JP3608892B2 - Silica-containing rubber composition - Google Patents
Silica-containing rubber composition Download PDFInfo
- Publication number
- JP3608892B2 JP3608892B2 JP34854896A JP34854896A JP3608892B2 JP 3608892 B2 JP3608892 B2 JP 3608892B2 JP 34854896 A JP34854896 A JP 34854896A JP 34854896 A JP34854896 A JP 34854896A JP 3608892 B2 JP3608892 B2 JP 3608892B2
- Authority
- JP
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- Prior art keywords
- silica
- rubber composition
- silane coupling
- present
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 75
- 229920001971 elastomer Polymers 0.000 title claims description 42
- 239000005060 rubber Substances 0.000 title claims description 42
- 239000000203 mixture Substances 0.000 title claims description 36
- 239000000377 silicon dioxide Substances 0.000 title claims description 36
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000004073 vulcanization Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 125000005372 silanol group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000005370 alkoxysilyl group Chemical group 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-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
- 239000003921 oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【0001】
【発明の属する技術分野】
本発明はシリカ配合ゴム組成物に関し、更に詳しくは未加硫時の加工性を改良した、加硫可能なシリカ配合ゴム組成物に関する。
【0002】
【従来の技術】
従来からカーボンブラック、炭酸カルシウム、アルミナ、硫酸アルミニウム、硫酸バリウム、硫酸カルシウム、シリカ、タルク、クレイ、ケイ藻土、雲母などの充填剤が各種ゴムに使われている。これらの充填剤は無機物質であったり、その表面に極性基を有している物質であったりするため、充填剤の配合によってゴムとの混合まとまりの低下が起るという問題があった。これらの充填剤の中で、ケイ素含有充填剤、特にシリカを配合したゴム組成物は、例えば低発熱性で耐摩耗性などに優れたタイヤトレッド用ゴム組成物として使用されている。しかしながら、シリカを配合したタイヤトレッドは転動抵抗が低く、湿潤路のグリップ性は良いが、タイヤ製造工程において未加硫配合物の粘度上昇、加硫遅延、混合まとまりの低下などの現象が起り、加工性に劣るという問題があった。かかる問題を解決すべく、従来から種々の提案があるが、いずれも実用上満足のいくまでには到っていないのが実情である。
【0003】
前記した提案としては、ジエチレングリコールや脂肪酸を添加したり(例えばゴム工業便覧<第四版>,517〜518頁、平成6年発行参照)、カルボン酸金属塩を添加したり(例えばTire Technology International 1995,107〜108頁参照)、シリカを予じめシリコーンオイルで処理したり(例えば特開平6−248116号公報参照)することなどがあるが、前述の如く、いずれも実用上充分な方法とは言えない。
【0004】
【発明が解決しようとする課題】
従って、本発明は、前述の従来技術の問題点を排除して、シリカ配合加硫性ゴム組成物の特性、例えば低発熱性や耐摩耗性などの特性を実質的に損なうことなく、未加硫ゴム組成物の加工性が改良されたシリカ配合加硫性ゴム組成物を提供することを目的とする。
【0005】
【課題を解決するための手段】
本発明に従えば、シリカを配合したゴム組成物において、式(I):
で表わされるアルコキシシラン(I)および硫黄含有シランカップリング剤を含んでなるシリカ含有ゴム組成物が提供される。
【化2】
(式中、R1 はメチル、ビニル又はフェニル基を示し、R2 は炭素数1〜6の炭化水素基又はエーテル結合含有炭化水素基を示し、nは1〜6である。)
【0006】
本発明の好ましい態様に従えば、前記ゴム組成物中に、シランカップリング剤の配合量が50重量%以下のシラノール縮合触媒を更に含むシリカ配合ゴム組成物が提供される。
【0007】
【発明の実施の形態】
以下、本発明の構成及び作用効果について詳しく説明する。
前述の如く、シリカはゴムの物性向上に貢献しているが、その表面に極性基を有している物質であるため、ゴムとの混合まとまりが低下し、加工性が劣るという問題があった。特に、含水シリカ等のシリカを配合したタイヤトレッドの加硫物性は良好であるが、未加硫時の加工性に劣るという欠点があった。本発明者らの知見によれば、これはシリカ表面に存在するシラノール基(≡Si−OH)に起因し、シラノール基の凝集力によりシリカ配合ゴム組成物中で構造体が生成して粘度が上昇したり、シラノール基の極性により加硫促進剤などが吸着されて加硫が遅延したり、非極性ゴムとの相溶性が十分でないために混合のまとまりが低下したりする現象のために、未加硫組成物の加工性が低下するのである。更に、シリカ配合ゴム組成物には、ゴムへの補強のために、シランカップリング剤が併用されることが多いが、シリカ粒子の内腔にもシラノール基が存在し、これがシランカップリング剤と反応してシランカップリング剤を損失させ、補強効果が低下するため多量のシランカップリング剤を配合しなければならないという問題があった。従来技術におけるように、これにジエチレングリコールなどの極性物質を添加すると、加硫促進剤などの極性配合剤が吸着される現象はある程度防止できるが、完全には防止できず、シランカップリング剤などのシリカ粒子と化学結合する物質が内腔に結合するのを防止することもできなかった。
【0008】
然るに、本発明に従えば、前記式(I)のアルコキシシランをシリカ配合ゴム組成物中に配合することによってアルコキシシリル基がシリカのシラノール基と反応して、シリカの表面を覆うので、従来技術の問題点を悉く解決して、極性基の凝集力や極性によって生ずる未加硫物の粘度上昇や加硫促進剤などの極性添加剤やシランカップリング剤などの無駄な消費を効果的に抑えることができる。
【0009】
本発明に従って、ゴム組成物中に配合されるシリカには特に限定はなく、従来から一般的に使用されているシリカを用いることができるが、具体的には湿式、疎水性シリカが例示される。
【0010】
本発明に従ってシリカ配合ゴム組成物中に配合されるアルコキシシラン(I)は、前述の如く、シラノール基と反応するアルコキシシリル基を有し、シリカの表面を覆って潤滑効果を示すこれらのアルコキシシランは重合を伴いながらシリカの表面と反応するものと思われる。従って、1分子中のアルコキシ基としては2つが好ましく、1つでは重合せず、3つ以上ではゲル化してしまう。又、nは1〜6が好ましく、6を超えるとシリカとの結合が弱くなるので好ましくない。かかるアルコキシシランは公知物質であり、市販あるいは例えば一般的には以下のようにして製造することができる。
【0011】
本発明で用いるアルコキシシラン(I)は、市販されている式(II):
【0012】
【化3】
【0013】
(式中、R1 及びR2 は前記定義の通りである。)
のメトキシ基を加水分解、縮合して合成するか又は式(III) :
【0014】
【化4】
【0015】
(式中、R1 及びnは前記定義の通りである。)
の水素基とアルコールを触媒存在下反応させることにより合成するか又は式(IV):
【0016】
【化5】
【0017】
(式中、R1 及びR2 は前記定義の通りである。)
のクロロ基を水の存在下にアルコールと反応させることにより合成することができる。
【0018】
前記アルコールとしては、メタノール、エタノール、プロパノール、ブタノール、ペンタノールなどがあげられ、更にエチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテルなど酸素原子を有するアルコールも例示することができる。
【0019】
更に前記触媒としては、塩化白金酸、白金−エーテル錯体、白金−オレフィン錯体、PdCl2 (PPh3 )2 ,RhCl2 (PPh3 )2 が例示できる。
【0020】
本発明において使用されるアルコキシシランの配合量はゴム組成物中のシリカ重量に対し、好ましくは100重量%以下、特に好ましくは1〜40重量%である。アルコキシシランの配合量が少な過ぎると所望の効果が得られず、逆に多過ぎるとシリカと結合しないアルコキシシランが加硫物からしみ出す場合があるので好ましくない。
【0021】
またシリカの配合量は特に限定されないがゴム100重量部に対し、5〜150重量部とするのが好ましく、更に好ましくは20〜120重量部である。本発明に係るシリカ配合ゴム組成物に主成分として配合されるゴムは従来から各種ゴム組成物に一般的に配合されている任意のゴム、例えば天然ゴム(NR)、ポリイソプレンゴム(IR)、各種スチレン−ブタジエン共重合体ゴム(SBR)、各種ポリブタジエンゴム(BR)、アクリロニトリル−ブタジエン共重合体ゴム(NBR)、ブチルゴム(IIR)などのジエン系ゴムやエチレン−プロピレン共重合体ゴム(EPR,EPDM)などを単独又は任意のブレンドとして使用することができる。
【0022】
本発明において使用される硫黄含有シランカップリング剤は従来からシリカと併用される任意のシランカップリング剤とすることができ、典型例としては下記表Iに示したものをあげることができる。このうち、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加工性の面から最も好ましい。
【0023】
【表1】
【0024】
本発明に係る加硫性ゴム組成物にシランカップリング剤を配合した場合、従来に比し、シランカップリング剤の使用量を少なくすることができ、耐摩耗性を更に改良することができる。本発明におけるシランカップリング剤の好ましい使用量は組成物中のシリカの配合量に対し、40重量%以下、更に好ましくは0.5〜40重量%、特に好ましくは1〜20重量%である。シランカップリング剤の配合量が少な過ぎると所望の効果が得られにくくなり、逆に多過ぎると混合や押出工程での焼け(スコーチ)が生じやすくなるおそれがあるので好ましくない。
【0025】
本発明に係るゴム組成物は、さらにシラノール縮合触媒を含むことができる。本発明において使用されるシラノール縮合触媒としては、スズ系、チタン系、アミン系があげられる。具体的にはジブチルスズジラウレート、ジオクチルスズ、テトライソプロポキシチタン、チタンアセチルアセトネート、トリブチルアミン、ステアリルジメチルアミンなどが例示される。
【0026】
本発明に係るゴム組成物には、前記した必須成分に加えて、カーボンブラックなどの充填剤、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、可塑性剤などのタイヤ用、その他一般ゴム用に一般的に配合されている各種添加剤を配合することができ、かかる配合物は一般的な方法で混練、加硫して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も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。
【0027】
【実施例】
以下、実施例及び比較例に従って、本発明を更に詳しく説明するが、本発明の技術的範囲をこれらの実施例に限定するものでないことは言うまでもない。
【0028】
以下の標準例、実施例及び比較例の各例の配合に用いた他の配合成分は以下の市販品を用いた。
天然ゴム:RSS#1
SBR:ニポールNS116(日本ゼオン)
シリカ:ニプシルAQ(日本シリカ)
シランカップリング剤:Si69(デクサ)(化学名:ビス−〔3−(トリエトキシシリル)−プロピル〕テトラスルフィド)
カーボンブラック:シーストKH(東海カーボン)
【0029】
酸化亜鉛:亜鉛華3号
ステアリン酸:工業用ステアリン酸
老化防止剤6C:N−フェニル−N′−(1,3−ジメチルブチル)−p−フェニレンジアミン
粉末硫黄:5%油処理の粉末硫黄
加硫促進剤CZ:N−シクロヘキシル−2−ベンゾチアジルスルフェンアミド
【0030】
サンプルの調製
加硫促進剤と硫黄を除く成分を1.8リットルの密閉型ミキサーで3〜5分間混練し、165±5℃に達したときに放出したマスターバッチに加硫促進剤と硫黄を8インチのオープンロール混練し、ゴム組成物を得た。得られたゴム組成物の未加硫物性を測定した。
次に、この組成物を15×15×0.2cmの金型中で160℃で20分間プレス加硫して目的とする試験片(ゴムシート)を調製し、加硫物性を評価した。
【0031】
各例において得られた組成物の未加硫物性及び加硫物性の試験方法は以下の通りである。
未加硫物性
1)ムーニー粘度:JIS K 6300に基づき100℃にて測定した。
2)加硫速度:JIS K 6300に基づき160℃にて95%加硫度に達する時間(分)を測定した。
3)スコーチ時間:JIS K 6300に基づき125℃にて粘度が5ポイント上昇する時間(分)を測定した。
【0032】
加硫物性
1)300%変形応力、破断強度、破断伸度:JIS K 6251(ダンベル状3号形)に準拠して測定
【0033】
得られた結果を表IIに示す。
【0034】
【表2】
【0035】
【表3】
【0036】
【発明の効果】
表IIの結果に示すように、本発明に従ってシリカ、アルコキシシラン及び硫黄含有シランカップリング剤を配合した実施例1〜8では、アルコキシシランを配合しない比較例1に比べて、ムーニー粘度が低く、加硫時間が短く、またスコーチ時間が長く、加工性の改良効果が認られた、一方加硫物性についても、シランカップリング剤を半減しても、同等の性能が得られた。またシラノール縮合触媒を配合した例ではアルコキシシランとシラノールの反応が促進したものと思われ、高い破断強度の加硫物性が得られた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silica-containing rubber composition, and more particularly to a vulcanizable silica-containing rubber composition having improved processability when unvulcanized.
[0002]
[Prior art]
Conventionally, fillers such as carbon black, calcium carbonate, alumina, aluminum sulfate, barium sulfate, calcium sulfate, silica, talc, clay, diatomaceous earth, and mica have been used for various rubbers. Since these fillers are inorganic substances or substances having polar groups on the surface thereof, there has been a problem that mixing of the fillers reduces the mixing of the fillers. Among these fillers, a rubber composition containing a silicon-containing filler, particularly silica, is used, for example, as a rubber composition for a tire tread having low heat build-up and excellent wear resistance. However, tire treads formulated with silica have low rolling resistance and good wet road grip, but phenomena such as increased viscosity of the unvulcanized compound, vulcanization delay, and decreased mixing density occur in the tire manufacturing process. There was a problem that the processability was inferior. Various proposals have heretofore been made to solve such problems, but none of them has been satisfied in practice.
[0003]
Examples of the proposals described above include addition of diethylene glycol and fatty acids (for example, see Rubber Industry Handbook <Fourth Edition>, pages 517 to 518, published in 1994), and addition of carboxylic acid metal salts (for example, Tire Technology International 1995). , 107-108), silica is treated with silicone oil in advance (see, for example, JP-A-6-248116), and as described above, all are practically sufficient methods. I can not say.
[0004]
[Problems to be solved by the invention]
Therefore, the present invention eliminates the above-mentioned problems of the prior art and does not substantially add to the characteristics of the silica-containing vulcanizable rubber composition, for example, properties such as low heat buildup and wear resistance. An object of the present invention is to provide a silica-containing vulcanizable rubber composition having improved processability of the vulcanized rubber composition.
[0005]
[Means for Solving the Problems]
According to the present invention, in a rubber composition compounded with silica, the formula (I):
A silica-containing rubber composition comprising an alkoxysilane (I) represented by formula (I) and a sulfur-containing silane coupling agent is provided.
[Chemical 2]
(Wherein R 1 represents a methyl, vinyl or phenyl group, R 2 represents a hydrocarbon group having 1 to 6 carbon atoms or an ether bond-containing hydrocarbon group, and n is 1 to 6).
[0006]
According to a preferred embodiment of the present invention, there is provided a silica-containing rubber composition further comprising a silanol condensation catalyst having a silane coupling agent content of 50% by weight or less in the rubber composition.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the configuration and operational effects of the present invention will be described in detail.
As described above, silica contributes to improving the physical properties of rubber, but since it is a substance having a polar group on its surface, there is a problem that the mixing with rubber is reduced and the processability is inferior. . In particular, the tire tread blended with silica such as hydrous silica has good vulcanization properties, but has the disadvantage of poor processability when unvulcanized. According to the knowledge of the present inventors, this is caused by silanol groups (≡Si—OH) present on the silica surface, and a structure is generated in the silica-containing rubber composition by the cohesive force of the silanol groups, resulting in a viscosity. Due to the phenomenon that the vulcanization accelerator is adsorbed by the polarity of the silanol group, the vulcanization is delayed, or the unity of the mixing decreases due to insufficient compatibility with the nonpolar rubber, The processability of the unvulcanized composition is reduced. Furthermore, in the silica compounded rubber composition, a silane coupling agent is often used in combination for reinforcing the rubber, but silanol groups are also present in the inner cavities of the silica particles. There was a problem that a large amount of the silane coupling agent had to be blended because the silane coupling agent was lost by reaction and the reinforcing effect was lowered. As in the prior art, when a polar substance such as diethylene glycol is added thereto, the phenomenon that a polar compounding agent such as a vulcanization accelerator is adsorbed can be prevented to some extent, but it cannot be completely prevented, such as a silane coupling agent. It was also impossible to prevent substances that chemically bond to the silica particles from binding to the lumen.
[0008]
However, according to the present invention, since the alkoxysilyl group of the formula (I) is blended in the silica-blended rubber composition, the alkoxysilyl group reacts with the silanol group of the silica and covers the surface of the silica. This effectively solves the above problem and effectively suppresses the wasteful consumption of polar additives such as vulcanization accelerators and silane coupling agents, as well as viscosity increase of unvulcanized products caused by the cohesive force of polar groups and polarity. be able to.
[0009]
According to the present invention, the silica compounded in the rubber composition is not particularly limited, and conventionally used silica can be used, and specific examples include wet and hydrophobic silica. .
[0010]
The alkoxysilane (I) blended in the silica-blended rubber composition according to the present invention has an alkoxysilyl group that reacts with a silanol group as described above, and covers the surface of the silica and exhibits a lubricating effect. Seems to react with the surface of silica with polymerization. Accordingly, two alkoxy groups in one molecule are preferable, and one does not polymerize and three or more gels. Further, n is preferably 1 to 6, and if it exceeds 6, the bond with silica becomes weak, which is not preferable. Such alkoxysilane is a known substance, and can be obtained commercially or, for example, generally as follows.
[0011]
The alkoxysilane (I) used in the present invention is a commercially available formula (II):
[0012]
[Chemical 3]
[0013]
(Wherein R 1 and R 2 are as defined above.)
Or synthesized by hydrolysis and condensation of the methoxy group of formula (III):
[0014]
[Formula 4]
[0015]
(Wherein R 1 and n are as defined above.)
Or a compound of the formula (IV):
[0016]
[Chemical formula 5]
[0017]
(Wherein R 1 and R 2 are as defined above.)
Can be synthesized by reacting the chloro group with alcohol in the presence of water.
[0018]
Examples of the alcohol include methanol, ethanol, propanol, butanol, pentanol and the like, and alcohols having an oxygen atom such as ethylene glycol monomethyl ether and diethylene glycol monomethyl ether can also be exemplified.
[0019]
Furthermore, examples of the catalyst include chloroplatinic acid, platinum-ether complexes, platinum-olefin complexes, PdCl 2 (PPh 3 ) 2 , and RhCl 2 (PPh 3 ) 2 .
[0020]
The compounding amount of the alkoxysilane used in the present invention is preferably 100% by weight or less, particularly preferably 1 to 40% by weight, based on the weight of silica in the rubber composition. If the amount of the alkoxysilane is too small, the desired effect cannot be obtained. On the other hand, if the amount is too large, the alkoxysilane that does not bind to the silica may ooze out from the vulcanizate.
[0021]
The amount of silica is not particularly limited, but is preferably 5 to 150 parts by weight, more preferably 20 to 120 parts by weight with respect to 100 parts by weight of rubber. The rubber blended as a main component in the silica-blended rubber composition according to the present invention is any rubber conventionally blended in various rubber compositions, for example, natural rubber (NR), polyisoprene rubber (IR), Diene rubbers such as various styrene-butadiene copolymer rubbers (SBR), various polybutadiene rubbers (BR), acrylonitrile-butadiene copolymer rubbers (NBR), butyl rubbers (IIR), and ethylene-propylene copolymer rubbers (EPR, EPDM) etc. can be used alone or as any blend.
[0022]
The sulfur-containing silane coupling agent used in the present invention can be any silane coupling agent conventionally used in combination with silica, and typical examples include those shown in Table I below. Of these, bis- [3- (triethoxysilyl) -propyl] tetrasulfide is most preferred from the viewpoint of processability.
[0023]
[Table 1]
[0024]
When a silane coupling agent is blended in the vulcanizable rubber composition according to the present invention, the amount of the silane coupling agent used can be reduced and the wear resistance can be further improved as compared with the conventional case. The amount of the silane coupling agent used in the present invention is preferably 40% by weight or less, more preferably 0.5 to 40% by weight, particularly preferably 1 to 20% by weight, based on the amount of silica in the composition. If the amount of the silane coupling agent is too small, it is difficult to obtain the desired effect. Conversely, if the amount is too large, there is a risk that scorching may occur in the mixing or extrusion process.
[0025]
The rubber composition according to the present invention can further contain a silanol condensation catalyst. Examples of the silanol condensation catalyst used in the present invention include tin-based, titanium-based, and amine-based catalysts. Specific examples include dibutyltin dilaurate, dioctyltin, tetraisopropoxytitanium, titanium acetylacetonate, tributylamine, and stearyldimethylamine.
[0026]
The rubber composition according to the present invention includes tires such as fillers such as carbon black, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, and plasticizers in addition to the essential components described above. Various additives that are generally blended for general rubbers can be blended, and these blends can be kneaded and vulcanized into a composition by a general method for vulcanization or crosslinking. Can be used. As long as the amount of these additives is not contrary to the object of the present invention, the conventional general amounts can be used.
[0027]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but it goes without saying that the technical scope of the present invention is not limited to these Examples.
[0028]
The following commercial item was used for the other compounding component used for the mixing | blending of each example of the following standard examples, an Example, and a comparative example.
Natural rubber: RSS # 1
SBR: Nipol NS116 (Zeon Japan)
Silica: Nipsil AQ (Nippon Silica)
Silane coupling agent: Si69 (dexa) (chemical name: bis- [3- (triethoxysilyl) -propyl] tetrasulfide)
Carbon black: Seast KH (Tokai Carbon)
[0029]
Zinc oxide: Zinc Hua 3 stearic acid: industrial stearic acid anti-aging agent 6C: N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine powder sulfur: 5% oil-treated powder sulfur Sulfur accelerator CZ: N-cyclohexyl-2-benzothiazylsulfenamide
Sample preparation Vulcanization accelerator and sulfur-excluded components were kneaded for 3 to 5 minutes in a 1.8 liter closed mixer, and vulcanization was accelerated to the master batch released when the temperature reached 165 ± 5 ° C. The rubber composition was obtained by kneading the agent and sulfur with an 8-inch open roll. The unvulcanized physical properties of the obtained rubber composition were measured.
Next, this composition was press vulcanized at 160 ° C. for 20 minutes in a 15 × 15 × 0.2 cm mold to prepare a target test piece (rubber sheet), and the vulcanized physical properties were evaluated.
[0031]
The test methods for the unvulcanized physical properties and the vulcanized physical properties of the compositions obtained in each example are as follows.
Unvulcanized physical properties 1) Mooney viscosity: measured at 100 ° C. based on JIS K 6300.
2) Vulcanization rate: Time (minutes) required to reach a 95% vulcanization degree at 160 ° C. was measured according to JIS K 6300.
3) Scorch time: Based on JIS K 6300, the time (minutes) for the viscosity to rise 5 points at 125 ° C. was measured.
[0032]
Vulcanized physical properties 1) 300% deformation stress, breaking strength, breaking elongation: measured according to JIS K 6251 (dumbbell shape No. 3)
The results obtained are shown in Table II.
[0034]
[Table 2]
[0035]
[Table 3]
[0036]
【The invention's effect】
As shown in the results of Table II, in Examples 1 to 8 in which silica, alkoxysilane and a sulfur-containing silane coupling agent were blended according to the present invention, the Mooney viscosity was low compared to Comparative Example 1 in which no alkoxysilane was blended. The vulcanization time was short, the scorch time was long, and the effect of improving the workability was recognized. On the other hand, the vulcanization properties were equivalent even if the silane coupling agent was halved. Moreover, in the example which mix | blended the silanol condensation catalyst, it seems that the reaction of alkoxysilane and silanol accelerated | stimulated, and the vulcanization | cure property of high breaking strength was obtained.
Claims (2)
で表わされるアルコキシシラン(I)および硫黄含有シランカップリング剤を含んでなるシリカ含有ゴム組成物。
A silica-containing rubber composition comprising an alkoxysilane (I) represented by formula (I) and a sulfur-containing silane coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34854896A JP3608892B2 (en) | 1996-12-26 | 1996-12-26 | Silica-containing rubber composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34854896A JP3608892B2 (en) | 1996-12-26 | 1996-12-26 | Silica-containing rubber composition |
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| Publication Number | Publication Date |
|---|---|
| JPH10182885A JPH10182885A (en) | 1998-07-07 |
| JP3608892B2 true JP3608892B2 (en) | 2005-01-12 |
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| JP34854896A Expired - Fee Related JP3608892B2 (en) | 1996-12-26 | 1996-12-26 | Silica-containing rubber composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3913346B2 (en) * | 1997-12-25 | 2007-05-09 | 住友ゴム工業株式会社 | Rubber composition for tire tread |
| EP1209194A4 (en) * | 1999-07-23 | 2002-10-30 | Mitsui Chemicals Inc | Rubber composition for extrusion molding and for molding with mold and use thereof |
| JP4676587B2 (en) * | 2000-02-28 | 2011-04-27 | 住友ゴム工業株式会社 | Rubber composition |
| JP3992523B2 (en) * | 2002-03-29 | 2007-10-17 | 横浜ゴム株式会社 | Rubber composition |
| CN101410405B (en) | 2006-04-05 | 2012-11-28 | 株式会社普利司通 | Activated silane compound, rubber composition and tire using same |
| WO2008102513A1 (en) | 2007-02-21 | 2008-08-28 | The Yokohama Rubber Co., Ltd. | Rubber composition |
| JP4930661B1 (en) | 2010-09-13 | 2012-05-16 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire |
| CN116285125B (en) * | 2023-03-28 | 2024-01-19 | 常州窗友塑胶有限公司 | Sealing adhesive tape and preparation method thereof |
| EP4700082A1 (en) * | 2023-06-01 | 2026-02-25 | The Yokohama Rubber Co., Ltd. | Rubber composition for tire and tire using same |
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