JP6101105B2 - Rubber composition for tire - Google Patents
Rubber composition for tire Download PDFInfo
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- JP6101105B2 JP6101105B2 JP2013029915A JP2013029915A JP6101105B2 JP 6101105 B2 JP6101105 B2 JP 6101105B2 JP 2013029915 A JP2013029915 A JP 2013029915A JP 2013029915 A JP2013029915 A JP 2013029915A JP 6101105 B2 JP6101105 B2 JP 6101105B2
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- 229920001971 elastomer Polymers 0.000 title claims description 105
- 239000005060 rubber Substances 0.000 title claims description 105
- 239000000203 mixture Substances 0.000 title claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000002736 nonionic surfactant Substances 0.000 claims description 21
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 18
- 230000003712 anti-aging effect Effects 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 16
- 244000043261 Hevea brasiliensis Species 0.000 claims description 14
- 229920003052 natural elastomer Polymers 0.000 claims description 14
- 229920001194 natural rubber Polymers 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 150000001412 amines Chemical group 0.000 claims description 11
- 229920002857 polybutadiene Polymers 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000001993 dienes Chemical class 0.000 claims description 6
- 229920003051 synthetic elastomer Polymers 0.000 claims description 6
- 239000005061 synthetic rubber Substances 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229920003049 isoprene rubber Polymers 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 229920001577 copolymer Polymers 0.000 claims 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 1
- 238000002845 discoloration Methods 0.000 description 16
- 238000005096 rolling process Methods 0.000 description 13
- 239000001993 wax Substances 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 208000030175 lameness Diseases 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、タイヤ用ゴム組成物に関し、耐摩耗性が優れ、転がり抵抗性を損なうことなく、タイヤ外皮ゴムの茶変を改善することも可能で、特にトレッドゴム用に好適に用いることができるタイヤ用ゴム組成物に関するものである。 The present invention relates to a tire rubber composition, which has excellent wear resistance and can improve browning of a tire outer rubber without impairing rolling resistance, and can be suitably used particularly for tread rubber. The present invention relates to a tire rubber composition.
一般に、天然ゴムやジエン系合成ゴムを原料としたゴム物品は、オゾンの存在下で劣化が進行し、表面に亀裂が生じる。この亀裂は、ゴム物品にかかる静的及び動的応力により進行し、その結果、ゴム物品が破壊に至ってしまう。
上記オゾンによる亀裂の発生及び進行を抑制するために、ゴム物品には、老化防止剤として、Ｎ-(１,３-ジメチルブチル)-Ｎ'-フェニル-ｐ-フェニレンジアミン等のアミン系老化防止剤を配合したゴム組成物が適用されている。また、該ゴム組成物には、オゾンからの静的保護を目的として、ゴム物品の表面に保護膜を形成するためにワックスが配合されている。
In general, a rubber article made from natural rubber or a diene synthetic rubber is deteriorated in the presence of ozone, and a crack occurs on the surface. This crack progresses due to static and dynamic stress applied to the rubber article, and as a result, the rubber article is broken.
In order to suppress the occurrence and progression of cracks due to ozone, the rubber article has an anti-aging agent such as N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine as an anti-aging agent. A rubber composition containing an agent is applied. The rubber composition contains a wax for forming a protective film on the surface of the rubber article for the purpose of static protection from ozone.
しかしながら、上記アミン系老化防止剤及びワックスは、オゾン存在下での亀裂の発生及び進行の抑制に有効であるものの、ゴム成分等のポリマー基質を通って移動しやすく、短期間でゴム物品、特にタイヤの表面に移行し、倉庫保管中及び使用中に該ゴム物品を変色させる等して外観を悪化させる。ここで、ワックスが表面に移行すると該表面が白変し、上記アミン系老化防止剤が表面に移行すると該表面が茶変してしまう。 However, although the amine-based anti-aging agent and the wax are effective in suppressing the generation and progress of cracks in the presence of ozone, they are easy to move through a polymer substrate such as a rubber component, and in a short period, particularly rubber articles, It shifts to the surface of the tire and deteriorates the appearance by changing the color of the rubber article during storage and use. Here, when the wax moves to the surface, the surface turns white, and when the amine-based anti-aging agent moves to the surface, the surface turns brown.
これに対し、タイヤサイドウォール用ゴム組成物では非イオン系界面活性剤を配合して、アミン系老化防止剤及びワックスによる変色を防止する技術が開示されている（特許文献１、特許文献２、特許文献３）が、これら技術では、トレッド用ゴム組成物に対しては、それら変色を十分に防止することはできず、本出願人は特定の非イオン系界面活性剤を選択することで、トレッド用ゴム組成物に対しても変色を十分に防止できることを見出した（国際出願番号：ＰＣＴ/ＪＰ２０１１/０６８３８１）。 On the other hand, in the rubber composition for tire sidewalls, a technique for blending a nonionic surfactant to prevent discoloration due to an amine anti-aging agent and wax is disclosed (Patent Document 1, Patent Document 2, Patent Document 3), however, these techniques cannot sufficiently prevent the discoloration of the rubber composition for treads, and the present applicant selects a specific nonionic surfactant, It has been found that discoloration can be sufficiently prevented even with respect to the rubber composition for tread (International Application No. PCT / JP2011 / 068381).
一方、通常タイヤに補強材として含まれるカーボンブラックは、特にトレッドゴム用には、タイヤの耐摩耗性をできるだけ向上させるものであることが好ましいが、転がり抵抗性、湿潤路面での制動性などのお互いが背反する他のタイヤ物性とのバランスがとれることを要する。 On the other hand, carbon black usually contained as a reinforcing material in a tire is preferably one that improves the wear resistance of the tire as much as possible, particularly for tread rubber. However, such as rolling resistance, braking performance on a wet road surface, etc. It needs to be balanced with other tire physical properties that are mutually exclusive.
そこで、本発明の目的は、耐摩耗性が優れ、背反する転がり抵抗性とのバランスがとれたものであり、タイヤ外皮ゴムの茶変を改善することも可能で、特にトレッドゴム用に好適に用いることができるタイヤ用ゴム組成物を提供することにある。 Therefore, the object of the present invention is excellent in wear resistance and balanced with the anti-rolling resistance, and it is possible to improve the browning of the tire outer rubber, particularly suitable for tread rubber. The object is to provide a rubber composition for a tire that can be used.
本発明者らは、上記目的を達成するために鋭意検討した結果、ゴム成分に、窒素吸着比表面積が１４０ｍ2／ｇ以上のカーボンブラック及び特定構造の非イオン系界面活性剤を配合することにより、タイヤのトレッド部に用いても、耐摩耗性が非常に優れ、転がり抵抗性などの背反するタイヤ物性とのバランスがとれていて、かつ、アミン系老化防止剤及びワックスによる変色をも防止することができるタイヤ用ゴム組成物が得られることを見出し、本発明を完成させるに至った。 As a result of diligent studies to achieve the above object, the present inventors have blended a rubber component with carbon black having a nitrogen adsorption specific surface area of 140 m 2 / g or more and a nonionic surfactant having a specific structure. Even when used in tire treads, it has excellent wear resistance, is well balanced with contradictory tire physical properties such as rolling resistance, and prevents discoloration due to amine-based anti-aging agents and waxes. The present inventors have found that a rubber composition for a tire that can be obtained is obtained, and have completed the present invention.
すなわち、本発明は、
［１］ジエン系合成ゴム及び天然ゴムから選択される少なくとも一種のゴム成分、窒素吸着比表面積が１４０ｍ2／ｇ以上のカーボンブラック及び下記式（Ｉ）で表される化合物から選択される少なくとも一種の非イオン系界面活性剤を配合してなることを特徴とするタイヤ用ゴム組成物、
Ｒ2Ｏ（Ｒ1Ｏ)nＨ ・・・（Ｉ）
［式（Ｉ）において、Ｒ2は、炭素数１〜１５のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は直鎖状、分枝鎖状及び環状のいずれでもよく；Ｒ1は、炭素数２〜４のアルキレン基であり；ｎは平均付加モル数を意味し、１１〜３０である。］
That is, the present invention
[1] At least one rubber component selected from diene synthetic rubber and natural rubber, at least one selected from carbon black having a nitrogen adsorption specific surface area of 140 m 2 / g or more, and a compound represented by the following formula (I) A rubber composition for tires, characterized by comprising a nonionic surfactant of
R 2 O (R 1 O) n H (I)
[In formula (I), R 2 represents an alkyl group or an alkenyl group having 1 to 15 carbon atoms, said alkyl and alkenyl groups which may be linear or branched and cyclic; R 1 is , An alkylene group having 2 to 4 carbon atoms; n means the average number of added moles and is 11 to 30. ]
［２］ワックスを配合した上記［１］に記載のタイヤ用ゴム組成物、
［３］老化防止剤を配合した上記［１］又は［２］に記載のタイヤ用ゴム組成物、
［４］前記老化防止剤がアミン系老化防止剤である上記［３］に記載のタイヤ用ゴム組成物、
［５］前記ゴム成分１００質量部に対し、前記非イオン系界面活性剤を０．１〜１０質量部配合した上記［１］〜［４］のいずれかに記載のタイヤ用ゴム組成物、
［６］前記ゴム成分として天然ゴム、イソプレンゴム、スチレン-ブタジエン共重合体ゴム及びポリブタジエンゴムから選ばれる少なくとも１種を含む上記［１］〜［５］のいずれかに記載のタイヤ用ゴム組成物、
［７］前記ゴム成分がスチレン-ブタジエン共重合体ゴム単独、スチレン-ブタジエン共重合体ゴム及びポリブタジエンゴム、天然ゴム及びスチレン-ブタジエン共重合体ゴム、又は天然ゴム及びポリブタジエンゴムである上記［１］〜［６］のいずれかに記載のタイヤ用ゴム組成物、
［８］前記ゴム成分１００質量部のうちスチレン-ブタジエン共重合体ゴムを５０〜１００質量部含む上記［１］〜［７］のいずれかに記載のタイヤ用ゴム組成物、
を提供するものである。
[2] A rubber composition for tires according to the above [1], which contains a wax,
[3] A rubber composition for tires according to the above [1] or [2], which contains an antioxidant.
[4] The tire rubber composition according to [3], wherein the anti-aging agent is an amine-based anti-aging agent,
[5] The rubber composition for tires according to any one of [1] to [4], wherein 0.1 to 10 parts by mass of the nonionic surfactant is blended with 100 parts by mass of the rubber component.
[6] The tire rubber composition according to any one of the above [1] to [5], wherein the rubber component includes at least one selected from natural rubber, isoprene rubber, styrene-butadiene copolymer rubber and polybutadiene rubber. ,
[7] The above [1], wherein the rubber component is styrene-butadiene copolymer rubber alone, styrene-butadiene copolymer rubber and polybutadiene rubber, natural rubber and styrene-butadiene copolymer rubber, or natural rubber and polybutadiene rubber. -The rubber composition for tires in any one of [6],
[8] The rubber composition for tires according to any one of [1] to [7], including 50 to 100 parts by mass of a styrene-butadiene copolymer rubber among 100 parts by mass of the rubber component.
Is to provide.
本発明によれば、ゴム成分に、窒素吸着比表面積が１４０ｍ2／ｇ以上のカーボンブラック及び特定構造の非イオン系界面活性剤を配合してなり、該微粒径のカーボンブラックが該界面活性剤によってゴム成分中に良好に分散される結果、トレッド部に用いても、耐摩耗性が非常に優れていて、転がり抵抗性などの背反するタイヤ物性とのバランスがとれており、かつ、アミン系老化防止剤及びワックスによる変色をも防止することができるタイヤ用ゴム組成物を提供することができる。 According to the present invention, a carbon component having a nitrogen adsorption specific surface area of 140 m 2 / g or more and a nonionic surfactant having a specific structure are blended with a rubber component, and the carbon black having a fine particle size is the surfactant. As a result of being well dispersed in the rubber component by the agent, even when used in the tread part, the wear resistance is very excellent, and it is balanced with the contradictory tire physical properties such as rolling resistance, and amine The rubber composition for tires which can also prevent discoloration by a system anti-aging agent and wax can be provided.
以下に、本発明を詳細に説明する。
本発明のタイヤ用ゴム組成物は、ジエン系合成ゴム及び天然ゴムから選択される少なくとも一種のゴム成分に、窒素吸着比表面積が１４０ｍ2／ｇ以上のカーボンブラック及び上記式（Ｉ）で表される非イオン系界面活性剤の少なくとも一種を配合してなることを特徴とする。
The present invention is described in detail below.
The rubber composition for tires of the present invention is represented by carbon black having a nitrogen adsorption specific surface area of 140 m 2 / g or more and at least one rubber component selected from diene-based synthetic rubber and natural rubber and the above formula (I). It is characterized by blending at least one nonionic surfactant.
本発明のタイヤ用ゴム組成物に用いるゴム成分としては、ジエン系合成ゴム及び天然ゴムが挙げられ、該ジエン系合成ゴムとしては、イソプレンゴム(ＩＲ)、ポリブタジエンゴム(ＢＲ)、スチレン-ブタジエン共重合体ゴム(ＳＢＲ)等が挙げられ、これらゴム成分は、１種単独で用いても２種以上をブレンドして用いてもよい。すなわち、ゴム成分として、天然ゴム、イソプレンゴム、スチレン-ブタジエン共重合体ゴム及びポリブタジエンゴムから選ばれる少なくとも１種を含むことが好ましい。そして、ゴム成分がスチレン-ブタジエン共重合体ゴム単独、スチレン-ブタジエン共重合体ゴム及びポリブタジエンゴムの混合物、天然ゴム及びスチレン-ブタジエン共重合体ゴムの混合物、又は天然ゴム及びポリブタジエンゴムの混合物であることがさらに好ましい。
なお、通常、トレッド部に好ましく用いられるゴム成分はＳＢＲが５０〜１００質量％とＳＢＲ主体である。
Examples of the rubber component used in the tire rubber composition of the present invention include diene-based synthetic rubber and natural rubber. Examples of the diene-based synthetic rubber include isoprene rubber (IR), polybutadiene rubber (BR), and styrene-butadiene copolymer. Examples thereof include polymer rubber (SBR). These rubber components may be used alone or in a blend of two or more. That is, the rubber component preferably contains at least one selected from natural rubber, isoprene rubber, styrene-butadiene copolymer rubber and polybutadiene rubber. The rubber component is a styrene-butadiene copolymer rubber alone, a mixture of styrene-butadiene copolymer rubber and polybutadiene rubber, a mixture of natural rubber and styrene-butadiene copolymer rubber, or a mixture of natural rubber and polybutadiene rubber. More preferably.
In general, the rubber component that is preferably used in the tread portion is mainly SBR with an SBR of 50 to 100% by mass.
本発明のタイヤ用ゴム組成物に用いるカーボンブラックは、窒素吸着比表面積が１４０ｍ2／ｇ以上であることを要する。従来、ゴム補強性、ゴム成分への分散性（生産性）が良好である点から、通常使用されてきたカーボンブラックは、窒素吸着比表面積が１３０程度である。
本発明は、耐摩耗性を向上させるために、窒素吸着比表面積が１４０ｍ2／ｇ以上の微粒径のカーボンブラックを用いるものであり、特定構造の非イオン系界面活性剤とともに配合することにより、凝集することなくゴム成分中に均一に分散することができる。その結果、カーボンブラックとゴム成分との接触面積が大きくなり、予想以上の耐摩耗性が発揮される。また、本発明のタイヤ用ゴム組成物は、耐摩耗性が向上しても、転がり抵抗性が損なわれることがない。
本発明のタイヤ用ゴム組成物において、窒素吸着比表面積が１４０ｍ2／ｇ以上の微粒径のカーボンブラックの配合量は、上記ゴム成分１００質量部に対し２〜１００質量部であることが好ましく、１０〜８０質量部であることがより好ましい。
なお、窒素吸着比表面積はＡＳＴＭ Ｄ３０３７法に準拠してカーボンブラック表面に吸着した窒素量を測定した値で、その値から比表面積を算出し、単位ｍ2／ｇで表示した。
The carbon black used for the tire rubber composition of the present invention is required to have a nitrogen adsorption specific surface area of 140 m 2 / g or more. Conventionally, carbon black that has been used normally has a nitrogen adsorption specific surface area of about 130 because of its good rubber reinforcement and dispersibility (productivity) in rubber components.
The present invention uses carbon black having a fine particle diameter with a nitrogen adsorption specific surface area of 140 m 2 / g or more in order to improve wear resistance, and is blended with a nonionic surfactant having a specific structure. , And can be uniformly dispersed in the rubber component without agglomeration. As a result, the contact area between the carbon black and the rubber component is increased, and wear resistance more than expected is exhibited. Moreover, even if abrasion resistance improves the rubber composition for tires of this invention, rolling resistance is not impaired.
In the tire rubber composition of the present invention, the blending amount of the carbon black having a fine particle diameter with a nitrogen adsorption specific surface area of 140 m 2 / g or more is preferably 2 to 100 parts by mass with respect to 100 parts by mass of the rubber component. 10 to 80 parts by mass is more preferable.
The nitrogen adsorption specific surface area is a value obtained by measuring the amount of nitrogen adsorbed on the carbon black surface in accordance with the ASTM D3037 method. The specific surface area was calculated from the value and expressed in units of m 2 / g.
本発明のタイヤ用ゴム組成物に用いる非イオン系界面活性剤は、上記式（I）で表される。該非イオン系界面活性剤は、１種単独で使用してもよいし、２種以上を併用してもよく、市販品を好適に使用することができる。
式（I）のＲ2は、炭素数１〜１５のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は直鎖状、分枝鎖状及び環状の何れでもよい。これらアルキル基及びアルケニル基の炭素数は、主にタック性、接着性及び変色度の観点から、好ましくは６〜１５、更に好ましくは６〜１４、より更に好ましくは８〜１２である。
式（I）のＲ1は、炭素数２〜４のアルキレン基であり、好ましくは炭素数２又は３のアルキレン基であり、更に好ましくは炭素数２のアルキレン基である。
式（I）のｎは、主にタック性、接着性及び変色度の観点から、１１〜３０であり、好ましくは１２〜２５であり、より好ましくは１６〜２５である。
The nonionic surfactant used for the tire rubber composition of the present invention is represented by the above formula (I). This nonionic surfactant may be used individually by 1 type, may use 2 or more types together, and can use a commercial item suitably.
R 2 in formula (I) represents an alkyl group or alkenyl group having 1 to 15 carbon atoms, and the alkyl group and alkenyl group may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group and alkenyl group is preferably 6 to 15, more preferably 6 to 14, and still more preferably 8 to 12 mainly from the viewpoint of tackiness, adhesiveness, and discoloration.
R 1 in formula (I) is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
N of Formula (I) is 11-30 mainly from a viewpoint of tack property, adhesiveness, and a discoloration degree, Preferably it is 12-25, More preferably, it is 16-25.
上記非イオン系界面活性剤は、ＨＬＢ値（親水性と親油性のバランス値）が１０〜１９であるのが好ましい。ここで、本発明において、ＨＬＢ値は、下記に示すグリフィンの式で定義される。
ＨＬＢ＝２０×Ｍｗ／Ｍ
（式中、Ｍは非イオン系界面活性剤の分子量で；Ｍｗは該非イオン系界面活性剤の親水性部分の分子量である。）
The nonionic surfactant preferably has an HLB value (balance between hydrophilicity and lipophilicity) of 10 to 19. Here, in the present invention, the HLB value is defined by the Griffin equation shown below.
HLB = 20 × Mw / M
(In the formula, M is the molecular weight of the nonionic surfactant; Mw is the molecular weight of the hydrophilic portion of the nonionic surfactant.)
上記非イオン系界面活性剤のＨＬＢ値が１０以上では親油性が抑制され、ゴムとの相溶性を抑えて、表面に移行させることができ、１９以下では、ゴムとの相溶性を高めて、混練を容易にし、かつ充填剤への吸着を抑制し、表面に移行させることができる。
上記非イオン系界面活性剤のＨＬＢ値は、１５〜１９であるのが更に好ましく、１５〜１８がより更に好ましい。ＨＬＢ値が１５以上では、表面への移行速度を高めて、茶変防止効果を促進することができる。
When the HLB value of the nonionic surfactant is 10 or more, the lipophilicity is suppressed, and the compatibility with rubber can be suppressed and transferred to the surface, and when it is 19 or less, the compatibility with rubber is increased. Kneading can be facilitated, adsorption to the filler can be suppressed, and transfer to the surface can be achieved.
The HLB value of the nonionic surfactant is more preferably 15-19, and still more preferably 15-18. When the HLB value is 15 or more, the transition speed to the surface can be increased, and the effect of preventing browning can be promoted.
本発明のタイヤ用ゴム組成物において、上記非イオン系界面活性剤の配合量は、上記ゴム成分１００質量部に対し０．１〜１０質量部であることが好ましく、０．５〜７質量部であることが更に好ましく、０．５〜５質量部であることが極めて好ましい。０．１質量部以上では、上記微粒径のカーボンブラックをゴム成分中に均一に分散することができ、かつ、アミン系老化防止剤やワックスによる変色を防止することができる。１０質量部以下では、界面活性剤のブルームによる過度の光沢を抑制することができ、表面粘着性による作業性の低下を抑えることができる。 In the tire rubber composition of the present invention, the amount of the nonionic surfactant is preferably 0.1 to 10 parts by mass, and 0.5 to 7 parts by mass with respect to 100 parts by mass of the rubber component. More preferably, it is very preferably 0.5 to 5 parts by mass. When the amount is 0.1 parts by mass or more, the carbon black having the fine particle diameter can be uniformly dispersed in the rubber component, and discoloration due to the amine-based anti-aging agent or wax can be prevented. When the amount is 10 parts by mass or less, excessive gloss due to the bloom of the surfactant can be suppressed, and deterioration in workability due to surface tackiness can be suppressed.
上記タイヤ用ゴム組成物には、オゾンによる亀裂の発生及び進行を抑制するために、アミン系老化防止剤及びワックスを配合するのが好ましい。ここで、アミン系老化防止剤としては、Ｎ-(１,３-ジメチルブチル)-Ｎ'-フェニル-ｐ-フェニレンジアミン等が挙げられる。
タイヤ外皮の茶変は、老化防止剤及びワックスがゴム成分等のポリマー基質を通ってタイヤ表面に移行し、タイヤの表面にワックスが析出して凹凸面を形成し光散乱が起こり、その凹凸面に付着した老化防止剤が酸化されて着色成分になることで、茶変色に見えるものであるが、本発明のタイヤ用ゴム組成物においては、上記式（I）で表される非イオン系界面活性剤が、表面に析出したワックスの凹凸面を平滑面化することにより、光散乱状態を改善して茶変を改良する。
すなわち、該非イオン系界面活性剤は、疎水基Ｒ2の長さ、親水基(Ｒ1Ｏ)nの長さが調整されゴム組成物との相溶性がコントロールされて、該ゴム組成物と適度の非相溶性を有しているために、タイヤ表面に析出して上記機能を発揮する。
In order to suppress the occurrence and progress of cracks due to ozone, the rubber composition for tires is preferably blended with an amine anti-aging agent and a wax. Here, examples of the amine-based antioxidant include N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine.
The browning of the tire hull is caused by the anti-aging agent and the wax passing through the polymer substrate such as a rubber component to the tire surface, and the wax deposits on the surface of the tire to form an uneven surface and light scattering occurs. The anti-aging agent adhering to the oxidant is oxidized to become a coloring component, so that it looks like a brown discoloration. In the tire rubber composition of the present invention, the nonionic interface represented by the above formula (I) The activator smoothes the uneven surface of the wax deposited on the surface, thereby improving the light scattering state and improving browning.
That is, the nonionic surfactant is adjusted to have a suitable length with the rubber composition by adjusting the length of the hydrophobic group R 2 and the length of the hydrophilic group (R 1 O) n to control the compatibility with the rubber composition. Therefore, it is deposited on the tire surface and exhibits the above functions.
該タイヤ用ゴム組成物には、更に、加硫剤、加硫促進剤、スコーチ防止剤、軟化剤、酸化亜鉛、ステアリン酸等のゴム業界で通常使用される配合剤を、本発明の目的を害しない範囲内で適宜選択し配合することができる。これら配合剤は、市販品を好適に使用することができる。 The rubber composition for tires further includes a compounding agent usually used in the rubber industry such as a vulcanizing agent, a vulcanization accelerator, a scorch preventing agent, a softening agent, zinc oxide, and stearic acid. It can be appropriately selected and blended within a range not harming. As these compounding agents, commercially available products can be suitably used.
なお、上記タイヤ用ゴム組成物は、ゴム成分と、微粒径のカーボンブラック及び非イオン系界面活性剤と、必要に応じて適宜選択した各種配合剤とを混練り、熱入れ、押出等することにより製造することができる。 The rubber composition for a tire is kneaded, heated, extruded, etc., with a rubber component, fine particle size carbon black and a nonionic surfactant, and various compounding agents appropriately selected as necessary. Can be manufactured.
上記タイヤ用ゴム組成物は、タイヤのゴム部材の何れかに適用されるが、タイヤ外皮、特にトレッド部に適用したものが好ましい。かかるタイヤは、上記微粒径のカーボンブラック及び非イオン系界面活性剤を配合することで、微粒径のカーボンブラックがゴム成分中に均一に分散されているため、タイヤの耐摩耗性が優れ、転がり抵抗性も損なわれず、かつ、アミン系老化防止剤やワックスがタイヤ表面に移行して変色するのが防止されており、外観が長期に亘って良好である。 The tire rubber composition is applied to any of the rubber members of the tire, but is preferably applied to the tire skin, particularly the tread portion. Such a tire has excellent wear resistance of the tire because the fine particle size carbon black is uniformly dispersed in the rubber component by blending the fine particle size carbon black and the nonionic surfactant. Further, the rolling resistance is not impaired, and the amine-based anti-aging agent and wax are prevented from being transferred to the tire surface and discolored, and the appearance is good for a long period of time.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
比較例１〜４及び実施例１〜２
表１に示す配合処方（配合成分量は質量部）で配合したタイヤ用ゴム組成物を調製し、１６０℃で１４分間加硫した。得られた加硫ゴム及びタイヤにつき、下記の方法で耐摩耗性、湿潤路面での制動性、転がり抵抗性、変色度を測定、評価した。その結果を表１に示す。
Comparative Examples 1-4 and Examples 1-2
A rubber composition for tires blended with the blending formulation shown in Table 1 (the amount of blending component is parts by mass) was prepared and vulcanized at 160 ° C. for 14 minutes. The obtained vulcanized rubber and tire were measured and evaluated for wear resistance, braking performance on wet road surfaces, rolling resistance and discoloration by the following methods. The results are shown in Table 1.
（１）耐摩耗性
ＪＩＳ−Ｋ６２６４のランボーン型摩耗試験に準じて試験を実施した。ランボーン型摩耗試験機を用い、室温２３℃におけるスリップ率２５％での摩耗量を測定し、比較例１を１００として指数表示した。指数が大きい程、耐摩耗性は良好である。
(1) Abrasion resistance A test was carried out in accordance with the lambone type abrasion test of JIS-K6264. The amount of wear at a slip rate of 25% at a room temperature of 23 ° C. was measured using a Lambone-type wear tester, and Comparative Example 1 was set as 100 and indicated as an index. The higher the index, the better the wear resistance.
（２）湿潤路面での制動性
各配合のゴム組成物から試作したタイヤを、排気量２０００ｃｃの乗用車に４本装着し、テストコースの湿潤アスファルト路面にて、初速度７０ｋｍ／ｈｒからの制動距離を測定した。比較例１の測定値を１００とし、他例については、比較例１の制動距離÷供試タイヤの制動距離×１００にて指数を求め指数表示した。指数が大なる程良好である。
(2) Braking performance on wet roads Four tires made from rubber compositions of each formulation were mounted on a 2000cc passenger car, and the braking distance from the initial speed of 70km / hr on the wet asphalt road surface of the test course. Was measured. The measured value of Comparative Example 1 was set to 100, and for the other examples, an index was calculated and displayed as an index by the braking distance of Comparative Example 1 / the braking distance of the test tire × 100. The higher the index, the better.
（３）転がり抵抗性
各配合のゴム組成物から試作したタイヤを、３．９２ｋＮの荷重の作用下で、直径１７００ｍｍの回転ドラムを用いて８０ｋｍ／ｈの速度で回転させたときの転がり抵抗を、惰行法により測定し、比較例１を１００とした指数として示した。転がり抵抗の指数が大きいほど、転がり抵抗は小さく良好であることを示す。
(3) Rolling resistance Rolling resistance when a tire made from a rubber composition of each blend was rotated at a speed of 80 km / h using a rotating drum having a diameter of 1700 mm under the action of a load of 3.92 kN. , Measured by the lameness method, and shown as an index with Comparative Example 1 as 100. The larger the rolling resistance index, the smaller and better the rolling resistance.
（４）変色度
色度計（「日本電色工業（株）、機種名ＮＦ３３３」）を用いて、顆粒ゴム試験片の変色度を評価した。測色したデータはｂ*で表わした。ｂ*は色味を示している。ｂ*値は０で無色、ｂ*値が正であるほど黄、負であるほど青であることを示す。変色度については、夏季の屋外放置（雨は当たらない屋根の下１日のうち特定の時間のみ直射日光が当たる）の環境条件下に、加硫ゴム片を１ヶ月放置した後のｂ*値及び目視による変色の度合いにより放置後の変色度を評価した。
(4) Discoloration degree Using a chromaticity meter (“Nippon Denshoku Industries Co., Ltd., model name NF333”), the discoloration degree of the granular rubber test piece was evaluated. The measured color data is represented by b *. b * indicates the color. The b * value is 0 and colorless, the positive b * value is yellow, and the negative is blue. For discoloration, b * value after leaving the vulcanized rubber piece for one month under the environmental conditions of leaving it outdoors in the summer (directly exposed to sunlight for a specific period of time under a roof that is not exposed to rain) The degree of discoloration after standing was evaluated based on the degree of discoloration visually.
＊１ ＪＳＲ(株）製「ＳＢＲ＃１５００」
＊２ 昭和キャボット(株）製「ショウブラックＮ２３４」（窒素吸着比表面積：１２３ｍ2／ｇ）
＊３ 昭和キャボット(株）製「ショウブラックＮ１３４」（窒素吸着比表面積：１４８ｍ2／ｇ）
＊４ 花王(株）製非イオン系界面活性剤「エマルゲン１１１８」（ポリオキシエチレンアルキルエーテル）（上記式(I)において、Ｒ2が主としてＣ11Ｈ23、Ｒ1がＣ2Ｈ4、ｎが１８、ＨＬＢ値が１６．４）
＊５ マイクロクリスタリンワックス，日本精蝋社製「オゾエース−０７０１」
＊６ 大内新興化学工業製 「ノクラック６Ｃ」：Ｎ−（１，３−ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレンジアミン
＊７ 大内新興化学工業製 「ノクセラーＣＺ」
* 1 "SBR # 1500" manufactured by JSR Corporation
* 2 “Show Black N234” manufactured by Showa Cabot Co., Ltd. (nitrogen adsorption specific surface area: 123 m 2 / g)
* 3 “Show Black N134” manufactured by Showa Cabot Co., Ltd. (nitrogen adsorption specific surface area: 148 m 2 / g)
* 4 Nonionic surfactant “Emulgen 1118” (polyoxyethylene alkyl ether) manufactured by Kao Corporation (in the above formula (I), R 2 is mainly C 11 H 23 , R 1 is C 2 H 4 , n 18 and HLB value is 16.4)
* 5 Microcrystalline wax, Nippon Seiwa Co., Ltd. “Ozoace-0701”
* 6 "Nocrack 6C" manufactured by Ouchi Shinsei Chemical Industry: N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine * 7 "Noxeller CZ" manufactured by Ouchi Shinsei Chemical Industry
表１から、カーボン（Ｂ）と界面活性剤（エマルゲン１１１８）を配合すると、微粒径カーボンを使用しても、分散性がよく、ゴム組成物は耐摩耗性に優れ、タイヤの転がり抵抗性や湿潤路面での制動性も損なわれることなく、変色度も良好であることがわかる。 From Table 1, when carbon (B) and a surfactant (Emulgen 1118) are blended, even if fine particle size carbon is used, the dispersibility is good, the rubber composition has excellent wear resistance, and rolling resistance of the tire. It can be seen that the degree of discoloration is also good without impairing the braking performance on wet road surfaces.
Claims (7)
Ｒ２Ｏ（Ｒ１Ｏ)ｎＨ ・・・（Ｉ）
［式（Ｉ）において、Ｒ２は、炭素数１〜１５のアルキル基又はアルケニル基を表し、該アルキル基及びアルケニル基は直鎖状、分枝鎖状及び環状のいずれでもよく；Ｒ１は、炭素数２〜４のアルキレン基であり；ｎは平均付加モル数を意味し、１１〜３０である。］ From 100 parts by mass of at least one rubber component selected from diene-based synthetic rubber and natural rubber, 10 to 80 parts by mass of carbon black having a nitrogen adsorption specific surface area of 140 m 2 / g or more, and a compound represented by the following formula (I) A tire rubber composition comprising 0.1 to 10 parts by mass of at least one nonionic surfactant selected .
R 2 O (R 1 O) n H (I)
[In formula (I), R 2 represents an alkyl group or an alkenyl group having 1 to 15 carbon atoms, said alkyl and alkenyl groups which may be linear or branched and cyclic; R 1 is , An alkylene group having 2 to 4 carbon atoms; n means the average number of added moles and is 11 to 30. ]
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