JP2017031281A - Rubber composition and pneumatic tire - Google Patents
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 39
- 239000005060 rubber Substances 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 hydrazine compound Chemical class 0.000 claims abstract description 26
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 21
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 8
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- JYSUYJCLUODSLN-UHFFFAOYSA-N 1,3-benzothiazol-2-ylhydrazine Chemical compound C1=CC=C2SC(NN)=NC2=C1 JYSUYJCLUODSLN-UHFFFAOYSA-N 0.000 claims description 4
- TZHQLYDPJQZYNF-UHFFFAOYSA-N n-(propan-2-ylideneamino)-1,3-benzothiazol-2-amine Chemical compound C1=CC=C2SC(NN=C(C)C)=NC2=C1 TZHQLYDPJQZYNF-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- 0 C*1NNc2ccccc2S[C@@]1NN(*)* Chemical compound C*1NNc2ccccc2S[C@@]1NN(*)* 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000007857 hydrazones Chemical class 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
本発明は、ゴム組成物及びそれを用いた空気入りタイヤに関するものである。 The present invention relates to a rubber composition and a pneumatic tire using the same.
近年、環境保護のため、車の低燃費性能の向上が求められている。この要求を満足させるため、ゴム組成物に対してヒドラジド化合物を配合することにより、発熱性を低減することが提案されているが（例えば特許文献１、２参照）、ヒドラジド化合物を配合することにより、スコーチ性が悪化する問題があった。 In recent years, in order to protect the environment, there has been a demand for improvement in low fuel consumption performance of vehicles. In order to satisfy this requirement, it has been proposed to reduce exothermicity by blending a hydrazide compound with a rubber composition (see, for example, Patent Documents 1 and 2), but by blending a hydrazide compound. There was a problem that the scorch property deteriorated.
そこで、スコーチ性の悪化を抑制しつつ、ゴム組成物の加工性（ムーニー粘度）及び発熱性を低減する技術が求められている。 Therefore, there is a demand for a technique for reducing the processability (Mooney viscosity) and heat build-up of the rubber composition while suppressing the deterioration of the scorch property.
なお、特許文献３に係る発明は、グリップ性能と生産性の問題を解決する目的でヒドラジド化合物を配合したものであり、発熱性の低減を目的としたものではない。 In addition, the invention which concerns on patent document 3 mix | blends the hydrazide compound in order to solve the problem of grip performance and productivity, and is not aimed at the reduction of exothermic property.
本発明に係るヒドラジン化合物はいずれも、特許文献１〜３には開示されていないものである。 None of the hydrazine compounds according to the present invention are disclosed in Patent Documents 1 to 3.
本発明は、以上の点に鑑み、耐スコーチ性能を損なうことなく、ムーニー粘度及び発熱性を低減することができるゴム組成物を提供することを目的とする。 An object of this invention is to provide the rubber composition which can reduce Mooney viscosity and exothermic property, without impairing scorch-proof performance in view of the above point.
本発明に係るゴム組成物は、上記課題を解決するために、ジエン系ゴム、補強性充填剤、並びに下記式（１）で表される化合物及び下記式（２）で表される化合物からなる群より選択された少なくとも１種のヒドラジン化合物を含有するゴム組成物とする。 In order to solve the above problems, the rubber composition according to the present invention comprises a diene rubber, a reinforcing filler, a compound represented by the following formula (1), and a compound represented by the following formula (2). The rubber composition contains at least one hydrazine compound selected from the group.
式中、Ｒ1〜Ｒ3は、それぞれ独立して選ばれる水素原子又は直鎖状もしくは分岐状のアルキル基を示し、Ｒ4は、直鎖状又は分岐状のアルキリデン基を示し、Ｒ5は、水素原子又は直鎖状もしくは分岐状のアルキル基を示す。 In the formula, R 1 to R 3 each independently represents a hydrogen atom or a linear or branched alkyl group, R 4 represents a linear or branched alkylidene group, and R 5 represents Represents a hydrogen atom or a linear or branched alkyl group.
当該ヒドラジン化合物としては、２−ヒドラジノベンゾチアゾール及び／又はアセトンベンゾチアゾリル−２−ヒドラゾンを好ましく用いることができる。 As the hydrazine compound, 2-hydrazinobenzothiazole and / or acetone benzothiazolyl-2-hydrazone can be preferably used.
当該ヒドラジン化合物の配合量は、ジエン系ゴム１００質量部に対して、０．１〜１０質量部であってもよい。また補強性充填剤の配合量は、ジエン系ゴム１００質量部に対して、１０〜１５０質量部であってもよい。 The amount of the hydrazine compound may be 0.1 to 10 parts by mass with respect to 100 parts by mass of the diene rubber. The compounding amount of the reinforcing filler may be 10 to 150 parts by mass with respect to 100 parts by mass of the diene rubber.
本発明の一実施形態に係る空気入りタイヤは、当該ゴム組成物からなるものである。 The pneumatic tire according to one embodiment of the present invention is made of the rubber composition.
本発明によれば、ジエン系ゴムに、補強性充填剤、及び特定の構造を持つヒドラジン化合物を配合することにより、耐スコーチ性能を損なうことなく、ムーニー粘度及び発熱性を低減することができる。 According to the present invention, Mooney viscosity and heat build-up can be reduced without impairing scorch resistance performance by blending a diene rubber with a reinforcing filler and a hydrazine compound having a specific structure.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本実施形態に係るゴム組成物は、ジエン系ゴム、補強性充填剤、並びに下記式（１）で表される化合物及び下記式（２）で表される化合物からなる群より選択された少なくとも１種のヒドラジン化合物を含有してなるものである。 The rubber composition according to this embodiment is at least one selected from the group consisting of a diene rubber, a reinforcing filler, a compound represented by the following formula (1), and a compound represented by the following formula (2). It contains a kind of hydrazine compound.
当該ゴム組成物において、ゴム成分として用いられるジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、スチレン−イソプレン共重合体ゴム、ブタジエン−イソプレン共重合体ゴム、スチレン−イソプレン−ブタジエン共重合体ゴム、アクリロニトリルブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、ブチルゴム（ＩＩＲ）などが挙げられる。これらジエン系ゴムは、いずれか１種を単独で、又は２種以上ブレンドして用いることができる。上記ゴム成分は、好ましくは、天然ゴム、ブタジエンゴム、スチレンブタジエンゴム、又はこれらの２種以上のブレンドである。 Examples of the diene rubber used as the rubber component in the rubber composition include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), and styrene-isoprene copolymer. Examples thereof include rubber, butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), and butyl rubber (IIR). These diene rubbers can be used alone or in a blend of two or more. The rubber component is preferably natural rubber, butadiene rubber, styrene butadiene rubber, or a blend of two or more thereof.
ジエン系ゴムとしては、上記で列挙したものの分子末端又は分子鎖中において、水酸基、アミノ基、カルボキシル基、アルコキシ基、アルコキシシリル基、エポキシ基、チオール基、スズ含有基、及びハロゲンからなる群から選択された少なくとも１種の官能基が導入されることで、当該官能基により変性された変性ジエン系ゴムを用いてもよい。 The diene rubber is selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an alkoxy group, an alkoxysilyl group, an epoxy group, a thiol group, a tin-containing group, and a halogen in the molecular terminal or molecular chain of those listed above. By introducing at least one selected functional group, a modified diene rubber modified with the functional group may be used.
補強性充填剤としては、カーボンブラック及び／又はシリカを用いることが好ましい。すなわち、補強性充填剤は、カーボンブラック単独でも、シリカ単独でも、カーボンブラックとシリカの併用でもよい。好ましくは、カーボンブラック、又はカーボンブラックとシリカの併用である。補強性充填剤の配合量は、特に限定されず、例えば上記ジエン系ゴム１００質量部に対して１０〜１５０質量部であることが好ましく、より好ましくは２０〜１００質量部であり、さらに好ましくは３０〜８０質量部である。 As the reinforcing filler, it is preferable to use carbon black and / or silica. That is, the reinforcing filler may be carbon black alone, silica alone, or a combination of carbon black and silica. Preferably, carbon black or a combination of carbon black and silica is used. The compounding amount of the reinforcing filler is not particularly limited, and for example, it is preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass, and further preferably 100 parts by mass of the diene rubber. 30 to 80 parts by mass.
上記カーボンブラックとしては、特に限定されず、公知の種々の品種を用いることができる。カーボンブラックの配合量としては、ジエン系ゴム１００質量部に対して１０〜８０質量部程度の範囲が好ましく、より好ましくは１０〜７０質量部である。補強性充填剤中のカーボンブラックの割合は、１０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、５０質量％以上であることがさらに好ましい。 The carbon black is not particularly limited, and various known varieties can be used. As a compounding quantity of carbon black, the range of about 10-80 mass parts is preferable with respect to 100 mass parts of diene rubber, More preferably, it is 10-70 mass parts. The proportion of carbon black in the reinforcing filler is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more.
シリカとしても、特に限定されないが、湿式沈降法シリカや湿式ゲル法シリカなどの湿式シリカが好ましく用いられる。シリカを配合する場合、その配合量としては、ゴムのｔａｎδのバランスや補強性などの観点からジエン系ゴム１００質量部に対して１０〜５０質量部であることが好ましく、より好ましくは１５〜５０質量部である。 The silica is not particularly limited, but wet silica such as wet precipitation silica or wet gel silica is preferably used. When silica is blended, the blending amount is preferably 10 to 50 parts by weight, more preferably 15 to 50 parts with respect to 100 parts by weight of the diene rubber from the viewpoint of balance of tan δ of rubber and reinforcement. Part by mass.
シリカを配合する場合、スルフィドシラン、メルカプトシランなどのシランカップリング剤を併用することが好ましく、その配合量はシリカ配合量に対して２〜２０質量％であることが好ましい。 When silica is blended, a silane coupling agent such as sulfide silane or mercaptosilane is preferably used in combination, and the blending amount is preferably 2 to 20% by mass with respect to the silica blending amount.
本実施形態で用いる上記ヒドラジン化合物において、上記式（１）で表される化合物は、ベンゾチアゾールとヒドラジンが結合した基本骨格を持つヒドラジン化合物である。上記式（１）中のＲ1〜Ｒ3は、それぞれ独立に選ばれる水素原子又は直鎖状もしくは分岐状のアルキル基を示す。アルキル基の炭素数は特に限定されないが、炭素数１〜５のアルキル基であることが好ましく、より好ましくは炭素数１〜３である。アルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、又はｎ−ペンチル基等が挙げられる。 In the hydrazine compound used in the present embodiment, the compound represented by the formula (1) is a hydrazine compound having a basic skeleton in which benzothiazole and hydrazine are bonded. R 1 to R 3 in the above formula (1) each independently represent a hydrogen atom or a linear or branched alkyl group. Although carbon number of an alkyl group is not specifically limited, It is preferable that it is a C1-C5 alkyl group, More preferably, it is C1-C3. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group.
上記式（１）で表されるヒドラジン化合物としては、特に限定されないが、例えば下記式で表される２−ヒドラジノベンゾチアゾールを好ましく用いることができる。 Although it does not specifically limit as a hydrazine compound represented by the said Formula (1), For example, 2-hydrazino benzothiazole represented by a following formula can be used preferably.
上記式（２）で表される化合物は、ベンゾチアゾールとヒドラゾンが結合した基本骨格を持つヒドラジン化合物である。上記式（２）中のＲ4は、直鎖状又は分岐状のアルキリデン基を示す。アルキリデン基の炭素数は特に限定されないが、炭素数１〜５のアルキリデン基であることが好ましく、より好ましくは炭素数２〜４である。アルキリデン基の具体例としては、メチリデン基、エチリデン基、プロピリデン基、プロパン−２−イリデン基、ブチリデン基等が挙げられる。Ｒ5は、水素原子又は直鎖状もしくは分岐状のアルキル基を示す。アルキル基の炭素数は特に限定されないが、炭素数１〜５のアルキル基であることが好ましく、より好ましくは炭素数１〜３である。アルキル基の具体例は、上記式（１）中のＲ1〜Ｒ3と同じである。 The compound represented by the above formula (2) is a hydrazine compound having a basic skeleton in which benzothiazole and hydrazone are bonded. R 4 in the above formula (2) represents a linear or branched alkylidene group. Although carbon number of an alkylidene group is not specifically limited, It is preferable that it is a C1-C5 alkylidene group, More preferably, it is C2-C4. Specific examples of the alkylidene group include a methylidene group, an ethylidene group, a propylidene group, a propane-2-ylidene group, and a butylidene group. R 5 represents a hydrogen atom or a linear or branched alkyl group. Although carbon number of an alkyl group is not specifically limited, It is preferable that it is a C1-C5 alkyl group, More preferably, it is C1-C3. Specific examples of the alkyl group are the same as R 1 to R 3 in the above formula (1).
上記式（２）で表されるヒドラジン化合物としては、特に限定されないが、例えば下記式で表されるアセトンベンゾチアゾリル−２−ヒドラゾンを好ましく用いることができる。 Although it does not specifically limit as a hydrazine compound represented by the said Formula (2), For example, the acetone benzothiazolyl-2-hydrazone represented by a following formula can be used preferably.
上記式（１）又は（２）で表されるヒドラジン化合物は、いずれか１種又は２種以上組み合わせて用いることができる。 The hydrazine compound represented by the above formula (1) or (2) can be used alone or in combination of two or more.
当該ヒドラジン化合物を配合することにより、耐スコーチ性能を損なうことなく、発熱性を低減することができるが、その理由は次のように考えられる。すなわち、このヒドラジン化合物中のベンゼン環が、補強性充填剤と相互作用し（例えば、カーボンブラック中のカーボンのグラファイト構造と相互作用し）、またベンゼン環とは反対に位置するヒドラジン又はヒドラゾンが、混練り中に発生したジエン系ゴム中のポリマーラジカルと反応し、ポリマーと補強性充填剤をつなぎ合わせることで、ポリマーの分子運動を抑制し、発熱性を低減できるものと考えられる。また、定かではないが、当該ヒドラジン化合物は、化学構造上、加硫反応に影響を与えにくいため、耐スコーチ性能を維持できるものと考えられる。 By adding the hydrazine compound, the exothermic property can be reduced without impairing the scorch resistance, and the reason is considered as follows. That is, the benzene ring in the hydrazine compound interacts with the reinforcing filler (for example, interacts with the graphite structure of carbon in carbon black), and hydrazine or hydrazone located opposite to the benzene ring By reacting with the polymer radical in the diene rubber generated during the kneading and joining the polymer and the reinforcing filler, it is considered that the molecular motion of the polymer can be suppressed and the exothermic property can be reduced. Moreover, although it is not certain, the hydrazine compound is considered to be able to maintain the scorch resistance performance because it hardly affects the vulcanization reaction due to its chemical structure.
当該ヒドラジン化合物の配合量は、特に限定されないが、ジエン系ゴム１００質量部に対して、０．１〜１０質量部であることが好ましく、０．１〜５質量部であることがより好ましく、０．５〜３質量部であることがさらに好ましい。０．１質量部以上であればムーニー粘度及び発熱性の低減効果に優れ、１０質量部以下であれば、耐スコーチ性能を損なうことなく、ムーニー粘度及び発熱性の十分な低減効果が得られるからである。 Although the compounding quantity of the said hydrazine compound is not specifically limited, It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of diene rubbers, and it is more preferable that it is 0.1-5 mass parts, More preferably, it is 0.5-3 mass parts. If it is 0.1 parts by mass or more, the Mooney viscosity and exothermic effect are excellent, and if it is 10 parts by mass or less, the Mooney viscosity and exothermic effect can be sufficiently reduced without impairing the scorch resistance. It is.
本実施形態に係るゴム組成物には、上記した各成分に加え、通常のゴム工業で使用されているプロセスオイル、亜鉛華、ステアリン酸、軟化剤、可塑剤、ワックス、老化防止剤、加硫剤、加硫促進剤などの配合薬品類を通常の範囲内で適宜配合することができる。 In the rubber composition according to the present embodiment, in addition to the above-described components, process oil, zinc white, stearic acid, softener, plasticizer, wax, anti-aging agent, vulcanization used in ordinary rubber industry Compounding chemicals such as an agent and a vulcanization accelerator can be appropriately blended within a normal range.
上記加硫剤としては、粉末硫黄、沈降硫黄、コロイド硫黄、不溶性硫黄、高分散性硫黄などの硫黄成分が挙げられ、特に限定するものではないが、その配合量はジエン系ゴム１００質量部に対して０．１〜１０質量部であることが好ましく、より好ましくは０．５〜５質量部である。また、加硫促進剤の配合量としては、ジエン系ゴム１００質量部に対して０．１〜７質量部であることが好ましく、より好ましくは０．５〜５質量部である。 Examples of the vulcanizing agent include sulfur components such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Although not particularly limited, the blending amount is 100 parts by mass of diene rubber. It is preferable that it is 0.1-10 mass parts with respect to it, More preferably, it is 0.5-5 mass parts. Moreover, as a compounding quantity of a vulcanization accelerator, it is preferable that it is 0.1-7 mass parts with respect to 100 mass parts of diene rubbers, More preferably, it is 0.5-5 mass parts.
当該ゴム組成物は、通常に用いられるバンバリーミキサーやニーダー、ロール等の混合機を用いて、常法に従い混練し調製することができる。例えば、第一混合段階（ノンプロ練り工程）で、ジエン系ゴムに対し、ヒドラジン化合物、補強性充填剤とともに、加硫剤及び加硫促進剤を除く他の添加剤を添加して混練し、次いで、得られた混合物に、最終混合段階（プロ練り工程）で加硫剤及び加硫促進剤を添加して混練することにより、ゴム組成物を調製することができる。 The rubber composition can be prepared by kneading according to a conventional method using a commonly used mixer such as a Banbury mixer, a kneader, or a roll. For example, in the first mixing stage (non-pro kneading process), the diene rubber is kneaded with hydrazine compound, reinforcing filler, and other additives excluding vulcanizing agent and vulcanization accelerator, A rubber composition can be prepared by adding a vulcanizing agent and a vulcanization accelerator to the obtained mixture and kneading in a final mixing step (pro kneading step).
得られたゴム組成物は、乗用車用空気入りタイヤ、トラックやバス等の重荷重用タイヤ等の各種タイヤのトレッド、サイドウォール、リムストリップ、ベルトコードやカーカスコード等の被覆用ゴム、インナーライナー、ビードフィラー等の部位に用いることができる。さらに本発明に係るゴム組成物は、防振ゴム、ベルト、ホースその他工業品等の用途にも用いることができる。 The resulting rubber composition is used for various tire treads such as pneumatic tires for passenger cars, tires for heavy loads such as trucks and buses, sidewalls, rim strips, rubbers for coverings such as belt cords and carcass cords, inner liners and beads. It can be used for parts such as fillers. Furthermore, the rubber composition according to the present invention can also be used for applications such as anti-vibration rubber, belts, hoses and other industrial products.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
バンバリーミキサーを使用し、下記表１，２に示す配合（質量部）に従い、まず、第一混合段階で、硫黄と加硫促進剤を除く成分を添加混合し（排出温度＝１６０℃）、次いで、得られた混合物に、最終混合段階で硫黄と加硫促進剤を添加混合して（排出温度＝９０℃）、ゴム組成物を調製した。 Using a Banbury mixer, according to the composition (parts by mass) shown in Tables 1 and 2 below, first, in the first mixing stage, components other than sulfur and vulcanization accelerator are added and mixed (discharge temperature = 160 ° C.), then In the final mixing stage, sulfur and a vulcanization accelerator were added and mixed with the obtained mixture (discharge temperature = 90 ° C.) to prepare a rubber composition.
表１，２中の各成分の詳細は以下の通りである。 Details of each component in Tables 1 and 2 are as follows.
・ＮＲ：ＲＳＳ＃３
・ＳＢＲ：ＪＳＲ（株）製「ＳＢＲ１５０２」
・カーボンブラック：ＩＳＡＦ，東海カーボン（株）製「シースト６」
・シリカ：エボニック社製「ウルトラジルＶＮ３」
・プロセスオイル：ＪＸ日鉱日石エネルギー（株）製「プロセスＮＣ１４０」
・シランカップリング剤：エボニック社製「Ｓｉ６９」
・亜鉛華：三井金属鉱業（株）製「亜鉛華３号」
・ステアリン酸：花王（株）製「ルナックＳ−２０」
・老化防止剤：大内新興化学工業（株）製「ノクラック６Ｃ」
・ヒドラジド化合物：東京化成工業（株）製「安息香酸ヒドラジド」
・ヒドラジン化合物Ａ：東京化成工業（株）製「２−ヒドラジノベンゾチアゾール」
・ヒドラジン化合物Ｂ：東京化成工業（株）製「アセトンベンゾチアゾリル−２−ヒドラゾン」
・硫黄：鶴見化学工業（株）製「粉末硫黄」
・加硫促進剤１：住友化学（株）製「ソクシノールＣＺ」
・加硫促進剤２：大内新興化学工業（株）製「ノクセラーＤ」
・ NR: RSS # 3
・ SBR: "SBR1502" manufactured by JSR Corporation
・ Carbon black: ISAF, Tokai Carbon Co., Ltd. “Seast 6”
・ Silica: “Ultrasil VN3” manufactured by Evonik
Process oil: “Process NC140” manufactured by JX Nippon Oil & Energy
Silane coupling agent: “Si69” manufactured by Evonik
・ Zinc flower: "Zinc flower 3" manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Stearic acid: “Lunac S-20” manufactured by Kao Corporation
Anti-aging agent: “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
・ Hydrazide compound: “benzoic acid hydrazide” manufactured by Tokyo Chemical Industry Co., Ltd.
Hydrazine compound A: “2-hydrazinobenzothiazole” manufactured by Tokyo Chemical Industry Co., Ltd.
Hydrazine compound B: “Acetone benzothiazolyl-2-hydrazone” manufactured by Tokyo Chemical Industry Co., Ltd.
・ Sulfur: “Powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.
・ Vulcanization accelerator 1: “Sokushinol CZ” manufactured by Sumitomo Chemical Co., Ltd.
・ Vulcanization accelerator 2: “Noxeller D” manufactured by Ouchi Shinsei Chemical Co., Ltd.
得られたゴム組成物について、発熱性、ムーニー粘度、及び耐スコーチ性能を評価した。評価方法は次の通りである。 About the obtained rubber composition, exothermic property, Mooney viscosity, and scorch-proof performance were evaluated. The evaluation method is as follows.
・発熱性：ＪＩＳ Ｋ６３９４に準拠して、１５０℃×３０分で加硫した試験片について、温度５０℃、静歪み５％、動歪み１％、周波数５０Ｈｚの条件で損失係数ｔａｎδを測定し、表１においては比較例１の値を１００とし、表２においては比較例３の値を１００とした指数で表示した。指数が小さいほどｔａｎδが小さく、発熱性が低いため低燃費性に優れることを示す。 Exothermic property: In accordance with JIS K6394, for a test piece vulcanized at 150 ° C. × 30 minutes, the loss factor tan δ was measured under the conditions of a temperature of 50 ° C., a static strain of 5%, a dynamic strain of 1%, and a frequency of 50 Hz. In Table 1, the value of Comparative Example 1 was set to 100, and in Table 2, the value of Comparative Example 3 was set to 100. The smaller the index is, the smaller tan δ is, and the lower the heat generation, the better the fuel efficiency.
・ムーニー粘度：ＪＩＳ Ｋ６３００に準拠して、（株）東洋精機製作所製ロータレスムーニー測定機を用い、未加硫ゴムを１００℃で１分間予熱後、４分後のトルク値をムーニー単位で測定した値であり、表１においては比較例１の値を１００とし、表２においては比較例３の値を１００とした指数で表示した。指数が小さいほどムーニー粘度が低く、加工性に優れることを示す。 ・ Mooney viscosity: Based on JIS K6300, using a rotorless Mooney measuring machine manufactured by Toyo Seiki Seisakusho Co., Ltd., preheated unvulcanized rubber at 100 ° C for 1 minute, and then measured the torque value after 4 minutes in Mooney units. In Table 1, the value of Comparative Example 1 was set to 100, and in Table 2, the value of Comparative Example 3 was set to 100. The smaller the index, the lower the Mooney viscosity and the better the workability.
・耐スコーチ性能：ＪＩＳ Ｋ６３００に準拠して、（株）東洋精機製作所製ロータレスムーニー測定機を用い、未加硫ゴム組成物を１２５℃で１分間予熱後、最低粘度Ｖｍより５ムーニー単位上昇するのに要した時間ｔ５を測定し、表１においては比較例１の値を１００とし、表２においては比較例３の値を１００とした指数で表示した。指数が大きいほど、スコーチタイムが長く、耐スコーチ性能に優れることを意味する。 -Scorch resistance performance: In accordance with JIS K6300, using a rotorless Mooney measuring machine manufactured by Toyo Seiki Seisakusho Co., Ltd., preheat the unvulcanized rubber composition at 125 ° C for 1 minute, then increase by 5 Mooney units from the minimum viscosity Vm The time t5 required for the measurement was measured, and in Table 1, the value of Comparative Example 1 was set to 100, and in Table 2, the value of Comparative Example 3 was set to 100. A larger index means longer scorch time and better scorch resistance.
結果は、表１，２に示す通りであり、実施例１〜６と比較例１との対比、及び実施例７〜１２と比較例３との対比より、ヒドラジン化合物を配合することで、耐スコーチ性能を損なうことなく、発熱性及びムーニー粘度を低減することができた。また、比較例１と比較例２との対比、及び比較例３と比較例４との対比より、ヒドラジド化合物を配合することで、発熱性を低減することができたものの、ムーニー粘度が上昇し、耐スコーチ性能が悪化した。 The results are as shown in Tables 1 and 2. From the comparison between Examples 1 to 6 and Comparative Example 1 and the comparison between Examples 7 to 12 and Comparative Example 3, the hydrazine compound was blended to improve resistance. The exothermic property and Mooney viscosity could be reduced without impairing the scorch performance. Moreover, although the exothermic property was able to be reduced by mix | blending a hydrazide compound from the comparison with the comparative example 1 and the comparative example 2 and the comparison with the comparative example 3 and the comparative example 4, Mooney viscosity rose. The scorch resistance performance deteriorated.
本発明に係るゴム組成物は、乗用車用空気入りタイヤ、トラックやバス等の重荷重用タイヤ等の各種タイヤに用いることができる。 The rubber composition according to the present invention can be used for various tires such as pneumatic tires for passenger cars and heavy duty tires such as trucks and buses.
さらに本発明に係るゴム組成物は、防振ゴム、ベルト、ホースその他工業品等の用途にも用いることができる。 Furthermore, the rubber composition according to the present invention can also be used for applications such as anti-vibration rubber, belts, hoses and other industrial products.
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