる。
The composite zinc white used preferably has a zinc oxide (zinc white) layer on the surface and contains an inorganic metal salt as a core component. The inorganic metal salt can be appropriately selected from those known as inorganic fillers in the rubber industry, and examples thereof include calcium carbonate and a combined use of calcium sulfate and calcium carbonate. Is not limited to these.
The ratio of zinc white to other components in this composite zinc white, the thickness of the surface zinc white layer in the composite zinc white, etc. can be appropriately selected according to the purpose, and these should be selected appropriately Thus, the characteristics of the composite zinc white can be arbitrarily controlled.
Further, the particle size of the composite zinc white is not particularly limited and can be appropriately selected according to the purpose. However, when the particle size is increased, the wear resistance and the like of the rubber composition may be deteriorated. preferable.
In a commercial item, META-Z series (L40, L50, L60, Z102 etc.) by Inoue Lime Industry Co., Ltd. can be used.
この複合亜鉛華は、酸化亜鉛成分としてゴム成分１００質量部に対し、０．５質量部以上２．０質量部未満、好ましくは、加硫の活性化と耐摩耗性の観点から、０．８質量部以上１．８質量部以下含むものが望ましい。
この酸化亜鉛成分が０．５質量部未満であると、加硫反応が十分活性化できず弾性率が低下し、一方、２．０質量部以上であると、耐摩耗性改良の効果がなくなってしまう。
This composite zinc white is 0.5 parts by mass or more and less than 2.0 parts by mass with respect to 100 parts by mass of the rubber component as a zinc oxide component, preferably 0.8 from the viewpoint of vulcanization activation and wear resistance. It is desirable to contain not less than 1.8 parts by mass.
When the zinc oxide component is less than 0.5 parts by mass, the vulcanization reaction cannot be sufficiently activated and the elastic modulus is lowered, whereas when it is 2.0 parts by mass or more, the effect of improving the wear resistance is lost. End up.
本発明のゴム組成物には、上記ゴム成分、充填剤としてのシリカ、シランカップリング剤、複合亜鉛華の他、本発明の効果を損なわない範囲でゴム工業で通常使用されている硫黄、過酸化物などの架橋剤、加硫促進剤、酸化防止剤、オゾン劣化防止剤、老化防止剤、プロセス油、、ステアリン酸などを含有することができ、また、シリカ以外の充填剤として本発明の効果を損なわない範囲でカーボンブラックを含有することができる。 The rubber composition of the present invention includes the above-mentioned rubber component, silica as a filler, silane coupling agent, composite zinc white, sulfur, and excessively used in the rubber industry as long as the effects of the present invention are not impaired. It can contain cross-linking agents such as oxides, vulcanization accelerators, antioxidants, ozone degradation inhibitors, anti-aging agents, process oils, stearic acid, etc. Carbon black can be contained as long as the effect is not impaired.
本発明のゴム組成物は、常法により製造することができ、例えば、前記ゴム成分、シリカ、シランカップリング剤、複合亜鉛華などの各成分を適宜、混練りし、熱入れし、押出等することにより得られる。
混練りの条件としては、特に制限はなく、混練り装置への投入体積、ローターの回転速度、ラム圧等、混練り温度、混練り時間、混練り装置の種類等の諸条件について目的に応じて適宜選択することができる。混練り装置としては、例えば、通常ゴム組成物の混練りに用いるバンバリーミキサー、インターミックス、ニーダー等が挙げられる。
The rubber composition of the present invention can be produced by a conventional method. For example, the rubber component, silica, silane coupling agent, composite zinc white and the like are appropriately kneaded, heated, extruded, etc. Can be obtained.
The kneading conditions are not particularly limited, and various conditions such as the input volume to the kneading apparatus, the rotational speed of the rotor, the ram pressure, the kneading temperature, the kneading time, the type of the kneading apparatus, and the like depend on the purpose. Can be selected as appropriate. Examples of the kneading apparatus include a Banbury mixer, an intermix, a kneader, etc. that are usually used for kneading a rubber composition.
熱入れの条件としては、特に制限はなく、熱入れ温度、熱入れ時間、熱入れ装置等の諸条件について目的に応じて適宜選択することができる。前記熱入れ装置としては、例えば、通常ゴム組成物の熱入れに用いるロール機等が挙げられる。 The heating conditions are not particularly limited, and various conditions such as the heating temperature, the heating time, and the heating apparatus can be appropriately selected according to the purpose. Examples of the heating device include a roll machine ordinarily used for heating a rubber composition.
押出の条件としては、特に制限はなく、押出時間、押出速度、押出装置、押出温度等の諸条件について目的に応じて適宜選択することができる。押出装置としては、例えば、通常タイヤ用ゴム組成物の押出に用いる押出機等が挙げられる。前記押出温度は、適宜決定することができる。
また、押出の際、前記ゴム組成物の流動性をコントロールする目的で、アロマ系オイル、ナフテン系オイル、パラフィン系オイル、エステル系オイル等の可塑剤、液状ポリイソプレンゴム、液状ポリブタジエンゴム等の液状ポリマーなどの加工性改良剤を前記ゴム組成物に適宜添加することができる。この場合、該ゴム組成物の加硫前の粘度を低下させ、その流動性を高めることができ、極めて良好に押出を行うことができる。
Extrusion conditions are not particularly limited, and various conditions such as extrusion time, extrusion speed, extrusion apparatus, and extrusion temperature can be appropriately selected according to the purpose. As an extrusion apparatus, the extruder etc. which are normally used for extrusion of the rubber composition for tires are mentioned, for example. The extrusion temperature can be appropriately determined.
In addition, for the purpose of controlling the fluidity of the rubber composition during extrusion, a liquid such as a plasticizer such as aroma oil, naphthene oil, paraffin oil, ester oil, liquid polyisoprene rubber, liquid polybutadiene rubber, etc. A processability improver such as a polymer can be appropriately added to the rubber composition. In this case, the viscosity of the rubber composition before vulcanization can be reduced, its fluidity can be increased, and extrusion can be carried out extremely well.
このように構成されるゴム組成物では、少なくとも一種のジエン系ゴムからなるゴム成分１００重量部に対し、充填剤として少なくともシリカを１０〜１５０質量部、シランカップリング剤をシリカに対して１〜２０質量％、酸化亜鉛成分として０．５質量部以上２．０質量部未満を含み、酸化亜鉛として複合亜鉛華を含有することにより、配合時、加硫時等に微細化し、該ゴム組成物中に広く分散される結果、酸化亜鉛の分散性が向上し、通常の亜鉛華よりも少ない量で、加硫反応が活性化できるので、未反応の亜鉛華が少なく、従来のシリカ配合ゴム組成物よりも、熱老化によるゴムの硬化が抑制されるため、熱老化による物性変化が少なく、長期にわたり初期の特性が維持されることとなる。また、亜鉛華を少なくできることにより、亜鉛によるシリカとカップリング剤の反応の阻害が減少するため、補強性が上がり、耐摩耗性が改良される。 In the rubber composition configured as described above, at least 10 to 150 parts by mass of silica as a filler and 1 to 1 of silane coupling agent with respect to silica with respect to 100 parts by weight of a rubber component composed of at least one diene rubber. 20% by mass, containing 0.5 parts by mass or more and less than 2.0 parts by mass as a zinc oxide component, and containing composite zinc white as zinc oxide, the rubber composition is refined at the time of compounding, vulcanization, etc. As a result of being widely dispersed in the inside, the dispersibility of zinc oxide is improved, and the vulcanization reaction can be activated in a smaller amount than normal zinc white, so there is little unreacted zinc white and the conventional silica compound rubber composition Since the curing of rubber due to heat aging is suppressed more than that of a material, there is little change in physical properties due to heat aging, and the initial characteristics are maintained over a long period of time. In addition, since the zinc white can be reduced, the inhibition of the reaction between the silica and the coupling agent by zinc is reduced, so that the reinforcement is improved and the wear resistance is improved.
本発明のゴム組成物は、各種乗り物の空気入りタイヤ、特に空気入りタイヤのトレッドに好適に使用することができる。
本発明の空気入りタイヤにおいて、トレッド以外に前記本発明のゴム組成物が適用される部位としては、特に制限はないが、例えば、カーカスコーティングゴム、ベルトコーティングゴム、サイドゴム、ビードフィラー、ゴムチェーファーゴム、インナーライナーゴム等が挙げられる。本発明の空気入りタイヤは、前記本発明のゴム組成物を用いること以外は、特に制限はなく、公知の空気入りタイヤの構成をそのまま採用することができる。
The rubber composition of the present invention can be suitably used for pneumatic tires of various vehicles, particularly pneumatic tire treads.
In the pneumatic tire of the present invention, there are no particular limitations on the part to which the rubber composition of the present invention is applied in addition to the tread. For example, carcass coating rubber, belt coating rubber, side rubber, bead filler, rubber chafer Examples thereof include rubber and inner liner rubber. The pneumatic tire of the present invention is not particularly limited except that the rubber composition of the present invention is used, and a known pneumatic tire configuration can be employed as it is.
本発明の空気入りタイヤの一例としては、一対のビード部、該ビード部にトロイド状をなして連なるカーカス、該カーカスのクラウン部をたが締めするベルト及びトレッドを有してなる空気入りタイヤなどが好適に挙げられる。なお、本発明の空気入りタイヤは、ラジアル構造を有していてもよいし、バイアス構造を有していてもよい。
また、空気入りタイヤのトレッドは、一般に、直接路面に接地する上層のキャップ部と、このキャップ部の空気入りタイヤの内側に隣接して配置される下層のベース部とから構成されており、いわゆるキャップ・ベース構造を有する。本発明においては、該キャップ・ベース構造の一部又は全部が前記本発明のゴム組成物で形成されていてもよいが、少なくとも前記キャップ部が前記本発明のゴム組成物で形成されていることが好ましい。
As an example of the pneumatic tire of the present invention, a pair of bead portions, a carcass connected to the bead portion in a toroid form, a pneumatic tire having a belt and a tread for tightening the crown portion of the carcass, etc. Are preferable. The pneumatic tire of the present invention may have a radial structure or a bias structure.
Further, the tread of a pneumatic tire is generally composed of an upper cap portion that directly contacts the road surface, and a lower base portion that is disposed adjacent to the inside of the pneumatic tire of the cap portion, so-called It has a cap base structure. In the present invention, part or all of the cap / base structure may be formed of the rubber composition of the present invention, but at least the cap portion is formed of the rubber composition of the present invention. Is preferred.
本発明の空気入りタイヤは、その製造方法につき特に制限はないが、例えば、以下のようにして製造することができる。すなわち、まず、前記本発明のゴム組成物を調製し、該ゴム組成物を、生空気入りタイヤケースのクラウン部に予め貼り付けられた未加硫のベース部の上に貼り付ける。そして、所定のモールドで所定温度、所定圧力の下で加硫成形することにより製造することができる。
また、本発明の空気入りタイヤは、いわゆる乗用車用のみならず、トラック・バス用等の各種の乗物にも好適に適用することができる。本発明の空気入りタイヤは、前記本発明のゴム組成物を用いているため、熱履歴による経時的な硬化が効果的に抑制され、特に走行性に大きな影響を及ぼすトレッドに本発明のゴム組成物を用いた場合、耐摩耗性が向上することができる。
The pneumatic tire of the present invention is not particularly limited with respect to its production method, but can be produced, for example, as follows. That is, first, the rubber composition of the present invention is prepared, and the rubber composition is pasted on an unvulcanized base portion that is preliminarily pasted on the crown portion of the raw pneumatic tire case. And it can manufacture by vulcanization-molding with a predetermined mold under a predetermined temperature and a predetermined pressure.
The pneumatic tire of the present invention can be suitably applied not only to so-called passenger cars but also to various vehicles such as trucks and buses. Since the pneumatic tire of the present invention uses the rubber composition of the present invention, the time-dependent curing due to the heat history is effectively suppressed, and the rubber composition of the present invention is particularly effective for a tread that greatly affects running performance. When an object is used, the wear resistance can be improved.
次に、本発明を実施例及び比較例に基づいて更に詳述するが、本発明は、これらの実施例に何ら限定されるものではない。 Next, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to these examples.
〔実施例１〜４及び比較例１〜４〕
下記表１に示す配合処方のゴム組成物を常法に従って調製し、下記に示す試験方法により、ムーニー粘度、引張試験〔破断時の伸び、破断強度、３００％伸長時の応力Ｍ３００、並びに、熱老化後の破断時の伸び、破断強度及び３００％伸長時の応力Ｍ３００〕、耐摩耗性試験〔ランボーン耐摩擦性（Ｉｎｄｅｘ）〕、動的粘弾性試験〔６０℃、ｔａｎδ〕を行った。
これらの結果を下記表１に示す。
[Examples 1-4 and Comparative Examples 1-4]
A rubber composition having the formulation shown in Table 1 below was prepared according to a conventional method, and the Mooney viscosity, tensile test [elongation at break, break strength, stress M300 at 300% elongation, Elongation at break after aging, break strength and stress M300 at 300% elongation, wear resistance test [Lambourne friction resistance (Index)], dynamic viscoelasticity test [60 ° C., tan δ] were performed.
These results are shown in Table 1 below.
（ムーニー粘度の評価方法）
ＪＩＳ Ｋ６３００：２００１に準拠して、各ゴム組成物の１２５℃におけるムーニー粘度を測定した。
(Evaluation method of Mooney viscosity)
Based on JIS K6300: 2001, the Mooney viscosity at 125 ° C. of each rubber composition was measured.
引張試験方法〔破断時の伸び、破断強度、３００％伸長時の応力（Ｍ３００）、並びに、熱老化後の破断時の伸び、破断強度及び３００％伸長時の応力Ｍ３００の試験方法〕
１６０℃で２０分加硫した厚さ２ｍｍのスラブシートから、ダンベル状３号形試験片を打ち抜き、ＪＩＳ Ｋ６２５１：２００４に準拠して、破断時の伸び、破断強度、３００％伸長時の応力（Ｍ３００）を測定した。また、加硫ゴムをギアー式オーブンの中で１００℃、２４時間空気加熱劣化させた後、同様に引張試験を行ったものを熱老化後の破断時の伸び、破断強度及び３００％伸長時の応力（Ｍ３００）とした。
Tensile test method [Elongation at break, break strength, stress at 300% elongation (M300), and elongation at break after heat aging, break strength, and test method for stress M300 at 300% elongation]
A dumbbell-shaped No. 3 test piece was punched out from a slab sheet having a thickness of 2 mm vulcanized at 160 ° C. for 20 minutes, in accordance with JIS K6251: 2004, elongation at break, breaking strength, stress at 300% elongation ( M300) was measured. The vulcanized rubber was subjected to air heating deterioration in a gear-type oven at 100 ° C. for 24 hours and then subjected to a tensile test in the same manner. Stress (M300) was used.
（耐摩耗性の評価方法）
ランボーン摩耗試験機を用いて、室温下でスリップ率５０％で試験を実施した。摩耗減量を求め、下記式に従い、比較例１の摩耗量に対するインデックスで表記した。数値は大きいほど、耐摩耗性が良好であることを示す。
耐摩耗性ＩＮＤＥＥＸ＝（比較例１の摩耗量／試料の摩耗量）×１００
(Abrasion resistance evaluation method)
The test was conducted at room temperature with a slip rate of 50% using a Lambourn abrasion tester. The amount of wear loss was determined and expressed as an index for the amount of wear in Comparative Example 1 according to the following formula. It shows that abrasion resistance is so favorable that a numerical value is large.
Abrasion resistance INDEXEX = (Abrasion amount of Comparative Example 1 / Amount of sample wear) × 100
動的粘弾性試験方法〔６０℃、ｔａｎδ〕
ＪＩＳ Ｋ６３９４：２００７に基づき、東洋精機社製、スペクトロメーター（動的粘弾性測定試験機）を用い、周波数５０Ｈｚ、歪２％、６０℃で、ｔａｎδ（損失係数）を測定した。
Dynamic viscoelasticity test method [60 ° C., tan δ]
Based on JIS K6394: 2007, tan δ (loss factor) was measured at a frequency of 50 Hz, a strain of 2%, and 60 ° C. using a spectrometer (dynamic viscoelasticity tester) manufactured by Toyo Seiki Co., Ltd.
上記表１の結果から明らかなように、本発明範囲となる実施例１〜４は、本発明の範囲外となる比較例１〜４に比べて、熱老化による物性変化が少なく耐摩耗性に優れたゴム組成物であることが判明した。
個別的に見ると、シランカップリング剤としてＳｉ７５、普通亜鉛華（酸化亜鉛２種）を２．５質量部を配合した比較例１に対して、複合亜鉛華を用いた実施例１〜３は、優れた耐摩耗性を示し、かつ、熱老化後の弾性率の上昇が少なく、ゴムの硬化が抑制されていることが判った。
比較例２は、複合亜鉛の含有量が正味０．４８質量部（酸化亜鉛含量６０％、０．８質量部×０．６）であるので、加硫反応が十分活性化できないために、弾性率の低下が大きくなり、耐摩耗性が低下しまうことが判る。また、比較例３は、複合亜鉛の含有量が正味２．１質量部（酸化亜鉛含量６０％、３．５質量部×０．６）であるので、耐摩耗性の効果がなくなってしまうことが判る。更に、比較例４は、シランカップリング剤として、ＮＸＴを用いた配合であり、この場合比較例１に対して未加硫ゴムのムーニー粘度が低く作業性に優れるが、耐摩耗性がやや劣るものである。
実施例４は、比較例４の普通亜鉛華（酸化亜鉛２種）を複合亜鉛華に変えたものであり、シランカップリング剤の種類によらず、複合亜鉛華にすることにより、耐摩耗性及び熱老化によるゴムの硬化が抑制される。また、未加硫ゴムのムーニー粘度が低く、作業性に優れることがわかる。
As is clear from the results of Table 1 above, Examples 1 to 4 that are within the scope of the present invention are less wear-resistant than those of Comparative Examples 1 to 4 that are outside the scope of the present invention due to less physical property change due to heat aging. It was found to be an excellent rubber composition.
When viewed individually, Examples 1 to 3 using composite zinc white are compared with Comparative Example 1 in which 2.5 parts by mass of Si75 and ordinary zinc white (two types of zinc oxide) are blended as silane coupling agents. It was found that excellent abrasion resistance was exhibited, the increase in elastic modulus after heat aging was small, and rubber curing was suppressed.
In Comparative Example 2, since the composite zinc content is 0.48 parts by mass (zinc oxide content 60%, 0.8 parts by mass × 0.6), the vulcanization reaction cannot be sufficiently activated. It can be seen that the decrease in the rate increases and the wear resistance decreases. In Comparative Example 3, the content of composite zinc is 2.1 parts by mass (zinc oxide content 60%, 3.5 parts by mass × 0.6), so that the effect of wear resistance is lost. I understand. Further, Comparative Example 4 is a formulation using NXT as the silane coupling agent. In this case, the uncured rubber has a low Mooney viscosity and excellent workability, but the wear resistance is slightly inferior to Comparative Example 1. Is.
In Example 4, ordinary zinc white (two types of zinc oxide) in Comparative Example 4 was changed to composite zinc white, and by using composite zinc white regardless of the type of silane coupling agent, abrasion resistance was obtained. In addition, curing of the rubber due to heat aging is suppressed. It can also be seen that the unvulcanized rubber has a low Mooney viscosity and excellent workability.
本発明では、シリカ配合系のゴム組成物において、熱老化による物性変化が少なく耐摩耗性に優れたているので、タイヤ用途をはじめベルト、ホース、防振ゴムその他のゴム製品に有用となる。 In the present invention, the silica-containing rubber composition has little change in physical properties due to heat aging and is excellent in wear resistance. Therefore, it is useful for tires, belts, hoses, anti-vibration rubber and other rubber products.
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| JP2011153220A (en) * | 2010-01-27 | 2011-08-11 | Sumitomo Rubber Ind Ltd | Rubber composition for inner liner, and pneumatic tire |
| WO2013015043A1 (en) * | 2011-07-25 | 2013-01-31 | 電気化学工業株式会社 | Polychloroprene latex composition and dip-molded article |
| JP2014077050A (en) * | 2012-10-10 | 2014-05-01 | Toyo Tire & Rubber Co Ltd | Rubber composition for vibration-proof rubber and vibration-proof rubber |
| JP2015089917A (en) * | 2013-11-06 | 2015-05-11 | 東洋ゴム工業株式会社 | Rubber composition for vibration-proof rubber and vibration-proof rubber |
| WO2016067358A1 (en) * | 2014-10-28 | 2016-05-06 | 電気化学工業株式会社 | Chloroprene rubber composition, vulcanized molded article, and anti-vibration rubber |
| WO2016120991A1 (en) * | 2015-01-27 | 2016-08-04 | 東洋ゴム工業株式会社 | Rubber composition for vibration damping rubbers, and vibration damping rubber |
| JP2017008161A (en) * | 2015-06-18 | 2017-01-12 | 株式会社ブリヂストン | Anti-vibration rubber composition and anti-vibration rubber |
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| JP2017136888A (en) * | 2016-02-01 | 2017-08-10 | 住友ゴム工業株式会社 | Pneumatic tire for heavy load |
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