JP2010138272A - Rubber composition for tire tread - Google Patents
Rubber composition for tire tread Download PDFInfo
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- JP2010138272A JP2010138272A JP2008315406A JP2008315406A JP2010138272A JP 2010138272 A JP2010138272 A JP 2010138272A JP 2008315406 A JP2008315406 A JP 2008315406A JP 2008315406 A JP2008315406 A JP 2008315406A JP 2010138272 A JP2010138272 A JP 2010138272A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 33
- 239000005060 rubber Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 239000001993 wax Substances 0.000 claims abstract description 30
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 23
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 23
- 229920001194 natural rubber Polymers 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 13
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 235000009566 rice Nutrition 0.000 claims abstract description 10
- 239000004204 candelilla wax Substances 0.000 claims abstract description 9
- 235000013868 candelilla wax Nutrition 0.000 claims abstract description 9
- 229940073532 candelilla wax Drugs 0.000 claims abstract description 9
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 240000007594 Oryza sativa Species 0.000 claims abstract 2
- 229920003244 diene elastomer Polymers 0.000 claims description 18
- 241000872198 Serjania polyphylla Species 0.000 claims 1
- 239000012178 vegetable wax Substances 0.000 abstract description 13
- 239000000945 filler Substances 0.000 abstract description 6
- 239000012763 reinforcing filler Substances 0.000 abstract description 4
- 150000001993 dienes Chemical class 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000047 product Substances 0.000 description 9
- 241000209094 Oryza Species 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000004203 carnauba wax Substances 0.000 description 3
- 235000013869 carnauba wax Nutrition 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- -1 silicon halides Chemical class 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 235000010919 Copernicia prunifera Nutrition 0.000 description 1
- 244000180278 Copernicia prunifera Species 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、タイヤトレッド用ゴム組成物に関する。さらに詳しくは、ジエン系ゴム、補強性充填剤および植物性ワックスを含有してなるタイヤトレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for a tire tread. More specifically, the present invention relates to a tire tread rubber composition containing a diene rubber, a reinforcing filler and a vegetable wax.
近年、石油資源の枯渇問題やCO2排出規制などの諸事情により、非石油資源由来原材料を用いた材料開発が求められている。非石油資源由来ゴムである天然ゴムは、スコーチ・タイムやグリップ性などの点で、石油資源由来原材料を用いた合成ゴムにみられるゴム性能の水準に達してはいない。 In recent years, material development using raw materials derived from non-petroleum resources is required due to various problems such as the problem of depletion of petroleum resources and CO 2 emission regulations. Natural rubber, which is a non-petroleum resource-derived rubber, has not reached the level of rubber performance found in synthetic rubbers using petroleum resource-derived raw materials in terms of scorch time, grip properties, and the like.
下記特許文献１には、石油外資源の含有比率を高め、石油資源由来の原材料を主成分とするタイヤトレッド用ゴム組成物と比較しても、さらに耐候性、低燃費性、耐摩耗性をバランスよく得ることができるタイヤトレッド用ゴム組成物として、ジエン系ゴム100重量部に対して、シリカを20〜100重量部および植物性ワックスを5〜18重量部含有せしめたトレッド用ゴム組成物が記載されている。
ジエン系ゴムとしては、NR、SBRおよびBRの少なくとも一種が選ばれると記載されており、各実施例ではこれら3種類のブレンドゴムが用いられている。また、植物性ワックスとしてカルナバワックスを3重量部用いた比較例３では、耐オゾン性試験におけるクラック発生までの日数がきわめて短いことが示され、植物性ワックスは5重量部以上用いられなければならないとされている。 It is described that at least one of NR, SBR and BR is selected as the diene rubber, and these three types of blend rubbers are used in each example. In Comparative Example 3 where 3 parts by weight of carnauba wax was used as the vegetable wax, it was shown that the number of days until the occurrence of cracks in the ozone resistance test was extremely short, and the vegetable wax had to be used in an amount of 5 parts by weight or more. It is said that.
本発明の目的は、ジエン系ゴム、補強性充填剤および植物性ワックスを含有してなるタイヤトレッド用ゴム組成物であって、加工性、ワックスブルーム性、充填剤分散性、耐候性などの点で合成ワックスを用いたものと同等程度以上を示すタイヤトレッド用ゴム組成物を提供することにある。 An object of the present invention is a rubber composition for a tire tread comprising a diene rubber, a reinforcing filler, and a vegetable wax, in terms of processability, wax bloom property, filler dispersibility, weather resistance, etc. It is an object of the present invention to provide a rubber composition for a tire tread that exhibits a degree equal to or higher than that using a synthetic wax.
かかる本発明の目的は、20重量％以上の天然ゴムおよび／またはエポキシ化天然ゴムを含有するジエン系ゴム100重量部当り、シリカを40重量部以上、シリカとの合計量が50〜150重量部となる量の窒素吸着比表面積N2SA(JIS K6217-2準拠)が70〜200×103 m2/kgのカーボンブラック、シリカ重量に対して2〜18重量％のシランカップリング剤およびライスワックスまたはキャンデリラワックス1〜4.5重量部を含有してなるタイヤトレッド用ゴム組成物によって達成される。 The object of the present invention is to provide 40 parts by weight or more of silica and 50 to 150 parts by weight in total with silica per 100 parts by weight of diene rubber containing 20% by weight or more of natural rubber and / or epoxidized natural rubber. Amount of nitrogen adsorption specific surface area N 2 SA (according to JIS K6217-2) of 70 to 200 × 10 3 m 2 / kg carbon black, 2 to 18% by weight of silane coupling agent and rice based on silica weight This is achieved by a rubber composition for a tire tread comprising 1 to 4.5 parts by weight of a wax or candelilla wax.
本発明に係るタイヤ用トレッドゴム組成物は、トレッド押出し性によって示される押出加工性、ワックスブルーム性、充填剤分散性、静オゾン試験によって示される耐候性などの点において、石油資源由来の合成ワックスを用いたものと同等程度以上の性能を示している。 The tire tread rubber composition according to the present invention is a synthetic wax derived from petroleum resources in terms of extrudability, wax bloom property, filler dispersibility, weather resistance indicated by a static ozone test, etc. The performance is equivalent to or better than that using.
すなわち、ジエン系ゴム中20重量％以上の天然ゴムおよびエポキシ化天然ゴムの少なくとも一種を含むブレンドゴムを用いることにより、トレッド押出物のブルームを抑制することができる。また、シリカを40重量部以上含有し、カーボンブラックと併せた合計量が50〜150重量部と規定された充填剤の分散性は、特定の植物性ワックスをシリカと組合せて用いることにより、その分散性を大幅に向上せしめることができる。特定の植物性ワックスとしては、ライスワックスおよびキャンデリラワックスの少なくとも一種が用いられ、やはり植物性ワックスの範疇に属するカルナバワックスなどにはみられない効果が奏せられる。 That is, by using a blend rubber containing at least one of natural rubber and epoxidized natural rubber in a diene rubber of 20% by weight or more, the bloom of the tread extrudate can be suppressed. Further, the dispersibility of the filler containing 40 parts by weight or more of silica and defined as a total amount of 50 to 150 parts by weight combined with carbon black can be obtained by using a specific vegetable wax in combination with silica. Dispersibility can be greatly improved. As the specific vegetable wax, at least one of rice wax and candelilla wax is used, and an effect not seen in carnauba wax belonging to the category of vegetable wax is exhibited.
ジエン系ゴムとしては、天然ゴムおよびエポキシ化天然ゴムの少なくとも一種と合成ゴムとのブレンドゴムが好んで用いられる。エポキシ化天然ゴムとしては、75モル％以下エポキシ化したものが用いられ、好ましくはゴムの引張強度と破断伸びとの関係上20〜55モル％エポキシ化したものが用いられる。天然ゴムおよび／またはエポキシ化天然ゴムとブレンドされて用いられる合成ゴムとしては、SBR、BR、IR、IIR、EPDM等が挙げられ、好ましくはSBRが用いられるが、押出物のブルームを抑制するためには、天然ゴムおよび／またはエポキシ化天然ゴムのブレンド割合を約20重量％以上、好ましくは25〜85重量％とすることが望ましい。また、BRは、シンジオタクチック-1,2-ポリブタジエンを含むポリブタジエンゴムであってもよい。 As the diene rubber, a blend rubber of at least one of natural rubber and epoxidized natural rubber and a synthetic rubber is preferably used. As the epoxidized natural rubber, those epoxidized in an amount of 75 mol% or less are used, and those epoxidized in an amount of 20 to 55 mol% are preferably used in view of the tensile strength and breaking elongation of the rubber. Synthetic rubber used by blending with natural rubber and / or epoxidized natural rubber includes SBR, BR, IR, IIR, EPDM, etc., and preferably SBR is used to suppress extrudate bloom. It is desirable that the blend ratio of natural rubber and / or epoxidized natural rubber be about 20% by weight or more, preferably 25 to 85% by weight. BR may be a polybutadiene rubber containing syndiotactic-1,2-polybutadiene.
補強性充填剤としては、シリカを40重量部以上、シリカとの合計量が50〜150重量部となる量のカーボンブラックが用いられる。 As the reinforcing filler, carbon black in an amount of 40 parts by weight or more of silica and a total amount of 50 to 150 parts by weight of silica is used.
シリカとしては、一般にCTAB吸着比表面積が30〜200m2/g、好ましくは50〜150m2/gのものが用いられる。これらは、ハロゲン化けい素または有機けい素化合物の熱分解法やけい砂を加熱還元し、気化したSiOを空気酸化する方法などで製造される乾式法シリカやけい酸ナトリウムの熱分解法などで製造される湿式法シリカなどであり、コストおよび性能の面からは、湿式法シリカが好んで用いられる。実際には、ゴム工業用として上市されている市販品をそのまま用いることができる。 As the silica, those having a CTAB adsorption specific surface area of 30 to 200 m 2 / g, preferably 50 to 150 m 2 / g are generally used. These include the pyrolysis method of silicon halides or organosilicon compounds, the dry method of silica produced by heat reduction of silica sand and the oxidation of vaporized SiO in air, or the pyrolysis method of sodium silicate. Wet process silica to be produced, etc., and wet process silica is preferably used in terms of cost and performance. Actually, a commercial product marketed for the rubber industry can be used as it is.
その配合割合は、一般にジエン系ゴム100重量部当り40重量部以上、好ましくは40〜110重量部である。このような割合でのシリカの配合は、植物性ワックスと組合せて用いたとき、充填剤の分散効果を著しく高めることができる。 The blending ratio is generally 40 parts by weight or more, preferably 40 to 110 parts by weight per 100 parts by weight of the diene rubber. When silica is blended in such a ratio, the filler dispersing effect can be remarkably enhanced when used in combination with vegetable wax.
このようにシリカに求められる特性およびジエン系ゴムとの分散性(シリカはゴムポリマーとの親和性に乏しく、またゴム中でシリカ同士がシラノール基を通して水素結合を生成し、シリカのゴム中への分散性を低下させる性質を有する)を高めるために、シランカップリング剤がシリカ重量に対して2〜18重量％、好ましくは5〜10重量％の割合で用いられる。シランカップリング剤の使用割合がこれよりも少ないと、シリカに求められる特性やジエン系ゴムとの分散性が十分に発揮されず、一方これよりも多い添加割合で用いられると、加工性が悪化するようになる。 Thus, the properties required of silica and dispersibility with diene rubbers (silica has poor affinity with rubber polymers, and silica in rubber forms hydrogen bonds through silanol groups, and silica is incorporated into rubber. In order to increase (having the property of reducing dispersibility), the silane coupling agent is used in a proportion of 2 to 18% by weight, preferably 5 to 10% by weight, based on the silica weight. If the proportion of the silane coupling agent used is less than this, the properties required for silica and dispersibility with the diene rubber will not be sufficiently exerted, whereas if used in a proportion higher than this, the processability will deteriorate. To come.
シランカップリング剤としては、一般式
(R′)3-n(OR)nSiR″SxR″Si(OR)n(R′)3-n
R ：炭素数1〜3のアルキル基
R′：炭素数1〜3のアルキル基
R″：炭素数1〜5のアルキレン基
X ：2〜4
n ：1〜3
で表わされるシリカ表面のシラノール基と反応するアルコキシシリル基とポリマーと反応するイオウ連鎖を有するポリスルフィド系シランカップリング剤が用いられる。具体的には、例えばビス(3-トリエトキシシリルプロピル)テトラスルフィド、ビス(2-トリエトキシシリルエチル)テトラスルフィド、ビス(3-トリメトキシシリルプロピル)テトラスルフィド、ビス(3-トリエトキシシリルプロピル)ジスルフィド等が好んで用いられる。
The silane coupling agent has a general formula
(R ′) 3-n (OR) n SiR ″ SxR ″ Si (OR) n (R ′) 3-n
R: an alkyl group having 1 to 3 carbon atoms
R ′: an alkyl group having 1 to 3 carbon atoms
R ″: an alkylene group having 1 to 5 carbon atoms
X: 2-4
n: 1 to 3
A polysulfide silane coupling agent having an alkoxysilyl group that reacts with a silanol group on the silica surface and a sulfur chain that reacts with a polymer is used. Specifically, for example, bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) ) Disulfide and the like are preferably used.
また、カーボンブラックとしは、窒素吸着比表面積N2SA(JIS K6217-2準拠)が70〜200×103 m2/kg、好ましくは70〜170×103 m2/kgのカーボンブラックが用いられる。これよりも小さいN2SA値を有するカーボンブラックを用いると、粘度は低くなるものの、耐摩耗性の低下が著しくなり、一方これよりも大きいN2SA値を有するカーボンブラックを用いると、粘度が上がりすぎて、生産性が悪化するようになる。カーボンブラックは、ジエン系ゴム100重量部当り40重量部以上の割合で用いられるシリカとの合計量として50〜150重量部、好ましくは55〜120重量部の割合で用いられる。これらの充填剤の合計配合量がこれよりも少ないと、強度など必要な物性値を有する加硫物が得られなくなり、一方これよりも多い割合で用いられると、粘度が上がりすぎて、生産性が悪化するようになる。 Carbon black having a nitrogen adsorption specific surface area N 2 SA (conforming to JIS K6217-2) of 70 to 200 × 10 3 m 2 / kg, preferably 70 to 170 × 10 3 m 2 / kg is used. It is done. If carbon black having a smaller N 2 SA value is used, the viscosity will be lowered, but the wear resistance will be significantly reduced.On the other hand, if carbon black having a larger N 2 SA value is used, the viscosity will be lower. It goes up too much and productivity becomes worse. Carbon black is used in a proportion of 50 to 150 parts by weight, preferably 55 to 120 parts by weight as a total amount with silica used in a proportion of 40 parts by weight or more per 100 parts by weight of diene rubber. If the total amount of these fillers is less than this, a vulcanizate having the necessary physical properties such as strength cannot be obtained. On the other hand, if it is used in a proportion higher than this, the viscosity will increase too much and the productivity will increase. Will get worse.
ジエン系ゴム100重量部当り0.1〜4.5重量部、好ましくは1.5〜2.8重量部の割合で用いられる植物性ワックスとしては、ライスワックスまたはキャンデリラワックスが用いられる。その使用割合がこれよりも少ないと、押出加工性、耐候性が低下するようになり、一方これよりも多い割合で用いられると、押出物の保管時にワックスがブルームするようになる。 Rice wax or candelilla wax is used as the vegetable wax used at a ratio of 0.1 to 4.5 parts by weight, preferably 1.5 to 2.8 parts by weight, per 100 parts by weight of the diene rubber. If the proportion used is less than this, the extrudability and weather resistance are lowered, whereas if used in a proportion larger than this, the wax blooms when the extrudate is stored.
本発明においては、植物性ワックスとしてライスワックスおよびキャンデリラワックスの少なくとも一種を用いた場合には、石油資源由来の合成ワックスと同程度以上の性能がみられるのに対して、植物性ワックスとしてカルナバワックスを用いた場合には、天然ゴムやエポキシ化天然ゴムとブレンドされるSBR等との相溶性が高くなく、ブルームし易いので、外観が悪化するようになる。 In the present invention, when at least one of rice wax and candelilla wax is used as the vegetable wax, the performance is comparable to or higher than that of a synthetic wax derived from petroleum resources, whereas carnauba is used as the vegetable wax. When wax is used, the compatibility with SBR and the like blended with natural rubber or epoxidized natural rubber is not high and the bloom tends to occur, so that the appearance deteriorates.
以上の各成分を必須成分とするジエン系ゴム組成物中には、ゴムの配合剤として一般的に用いられている配合剤、例えばジエン系ゴムの種類に応じて硫黄等の加硫剤、チアゾール系、スルフェンアミド系、グアニジン系、チウラム系等の加硫促進剤、ステアリン酸、アロマオイル等の加工助剤、老化防止剤、可塑剤などが必要に応じて適宜配合されて用いられる。 In the diene rubber composition containing the above components as essential components, a compounding agent generally used as a compounding agent for rubber, for example, a vulcanizing agent such as sulfur depending on the type of diene rubber, thiazole Vulcanization accelerators such as sulfenamides, guanidines, and thiurams, processing aids such as stearic acid and aroma oil, anti-aging agents, plasticizers, and the like are appropriately blended and used as necessary.
組成物の調製は、ニーダ、バンバリーミキサ等の混練機およびオープンロール等を用いる一般的な方法で混練することによって行われ、得られたタイヤトレッド用ゴム組成物を未加硫の状態で空気入りタイヤのトレッドの形状に押出加工し、タイヤ成形機上で通常の方法によりケーシング部と貼り合せて未加硫タイヤを成形し、これを加硫機中で加熱・加圧して、タイヤトレッド用ゴム組成物からトレッド部分を形成させた空気入りタイヤを得ることができる。 The composition was prepared by kneading by a general method using a kneader such as a kneader or a Banbury mixer and an open roll, and the obtained rubber composition for a tire tread was put in a pneumatic state in an unvulcanized state. Extruded into the shape of a tire tread, and bonded to the casing part by a normal method on a tire molding machine to form an unvulcanized tire, which is heated and pressurized in a vulcanizer, and tire tread rubber A pneumatic tire having a tread portion formed from the composition can be obtained.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
比較例１(標準例)
天然ゴム(RSS#3) 30重量部
SBR(日本ゼオン製品Nipol NS116) 70 〃
カーボンブラック(新日化カーボン製品ニテロン#200IS； 10 〃
N2SA 88×103 m2/kg)
シリカ(Degussa製品VN-3) 70 〃
シランカップリング剤(同社製品Si69) 5.6 〃
亜鉛華(正同化学工業製品酸化亜鉛3種) 3 〃
ステアリン酸(日油製品ビーズステアリン酸) 2 〃
老化防止剤(フレキシス社製品SANTOFLEX 6PPD) 2 〃
老化防止剤(同社製品SANTOFLEX RD) 1 〃
合成ワックス(大内新興化学工業製品サンノック) 2.5 〃
アロマオイル(昭和シェル石油製品エキストラクト4号S) 15 〃
硫黄(細井化学工業製品5％油処理硫黄) 2 〃
加硫促進剤(大内新興化学工業製品ノクセラーCZ-G) 2.1 〃
加硫促進剤(三新化学工業製品サンセラーD-G) 0.5 〃
以上の各成分の内、硫黄および加硫促進剤を除く各成分を、密閉式バンバリーミキサを用いて5分間混合し、これらの混合物を混合機外に放出して室温まで冷却させた後、オープンロールを用いて、硫黄および加硫促進剤を配合し、混合した。
Comparative example 1 (standard example)
Natural rubber (RSS # 3) 30 parts by weight
SBR (Nippon ZEON product Nipol NS116) 70 〃
Carbon Black (Nippon Nidec Carbon Product Niteron # 200IS; 10 〃
(N 2 SA 88 × 10 3 m 2 / kg)
Silica (Degussa product VN-3) 70 〃
Silane coupling agent (manufactured by Si69) 5.6 〃
Zinc Hana (Zinc Oxide Industrial Products, 3 types of zinc oxide) 3 〃
Stearic acid (NOF product beads stearic acid) 2 〃
Anti-aging agent (SANYOFLEX 6PPD, product of Flexis) 2 〃
Anti-aging agent (manufactured by SANTOFLEX RD) 1 〃
Synthetic wax (Onouchi Emerging Chemical Industries Sannock) 2.5 〃
Aroma oil (Showa Shell Petroleum Product Extract No. 4 S) 15 〃
Sulfur (5% oil-treated sulfur from Hosoi Chemical Industries) 2 製品
Vulcanization accelerator (Ouchi Emerging Chemical Industry Noxeller CZ-G) 2.1 〃
Vulcanization accelerator (Sanshin Chemical Industrial Products Sunseller DG) 0.5 〃
Among the above components, components other than sulfur and vulcanization accelerator are mixed for 5 minutes using a closed Banbury mixer, and these mixtures are discharged to the outside of the mixer and cooled to room temperature, and then opened. Using a roll, sulfur and a vulcanization accelerator were blended and mixed.
このようにして得られた加硫性ジエン系ゴム組成物を160℃で20分間加硫して所定の加硫ゴム試験片を得、ジエン系ゴム組成物および加硫ゴム試験片について、次の各項目の測定、評価を行った。
トレッド押出し性：5インチオープンロールを用いて3分間混練を行い、シートが厚さ
5mmになるようにシート出しを行い、シート出し直後のゲージと
2時間後のゲージの差を測定
(この標準例を100とする指数で示し、この値が大きいもの程押出
加工性がよいことを示している)
ワックスブルーム性：35℃の恒温槽内に96時間放置した後目視し、変化ないものを◎
、光沢がないものを○、一部白化しているものを△、全体的に
白化しているものを×と評価
ペイン効果：α-テクノロジー社製歪せん断応力測定機RPA2000を用い、未加硫ゴムを
用いて160℃、20分間の加硫を行い、歪0.28％と30.0％の歪せん断応力
G′を測定し、その差G′0.28(MPa)−G′30.0(MPa)を、充填剤の分散状
態を示す値として測定
(この標準例を100とする指数で示し、この値が大きいもの程充填剤を分
散状態が良好であることを示している)
耐候性：40℃、オゾン濃度50ppm、歪20％の条件下で静的オゾン試験を行い、亀裂の
数および大きさを下記基準により判定
（数） A：1〜10個未満
B：10〜50個未満
C：50個以上
K：サンプルの破断
（大きさ） 1：肉眼でやっと見える
2：1mm未満
3：1mm以上〜3mm未満
4：3mm以上〜5mm未満
5：5mm以上
N：クラックの発生が認められない
The vulcanizable diene rubber composition thus obtained was vulcanized at 160 ° C. for 20 minutes to obtain a predetermined vulcanized rubber test piece. For the diene rubber composition and the vulcanized rubber test piece, Each item was measured and evaluated.
Tread extrudability: Kneaded for 3 minutes using a 5-inch open roll, resulting in a thick sheet
Take out the sheet so that it is 5 mm,
Measure the difference in gauge after 2 hours
(This standard example is indicated with an index of 100.
(Indicates good workability)
Wax bloom property: A thing that does not change after standing in a constant temperature bath at 35 ° C for 96 hours.
◯ for non-glossy, △ for partly whitened, overall
Pain effect: α-Technology's strain shear stress measuring machine RPA2000 is used to remove unvulcanized rubber.
Used for vulcanization at 160 ℃ for 20 minutes, strain shear stress of strain 0.28% and 30.0%
G ′ is measured and the difference G′0.28 (MPa) −G′30.0 (MPa)
Measured as a state value
(Indicates this index as an index with 100 as the standard value.
(It shows that the scattered state is good)
Weather resistance: Static ozone test was conducted under the conditions of 40 ℃, ozone concentration 50ppm, and strain 20%.
Number and size are judged according to the following criteria
(Number) A: 1 to less than 10
B: Less than 10-50
C: 50 or more
K: Sample break
(Size) 1: It is finally visible with the naked eye
2: Less than 1mm
3: 1mm to less than 3mm
4: 3mm or more to less than 5mm
5: 5mm or more
N: No cracks are observed
比較例２
比較例１において、合成ワックス(サンノック)量が1重量部に変更された。
Comparative Example 2
In Comparative Example 1, the amount of synthetic wax (Sannok) was changed to 1 part by weight.
比較例３
比較例１において、合成ワックス(サンノック)の代りに同量(2.5重量部)のライスワックス(東亜化成製品TOWAX 36F)が用いられ、またカーボンブラック(ニテロン#200IS)量が50重量部に、シリカ(VN-3)量が30重量部に、シランカップリング剤(Si69)量が2.4重量部に変更された。
Comparative Example 3
In Comparative Example 1, the same amount (2.5 parts by weight) of rice wax (TOA Kasei product TOWAX 36F) was used instead of the synthetic wax (Sannok), and the amount of carbon black (Niteron # 200IS) was 50 parts by weight. The amount of (VN-3) was changed to 30 parts by weight, and the amount of silane coupling agent (Si69) was changed to 2.4 parts by weight.
比較例４
比較例１において、合成ワックスの代りに、5重量部のカルナバワックス(三精産業製品カルナバ2号)が用いられた。
Comparative Example 4
In Comparative Example 1, 5 parts by weight of carnauba wax (Sansei Sangyo Carnava No. 2) was used in place of the synthetic wax.
比較例５
比較例１において、天然ゴム(RSS#3)量が10重量部に、SBR(Nipol NS116)量が90重量部にそれぞれ変更され、また合成ワックスの代りに、キャンデリラワックス(三精産業製品)0.5重量部が用いられた。
Comparative Example 5
In Comparative Example 1, the amount of natural rubber (RSS # 3) was changed to 10 parts by weight and the amount of SBR (Nipol NS116) was changed to 90 parts by weight, and candelilla wax (Sansei Industrial Products) instead of synthetic wax. 0.5 parts by weight were used.
比較例６
比較例５において、キャンデリラワックス(三精産業製品)量が5重量部に変更された。
Comparative Example 6
In Comparative Example 5, the amount of candelilla wax (Sansei Sangyo Co., Ltd.) was changed to 5 parts by weight.
比較例７
比較例３において、ライスワックスの代りに、同量(2.5重量部)の合成ワックス(サンノック)が用いられた。
Comparative Example 7
In Comparative Example 3, the same amount (2.5 parts by weight) of synthetic wax (Sannok) was used instead of rice wax.
実施例１
比較例１において、合成ワックスの代りに、同量(2.5重量部)のライスワックス(TOWAX 36F)が用いられた。
Example 1
In Comparative Example 1, the same amount (2.5 parts by weight) of rice wax (TOWAX 36F) was used instead of the synthetic wax.
実施例２
比較例２において、合成ワックスの代りに、同量(1重量部)のライスワックス(TOWAX 36F)が用いられた。
Example 2
In Comparative Example 2, the same amount (1 part by weight) of rice wax (TOWAX 36F) was used instead of the synthetic wax.
実施例３
実施例１において、天然ゴム(RSS#3)量が40重量部に、SBR(Nipol NS116)量が60重量部にそれぞれ変更された。
Example 3
In Example 1, the amount of natural rubber (RSS # 3) was changed to 40 parts by weight, and the amount of SBR (Nipol NS116) was changed to 60 parts by weight.
実施例４
実施例１において、カーボンブラック(ニテロン#200IS)量が40重量部に、シリカ(VN-3)量が40重量部、シランカップリング剤(Si69)量が3.2重量部にそれぞれ変更された。
Example 4
In Example 1, the amount of carbon black (Niteron # 200IS) was changed to 40 parts by weight, the amount of silica (VN-3) was changed to 40 parts by weight, and the amount of silane coupling agent (Si69) was changed to 3.2 parts by weight.
実施例５
比較例１において、合成ワックスの代りに、同量(2.5重量部)のキャンデリラワックス(三精産業製品)が用いられた。
Example 5
In Comparative Example 1, the same amount (2.5 parts by weight) of candelilla wax (Sansei Sangyo Co., Ltd.) was used instead of the synthetic wax.
以上の各比較例および実施例で得られた結果は、次の表に示される。
表
トレッド ワックス
例 押出し性 ブルーム性 ペイン効果 耐候性
比較例１ 100 ○ 100 C4
〃 ２ 98 ○ 100 C5
〃 ３ 98 ○ 90 C2
〃 ４ 104 × 106 C3
〃 ５ 96 ○ 102 C5
〃 ６ 106 × 110 C3
〃 ７ 97 ○ 89 C2
実施例１ 103 ○ 115 C2
〃 ２ 100 ○ 104 C4
〃 ３ 106 ◎ 112 C2
〃 ４ 101 ○ 103 C2
〃 ５ 100 ○ 110 C3
The results obtained in the above comparative examples and examples are shown in the following table.
table
Tread wax
Examples extrusion of bloom of Payne effect weather resistance
Comparative Example 1 100 ○ 100 C4
〃 2 98 ○ 100 C5
〃 3 98 ○ 90 C2
４ 4 104 × 106 C3
５ 5 96 ○ 102 C5
６ 6 106 × 110 C3
97 7 97 ○ 89 C2
Example 1 103 ○ 115 C2
〃 2 100 ○ 104 C4
３ 3 106 ◎ 112 C2
４ 4 101 ○ 103 C2
５ 5 100 ○ 110 C3
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| JP2012021057A (en) * | 2010-07-13 | 2012-02-02 | Sumitomo Rubber Ind Ltd | Rubber composition for tire and pneumatic tire |
| JP2013534269A (en) * | 2010-08-16 | 2013-09-02 | 株式会社ブリヂストン | Mixture for tire outer part with improved appearance |
| JP2015003548A (en) * | 2013-06-19 | 2015-01-08 | 住友ゴム工業株式会社 | Tire |
| WO2019077885A1 (en) * | 2017-10-17 | 2019-04-25 | 日本精蝋株式会社 | Surface modifier for rubber composition, and rubber composition containing same |
| US10808106B2 (en) | 2015-11-11 | 2020-10-20 | Bridgestone Americas Tire Operations, Llc | Saturated triglyceride-containing rubber composition, tires and tire components containing the rubber composition, and related methods |
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| JP2008297392A (en) * | 2007-05-30 | 2008-12-11 | Sumitomo Rubber Ind Ltd | Clinch rubber composition and pneumatic tire using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012021057A (en) * | 2010-07-13 | 2012-02-02 | Sumitomo Rubber Ind Ltd | Rubber composition for tire and pneumatic tire |
| JP2013534269A (en) * | 2010-08-16 | 2013-09-02 | 株式会社ブリヂストン | Mixture for tire outer part with improved appearance |
| JP2015003548A (en) * | 2013-06-19 | 2015-01-08 | 住友ゴム工業株式会社 | Tire |
| US9387724B2 (en) | 2013-06-19 | 2016-07-12 | Sumitomo Rubber Industries, Ltd. | Tire |
| US10808106B2 (en) | 2015-11-11 | 2020-10-20 | Bridgestone Americas Tire Operations, Llc | Saturated triglyceride-containing rubber composition, tires and tire components containing the rubber composition, and related methods |
| WO2019077885A1 (en) * | 2017-10-17 | 2019-04-25 | 日本精蝋株式会社 | Surface modifier for rubber composition, and rubber composition containing same |
| JPWO2019077885A1 (en) * | 2017-10-17 | 2020-04-16 | 日本精蝋株式会社 | Surface modifier for rubber composition and rubber composition containing the same |
| CN111212872A (en) * | 2017-10-17 | 2020-05-29 | 日本精蜡株式会社 | Surface modifier for rubber composition and rubber composition containing the same |
| CN111212872B (en) * | 2017-10-17 | 2022-07-19 | 日本精蜡株式会社 | Surface modifier for rubber composition and rubber composition containing the same |
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| JP5499466B2 (en) | 2014-05-21 |
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