JP6517639B2 - Method of producing rubber composition - Google Patents
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- JP6517639B2 JP6517639B2 JP2015175954A JP2015175954A JP6517639B2 JP 6517639 B2 JP6517639 B2 JP 6517639B2 JP 2015175954 A JP2015175954 A JP 2015175954A JP 2015175954 A JP2015175954 A JP 2015175954A JP 6517639 B2 JP6517639 B2 JP 6517639B2
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- 229920001971 elastomer Polymers 0.000 title claims description 41
- 239000005060 rubber Substances 0.000 title claims description 41
- 239000000203 mixture Substances 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 61
- -1 hydrazine compound Chemical class 0.000 claims description 58
- 239000012763 reinforcing filler Substances 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920003244 diene elastomer Polymers 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 239000006229 carbon black Substances 0.000 description 21
- 235000019241 carbon black Nutrition 0.000 description 21
- 239000000377 silicon dioxide Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 238000013329 compounding Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000001993 dienes Chemical class 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
- 230000000052 comparative effect Effects 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- JYSUYJCLUODSLN-UHFFFAOYSA-N 1,3-benzothiazol-2-ylhydrazine Chemical compound C1=CC=C2SC(NN)=NC2=C1 JYSUYJCLUODSLN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 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
- 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 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
- 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
- 238000012545 processing Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 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
- 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007613 environmental effect 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 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
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 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
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 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
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゴム組成物及びその製造方法に関するものである。 The present invention relates to a rubber composition and a method for producing 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（例えば特許文献１、２参照）。 In recent years, improvement of fuel efficiency performance of a car is required for environmental protection. In order to satisfy this requirement, it has been proposed to reduce the heat buildup by blending a hydrazide compound with the rubber composition (see, for example, Patent Documents 1 and 2).
特許文献３には、発熱性を低減する方法として、ジアミン化合物で表面処理された補強性充填剤を用いることが開示されているが、補強性充填剤の分散性向上を目的として、補強性充填剤の表面を処理したものであり、他の化合物の分散性を向上させる媒介として、補強性充填剤を用いたものではない。また、耐疲労性についての記載もない。 Although Patent Document 3 discloses that a reinforcing filler surface-treated with a diamine compound is used as a method of reducing heat buildup, reinforcing filling for the purpose of improving the dispersibility of the reinforcing filler is disclosed. The surface of the agent is treated, and no reinforcing filler is used as a medium for improving the dispersibility of other compounds. There is also no mention of fatigue resistance.
発明者は、ゴム組成物に対してある特定のヒドラジン化合物を配合することにより、発熱性を低減することを見出したが、当該ヒドラジン化合物を配合することにより耐疲労性が悪化することが判明した。 The inventor found that the heat buildup was reduced by blending a specific hydrazine compound to the rubber composition, but it was found that the fatigue resistance is deteriorated by blending the hydrazine compound. .
そこで、本発明は、以上の点に鑑み、発熱性を低減しつつ、耐疲労性を向上させ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。 Then, in view of the above point, this invention aims at providing a rubber composition which can improve fatigue resistance, reducing heat buildup.
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 represent a hydrogen atom or a linear or branched alkyl group selected, R 4 represents a linear or branched alkylidene group, and R 5 is And a hydrogen atom or a linear or branched alkyl group.
当該ゴム組成物は、加硫剤及び加硫促進剤を除く他の添加剤を配合するノンプロ練り工程において、上記式（１）で表される化合物及び上記式（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で表面処理された補強性充填剤を、ジエン系ゴムに混合する工程を含む、ゴム組成物の製造方法により製造することができる。 The said rubber composition is a compound represented by said Formula (1), and a compound represented by said Formula (2) in the non-pro kneading process which mix | blends the other additive except a vulcanizing agent and a vulcanization accelerator. The reinforcing filler surface-treated with at least one hydrazine compound selected from the group consisting of the following can be produced by a method for producing a rubber composition comprising the step of mixing into a diene rubber.
上記ゴム組成物の製造方法において、ヒドラジン化合物で表面処理された補強性充填剤として、ヒドラジン化合物の融点以上の温度で、ヒドラジン化合物と補強性充填剤とを混合する表面処理方法により得られたものを用いることができる。 What was obtained by the surface treatment method of mixing the hydrazine compound and the reinforcing filler at a temperature above the melting point of the hydrazine compound as the reinforcing filler surface-treated with the hydrazine compound in the method for producing the rubber composition Can be used.
また、上記ゴム組成物の製造方法において、ヒドラジン化合物で表面処理された補強性充填剤として、ヒドラジン化合物を溶剤に溶解した処理液と補強性充填剤とを混合する表面処理方法により得られたものを用いることもできる。 Further, in the above method for producing a rubber composition, as a reinforcing filler surface-treated with a hydrazine compound, one obtained by a surface treatment method in which a treating solution in which a hydrazine compound is dissolved in a solvent and a reinforcing filler are mixed. Can also be used.
本発明によれば、ヒドラジン化合物で表面処理された補強性充填剤を配合することにより、発熱性を低減しつつ、耐疲労性を向上させることができる。 According to the present invention, it is possible to improve fatigue resistance while reducing heat generation by blending a reinforcing filler surface-treated with a hydrazine compound.
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、ジエン系ゴムと、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で表面処理された補強性充填剤を含有するものである。 The rubber composition according to the present embodiment is a diene rubber, and at least one hydrazine compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) It contains a surface-treated reinforcing filler.
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 diene-based rubbers used as rubber components in the rubber composition include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), and styrene-isoprene copolymer. Rubber, butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR) and the like can be mentioned. These diene rubbers can be used alone or in combination 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。 As a diene rubber, from the group which consists of a hydroxyl group, an amino group, a carboxyl group, an alkoxy group, an alkoxy silyl group, an epoxy group, a thiol group, a tin containing group, and halogen in the molecular terminal or molecular chain of what was enumerated above. By introducing at least one selected functional group, a modified diene-based rubber modified with the functional group may be used.
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、ｎ−ペンチル基等が挙げられる。 In the above-mentioned hydrazine compound used in the present embodiment, the compound represented by the above 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 selected. The carbon number of the alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group and the like.
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。 The hydrazine compound represented by the above formula (1) is not particularly limited, but for example, 2-hydrazinobenzothiazole represented by the following formula can be preferably used.
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 said Formula (2) is a hydrazine compound which has the basic skeleton which benzothiazole and hydrazone couple | bonded. R 4 in the above formula (2) represents a linear or branched alkylidene group. The carbon number of the alkylidene group is not particularly limited, but is preferably an alkylidene group having 1 to 5 carbon atoms, and more preferably 2 to 4 carbon atoms. Specific examples of the alkylidene group include methylidene group, ethylidene group, propylidene group, propan-2-ylidene group, butylidene group and the like. R 5 represents a hydrogen atom or a linear or branched alkyl group. The carbon number of the alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. 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 said Formula (2), For example, acetone benzo thiazolyl 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 said Formula (1) or (2) can be used combining any one sort or two sorts or more.
ヒドラジン化合物を配合することにより、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。 The heat buildup can be reduced by blending the hydrazine compound, and the reason is considered as follows. That is, the benzene ring in the hydrazine compound interacts with the reinforcing filler (eg, interacts with the graphite structure of carbon in carbon black), and the hydrazine or hydrazone located opposite to the benzene ring is It is thought that the molecular motion of the polymer can be suppressed and the heat buildup can be reduced by reacting with the polymer radical in the diene rubber generated during the kneading and connecting the polymer and the reinforcing filler.
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発熱性の低減効果に優れ、１０質量部以下であれば、発熱性の低減効果が十分得られるからである。 The blending amount of the hydrazine compound is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the diene rubber. More preferably, it is 0.5 to 3 parts by mass. If the content is 0.1 parts by mass or more, the effect of reducing heat generation is excellent, and if the amount is 10 parts by mass or less, the effect of reducing heat generation can be sufficiently obtained.
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（表面処理された補強性充填剤のヒドラジン化合物を除く補強性充填剤と表面処理されていない補強性充填剤の合計量）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 a 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 (the total amount of the reinforcing filler excluding the hydrazine compound in the surface-treated reinforcing filler and the non-surface-treated reinforcing filler) is not particularly limited, and, for example, the above diene system The amount is preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass, and still more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the rubber.
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 types 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 based rubbers, 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 still more 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 sedimentation silica or wet gel silica is preferably used. When silica is compounded, the compounding amount is preferably 10 to 50 parts by mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of diene rubber, from the viewpoint of the balance of tan δ of the rubber and reinforcing properties. It is a mass part.
ヒドラジン化合物で表面処理された補強性充填剤とは、上記ヒドラジン化合物を表面の全部又は一部に有する補強性充填剤のことである。 The reinforcing filler surface-treated with a hydrazine compound is a reinforcing filler having the above-mentioned hydrazine compound on all or part of the surface.
ヒドラジン化合物で表面処理された補強性充填剤に用いる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が、カーボンブラック単独であることがより好ましい。 As a reinforcing filler used for a reinforcing filler surface-treated with a hydrazine compound, 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, but carbon black alone is more preferable.
ゴム組成物中に含まれる補強性充填剤の上記配合量のうち、全てをヒドラジン化合物で表面処理してもよく、一部をヒドラジン化合物で表面処理してもよい。該ゴム組成物中に含まれる補強性充填剤のうち１０質量％以上（より好ましくは３０質量％以上、さらに好ましくは５０質量％以上）が、ヒドラジン化合物で表面処理された補強性充填剤由来であることが好ましい。 Among the above-mentioned compounding amounts of the reinforcing filler contained in the rubber composition, all may be surface-treated with a hydrazine compound, and a part may be surface-treated with a hydrazine compound. Among the reinforcing fillers contained in the rubber composition, 10% by mass or more (more preferably 30% by mass or more, more preferably 50% by mass or more) is derived from the reinforcing filler surface-treated with a hydrazine compound Is preferred.
ヒドラジン化合物で表面処理された補強性充填剤の配合量は、特に限定されないが、ジエン系ゴム１００質量部に対して、１０〜１６０質量部であることが好ましく、２０〜１１０質量部であることがより好ましく、３０〜９０質量部であることがさらに好ましい。 Although the compounding quantity of the reinforcing filler surface-treated with the hydrazine compound is not specifically limited, It is preferable that it is 10-160 mass parts with respect to 100 mass parts of diene based rubbers, and it is 20-110 mass parts. Is more preferable, and 30 to 90 parts by mass is more preferable.
補強性充填剤の表面処理方法は、特に限定されないが、例えば、ヒドラジン化合物の融点以上の温度で、ヒドラジン化合物と補強性充填剤とを混合する表面処理方法や、ヒドラジン化合物を溶剤に溶解した処理液と補強性充填剤とを混合する表面処理方法が挙げられる。 The surface treatment method of the reinforcing filler is not particularly limited. For example, the surface treatment method in which the hydrazine compound and the reinforcing filler are mixed at a temperature higher than the melting point of the hydrazine compound, or the treatment in which the hydrazine compound is dissolved in a solvent The surface treatment method which mixes a liquid and a reinforcing filler is mentioned.
融点以上の温度としては、融点以上であれば特に限定されないが、融点より１０〜５０℃高い温度であることが好ましく、１０〜４０℃高い温度であることがより好ましく、１０〜３０℃高い温度であることがさらに好ましい。 The temperature above the melting point is not particularly limited as long as it is above the melting point, but is preferably 10 to 50 ° C. higher than the melting point, more preferably 10 to 40 ° C. higher, and 10 to 30 ° C. higher It is further preferred that
融点以上の温度で、ヒドラジン化合物と補強性充填剤とを混合する方法としては、特に限定されないが、例えば、融点以上の温度に設定した、ヘンシェルミキサー等の混合機にヒドラジン化合物と補強性充填剤を投入し、混合することが挙げられる。 The method for mixing the hydrazine compound and the reinforcing filler at a temperature above the melting point is not particularly limited. For example, the hydrazine compound and the reinforcing filler are added to a mixer such as a Henschel mixer set at a temperature above the melting point. And mixing.
ヒドラジン化合物を溶解させる溶剤としては、ヒドラジン化合物が溶解し、補強性充填剤と混合後、蒸発させることができれば特に限定されないが、ヒドラジン化合物を溶解させる点から極性有機溶剤であることが好ましく、例えば、テトラヒドロフラン、アセトン等が挙げられる。 The solvent for dissolving the hydrazine compound is not particularly limited as long as the hydrazine compound is dissolved and can be evaporated after being mixed with the reinforcing filler, but it is preferably a polar organic solvent from the viewpoint of dissolving the hydrazine compound, for example , Tetrahydrofuran, acetone and the like.
ヒドラジン化合物を溶剤に溶解した処理液の濃度としては、特に限定されないが、５〜３０質量％であることが好ましい。 Although it does not specifically limit as a density | concentration of the process liquid which melt | dissolved the hydrazine compound in the solvent, It is preferable that it is 5-30 mass%.
ヒドラジン化合物を溶剤に溶解した処理液と補強性充填剤とを混合する方法としては、特に限定されないが、例えば、ヘンシェルミキサー等の混合機を用いて、予め投入した補強性充填剤に処理液を噴霧して混合することが挙げられる。上記溶剤は、処理液と補強性充填剤との混合時に加熱し蒸発させてもよく、混合後、別の工程で加熱し蒸発させてもよい。 The method for mixing the processing solution in which the hydrazine compound is dissolved in the solvent and the reinforcing filler is not particularly limited. For example, using a mixer such as a Henschel mixer, the processing solution may be added to the reinforcing filler previously added. Spraying and mixing may be mentioned. The solvent may be heated and evaporated at the time of mixing of the treatment liquid and the reinforcing filler, or may be heated and evaporated at another step after mixing.
ヒドラジン化合物で表面処理された補強性充填剤を調製する際のヒドラジン化合物の配合量は、特に限定されないが、カーボンブラック１００質量部に対して、１〜３０質量部であることが好ましく、１〜２０質量部であることがより好ましく、１〜１０質量部であることがさらに好ましい。 Although the compounding quantity of the hydrazine compound at the time of preparing the reinforcing filler surface-treated with the hydrazine compound is not specifically limited, It is preferable that it is 1-30 mass parts with respect to 100 mass parts of carbon blacks, The amount is more preferably 20 parts by mass, and further preferably 1 to 10 parts by mass.
ヒドラジン化合物で補強性充填剤の表面を処理することにより、発熱性を低減しつつ、耐疲労性を向上させることができるが、その理由は次のように考えられる。すなわち、ヒドラジン化合物は融点が高く、分散性に問題があったが、予め補強性充填剤の表面に処理することにより、ヒドラジン化合物の分散性が向上し、耐疲労性を向上させることができると考えられる。また、上述の通り、ヒドラジン化合物は、補強性充填剤との相互作用により、発熱性の低減効果を発揮すると考えられるが、予め補強性充填剤の表面に処理することにより、発熱性の低減効果がさらに向上すると考えられる。 By treating the surface of the reinforcing filler with a hydrazine compound, it is possible to improve the fatigue resistance while reducing the heat buildup, and the reason is considered as follows. That is, although the hydrazine compound has a high melting point and there is a problem with dispersibility, when the surface of the reinforcing filler is treated in advance, the dispersibility of the hydrazine compound can be improved and the fatigue resistance can be improved. Conceivable. Further, as described above, the hydrazine compound is considered to exert the effect of reducing the heat buildup by the interaction with the reinforcing filler, but the heat buildup reduction effect is obtained by treating the surface of the reinforcing filler in advance. Is expected to improve further.
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 flower, stearic acid, softener, plasticizer, wax, anti-aging agent, vulcanized used in the ordinary rubber industry Compounding chemicals such as the agent and the vulcanization accelerator can be appropriately blended within the usual 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 powdery sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur and highly dispersible sulfur, which are not particularly limited, but the compounding amount thereof is 100 parts by mass of diene rubber. The amount is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass. 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 based 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、ヒドラジン化合物で表面処理された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 said rubber composition can be knead | mixed and prepared in accordance with a conventional method using mixers, such as a Banbury mixer used normally, a kneader, and a roll. For example, in the first mixing step (non-pro kneading step), the diene rubber is added with a reinforcing filler surface-treated with a hydrazine compound, and other additives other than the vulcanizing agent and the vulcanization accelerator The rubber composition can be prepared by kneading and then adding and kneading a vulcanizing agent and a vulcanization accelerator in the final mixing step (pro-kneading step) to the obtained mixture.
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 obtained rubber composition can be used for treads, sidewalls, rim strips, covering rubbers such as belt cords and carcass cords, inner liners, beads of various tires such as pneumatic tires for passenger cars, heavy load tires such as trucks and buses. It can be used in sites 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。 Hereinafter, although the example of the present invention is shown, the present invention is not limited to these examples.
ヘンシェルミキサーを使用し、下記表１に示す配合（質量部）に従い、表面処理方法Ａ又はＢによりカーボンブラックとヒドラジン化合物を混合し、表面処理カーボンブラックを調製した。 Using a Henschel mixer, according to the composition (parts by mass) shown in Table 1 below, carbon black and a hydrazine compound were mixed by surface treatment method A or B to prepare surface treated carbon black.
表面処理方法Ａ、Ｂの詳細は以下の通りである。
・表面処理方法Ａ：ヘンシェルミキサーに、カーボンブラックとヒドラジン化合物を投入し、２２０℃にて、混合処理する。
・表面処理方法Ｂ：ヒドラジン化合物をテトラヒドロフランに対して１０質量％となるように溶解させた後、あらかじめカーボンブラックを投入したヘンシェルミキサー内（８０℃）に噴霧し、混合処理する。なお、テトラヒドロフランは、混合時に蒸発する。
The details of the surface treatment methods A and B are as follows.
Surface treatment method A: A carbon black and a hydrazine compound are charged into a Henschel mixer and mixed at 220 ° C.
Surface treatment method B: After a hydrazine compound is dissolved in tetrahydrofuran so as to be 10% by mass, the mixture is sprayed in a Henschel mixer (80 ° C.) to which carbon black has been charged in advance and mixed. Tetrahydrofuran evaporates upon mixing.
バンバリーミキサーを使用し、下記表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 Table 2 below, at first mixing stage, the components except sulfur and the vulcanization accelerator are added and mixed (discharge temperature = 160 ° C), then obtained The rubber composition was prepared by adding and mixing sulfur and a vulcanization accelerator in the final mixing stage (discharge temperature = 90 ° C) to the mixture obtained.
表１，２中の各成分の詳細は以下の通りである。
・ＮＲ：ＲＳＳ＃３
・ＢＲ：ランクセス（株）製「ＣＢ２２」
・カーボンブラック：ＩＳＡＦ，東海カーボン（株）製「シースト６」
・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」
・表面処理カーボンブラック：上記調製例で得られたカーボンブラック
・プロセスオイル：ＪＸ日鉱日石エネルギー（株）製「プロセスＮＣ１４０」
・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」
・硫黄：鶴見化学工業（株）製「粉末硫黄」
・加硫促進剤：住友化学（株）製「ソクシノールＣＺ」
The details of each component in Tables 1 and 2 are as follows.
・ NR: RSS # 3
・ BR: "CB22" manufactured by LANXESS Corporation
・ Carbon black: ISAF, Tokai Carbon Co., Ltd. “Siest 6”
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.
Surface-treated carbon black: Carbon black process oil obtained in the above preparation example: "Process NC 140" manufactured by JX Nippon Oil & Energy Corporation
・ Zinc flower: “Zinc flower No. 3” manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Stearic acid: Kao Corporation "Lunack S-20"
・ Anti-aging agent: Ouchi Shinko Chemical Co., Ltd. product "Nocrac 6C"
Sulfur: "Powder sulfur" manufactured by Tsurumi Chemical Industries, Ltd.
・ Vulcanization accelerator: "Succinol CZ" manufactured by Sumitomo Chemical Co., Ltd.
得られたゴム組成物について、発熱性及び耐疲労性を評価した。評価方法は次の通りである。 The heat buildup and fatigue resistance of the obtained rubber composition 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、比較例１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: According to JIS K 6394, with respect to a test piece vulcanized at 150 ° C. × 30 minutes, the loss coefficient tan δ is measured under the conditions of temperature 50 ° C., static strain 5%, dynamic strain 1%, frequency 50 Hz, The value of Comparative Example 1 is represented by an index of 100. The smaller the index, the smaller the tan δ and the lower the heat build-up, indicating that the fuel economy is excellent.
・耐疲労性：ＪＩＳ Ｋ６２６０に準拠して、１５０℃×３０分で加硫した試験片について、デマチャ屈曲亀裂成長試験を行った。測定温度は２３℃の条件下で行い、亀裂成長が２ｍｍになるまでの回数を測定し、比較例１の値を１００とした指数で表示した。指数が大きいほど耐疲労性に優れることを示す。 Fatigue resistance: A demature flex crack growth test was conducted on a test piece vulcanized at 150 ° C. for 30 minutes in accordance with JIS K6260. The measurement was carried out at a temperature of 23 ° C., and the number of times for the crack growth to reach 2 mm was measured, and the index of Comparative Example 1 was 100. The larger the index, the better the fatigue resistance.
結果は、表２に示す通りであり、比較例１と実施例１、４との対比、比較例２と実施例２，５との対比、比較例３と実施例３，６との対比より、ヒドラジン化合物を補強性充填剤の表面に処理することで、耐疲労性を向上させることができ、発熱性がさらに低減することが認められた。 The results are as shown in Table 2. Comparison of Comparative Example 1 with Examples 1 and 4, Comparison of Comparative Example 2 with Examples 2 and 5, Comparison of Comparative Example 3 with Examples 3 and 6 The fatigue resistance can be improved by treating the surface of the reinforcing filler with a hydrazine compound, and it has been recognized that the heat buildup can be further reduced.
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 load 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.
Claims (3)
As a reinforcing filler surface-treated with a hydrazine compound, one obtained by a surface treatment method in which a treating solution in which the hydrazine compound is dissolved in a solvent and a reinforcing filler are mixed is used. The manufacturing method of the rubber composition as described in 1 .
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| US3860602A (en) * | 1967-12-26 | 1975-01-14 | Firestone Tire & Rubber Co | Hydrazinium salts of mercaptobenzothiazole |
| JPS61250042A (en) * | 1985-04-30 | 1986-11-07 | Bridgestone Corp | Rubber composition with high wear resistance |
| JPH10158435A (en) * | 1996-12-02 | 1998-06-16 | Yokohama Rubber Co Ltd:The | Tire rubber composition |
| JP2004339276A (en) * | 2003-05-13 | 2004-12-02 | Yokohama Rubber Co Ltd:The | Rubber composition |
| FR2969165B1 (en) * | 2010-12-21 | 2014-06-06 | Michelin Soc Tech | COMPOSITION BASED ON NATURAL RUBBER AND CARBON BLACK COMPRISING HYDRAZIDE, HYDRAZONE OR POLYAMINO |
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