JP2009256439A - Rubber composition - Google Patents
Rubber composition Download PDFInfo
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- JP2009256439A JP2009256439A JP2008105970A JP2008105970A JP2009256439A JP 2009256439 A JP2009256439 A JP 2009256439A JP 2008105970 A JP2008105970 A JP 2008105970A JP 2008105970 A JP2008105970 A JP 2008105970A JP 2009256439 A JP2009256439 A JP 2009256439A
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- silica
- rubber
- rubber composition
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 62
- 239000005060 rubber Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 44
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 abstract description 19
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 19
- 230000003014 reinforcing effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 6
- 238000002444 silanisation Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- -1 silica compound Chemical class 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 125000003386 piperidinyl group Chemical group 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920003986 novolac Polymers 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
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- YRVRZDIWEXCJSX-UHFFFAOYSA-N 2-methyl-3-(3-triethoxysilylpropyl)thiirane-2-carboxylic acid Chemical compound CCO[Si](OCC)(OCC)CCCC1SC1(C)C(O)=O YRVRZDIWEXCJSX-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- MFNWUMRYUYUAAV-UHFFFAOYSA-N 4-(3-trimethoxysilylpropyl)-3H-1,3-benzothiazole-2-thione Chemical compound CO[Si](OC)(OC)CCCC1=CC=CC2=C1N=C(S2)S MFNWUMRYUYUAAV-UHFFFAOYSA-N 0.000 description 1
- ZZOXWBGGPBLVNQ-UHFFFAOYSA-N CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC Chemical compound CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC ZZOXWBGGPBLVNQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000012658 bimolecular nucleophilic substitution Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- HBACTRZJLWXFBM-UHFFFAOYSA-N s-[[methyl(4-trimethoxysilylbutyl)carbamoyl]trisulfanyl] n-methyl-n-(4-trimethoxysilylbutyl)carbamothioate Chemical compound CO[Si](OC)(OC)CCCCN(C)C(=O)SSSSC(=O)N(C)CCCC[Si](OC)(OC)OC HBACTRZJLWXFBM-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明はシリカ配合ゴム組成物に関し、更に詳しくはジフェニルグアニジン（ＤＰＧ）を配合することなく、又はＤＰＧの配合量を減らして、ゴム組成物の加硫速度、シリカの分散性、補強性及び粘弾性特性を向上させることができるゴム組成物及びそれを用いた空気入りタイヤに関する。 The present invention relates to a silica-containing rubber composition, and more specifically, without adding diphenylguanidine (DPG) or reducing the amount of DPG, the vulcanization rate, silica dispersibility, reinforcing property and viscosity of the rubber composition. The present invention relates to a rubber composition capable of improving elastic characteristics and a pneumatic tire using the same.
自動車の高性能化、高機能化に伴い、タイヤへの要求性能は年々高度になってきている。その一つとして、湿潤路面でのグリップ力、即ちウェットグリップ力を維持しながらも、低燃費性も兼ね備えたタイヤの開発が強く望まれている。従来、タイヤトレッドに用いられてきた補強性充填剤は、カーボンブラックであったが、最近では上記の要望からカーボンブラックと比較して良好な低ヒステリシスロス性とウェットスキッド性を有する超微粒子シリカが、タイヤトレッド用の補強性充填剤として用いられ始めてきた（例えば特許文献１参照）。しかしながら、シリカ系充填剤は、表面上に親水性シラノール基を有するため、カーボンブラックに比較してゴム分子に対する親和性が劣り、そのためシリカ系充填剤は、低ヒステリシスロス性とウェットスキッド性には優れるものの、補強性や耐摩耗性においてはカーボンブラックには及ばないという問題があった。そこで、シリカ系充填剤の補強性をカーボンブラックと同程度にするために、ゴム分子とシリカ粒子表面を化学的に結び付け、補強性を増大させることを可能とするシランカップリング剤の併用がなされてきた（例えば特許文献２参照）。代表的な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）テトラスルフィドが挙げられる。 As the performance and functionality of automobiles increase, the required performance of tires has become higher year by year. As one of them, there is a strong demand for the development of a tire that has low fuel consumption while maintaining a grip force on a wet road surface, that is, a wet grip force. Conventionally, the reinforcing filler used in tire treads has been carbon black. However, recently, ultrafine silica particles having better low hysteresis loss and wet skid properties than carbon black have been used due to the above demand. It has begun to be used as a reinforcing filler for tire treads (see, for example, Patent Document 1). However, since silica-based fillers have hydrophilic silanol groups on the surface, they have poor affinity for rubber molecules compared to carbon black, so silica-based fillers have low hysteresis loss and wet skid properties. Although excellent, there was a problem that the reinforcing property and wear resistance were not as good as those of carbon black. Therefore, in order to make the reinforcing property of the silica-based filler the same as that of carbon black, a silane coupling agent that can increase the reinforcing property by chemically linking the rubber molecules and the silica particle surface has been used. (For example, see Patent Document 2). A typical silane coupling agent is bis (3-triethoxysilylpropyl) tetrasulfide.
然るに、シリカ含有ゴム組成物にシランカップリング剤を配合する場合、シリカとシランカップリング剤とのカップリング反応が不十分であると、シリカの良好な分散性は得られず、またカップリング反応が過剰であるとゴム焼けを招いて品質が低下するという問題があった。そのため、従来の混練方法では、混練作業中に熱電対などで常時ゴム温度を測定してゴム温度を一定範囲に維持しながら、経験的に設定した時間内に混練操作をしていたが、シリカとシランカップリング剤の反応量がバッチ毎に必ずしも一定するとは限らず、シリカ配合の混合加工性と所望のゴム特性のバランス化は難易度が高い。 However, when a silane coupling agent is added to the silica-containing rubber composition, if the coupling reaction between the silica and the silane coupling agent is insufficient, good dispersibility of the silica cannot be obtained, and the coupling reaction If the amount is excessive, there is a problem that the quality of the rubber deteriorates due to rubber burning. Therefore, in the conventional kneading method, the kneading operation was carried out within an empirically set time while constantly measuring the rubber temperature with a thermocouple during the kneading operation and maintaining the rubber temperature within a certain range. The amount of reaction between the silane coupling agent and the silane coupling agent is not always constant for each batch, and it is difficult to balance the mixing processability of the silica compound and the desired rubber properties.
ところで、シリカ配合ゴム組成物には従来加硫促進剤としてジフェニルグアニジン（ＤＰＧ）が多用されてきたが、ゴム／スチールコード接着への悪影響が懸念されており、ＤＰＧの使用量を削減する動きがある。しかしながら、シリカ多量配合系ゴム組成物ではＤＰＧの使用量を削減すると、加硫速度が低下、ゴム中のシリカの分散が悪化するという問題があった。 By the way, diphenylguanidine (DPG) has been widely used as a vulcanization accelerator in silica compounded rubber compositions, but there is concern about adverse effects on rubber / steel cord adhesion, and there is a movement to reduce the amount of DPG used. is there. However, in the silica-rich rubber composition, there is a problem that when the amount of DPG used is reduced, the vulcanization rate is lowered and the dispersion of silica in the rubber is deteriorated.
特許文献３にはジエン系ゴムに、ピペリジン骨格を有する２級アミン化合物である2,2,6,6-テトラメチルピペリジン又はその誘導体を配合することにより、高いグリップ性能を有するゴム組成物を得ることができる旨が開示されているが、この文献には当該化合物をシリカと共に配合することは記載されておらず、従ってシリカの分散性や加工性に関する記載もない。 In Patent Document 3, a rubber composition having high grip performance is obtained by blending 2,2,6,6-tetramethylpiperidine or a derivative thereof, which is a secondary amine compound having a piperidine skeleton, into a diene rubber. However, this document does not describe that the compound is blended with silica, and therefore does not describe the dispersibility and processability of silica.
特許文献４にはジエンエラストマーポリマーに有機性第４級アンモニウム塩を、シリカやその他の添加剤と共に、配合することによって二次加硫促進剤が添加されないときでも許容加硫速度を維持しながら良好な機械的特性を示す加硫製品が得られる旨記載されている。この文献には、１，４−ジアザビシクロ［２，２，２］オクタンを有機性第４級アンモニウム塩の調製に使用することは記載されているが（実施例１及び２参照）、１，５−ジアザビシクロ［４，３，０］ノネン−５（ＤＢＮ）をゴム組成物に配合することは全く記載されていない。 Patent Document 4 discloses that an organic quaternary ammonium salt is mixed with a diene elastomer polymer together with silica and other additives while maintaining an allowable vulcanization speed even when a secondary vulcanization accelerator is not added. It is stated that a vulcanized product exhibiting excellent mechanical properties can be obtained. Although this document describes the use of 1,4-diazabicyclo [2,2,2] octane for the preparation of organic quaternary ammonium salts (see Examples 1 and 2), 1,5 There is no mention of blending diazabicyclo [4,3,0] nonene-5 (DBN) into the rubber composition.
従って、本発明の目的は、ゴム組成物中のＤＰＧの使用量を削減するか、又はＤＰＧを使用することなく、加硫速度の低下やゴム中のシリカの分散悪化の問題を解決したゴム組成物を提供することにある。 Accordingly, an object of the present invention is to reduce the amount of DPG used in a rubber composition or to solve a problem of a decrease in vulcanization rate and deterioration of dispersion of silica in rubber without using DPG. To provide things.
本発明に従えば、ジエン系ゴム１００重量部、シリカ２０〜１２０重量部、硫黄含有シランカップリング剤がシリカの３〜１５重量％及び式（Ｉ）： According to the present invention, 100 parts by weight of diene rubber, 20 to 120 parts by weight of silica, 3 to 15% by weight of silica containing sulfur-containing silane coupling agent and formula (I):
を有する１，５−ジアザビシクロ［４，３，０］ノネン−５（ＤＢＮ）及び／又はその塩を含んでなるゴム組成物が提供される。 A rubber composition comprising 1,5-diazabicyclo [4,3,0] nonene-5 (DBN) and / or a salt thereof having the formula:
本発明に従えば、更に、前記ゴム組成物を空気入りタイヤ、特にそのキャップトレッドに用いた空気入りタイヤが提供される。 According to the present invention, there is further provided a pneumatic tire, particularly a pneumatic tire using the rubber composition for its cap tread.
本発明によれば、シリカ配合ゴム組成物に、ピペリジン骨格を有する前記式（Ｉ）の１，５−ジアザビシクロ［４．３．０］ノネン−５（ＤＢＮ）及び／又はその塩をシリカ配合ゴム組成物に配合することにより、ゴム組成物の加硫速度やシリカの分散、補強性、粘弾性特性を向上させ、かつＤＰＧの削減が可能となる。 According to the present invention, 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) of formula (I) having a piperidine skeleton and / or a salt thereof is added to a silica-containing rubber composition. By blending in the composition, the vulcanization rate of the rubber composition, the dispersion of silica, the reinforcing properties and the viscoelastic properties can be improved, and the DPG can be reduced.
本発明者らは、前記課題を解決すべく研究を進めた結果、ジエン系ゴムにシリカを配合したゴム組成物に、前記式（Ｉ）のＤＢＮ及び／又はその塩を配合することにより、ゴム組成物の加硫速度やシリカの分散、補強性、更には粘弾性特性を向上させることができ、かつＤＰＧの一部又は全部の代替が可能となることを見出した。 As a result of advancing research to solve the above problems, the present inventors have formulated a rubber composition in which a silica is blended with a diene rubber and a rubber composition by blending the DBN of the formula (I) and / or a salt thereof. It has been found that the vulcanization rate of the composition, silica dispersion, reinforcing properties, and viscoelastic properties can be improved, and a part or all of DPG can be substituted.
本発明によれば、ジエン系ゴム１００重量部に対し、シリカを２０〜１２０重量部、好ましくは４０〜８０重量部、硫黄含有シランカップリング剤をシリカ重量の３〜１５重量％、好ましくは５〜１０重量％並びに前記化学式（Ｉ）で表わされるＤＢＮ及び／又はその塩を配合する。 According to the present invention, the silica is 20 to 120 parts by weight, preferably 40 to 80 parts by weight, and the sulfur-containing silane coupling agent is 3 to 15% by weight, preferably 5 to 100 parts by weight of the diene rubber. 10 wt% and DBN represented by the above chemical formula (I) and / or a salt thereof are blended.
本発明のゴム組成物に使用するジエン系ゴムとしては、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリルブタジエンゴム、エチレン−プロピレン−ジエン共重合体ゴム、スチレン−イソプレン共重合体ゴム、イソプレン−ブタジエン共重合体ゴムなどをあげることができ、これらは単独又は任意のブレンドで使用することができる。 Examples of the diene rubber used in the rubber composition of the present invention include natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber, ethylene. -Propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, isoprene-butadiene copolymer rubber and the like can be mentioned, and these can be used alone or in any blend.
本発明のゴム組成物に使用するシリカとしては、従来からタイヤその他用のゴム組成物として配合されている任意のシリカとすることができる。シリカの配合量が少ないと強度と耐摩耗が不十分なだけでなく、シリカ配合によるウェット摩擦力と低発熱性の両立も不十分となるので好ましくなく、逆に多いと混合加工性の低下や発熱性の増加となるので好ましくない。 The silica used in the rubber composition of the present invention can be any silica conventionally blended as a tire or other rubber composition. When the amount of silica is small, not only the strength and wear resistance are insufficient, but also the wet friction force and low heat build-up due to the silica are insufficient, which is not preferable. This is not preferable because it increases heat generation.
本発明のゴム組成物に使用する硫黄含有シランカップリング剤としては、これも従来からシリカと共に配合されるもののうち、好ましくは分子中に硫黄原子を含有する任意のものとすることができ、例えば３−トリメトキシシリルプロピル−Ｎ，Ｎ−ジメチルカルバモイル−テトラスルフィド、トリメトキシシリルプロピル−メルカプトベンゾチアゾールテトラスルフィド、トリエトキシシリルプロピル−メタクリレート−モノスルフィド、ジメトキシメチルシリルプロピル−Ｎ，Ｎ−ジメチルチオカルバモイル−テトラスルフィド、ビス−〔３−（トリエトキシシリル）−プロピル〕テトラスルフィド、ビス−〔３−（トリエトキシシリル）−プロピル〕ジスルフィド、３−メルカプトプロピルトリメトキシシランなどを用いることができる。これらは公知の化合物であり、数多くの市販品が利用できる。このシランカップリング剤の配合量が少ないと、シリカの補強性不足によるゴム強度や耐摩耗性の低下が起こるおそれがあるので好ましくなく、逆に多いと加工中のヤケが発生するおそれがあるので好ましくない。 As the sulfur-containing silane coupling agent used in the rubber composition of the present invention, among those conventionally blended with silica, it can be preferably any containing a sulfur atom in the molecule, for example, 3-trimethoxysilylpropyl-N, N-dimethylcarbamoyl-tetrasulfide, trimethoxysilylpropyl-mercaptobenzothiazole tetrasulfide, triethoxysilylpropyl-methacrylate-monosulfide, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl -Tetrasulfide, bis- [3- (triethoxysilyl) -propyl] tetrasulfide, bis- [3- (triethoxysilyl) -propyl] disulfide, 3-mercaptopropyltrimethoxysilane, etc. can be used. . These are known compounds, and many commercially available products can be used. If the amount of this silane coupling agent is small, the rubber strength and wear resistance may be lowered due to insufficient reinforcement of silica, and if it is too large, there is a risk of burning during processing. It is not preferable.
前記式（Ｉ）で表わされるＤＢＮ及び／又はその塩の配合量は、それら単独で、又はＤＰＧと併用する場合には、それとの合計量で、ゴム１００重量部に対して、好ましくは０．１〜１０重量部、更に好ましくは０．５〜３重量部であり、これらの式（Ｉ）で表わされるＤＢＮ及び／又はその塩はシラニゼーション反応（即ち、シリカとシランカップリング剤との反応）の段階でシリカ及びシランカップリング剤と同時にゴム組成物中に添加し、混練配合するのが好ましい。ＤＢＮの塩としては、例えばオクチル酸塩、ＤＢＮ−フェノールノボラック樹脂塩などがあげられる。 The compounding amount of DBN represented by the above formula (I) and / or a salt thereof, alone or in combination with DPG, is preferably 0.1% relative to 100 parts by weight of rubber. 1 to 10 parts by weight, more preferably 0.5 to 3 parts by weight. These DBNs represented by the formula (I) and / or their salts are subjected to silanization reaction (that is, between silica and a silane coupling agent). It is preferable to add to the rubber composition at the same time as the silica and the silane coupling agent and knead and mix in the stage of reaction. Examples of the DBN salt include octylate, DBN-phenol novolak resin salt, and the like.
式（Ｉ）で表わされるＤＢＮ又はその塩は公知の化合物であり、市販品を使用することができるので特別に合成する必要はなく、例えばサンアプロ社よりＤＢＮとして、またＵ−ＣＡＴ１１０２（ＤＢＮのオクチル酸塩）、ＤＢＮ−フェノールノボラック樹脂塩（Ｕ−ＣＡＴ８８１）などとして市販されている。 DBN represented by the formula (I) or a salt thereof is a known compound, and it is not necessary to synthesize specially since it can be used as a commercial product. For example, DBN from San Apro and U-CAT1102 (octyl of DBN) Acid salt), DBN-phenol novolac resin salt (U-CAT881) and the like.
ＤＰＧは、シリカを配合したゴム組成物において、以下の利点があるため、従来から一般的に使用されている。
（１）２次加硫促進剤として使用することで、シリカの酸性度による加硫速度低下を抑制できる。
（２）シリカ表面との相互作用によりシリカ粒子同士の凝集を防いで、ペイン効果（即ち、シリカ間の相互作用による貯蔵弾性率の増加）を低減することができ、またシラニゼーション促進により補強性を上げることができる。
Since DPG has the following advantages in a rubber composition containing silica, it has been generally used.
(1) By using as a secondary vulcanization accelerator, a decrease in vulcanization speed due to the acidity of silica can be suppressed.
(2) By preventing the silica particles from agglomerating due to interaction with the silica surface, the Payne effect (that is, increase in storage elastic modulus due to the interaction between silica) can be reduced, and reinforcement by promoting silanization Can raise the sex.
しかしながら、前述の如く、ゴム／スチールコード接着への悪影響が懸念されており、ＤＰＧ使用量の削減もしくはその代替品の探索が課題となっている。 However, as described above, there are concerns about adverse effects on rubber / steel cord adhesion, and there is a problem of reducing the amount of DPG used or searching for alternatives.
本発明者らは、ＤＰＧの代替品としてアミン系化合物でｐＫａ値が大きいものに着目した。シラニゼーション反応（シリカ−シランカップリング剤の反応）では、シランカップリング剤の加水分解速度が重要となる。アミン化合物は、この加水分解を2分子的求核置換反応（SN2）で促進する。特に３級アミン化合物は、窒素原子は全てアルキル鎖と結合しており、アルキル基は、電子供与性が高く窒素原子の求核性を著しく向上させる。その結果、シラニゼーションを促進する。また、一般的にシリカ表面の酸性度（pH）は６〜７程度であり、シラニゼーション反応促進のためにはシリカ表面pHよりｐＫａ値を大きくすることが重要となる。 The inventors of the present invention focused on an amine compound having a large pKa value as an alternative to DPG. In the silanization reaction (silica-silane coupling agent reaction), the hydrolysis rate of the silane coupling agent is important. The amine compound promotes this hydrolysis by a bimolecular nucleophilic substitution reaction (SN2). In particular, in the tertiary amine compound, all nitrogen atoms are bonded to an alkyl chain, and the alkyl group has a high electron donating property and remarkably improves the nucleophilicity of the nitrogen atom. As a result, it promotes silanization. In general, the acidity (pH) of the silica surface is about 6 to 7, and in order to promote silanization reaction, it is important to make the pKa value larger than the silica surface pH.
本発明で用いるＤＢＮは、ｐＫａが約１２．９である。これらの化合物は高い求核性によりシラニゼーション反応を促進し、ペイン効果を低減することが可能である。また、これらの化合物は、ＤＰＧと置き換えて使用しても、加硫速度に悪影響を及ぼさない点も大きなメリットのひとつである。 The DBN used in the present invention has a pKa of about 12.9. These compounds can promote silanization reaction due to high nucleophilicity, and can reduce the Payne effect. In addition, one of the great merits is that these compounds do not adversely affect the vulcanization rate even if they are used in place of DPG.
本発明に係るゴム組成物には、前記した成分に加えて、カーボンブラックなどのその他の補強剤（フィラー）、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用、その他のゴム組成物用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the components described above, the rubber composition according to the present invention includes other reinforcing agents (fillers) such as carbon black, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, plastics Various additives that are generally blended for tires such as additives and other rubber compositions can be blended, and these additives are kneaded into a composition by a general method to be vulcanized or crosslinked. Can be used to do. The blending amounts of these additives may be conventional conventional blending amounts as long as the object of the present invention is not adversely affected.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
標準例及び実施例１〜８
サンプルの調製
表Ｉに示す配合において、加硫促進剤と硫黄を除く成分を１．５リットルの密閉型ミキサーで９分間混練し、１５０℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄をオープンロールで混練し、ゴム組成物を得た。このゴム組成物を用いて以下に示す試験法で未加硫物性を評価した。結果は表Ｉに示す。
Standard Examples and Examples 1-8
Sample preparation In the formulation shown in Table I, the components other than the vulcanization accelerator and sulfur were kneaded for 9 minutes with a 1.5 liter hermetic mixer, and when the temperature reached 150 ° C, a master batch was obtained. A vulcanization accelerator and sulfur were kneaded with this master batch with an open roll to obtain a rubber composition. Using this rubber composition, unvulcanized physical properties were evaluated by the following test methods. The results are shown in Table I.
表Ｉに示す成分以外の配合量は以下の通りである。
ＳＢＲ：ＬＡＮＸＣＥＳＳ社製ＶＳＬ−５０２５ ＨＭ−１（Ｏｉｌ ｅｘｔｅｎｄｅｄ）（１０３．１重量部、ゴム分７５重量部）
ＢＲ：Ｎｉｐｐｏｎ Ｚｅｏｎ（株）製Ｎｉｐｐｏｌ ＢＲ １２２０（２５重量部）
シリカ：Ｒｈｏｄｉａ社製Ｚｅｏｓｉｌ １１６５ＭＰ（８０重量部）
シランカップリング剤：Ｄｅｇｕｓｓａ社製Ｓｉ６９（６．４重量部）
オイル：出光興産（株）製ダイアナプロセス ＡＨ−２４（４．３２重量部）
ＺｎＯ：正同化学工業（株）製酸化亜鉛 ３種（２．５重量部）
ステアリン酸：日本油脂（株）製ビーズステアリン酸 ＹＲ（２．５重量部）
硫黄：細井化学工業（株）製油処理硫黄（１．４重量部、硫黄分１．１重量部）
加硫促進剤：大内新興化学工業（株）製ＣＢＳ ノクセラーＣＺ−Ｇ（１．７重量部）
The compounding amounts other than the components shown in Table I are as follows.
SBR: VSL-5025 HM-1 (Oil extended) manufactured by LANXCESS (103.1 parts by weight, 75 parts by weight of rubber)
BR: Nippon BR 1220 (25 parts by weight) manufactured by Nippon Zeon Co., Ltd.
Silica: Zeosil 1165MP (80 parts by weight) manufactured by Rhodia
Silane coupling agent: Si69 (6.4 parts by weight) manufactured by Degussa
Oil: Idemitsu Kosan Co., Ltd. Diana Process AH-24 (4.32 parts by weight)
ZnO: 3 types of zinc oxide (2.5 parts by weight) manufactured by Shodo Chemical Industry Co., Ltd.
Stearic acid: Beads stearic acid YR (2.5 parts by weight) manufactured by NOF Corporation
Sulfur: Hosei Chemical Industry Co., Ltd. oil-treated sulfur (1.4 parts by weight, sulfur content 1.1 parts by weight)
Vulcanization accelerator: Ouchi Shinsei Chemical Co., Ltd. CBS Noxeller CZ-G (1.7 parts by weight)
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１６０℃で３０分間加硫して加硫ゴムシートを調製し、以下に示す試験法で加硫ゴムの物性を測定した。結果は表Ｉに示す。 Next, the resulting rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 30 minutes to prepare a vulcanized rubber sheet. The physical properties of the vulcanized rubber were measured by the following test methods. It was measured. The results are shown in Table I.
ゴム物性評価試験法
以下の方法で評価し、結果はすべて標準例１の値を１００として指数表示した。この値が大きいほど結果が良好であることを示す。
Ｔ９５：ＯＤＲにて測定温度１６０℃で測定した（ＡＳＴＭ−Ｄ２０８４に準拠）。
分散性：αテクノロジー社製ＲＰＡ２０００を用い、未加硫ゴムを用いて歪せん断応力Ｇ’を測定した。歪０．２８％〜１００．０％までのＧ’を測定し、その差異（Ｇ’０．２８％（ＭＰａ）−Ｇ’１００．０％（ＭＰａ））を求めた。
）
補強性：Ｍ３００／Ｍ１００を補強性の評価として使用した（ＪＩＳ−Ｋ６２５１に準拠）。
転がり抵抗：東洋精機製作所製粘弾性スペクトロメータを用い、初期歪１０％、振幅±２％、周波数２０Ｈｚの条件下で、６０℃における損失正接（ｔａｎδ）を測定した。
Rubber physical property evaluation test method The evaluation was carried out by the following method, and all results were expressed as an index with the value of standard example 1 being 100. The larger this value, the better the result.
T95: Measured with ODR at a measurement temperature of 160 ° C. (according to ASTM-D2084).
Dispersibility: Strain shear stress G ′ was measured using RPA2000 manufactured by α Technology Co., Ltd. using unvulcanized rubber. G ′ of strains ranging from 0.28% to 100.0% was measured, and the difference (G′0.28% (MPa) −G′100.0% (MPa)) was determined.
)
Reinforcing property: M300 / M100 was used as an evaluation of reinforcing property (based on JIS-K6251).
Rolling resistance: Loss tangent (tan δ) at 60 ° C. was measured using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho under conditions of an initial strain of 10%, an amplitude of ± 2%, and a frequency of 20 Hz.
表Ｉ脚注
＊１：サンアプロ社製ＤＢＮ ＤＢＮ
＊２：サンアプロ社製ＤＢＮオクチル酸塩 Ｕ−ＣＡＴ１１０２
＊３：Ｆｌｅｘｓｙｓ社製ＤＰＧ ＰＥＲＫＡＣＩＴ ＤＰＧ
＊４：脚注＊１〜３の投入時期を表す。第１段とは加硫剤（硫黄及び加硫促進剤）を除く配合剤を混合する混合ステップ、第２段とは、加硫剤を混合するステップで＊１〜３の配合剤を投入することを意味する。
Table I footnote * 1: DBA DBN manufactured by San Apro
* 2: DBN octylate U-CAT1102 manufactured by San Apro
* 3: Flexsys DPG PERKACIT DPG
* 4: Indicates the timing of footnotes * 1-3. The first stage is a mixing step of mixing compounding agents excluding vulcanizing agents (sulfur and vulcanization accelerators), and the second stage is a step of mixing vulcanizing agents, and * 1 to 3 compounding agents are introduced. Means that.
本発明によれば、シリカ配合ゴム組成物に、ピペリジン骨格を有する前記式（Ｉ）のＤＢＮ及び／又はその塩をシリカ配合ゴム組成物に配合することにより、ゴム組成物の加硫速度やシリカの分散、補強性、粘弾性特性を向上させ、かつＤＰＧの削減が可能となるので、空気入りタイヤ用ゴム組成物として有用である。 According to the present invention, the vulcanization rate of the rubber composition and the silica can be increased by blending the silica-blended rubber composition with DBN of the formula (I) having a piperidine skeleton and / or a salt thereof in the silica-blended rubber composition. This is useful as a rubber composition for pneumatic tires because it can improve the dispersion, reinforcing properties and viscoelastic properties of the rubber, and can reduce DPG.
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| DE112011103471T5 (en) | 2010-10-15 | 2013-08-01 | The Yokohama Rubber Co., Ltd. | Rubber composition and air filled rubber tire |
| US8993659B2 (en) | 2010-10-15 | 2015-03-31 | The Yokohama Rubber Company, Limited | Rubber composition and pneumatic tire |
| DE112011103471B4 (en) | 2010-10-15 | 2021-07-29 | The Yokohama Rubber Co., Ltd. | Rubber composition, use of the rubber composition for producing air-filled rubber tires and vulcanized rubber composition |
| JP2013159669A (en) * | 2012-02-02 | 2013-08-19 | Bridgestone Corp | Method for producing rubber composition |
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