JP2013112743A - Rubber composition for tire tread and pneumatic tire by using the same - Google Patents
Rubber composition for tire tread and pneumatic tire by using the same Download PDFInfo
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- JP2013112743A JP2013112743A JP2011260190A JP2011260190A JP2013112743A JP 2013112743 A JP2013112743 A JP 2013112743A JP 2011260190 A JP2011260190 A JP 2011260190A JP 2011260190 A JP2011260190 A JP 2011260190A JP 2013112743 A JP2013112743 A JP 2013112743A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 39
- 239000005060 rubber Substances 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000000945 filler Substances 0.000 claims abstract description 36
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 10
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 10
- 229960003237 betaine Drugs 0.000 claims description 10
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 abstract description 14
- 150000001993 dienes Chemical class 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 238000002156 mixing Methods 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 12
- 239000011324 bead Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- -1 alkyl imidazole Chemical compound 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 2
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000012360 testing method Methods 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
- BKUWWVKLLKXDJK-UHFFFAOYSA-N 2-(dimethylamino)icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(N(C)C)C(O)=O BKUWWVKLLKXDJK-UHFFFAOYSA-N 0.000 description 1
- XPALGXXLALUMLE-UHFFFAOYSA-N 2-(dimethylamino)tetradecanoic acid Chemical compound CCCCCCCCCCCCC(N(C)C)C(O)=O XPALGXXLALUMLE-UHFFFAOYSA-N 0.000 description 1
- UNWFFCPRJXMCNV-UHFFFAOYSA-N 3-[dodecanoyl(methyl)amino]propanoic acid Chemical compound CCCCCCCCCCCC(=O)N(C)CCC(O)=O UNWFFCPRJXMCNV-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-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
- IVLBGFRTARNACQ-UHFFFAOYSA-N [3-[3,3-bis(triethoxysilyl)propyltetrasulfanyl]-1-triethoxysilylpropyl]-triethoxysilane Chemical group CCO[Si](OCC)(OCC)C([Si](OCC)(OCC)OCC)CCSSSSCCC([Si](OCC)(OCC)OCC)[Si](OCC)(OCC)OCC IVLBGFRTARNACQ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JOLYVEWZEPKDIJ-UTLKBRERSA-L dipotassium;(2s)-2-(dodecanoylamino)pentanedioate Chemical compound [K+].[K+].CCCCCCCCCCCC(=O)N[C@H](C([O-])=O)CCC([O-])=O JOLYVEWZEPKDIJ-UTLKBRERSA-L 0.000 description 1
- 238000005516 engineering process 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
- 239000000835 fiber Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229940099874 potassium lauroyl glutamate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229940045944 sodium lauroyl glutamate Drugs 0.000 description 1
- IWIUXJGIDSGWDN-UQKRIMTDSA-M sodium;(2s)-2-(dodecanoylamino)pentanedioate;hydron Chemical compound [Na+].CCCCCCCCCCCC(=O)N[C@H](C([O-])=O)CCC(O)=O IWIUXJGIDSGWDN-UQKRIMTDSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method 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
- 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
Abstract
Description
本発明は、タイヤトレッド用ゴム組成物およびそれを用いた空気入りタイヤに関するものであり、詳しくは、優れた加工性および低転がり抵抗を有するタイヤトレッド用ゴム組成物およびそれを用いた空気入りタイヤに関するものである。 TECHNICAL FIELD The present invention relates to a rubber composition for a tire tread and a pneumatic tire using the same, and more specifically, a rubber composition for a tire tread having excellent processability and low rolling resistance, and a pneumatic tire using the same. It is about.
自動車の燃費を向上させるため、タイヤは低転がり抵抗であることが求められている。この要求を解決するために、例えばタイヤにシリカのような白色充填剤を配合する手法が知られている。しかしながら白色充填剤をゴム組成物中に均一に分散させるのは一般的に困難であり、また、混練時に粘度が高くなり加工性を悪化させるという問題点がある。例えばシリカは、その粒子表面に存在するシラノール基による水素結合の形成のために凝集する傾向を有し、混練時の粘度の上昇が顕著である。このため、ゴム組成物に白色充填剤を十分な量で配合することができず、所望の低転がり抵抗を得ることが困難であった。
一方、シリカのような白色充填剤の分散性を向上させるために、シランカップリング剤を配合する手法も知られている。しかし、シランカップリング剤を多く配合すると、スコーチ時間が短くなりすぎたり、さらにトレッドの押出性が悪化する。
In order to improve the fuel consumption of automobiles, tires are required to have low rolling resistance. In order to solve this requirement, for example, a method of blending a white filler such as silica in a tire is known. However, it is generally difficult to uniformly disperse the white filler in the rubber composition, and there is a problem that the viscosity becomes high during kneading and deteriorates the workability. For example, silica has a tendency to agglomerate due to the formation of hydrogen bonds due to silanol groups present on the particle surface, and the increase in viscosity during kneading is remarkable. For this reason, the white filler cannot be blended in a sufficient amount in the rubber composition, and it has been difficult to obtain a desired low rolling resistance.
On the other hand, in order to improve the dispersibility of a white filler such as silica, a method of blending a silane coupling agent is also known. However, when a large amount of the silane coupling agent is blended, the scorch time becomes too short, and the extrudability of the tread deteriorates.
なお、下記特許文献１〜３は、界面活性剤をゴム組成物に配合する技術を開示している。しかしながら、これらの技術はカチオン性界面活性剤、アニオン性界面活性剤または非イオン性界面活性剤をゴム組成物に添加するものであり、下記で説明する本発明のように両性界面活性剤を使用するものではない。 In addition, the following patent documents 1-3 are disclosing the technique of mix | blending surfactant with a rubber composition. However, these technologies add a cationic surfactant, an anionic surfactant or a nonionic surfactant to the rubber composition, and use an amphoteric surfactant as in the present invention described below. Not what you want.
本発明の目的は、優れた加工性および低転がり抵抗を有するタイヤトレッド用ゴム組成物およびそれを用いた空気入りタイヤを提供することにある。 An object of the present invention is to provide a rubber composition for a tire tread having excellent processability and low rolling resistance, and a pneumatic tire using the same.
本発明者らは鋭意研究を重ねた結果、ジエン系ゴムに白色充填剤の特定量、シランカップリング剤の特定量および両性界面活性剤の特定量を配合することにより、上記課題を解決できることを見出し、本発明を完成することができた。
すなわち本発明は以下のとおりである。
As a result of intensive studies, the present inventors have found that the above problem can be solved by blending a specific amount of white filler, a specific amount of silane coupling agent and a specific amount of amphoteric surfactant with diene rubber. The headline and the present invention could be completed.
That is, the present invention is as follows.
１．ジエン系ゴム１００質量部に対し、
（Ａ）白色充填剤を５〜１５０質量部、
（Ｂ）シランカップリング剤を前記白色充填剤に対して１〜２５質量％、および
（Ｃ）両性界面活性剤を前記白色充填剤に対して１．５〜３０質量％
配合することを特徴とするタイヤトレッド用ゴム組成物。
２．前記両性界面活性剤が、ベタイン型またはアミンオキシド型であることを特徴とする前記１に記載のタイヤトレッド用ゴム組成物。
３．前記１または２に記載のゴム組成物をトレッドに使用した空気入りタイヤ。
1. For 100 parts by mass of diene rubber,
(A) 5 to 150 parts by mass of a white filler,
(B) The silane coupling agent is 1 to 25% by mass with respect to the white filler, and (C) the amphoteric surfactant is 1.5 to 30% by mass with respect to the white filler.
A rubber composition for a tire tread characterized by being compounded.
2. 2. The rubber composition for a tire tread according to 1 above, wherein the amphoteric surfactant is a betaine type or an amine oxide type.
3. A pneumatic tire using the rubber composition according to 1 or 2 as a tread.
本発明によれば、ジエン系ゴムに白色充填剤の特定量、シランカップリング剤の特定量および両性界面活性剤の特定量を配合したので、優れた加工性および低転がり抵抗を有するタイヤトレッド用ゴム組成物およびそれを用いた空気入りタイヤを提供することができる。 According to the present invention, since a specific amount of a white filler, a specific amount of a silane coupling agent, and a specific amount of an amphoteric surfactant are blended in a diene rubber, the tire tread has excellent processability and low rolling resistance. A rubber composition and a pneumatic tire using the rubber composition can be provided.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
図１は、乗用車用の空気入りタイヤの一例の部分断面図である。
図１において、空気入りタイヤは左右一対のビード部１およびサイドウォール２と、両サイドウォール２に連なるトレッド３からなり、ビード部１、１間に繊維コードが埋設されたカーカス層４が装架され、カーカス層４の端部がビードコア５およびビードフィラー６の廻りにタイヤ内側から外側に折り返されて巻き上げられている。トレッド３においては、カーカス層４の外側に、ベルト層７がタイヤ１周に亘って配置されている。また、ビード部１においてはリムに接する部分にリムクッション８が配置されている。
以下に説明する本発明のゴム組成物は、とくにトレッド３に有用である。
FIG. 1 is a partial cross-sectional view of an example of a pneumatic tire for a passenger car.
In FIG. 1, the pneumatic tire is composed of a pair of left and
The rubber composition of the present invention described below is particularly useful for the
（ゴム成分）
本発明で使用されるゴム成分は、ゴム組成物に配合することができる任意のゴムを用いることができ、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。また、その分子量やミクロ構造はとくに制限されず、アミン、アミド、シリル、アルコキシシリル、カルボキシル、ヒドロキシル基等で末端変性されていても、エポキシ化されていてもよい。
これらの中でも、本発明の効果の点からジエン系ゴムはＳＢＲ、ＢＲが好ましい。
(Rubber component)
As the rubber component used in the present invention, any rubber that can be blended in the rubber composition can be used. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene- Examples thereof include butadiene copolymer rubber (SBR) and acrylonitrile-butadiene copolymer rubber (NBR). These may be used alone or in combination of two or more. The molecular weight and microstructure are not particularly limited, and may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or may be epoxidized.
Among these, the diene rubber is preferably SBR or BR from the viewpoint of the effect of the present invention.
（白色充填剤）
本発明で使用する白色充填剤とは、黒色を呈する充填剤以外の充填剤、例えば黒色を呈する充填剤以外の無機充填剤を意味し、具体的にはシリカ、炭酸カルシウム、クレー等が挙げられる。
なお、シリカを使用する場合、本発明の効果がさらに向上するという観点から、シリカの窒素吸着比表面積（Ｎ２ＳＡ）が５０〜２００ｍ２／ｇであるのが好ましい。なお、窒素吸着比表面積（Ｎ２ＳＡ）はＪＩＳ Ｋ６２１７−２に準拠して求めた値である。
(White filler)
The white filler used in the present invention means a filler other than a filler exhibiting a black color, for example, an inorganic filler other than a filler exhibiting a black color, and specifically includes silica, calcium carbonate, clay and the like. .
In the case of using silica, from the viewpoint that the effect is further enhanced in the present invention, the nitrogen adsorption
（シランカップリング剤）
本発明で使用するシランカップリング剤は、その効果向上の観点から、硫黄含有シランカップリング剤を使用するのが好ましい。シランカップリング剤としては、シリカ配合のゴム組成物に使用可能なものであればよく、例えばビス−（３−トリエトキシシリルプロピル）テトラサルファイド、ビス（３−トリエトキシシリルプロピル）ジサルファイド、３−トリメトキシシリルプロピルベンゾチアゾールテトラサルファイド、γ−メルカプトプロピルトリエトキシシラン、３−オクタノイルチオプロピルトリエトキシシラン等を例示することができる。
(Silane coupling agent)
The silane coupling agent used in the present invention is preferably a sulfur-containing silane coupling agent from the viewpoint of improving its effect. Any silane coupling agent may be used as long as it can be used in a rubber composition containing silica. For example, bis- (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, 3 Examples thereof include -trimethoxysilylpropylbenzothiazole tetrasulfide, γ-mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane and the like.
（両性界面活性剤）
本発明で使用する両性界面活性剤としては、例えば、ベタイン型、アミノ酸型、アミンオキシド型等が挙げられる。
ベタイン型としては、ラウリルジメチルアミノ酢酸ベタイン、ステアリルジメチルアミノ酢酸ベタイン、ドデシルアミノメチルジメチルスルホプロピルベタイン、オクタデシルアミノメチルジメチルスルホプロピルベタイン等のアルキルベタイン型；コカミドプロピルベタイン、コカミドプロピルヒドロキシスルタイン等の脂肪酸アミドプロピルベタイン型；2-アルキル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタイン等のアルキルイミダゾール型等が挙げられる。
アミノ酸型としては、ラウロイルグルタミン酸ナトリウム、ラウロイルグルタミン酸カリウム、ラウロイルメチル-β-アラニン等が挙げられる。
アミンオキシド型としては、ラウリルジメチルアミンN‐オキシド、オレイルジメチルアミンN‐オキシド等が挙げられる。
両性界面活性剤は、白色充填剤、例えばシリカの表面に吸着して相互作用を生じ、凝集を抑制する。これにより、白色充填剤、例えばシリカの分散性が向上し、優れた加工性および低転がり抵抗を両立させることができる。
上記効果は、両性界面活性剤としてとくにベタイン型またはアミンオキシド型を使用することにより、一層向上する。
(Amphoteric surfactant)
Examples of the amphoteric surfactant used in the present invention include betaine type, amino acid type, and amine oxide type.
The betaine type includes alkylbetaines such as lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, dodecylaminomethyldimethylsulfopropylbetaine, octadecylaminomethyldimethylsulfopropylbetaine; cocamidopropyl betaine, cocamidopropylhydroxysultain, etc. Fatty acid amidopropyl betaine type; alkyl imidazole type such as 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.
Examples of amino acid types include sodium lauroyl glutamate, potassium lauroyl glutamate, lauroylmethyl-β-alanine, and the like.
Examples of the amine oxide include lauryl dimethylamine N-oxide and oleyldimethylamine N-oxide.
The amphoteric surfactant is adsorbed on the surface of a white filler, for example, silica to cause an interaction and suppress aggregation. Thereby, the dispersibility of a white filler, for example, silica is improved, and both excellent processability and low rolling resistance can be achieved.
The above effect is further improved by using a betaine type or amine oxide type as the amphoteric surfactant.
（ゴム組成物の配合割合）
本発明のゴム組成物は、ジエン系ゴム１００質量部に対し、
（Ａ）白色充填剤を５〜１５０質量部、
（Ｂ）シランカップリング剤を前記白色充填剤に対して１〜２５質量％、および
（Ｃ）両性界面活性剤を前記白色充填剤に対して１．５〜３０質量％
配合することを特徴とする。
前記（Ａ）白色充填剤の配合量が５質量部未満であると、低転がり抵抗が得られない。逆に１５０質量部を超えると、耐摩耗性が悪化する。
前記（Ｂ）シランカップリング剤の配合量が白色充填剤に対して１質量％未満であると、配合量が少な過ぎて本発明の効果を奏することができない。逆に白色充填剤に対して２５質量％を超えると加工性が悪化する。
前記（Ｃ）両性界面活性剤の配合量が前記白色充填剤に対して１．５質量％未満であると、配合量が少な過ぎて本発明の効果を奏することができない。逆に３０質量％を超えると加工性が悪化する。
(Rubber composition ratio)
The rubber composition of the present invention is based on 100 parts by mass of the diene rubber.
(A) 5 to 150 parts by mass of a white filler,
(B) The silane coupling agent is 1 to 25% by mass with respect to the white filler, and (C) the amphoteric surfactant is 1.5 to 30% by mass with respect to the white filler.
It is characterized by blending.
When the blending amount of the (A) white filler is less than 5 parts by mass, low rolling resistance cannot be obtained. Conversely, when it exceeds 150 mass parts, abrasion resistance will deteriorate.
When the blending amount of the (B) silane coupling agent is less than 1% by mass with respect to the white filler, the blending amount is too small to achieve the effects of the present invention. On the contrary, if it exceeds 25% by mass with respect to the white filler, the workability deteriorates.
When the blending amount of the (C) amphoteric surfactant is less than 1.5% by mass with respect to the white filler, the blending amount is too small to achieve the effects of the present invention. Conversely, when it exceeds 30 mass%, workability will deteriorate.
前記（Ａ）白色充填剤のさらに好ましい配合量は、ジエン系ゴム１００質量部に対し、２０〜１００質量％である。
前記（Ｂ）シランカップリング剤のさらに好ましい配合量は、白色充填剤に対し、３〜１５質量％である。
前記（Ｃ）両性界面活性剤のさらに好ましい配合量は、白色充填剤に対し、３〜２０質量％である。
A more preferable blending amount of the (A) white filler is 20 to 100% by mass with respect to 100 parts by mass of the diene rubber.
The more preferable compounding quantity of the said (B) silane coupling agent is 3-15 mass% with respect to a white filler.
The more preferable compounding quantity of the said (C) amphoteric surfactant is 3-20 mass% with respect to a white filler.
本発明に係るゴム組成物には、前記した成分に加えて、加硫又は架橋剤、加硫又は架橋促進剤、充填剤、老化防止剤、可塑剤などのゴム組成物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。また本発明のゴム組成物は従来の空気入りタイヤの製造方法に従って空気入りタイヤを製造するのに使用することができる。 In addition to the above-described components, the rubber composition according to the present invention is generally blended with a rubber composition such as a vulcanization or crosslinking agent, a vulcanization or crosslinking accelerator, a filler, an antioxidant, and a plasticizer. Various additives can be blended, and such additives can be kneaded by a general method to form a composition, which can be used for vulcanization or crosslinking. The blending amounts of these additives can be set to conventional general blending amounts as long as the object of the present invention is not violated. The rubber composition of the present invention can be used to produce a pneumatic tire according to a conventional method for producing a pneumatic tire.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.
実施例１〜４および比較例１〜３
サンプルの調製
表１に示す配合（質量部）において、加硫促進剤と硫黄を除く成分を１．７リットルの密閉式バンバリーミキサーで５分間混練した後、ミキサー外に放出させて室温冷却した。続いて、該組成物を同バンバリーミキサーに再度入れ、加硫促進剤および硫黄を加えて混練し、ゴム組成物を得た。次に得られたゴム組成物を所定の金型中で１５０℃で３０分間プレス加硫して加硫ゴム試験片を得、以下に示す試験法で該ゴム組成物および加硫ゴム試験片の物性を測定した。
Examples 1-4 and Comparative Examples 1-3
Preparation of Sample In the formulation (parts by mass) shown in Table 1, components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes with a 1.7 liter closed Banbury mixer, then discharged outside the mixer and cooled at room temperature. Subsequently, the composition was put into the Banbury mixer again, and a vulcanization accelerator and sulfur were added and kneaded to obtain a rubber composition. Next, the obtained rubber composition was press vulcanized at 150 ° C. for 30 minutes in a predetermined mold to obtain a vulcanized rubber test piece, and the rubber composition and the vulcanized rubber test piece were tested by the following test method. Physical properties were measured.
ムーニー粘度：ゴム組成物のムーニー粘度を、ＪＩＳ Ｋ６３００に基づき１００℃で測定した。結果は、比較例１の値を１００として指数で示した。指数が大きいほど粘度が低く、加工性が良好であることを示す。
転がり抵抗：レオメトリックス社製ＲＤＡ−ＩＩを用い、１％ねじれ、２０Ｈｚ、６０℃の条件でｔａｎδ（６０℃）を測定し、この値をもって転がり抵抗性を評価した。結果は、比較例１を１００として指数で示した。指数が大きいほど、低転がり抵抗であることを示す。
ペイン効果：未加硫のゴム組成物を用いて１６０℃、２０分の加硫を行ない、歪０．２８％〜３０．０％までの歪せん断応力Ｇ’を測定した。結果は、比較例１を１００として指数で示した。指数が大きいほど、シリカ分散が良好であることを示す。
結果を併せて表１に示す。
Mooney viscosity: The Mooney viscosity of the rubber composition was measured at 100 ° C. based on JIS K6300. The results are shown as an index with the value of Comparative Example 1 being 100. The larger the index, the lower the viscosity and the better the workability.
Rolling resistance: Using RDA-II manufactured by Rheometrics, tan δ (60 ° C.) was measured under the conditions of 1% twist, 20 Hz and 60 ° C., and the rolling resistance was evaluated based on this value. The results are shown as an index with Comparative Example 1 as 100. The larger the index, the lower the rolling resistance.
Payne effect: An unvulcanized rubber composition was used for vulcanization at 160 ° C. for 20 minutes, and strain shear stress G ′ of strains from 0.28% to 30.0% was measured. The results are shown as an index with Comparative Example 1 as 100. The larger the index, the better the silica dispersion.
The results are also shown in Table 1.
＊１：ＳＢＲ（日本ゼオン（株）製Ｎｉｐｏｌ １５０２、油展量＝ＳＢＲ１００質量部に対し３７．５質量部）
＊２：ＢＲ（日本ゼオン（株）製Ｎｉｐｏｌ １２２０）
＊３：シリカ（ローディア社製Ｚｅｏｓｉｌ １１６５ＭＰ、Ｎ２ＳＡ＝１６５ｍ２／ｇ）
＊４：カーボンブラック（東海カーボン（株）製シースト６、Ｎ２ＳＡ＝１１９ｍ２／ｇ）
＊５：シランカップリング剤（エボニックデグッサジャパン（株）製Ｓｉ６９、化合物名＝ビス−トリエトキシシリルプロピルテトラスルフィド）
＊６：両性界面活性剤−１（花王（株）製アンヒトール２０Ｎ。ラウリルジメチルアミンＮ−オキシド）
＊７：両性界面活性剤−２（花王（株）製アンヒトール２０ＡＢ。コカミドプロピルベタイン）
＊８：両性界面活性剤−３（花王（株）製アンヒトール２０Ｙ−Ｎ。2-アルキル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタイン（アルキルはＣ１１主成分））
＊９：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊１０：ステアリン酸（日油(株)製ビーズステアリン酸）
＊１１：老化防止剤（ＦＬＥＸＳＹＳ製ＳＡＮＴＯＦＬＥＸ ６ＰＰＤ）
＊１２：アロマオイル（昭和シェル石油（株）製エキストラクト４号Ｓ）
＊１３：硫黄（鶴見化学工業（株）製金華印油入微粉硫黄）
＊１４：加硫促進剤−１（大内新興化学工業（株）製ノクセラーＣＺ−Ｇ）
＊１５：加硫促進剤−２（住友化学（株）製ソクシノールＤ−Ｇ）
* 1: SBR (Nipol 1502, manufactured by Nippon Zeon Co., Ltd., oil extended amount = 37.5 parts by mass with respect to 100 parts by mass of SBR)
* 2: BR (Nipol 1220 manufactured by Nippon Zeon Co., Ltd.)
* 3: Silica (Zeosil 1165MP manufactured by Rhodia, N 2 SA = 165 m 2 / g)
* 4: Carbon black (Toast Carbon Co., Ltd.
* 5: Silane coupling agent (Si69 manufactured by Evonik Degussa Japan Co., Ltd., compound name = bis-triethoxysilylpropyltetrasulfide)
* 6: Amphoteric surfactant-1 (Ahitole 20N manufactured by Kao Corporation. Lauryldimethylamine N-oxide)
* 7: Amphoteric surfactant-2 (Ahitole 20AB manufactured by Kao Corporation. Cocamidopropyl betaine)
* 8: Amphoteric surfactant-3 (Ahitole 20Y-N manufactured by Kao Corporation. 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (alkyl is the main component of C11))
* 9: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 10: Stearic acid (beef stearic acid manufactured by NOF Corporation)
* 11: Anti-aging agent (SANTOFLEX 6PPD manufactured by FLEXSYS)
* 12: Aroma oil (Extract No. 4 S manufactured by Showa Shell Sekiyu KK)
* 13: Sulfur (fine powdered sulfur with Jinhua seal oil from Tsurumi Chemical Co., Ltd.)
* 14: Vulcanization accelerator-1 (Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.)
* 15: Vulcanization accelerator-2 (Sokushinol DG manufactured by Sumitomo Chemical Co., Ltd.)
上記の表から明らかなように、実施例１〜４で調製されたゴム組成物は、ジエン系ゴムに白色充填剤の特定量、シランカップリング剤の特定量および両性界面活性剤の特定量を配合したので、従来の代表的な比較例１に比べて、優れた加工性および低転がり抵抗を両立していることが分かる。
これに対し、比較例２は、両性界面活性剤の配合量が本発明で規定する下限未満であるので、シリカの分散性が向上せず、加工性および低転がり抵抗も改善されなかった。
比較例３は、両性界面活性剤の配合量が本発明で規定する上限を超えているので、シリカの分散性が向上せず、加工性および低転がり抵抗も改善されなかった。
As is clear from the above table, the rubber compositions prepared in Examples 1 to 4 have a specific amount of white filler, a specific amount of silane coupling agent, and a specific amount of amphoteric surfactant in the diene rubber. Since it mix | blended, compared with the conventional typical comparative example 1, it turns out that the outstanding workability and the low rolling resistance are compatible.
On the other hand, since the compounding quantity of the amphoteric surfactant was less than the lower limit prescribed | regulated by this invention in the comparative example 2, the dispersibility of a silica was not improved and workability and low rolling resistance were not improved.
In Comparative Example 3, the compounding amount of the amphoteric surfactant exceeded the upper limit defined in the present invention, so that the dispersibility of silica was not improved, and the workability and the low rolling resistance were not improved.
１ ビード部
２ サイドウォール
３ トレッド
４ カーカス層
５ ビードコア
６ ビードフィラー
７ ベルト層
８ リムクッション
1 Bead
Claims (3)
（Ａ）白色充填剤を５〜１５０質量部、
（Ｂ）シランカップリング剤を前記白色充填剤に対して１〜２５質量％、および
（Ｃ）両性界面活性剤を前記白色充填剤に対して１．５〜３０質量％
配合することを特徴とするタイヤトレッド用ゴム組成物。 For 100 parts by mass of diene rubber,
(A) 5 to 150 parts by mass of a white filler,
(B) The silane coupling agent is 1 to 25% by mass with respect to the white filler, and (C) the amphoteric surfactant is 1.5 to 30% by mass with respect to the white filler.
A rubber composition for a tire tread characterized by being compounded.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101748671B1 (en) | 2014-06-26 | 2017-06-19 | 요코하마 고무 가부시키가이샤 | Rubber composition for tire |
| US20230124971A1 (en) * | 2021-10-11 | 2023-04-20 | The Goodyear Tire & Rubber Company | Rubber composition and a tire |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005105913A1 (en) * | 2004-04-28 | 2005-11-10 | Mitsui Chemicals, Inc. | Rubber composition and use thereof |
| JP2010059272A (en) * | 2008-09-02 | 2010-03-18 | Toyo Tire & Rubber Co Ltd | Surface-treated inorganic oxide, rubber composition using the same, and pneumatic tire |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005105913A1 (en) * | 2004-04-28 | 2005-11-10 | Mitsui Chemicals, Inc. | Rubber composition and use thereof |
| JP2010059272A (en) * | 2008-09-02 | 2010-03-18 | Toyo Tire & Rubber Co Ltd | Surface-treated inorganic oxide, rubber composition using the same, and pneumatic tire |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101748671B1 (en) | 2014-06-26 | 2017-06-19 | 요코하마 고무 가부시키가이샤 | Rubber composition for tire |
| US20230124971A1 (en) * | 2021-10-11 | 2023-04-20 | The Goodyear Tire & Rubber Company | Rubber composition and a tire |
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