JP3410938B2 - Rubber composition for tire tread - Google Patents
Rubber composition for tire treadInfo
- Publication number
- JP3410938B2 JP3410938B2 JP24831797A JP24831797A JP3410938B2 JP 3410938 B2 JP3410938 B2 JP 3410938B2 JP 24831797 A JP24831797 A JP 24831797A JP 24831797 A JP24831797 A JP 24831797A JP 3410938 B2 JP3410938 B2 JP 3410938B2
- Authority
- JP
- Japan
- Prior art keywords
- kneading
- rubber
- weight
- rubber composition
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001971 elastomer Polymers 0.000 title claims description 57
- 239000005060 rubber Substances 0.000 title claims description 57
- 239000000203 mixture Substances 0.000 title claims description 36
- 238000004898 kneading Methods 0.000 claims description 38
- 238000004073 vulcanization Methods 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 19
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 16
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 9
- 239000012990 dithiocarbamate Substances 0.000 claims description 9
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 18
- 238000005096 rolling process Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 235000014692 zinc oxide Nutrition 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 238000004904 shortening Methods 0.000 description 4
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 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 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- IQAOOXSQYILFSN-UHFFFAOYSA-N C(N)(S)=S.C(CCC)[Zn]CCCC Chemical compound C(N)(S)=S.C(CCC)[Zn]CCCC IQAOOXSQYILFSN-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- Tyre Moulding (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高ウェットグリッ
プ性および低転がり抵抗が両立したタイヤを提供するト
レッド用ゴム組成物に関する。TECHNICAL FIELD The present invention relates to a rubber composition for a tread which provides a tire having both high wet grip properties and low rolling resistance.
【０００２】[0002]
【従来の技術】従来から、自動車の低燃費化の要請に応
じて、転がり抵抗の低いタイヤを提供するトレッド用ゴ
ム組成物が求められており、かつ安全面からは湿潤路面
でのグリップ性、すなわちウェットグリップ性の高いタ
イヤを提供するトレッド用ゴム組成物が求められてい
る。2. Description of the Related Art Conventionally, there has been a demand for a rubber composition for a tread which provides a tire with low rolling resistance in response to a request for low fuel consumption of an automobile, and from the viewpoint of safety, gripping property on a wet road surface, That is, there is a need for a rubber composition for a tread that provides a tire with high wet grip properties.
【０００３】これらタイヤの転がり抵抗およびウェット
グリップ性は、トレッドゴムのヒステリシスロス（ｔａ
ｎδ）に関連しており、約７０℃におけるｔａｎδが小
さいほど転がり抵抗が低く、約０℃におけるｔａｎδが
大きいほどウェットグリップ性が高いという関係にあ
り、両者を両立させることは困難であった。The rolling resistance and wet grip properties of these tires depend on the hysteresis loss (ta) of the tread rubber.
n.delta.), the smaller the tan.delta. at about 70.degree. C., the lower the rolling resistance, and the larger the tan.delta. at about 0.degree. C., the higher the wet grip property, and it was difficult to satisfy both.
【０００４】ところで、特願平９−１８３４２５号明細
書においては、タイヤのインナーライナーやケースに好
適なゴム組成物として、低空気透過性の官能基加硫性ゴ
ムと二重結合加硫性ゴムという特定のゴムの組合せを特
定の配合割合で用い、かつ２段階の混練りを行なうこと
により、選択的に加硫した前記官能基加硫性ゴムを含む
ゴム組成物をうる技術を開示している。かかる技術によ
りえられるゴム組成物は、他のジエン系ゴム組成物との
加硫接着性および低空気透過性に優れているというもの
である。In Japanese Patent Application No. 9-183425, a rubber composition suitable for an inner liner or a case of a tire is disclosed as a low air permeability functional group vulcanizable rubber and double bond vulcanizable rubber. Disclosed is a technique for obtaining a rubber composition containing the selectively vulcanized functional group vulcanizable rubber by using a specific rubber combination in a specific compounding ratio and performing two-stage kneading. There is. The rubber composition obtained by such a technique is excellent in vulcanization adhesion to other diene rubber compositions and low air permeability.
【０００５】本発明者らは、前記技術にもとづき、前記
低空気透過性の官能基加硫性ゴムとしてイソブチレン／
ｐ−メチルスチレン共重合体の臭素化物を用い、かつ特
定の配合割合を選択することによりえられたゴム組成物
を、タイヤのトレッドに適用してみたところ、前述した
高ウェットグリップ性および低転がり抵抗を両立するこ
とができることを見出し、本発明を完成するに至った。Based on the above-mentioned technique, the inventors of the present invention have proposed isobutylene / isobutylene as the low-air permeability functional group vulcanizable rubber.
When a rubber composition obtained by using a bromide of a p-methylstyrene copolymer and selecting a specific blending ratio was applied to a tread of a tire, the above-mentioned high wet grip property and low rolling property were obtained. They have found that they can achieve both resistance, and have completed the present invention.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、高ウ
ェットグリップ性および低転がり抵抗を両立させたタイ
ヤを提供することのできるタイヤトレッド用ゴム組成物
をうることにある。SUMMARY OF THE INVENTION An object of the present invention is to obtain a rubber composition for a tire tread capable of providing a tire having both high wet grip properties and low rolling resistance.
【０００７】[0007]
【課題を解決するための手段】本発明は、（ａ）ポリイ
ソブチレン／ｐ−メチルスチレン共重合体の臭素化物１
００重量部とＺｎＯ ０．１〜５重量部およびジチオカ
ルバミン酸塩系加硫促進剤０．１〜５重量部とを予備混
練りし、ついで
（ｂ）えられる予備混練物と他のゴム成分とを混練りす
ることによりえられるタイヤトレッド用ゴム組成物に関
する。The present invention provides (a) a bromide 1 of a polyisobutylene / p-methylstyrene copolymer.
00 parts by weight and ZnO 0.1-5 parts by weight and dithioca
A rubber composition for a tire tread obtained by pre-kneading 0.1 to 5 parts by weight of a rubamate vulcanization accelerator and then (b) kneading the pre-kneaded product and other rubber components. Regarding things.
【０００８】このばあい、予備混練りは４０〜１００℃
の温度範囲で行なうのが好ましい。In this case, the preliminary kneading is 40 to 100 ° C.
It is preferable to carry out in the temperature range.
【０００９】[0009]
【発明の実施の形態】本発明は、（ａ）ポリイソブチレ
ン／ｐ−メチルスチレン共重合体の臭素化物とＺｎＯお
よびジチオカルバミン酸塩系加硫促進剤とを予備混練り
し、ついで
（ｂ）えられる予備混練物と他のゴム成分とを混練りす
ることによりえられるタイヤトレッド用ゴム組成物に関
する。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, (a) a bromide of a polyisobutylene / p-methylstyrene copolymer is pre-kneaded with ZnO and a dithiocarbamate vulcanization accelerator, and then (b) The present invention relates to a rubber composition for a tire tread obtained by kneading the pre-kneaded product and another rubber component.
【００１０】工程（ａ）においては、まずイソブチレン
／ｐ−メチルスチレン共重合体の臭素化物とＺｎＯおよ
びジチオカルバミン酸塩系加硫促進剤とを予備混練りす
る。In the step (a), first, a bromide of isobutylene / p-methylstyrene copolymer is preliminarily kneaded with ZnO and a dithiocarbamate vulcanization accelerator .
【００１１】前記ＺｎＯは、後述する（ｂ）工程におい
て、イソブチレン／ｐ−メチルスチレン共重合体の臭素
化物を加硫する役割を果たすものであり、反応性が高い
という点から好ましい。[0011] The ZnO, in later-described step (b), Ri playing a role der vulcanizing the brominated isobutylene / p- methylstyrene copolymer, RaYoshimi Masui or terms of high reactivity .
【００１２】工程（ａ）におけるＺｎＯの混練割合とし
ては、イソブチレン／ｐ−メチルスチレン共重合体の臭
素化物１００重量部に対して、ゴムの物性の向上という
点から０．１〜５重量部であるのが好ましく、さらに混
練り時間の短縮という点から０．５〜５重量部であるの
が好ましい。[0012] As the kneading ratio of ZnO in the step (a), the in respect bromide 100 parts by weight of isobutylene / p- methylstyrene copolymer, 0.1 to 5 parts by weight from the viewpoint of improving the property of the rubber It is preferably 0.5 to 5 parts by weight from the viewpoint of shortening the kneading time.
But good Masui.
【００１３】つぎに、本発明において用いるジチオカル
バミン酸塩系加硫促進剤は、本発明のゴム組成物におい
てイソブチレン／ｐ−メチルスチレン共重合体の臭素化
物を（ｂ）工程でＺｎＯで加硫するときの加硫促進剤と
しての役割を果たすものである。前記ジチオカルバミン
酸塩系加硫促進剤としては、たとえばつぎのようなもの
があげられる：ジメチルジチオカルバミン酸亜鉛、ジエ
チルジチオカルバミン酸亜鉛、ジ−ｎ−ブチルジチオカ
ルバミン酸亜鉛など。これらは、通常ゴムの分野でジチ
オカルバミン酸塩系加硫促進剤として用いられている。 Next, the dithiocal used in the present invention
The baminate vulcanization accelerator plays a role as a vulcanization accelerator when vulcanizing the bromide of the isobutylene / p-methylstyrene copolymer with ZnO in the step (b) in the rubber composition of the present invention. To fulfill. The dithiocarbamine
The acid salt-based vulcanization accelerator, for example, those as follows: di-methyl dithiocarbamate, zinc diethyl dithiocarbamate, di -n- butyl zinc dithiocarbamate like. These are usually used as dithiocarbamate vulcanization accelerators in the field of rubber.
【００１４】前記ジチオカルバミン酸塩系加硫促進剤
は、混練り時間を短くするという点およびゴムの加硫を
制御しやすいという点から特に好ましい。The dithiocarbamate vulcanization accelerator
Preferably, the point or al Patent in that it permits easy control of the vulcanization point and rubber of shortening the kneading time.
【００１５】前記ジチオカルバミン酸塩系加硫促進剤の
混練割合としては、イソブチレン／ｐ−メチルスチレン
共重合体の臭素化物１００重量部に対して、ゴム物性の
向上という点から０．１〜５重量部であるのが好まし
く、さらに、混練り時間の短縮という点から０．５〜５
重量部であるのが好ましい。[0015] As the kneading ratio of the dithiocarbamate vulcanization accelerator, and to isobutylene / p- methylstyrene copolymer brominated 100 parts by weight of 0.1 to 5 weight from the viewpoint of improvement in rubber properties It is preferably 0.5 to 5 parts from the viewpoint of shortening the kneading time.
Virtuous preferable in the range of parts by weight.
【００１６】前記工程（ａ）の予備混練りの条件として
は、予備混練りをイソブチレン／ｐ−メチルスチレン共
重合体の臭素化物を加硫させない温度範囲で行なえばよ
く、４０〜１００℃であればよいが、加工性の向上とい
う点から６０〜１００℃の温度範囲で行なうのが好まし
く、さらに、物性の改善という点から６０〜９０℃の温
度範囲で行なうのが特に好ましい。また、予備混練り
は、えられるゴム組成物の物性を安定させるという点か
らはオープンロールを用いて行なうのが好ましく、加工
性および作業性を高めるという点からはバンバリーミキ
サーを用いて行なうのが好ましい。The conditions for the preliminary kneading in the step (a) may be such that the preliminary kneading is carried out within a temperature range in which the bromide of the isobutylene / p-methylstyrene copolymer is not vulcanized, and it is 40 to 100 ° C. Although it is sufficient, it is preferably carried out in the temperature range of 60 to 100 ° C. from the viewpoint of improving workability, and particularly preferably in the temperature range of 60 to 90 ° C. from the viewpoint of improving physical properties. Further, the pre-kneading is preferably performed using an open roll from the viewpoint of stabilizing the physical properties of the obtained rubber composition, and is performed using a Banbury mixer from the viewpoint of improving workability and workability. preferable.
【００１７】なお、工程（ａ）においては、本発明の効
果を損なわない範囲で加硫促進助剤、ミネラルオイルな
どのプロセスオイル、カーボンブラックなどの充填剤な
どを添加してもよい。In the step (a), a vulcanization accelerating aid, a process oil such as mineral oil, a filler such as carbon black and the like may be added within a range not impairing the effects of the present invention.
【００１８】ついで本発明においては、工程（ｂ）によ
り、工程（ａ）でえられた予備混練物と他のゴム成分と
を混練りして予備混練物中のイソブチレン／ｐ−メチル
スチレン共重合体の臭素化物を選択的に加硫して本発明
のゴム組成物をうることができる。Then, in the present invention, in step (b), the pre-kneaded product obtained in step (a) is kneaded with other rubber components to obtain an isobutylene / p-methylstyrene copolymerization weight in the pre-kneaded product. The combined bromide can be selectively vulcanized to obtain the rubber composition of the present invention.
【００１９】他のゴム成分としては、従来からタイヤト
レッド用に使用されており、かつ工程（ｂ）における混
練りにより前述のＺｎＯや前記ジチオカルバミン酸塩系
加硫促進剤では加硫せず、イオウにより加硫しうるもの
であればよい。かかるゴム成分としては、たとえば天然
ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴ
ム（ＢＲ）、スチレン−ブタジエンゴム（ＳＢＲ）、ア
クリロニトリル−ブタジエンゴム（ＮＢＲ）などの、炭
素−炭素二重結合部分で加硫しうるものなどがあげら
れ、単独で、または任意に組合せて用いることができ
る。これらのなかでも、えられるタイヤトレッドの機械
的強度を向上させるという点、さらに、えられるゴム組
成物に粘着性を付与するという点からＮＲ、ＳＢＲを用
いるのが特に好ましい。Other rubber components have been conventionally used for tire treads, and by the kneading in the step (b), the above-mentioned ZnO or dithiocarbamate-based compounds are used.
Any vulcanization accelerator may be used as long as it can be vulcanized by sulfur without being vulcanized. Examples of such rubber component include carbon-carbon double bond moieties such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), and acrylonitrile-butadiene rubber (NBR). Examples thereof include those that can be vulcanized, and these can be used alone or in any combination. Among these, it is particularly preferable to use NR and SBR from the viewpoint of improving the mechanical strength of the obtained tire tread and further imparting tackiness to the obtained rubber composition.
【００２０】工程（ｂ）において、工程（ａ）でえられ
た予備混練物と他のゴム成分との混練割合については、
イソブチレン／ｐ−メチルスチレン共重合体の臭素化物
１００重量部に対する他のゴム成分の配合量は５０〜９
００重量部であればよいが、耐摩耗性という点から２０
０〜９００重量部であるのが好ましく、さらに、ウェッ
トグリップ性を高めるという点から２００〜７００重量
部であるのが特に好ましい。In step (b), the kneading ratio of the pre-kneaded product obtained in step (a) and the other rubber component is as follows:
The compounding amount of the other rubber component is 50 to 9 with respect to 100 parts by weight of the bromide of the isobutylene / p-methylstyrene copolymer.
It may be 100 parts by weight, but 20 from the viewpoint of wear resistance.
The amount is preferably 0 to 900 parts by weight, and more preferably 200 to 700 parts by weight from the viewpoint of enhancing wet grip properties.
【００２１】工程（ｂ）においては、イソブチレン／ｐ
−メチルスチレン共重合体の臭素化物と他のゴム成分と
のブレンド物中のイソブチレン／ｐ−メチルスチレン共
重合体の臭素化物のみを選択的に加硫させる。In step (b), isobutylene / p
Selectively vulcanize only the bromide of isobutylene / p-methylstyrene copolymer in the blend of the bromide of methylstyrene copolymer with other rubber components.
【００２２】工程（ｂ）における混練りはイソブチレン
／ｐ−メチルスチレン共重合体の臭素化物が加硫しうる
温度範囲で行なえばよいが、天然ゴムが含まれているば
あいは１００〜１６０℃の温度範囲で行なうのが好まし
く、さらに、混練時間の短縮という点から１２０〜１６
０℃の温度範囲で行なうのが特に好ましい。The kneading in the step (b) may be carried out within a temperature range in which the bromide of the isobutylene / p-methylstyrene copolymer can be vulcanized, but when natural rubber is contained, it is 100 to 160 ° C. Is preferably carried out within the temperature range of 120 to 16 from the viewpoint of shortening the kneading time.
It is particularly preferable to carry out in the temperature range of 0 ° C.
【００２３】なお、工程（ｂ）における混練り（選択的
加硫）時の温度は、工程（ａ）における予備混練り時の
温度よりも高い。また、工程（ｂ）の混練りは、加工性
および作業性の向上という点からバンバリーミキサーを
用いて行なうのが好ましい。The temperature during kneading (selective vulcanization) in step (b) is higher than the temperature during pre-kneading in step (a). Further, the kneading in the step (b) is preferably performed using a Banbury mixer from the viewpoint of improving workability and workability.
【００２４】また、工程（ｂ）においては、本発明の効
果を損なわない範囲で、加硫促進助剤、加硫促進剤、プ
ロセスオイル、カーボンブラックなどの充填剤などを添
加してもよい。Further, in the step (b), a vulcanization accelerator auxiliary agent, a vulcanization accelerator, a process oil, a filler such as carbon black and the like may be added to the extent that the effects of the present invention are not impaired.
【００２５】他のゴム成分の加硫は、えられた本発明の
ゴム組成物に、たとえば他のゴム成分用の加硫剤である
イオウを所定量（たとえば他のゴム成分１００重量部に
対して０．５〜５重量部）加え、要すればＮ−ｔｅｒｔ
−ブチル−２−ベンゾチアゾリルスルフェンアミドなど
の加硫促進剤、亜鉛華などを適宜配合してロールなどで
混練りし、成形したのち加熱することにより行なえばよ
い。The vulcanization of the other rubber component is carried out by adding a predetermined amount of sulfur, which is a vulcanizing agent for the other rubber component, to the obtained rubber composition of the present invention (for example, 100 parts by weight of the other rubber component). 0.5-5 parts by weight), and if necessary, N-tert
A vulcanization accelerator such as -butyl-2-benzothiazolyl sulfenamide, zinc white, etc. may be appropriately mixed, kneaded with a roll or the like, molded, and then heated.
【００２６】本発明においては、ゴム組成物の組成およ
び混練条件として、たとえばつぎのような組合せを好ま
しくあげることができる。In the present invention, as the composition of the rubber composition and the kneading conditions, the following combinations can be preferably exemplified.
【００２７】 （例１） イソブチレン／ｐ−メチルスチレン共重合体の臭素化物 １００重量部 ＺｎＯ ０．５〜３重量部 ジチオカルバミン酸塩系加硫促進剤（ジエチルジチオカルバミン酸亜鉛） ０．５〜３重量部 他のゴム成分（天然ゴム） １００〜５００重量部 工程（ａ）の予備混練温度 ６０〜９０℃ 工程（ａ）の予備混練時間 ２〜８分間 工程（ｂ）の混練温度 １００〜１３０℃ 工程（ｂ）の混練時間 ６〜１０分間[0027] (Example 1) isobutylene / p- methylstyrene copolymers of brominated 100 parts by weight Z nO 0.5-3 parts by weight Dithiocarbamate vulcanization accelerator (zinc diethyldithiocarbamate) 0.5-3 parts by weight Other rubber component (natural rubber) 100-500 parts by weight Pre-kneading temperature of step (a) 60 ~ 90 ° C Pre-kneading time of step (a) 2-8 minutes Kneading temperature of step (b) 100-130 ° C Kneading time of step (b) 6-10 minutes
【００２８】[0028]
【００２９】 （例２） イソブチレン／ｐ−メチルスチレン共重合体の臭素化物 １００重量部 ＺｎＯ ０．５〜３重量部 ジチオカルバミン酸塩系加硫促進剤（ジエチルジチオカルバミン酸亜鉛） ０．５〜３重量部 他のゴム成分（ＳＢＲ） ２００〜７００重量部 工程（ａ）の予備混練温度 ６０〜９０℃ 工程（ａ）の予備混練時間 ２〜８分間 工程（ｂ）の混練温度 １００〜１３０℃ 工程（ｂ）の混練時間 ４〜１０分間[0029] (Example 2) isobutylene / p- methylstyrene copolymers of brominated 100 parts by weight Z nO 0.5-3 parts by weight Dithiocarbamate vulcanization accelerator (zinc diethyldithiocarbamate) 0.5-3 parts by weight Other rubber component (SBR) 200-700 parts by weight Pre-kneading temperature of step (a) 60- 90 ° C Step (a) pre-kneading time 2 to 8 minutes Step (b) kneading temperature 100 to 130 ° C Step (b) kneading time 4 to 10 minutes
【００３０】[0030]
【実施例】つぎに、本発明のゴム組成物の製法を実施例
にもとづいてさらに具体的に説明するが、本発明はこれ
らのみに限定されるものではない。EXAMPLES Next, the method for producing the rubber composition of the present invention will be described more specifically based on examples, but the present invention is not limited to these.
【００３１】実施例１〜２および参考例１〜２
まず、表１に示す混練割合および条件で混練りをするこ
とにより、本発明の工程（ａ）による予備混練物１〜２
および参考予備混合物１〜２をえた。Examples 1 and 2 and Reference Examples 1 and 2 First, the preliminary kneaded products 1 and 2 according to the step (a) of the present invention were kneaded at the kneading ratios and conditions shown in Table 1.
And reference premixes 1-2 were obtained.
【００３２】イソブチレン／ｐ−メチルスチレン共重合
体の臭素化物としては、エクソン化学（株）製のＥＸＸ
ＰＲＯ ９０−１０を用い、ＺｎＯを用いた。表１中の
チッ素原子含有有機化合物１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（大内新興化学工業（株）製のノクラック６Ｃ）、
チッ素原子含有有機化合物２としては１，３−ジエチル
チオウレア（大内新興化学工業（株）製のノクセラーＥ
ＵＲ）、チッ素原子含有有機化合物３としてはジエチル
ジチオカルバミン酸亜鉛（大内新興化学工業（株）製の
ノクセラーＥＺ）を用いた。カーボンブラックとしては
昭和キャボット（株）製のショウワブラックＮ３５１を
用いた。The bromide of the isobutylene / p-methylstyrene copolymer is EXX manufactured by Exxon Chemical Co., Ltd.
Using the PRO 90-10, using the Z nO. As the nitrogen atom-containing organic compound 1 in Table 1, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (Nocrac 6C manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) ),
As the nitrogen atom-containing organic compound 2, 1,3-diethylthiourea (Nox Cellar E manufactured by Ouchi Shinko Chemical Co., Ltd.)
UR), as the nitrogen atom-containing organic compound 3, zinc diethyldithiocarbamate (Noxeller EZ manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) was used. Showa Black N351 manufactured by Showa Cabot Corporation was used as the carbon black.
【００３３】ついで、えられた予備混練物１〜２および
参考予備混練物１〜２を用い、イソブチレン／ｐ−メチ
ルスチレン共重合体の臭素化物１００重量部に対して表
１に示す混練割合でバンバリーを用いて本発明のタイヤ
トレッド用ゴム組成物１〜２および参考タイヤトレッド
用ゴム組成物１〜２をえた。なお、ＳＢＲとしては、住
友化学工業（株）製のＳＢＲ１５０２を用い、ミネラル
オイルとしては出光興産（株）製のダイアナプロセスオ
イルＰＳ−３２を用いた。Then, the obtained pre-kneaded products 1 and 2 and
Using the reference pre-kneaded products 1 and 2 , the rubber composition 1 for tire tread of the present invention was used by using Banbury at a kneading ratio shown in Table 1 with respect to 100 parts by weight of a bromide of an isobutylene / p-methylstyrene copolymer. 2 and reference tire tread
Rubber compositions 1 to 2 were obtained. In addition, SBR1502 manufactured by Sumitomo Chemical Co., Ltd. was used as the SBR, and Diana Process Oil PS-32 manufactured by Idemitsu Kosan Co., Ltd. was used as the mineral oil.
【００３４】［評価］
ｔａｎδ（０℃および７０℃）
前記のようにしてえられた本発明のゴム組成物１〜２お
よび参考ゴム組成物１〜２に、加硫剤であるイオウ２重
量部、加硫促進剤であるＮ−ｔｅｒｔ−ブチル−２−ベ
ンゾチアジルスルフェンアミド（大内新興化学工業
（株）製のノクセラーＮＳ）１重量部および亜鉛華１２
重量部をロールを用いて混合し、１７０℃、１５分間の
条件で加硫して評価用サンプル１〜２および参考評価用
サンプル１〜２をえた。[Evaluation] tan δ (0 ° C. and 70 ° C.) Rubber compositions 1 and 2 of the present invention obtained as described above .
And 2 parts by weight of sulfur, which is a vulcanizing agent, and N-tert-butyl-2-benzothiazylsulfenamide (a product of Ouchi Shinko Chemical Industry Co., Ltd.), which is a vulcanization accelerator. Nox cellar NS) 1 part by weight and zinc flower 12
Parts by weight are mixed using a roll and vulcanized under the conditions of 170 ° C. for 15 minutes to be evaluated Samples 1 to 2 and for reference evaluation.
Samples 1-2 were obtained.
【００３５】評価用サンプル１〜２および参考評価用サ
ンプル１〜２について、（株）岩本製作所製のＶＥＳ−
ＦＩＩＩ２を用いて、１０Ｈｚ、動的振幅±０．２５％
の条件で、０℃および７０℃におけるｔａｎδを測定し
た。０℃におけるｔａｎδが大きいとウェットグリップ
性が大きくなる点で好ましく、７０℃におけるｔａｎδ
が小さいと転がり抵抗が小さくなる点で好ましい。結果
を表１に示す。Evaluation Samples 1 and 2 and Reference Evaluation Service
Samples 1-2 are VES- manufactured by Iwamoto Manufacturing Co., Ltd.
Using FIII2, 10 Hz, dynamic amplitude ± 0.25%
Under the conditions, tan δ at 0 ° C. and 70 ° C. was measured. A large tan δ at 0 ° C. is preferable in that the wet grip property becomes large, and a tan δ at 70 ° C.
Is preferable because the rolling resistance is reduced. The results are shown in Table 1.
【００３６】ランボーン摩耗（２０％および４０％）
前記の評価用サンプル１〜２および参考評価用サンプ
ル１〜２について、ランボーン摩耗試験機を用いて、荷
重１．５ｋｇｆでスリップ率を２０％および４０％とし
てランボーン摩耗を測定し、後述する比較例１のゴム組
成物を用いたばあいの値を１００として指数にして示し
た。指数が大きいほど摩耗が少なく良好である。結果を
表１に示す。Lambourn wear (20% and 40%) Samples 1-2 for evaluation and the reference evaluation sump
With respect to Nos. 1 and 2 , the Lambourn abrasion tester was used to measure Lambourn abrasion with a slip ratio of 20% and 40% under a load of 1.5 kgf, and a value in the case of using the rubber composition of Comparative Example 1 described later was calculated. It was shown as an index as 100. The larger the index, the less wear and the better. The results are shown in Table 1.
【００３７】ウェットグリップ性
本発明のゴム組成物１〜２および参考ゴム組成物１〜２
をトレッドに適用し、常法でタイヤ１〜２および参考タ
イヤ１〜２を作製した。えられたタイヤ１〜２および参
考タイヤ１〜２を取付けたμ−ｓ測定車で湿潤路面を４
０ｋｍ／ｈで走行し、ブレーキをかけて車輪をロックさ
せた時点から測定車が停止するまでのあいだの摩擦係数
（μ）を測定し、このあいだの最大摩擦係数を測定し
た。結果は、後述する比較例１のゴム組成物を用いたば
あいの値を１００として指数で示した。指数が大きいほ
どウェットグリップ性がよい。結果を表１に示す。Wet grip properties Rubber compositions 1-2 of the present invention and reference rubber compositions 1-2
Applied to the tread, and tires 1-2 and reference
Ears 1 and 2 were produced. Obtained tires 1-2 and ginseng
Consider a wet road surface with a μ-s measurement vehicle equipped with tires 1-2.
The friction coefficient (μ) was measured from the time when the vehicle was driven at 0 km / h and the brake was applied to lock the wheels until the measurement vehicle stopped, and the maximum friction coefficient during this period was measured. The results are shown by indexes with the value of 100 when the rubber composition of Comparative Example 1 described later was used. The larger the index, the better the wet grip. The results are shown in Table 1.
【００３８】転がり抵抗
前記で用いたタイヤを、荷重３５０ｋｇｆをかけた状
態で８０ｋｍ／ｈでドラム試験機上で回転させて転がり
抵抗係数を測定した。結果は、後述する比較例１のゴム
組成物を用いたばあいの値を１００として指数で示し
た。指数が小さいほど転がり抵抗が小さく好ましい。結
果を表１に示す。Rolling Resistance The rolling resistance coefficient was measured by rotating the tire used above at 80 km / h under a load of 350 kgf on a drum tester. The results are shown by indexes with the value of 100 when the rubber composition of Comparative Example 1 described later was used. The smaller the index, the smaller the rolling resistance, which is preferable. The results are shown in Table 1.
【００３９】[0039]
【表１】 [Table 1]
【００４０】比較例１および２
表２に示す混練割合および１００℃で４分間という混練
条件で、バンバリーを用いて比較ゴム組成物１および２
をえた。比較ゴム組成物１はイソブチレン／ｐ−メチル
スチレン共重合体の臭素化物を用いないばあい、比較ゴ
ム組成物２は２段階の混練りを行なわずに１回の混練り
を行なったばあいのものである。なお、比較例１におい
ては、一般的にウェットグリップ性をよくするために用
いられるコストの高い溶液重合ＳＢＲ（Ｓ−ＳＢＲ）を
用いた。Comparative Examples 1 and 2 Comparative rubber compositions 1 and 2 using Banbury under the kneading ratios shown in Table 2 and the kneading conditions of 100 ° C. for 4 minutes.
I got it. Comparative rubber composition 1 was used when no bromide of isobutylene / p-methylstyrene copolymer was used, and comparative rubber composition 2 was used when one kneading was performed without performing two-step kneading. Is. In Comparative Example 1, high-cost solution-polymerized SBR (S-SBR), which is generally used to improve wet grip properties, was used.
【００４１】ついで、えられた比較ゴム組成物１および
２について実施例１と同様の評価を行った。結果を表２
に示す。The comparative rubber compositions 1 and 2 thus obtained were evaluated in the same manner as in Example 1. The results are shown in Table 2.
Shown in.
【００４２】[0042]
【表２】 [Table 2]
【００４３】[0043]
【発明の効果】本発明によれば、高ウェットグリップ性
および低転がり抵抗を両立させたタイヤを提供するトレ
ッド用ゴム組成物をうることができる。According to the present invention, it is possible to obtain a rubber composition for a tread which provides a tire having both high wet grip properties and low rolling resistance.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｋ 5/39 Ｃ０８Ｋ 5/39 //(Ｃ０８Ｌ 21/00 Ｃ０８Ｌ 23:28 23:28） 25:16 (Ｃ０８Ｌ 21/00 25:16） (56)参考文献 特開 平８−283464（ＪＰ，Ａ) 特開 平８−283462（ＪＰ，Ａ) 特開 平８−283461（ＪＰ，Ａ) 特開 平８−225683（ＪＰ，Ａ) 特開 平７−304903（ＪＰ，Ａ) 特開 平９−302154（ＪＰ，Ａ) 特表 平５−507517（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 9/00 - 21/00 C08L 23/26 - 23/28 C08K 3/18 - 3/22 C08K 5/39 - 5/405 B29D 30/00 B60C 1/00 C08J 3/20 ─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. 7 Identification Code FI C08K 5/39 C08K 5/39 // (C08L 21/00 C08L 23:28 23:28) 25:16 (C08L 21/00 25 : 16) (56) Reference JP-A-8-283464 (JP, A) JP-A-8-283462 (JP, A) JP-A-8-283461 (JP, A) JP-A-8-225683 (JP, A) A) JP-A-7-304903 (JP, A) JP-A-9-302154 (JP, A) JP-A-5-507517 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) ) C08L 9/00-21/00 C08L 23/26-23/28 C08K 3/18-3/22 C08K 5/39-5/405 B29D 30/00 B60C 1/00 C08J 3/20
Claims (2)
チレン共重合体の臭素化物１００重量部とＺｎＯ ０．
１〜５重量部およびジチオカルバミン酸塩系加硫促進剤
０．１〜５重量部とを予備混練りし、ついで （ｂ）えられる予備混練物と他のゴム成分とを混練りす
ることによりえられるタイヤトレッド用ゴム組成物。1. (a) 100 parts by weight of a bromide of polyisobutylene / p-methylstyrene copolymer and ZnO 0.
1-5 parts by weight and dithiocarbamate vulcanization accelerator
A rubber composition for a tire tread obtained by pre-kneading 0.1 to 5 parts by weight , and then (b) kneading the pre-kneaded product and other rubber components.
範囲で行なう請求項１記載のタイヤトレッド用ゴム組成
物。2. The rubber composition for a tire tread according to claim 1, wherein the preliminary kneading is performed in a temperature range of 40 to 100 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24831797A JP3410938B2 (en) | 1997-09-12 | 1997-09-12 | Rubber composition for tire tread |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24831797A JP3410938B2 (en) | 1997-09-12 | 1997-09-12 | Rubber composition for tire tread |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1180433A JPH1180433A (en) | 1999-03-26 |
| JP3410938B2 true JP3410938B2 (en) | 2003-05-26 |
Family
ID=17176291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24831797A Expired - Fee Related JP3410938B2 (en) | 1997-09-12 | 1997-09-12 | Rubber composition for tire tread |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3410938B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100381910B1 (en) * | 2000-04-17 | 2003-05-01 | 금호산업 주식회사 | For Improving Endurance in TBR Tire Applied Thin Cushion |
| JP4268923B2 (en) | 2004-10-26 | 2009-05-27 | 住友ゴム工業株式会社 | Rubber composition for tire tread and pneumatic tire comprising the same |
| JP5073189B2 (en) * | 2005-09-20 | 2012-11-14 | 住友ゴム工業株式会社 | Method for producing rubber composition and rubber composition obtained thereby |
| US20090151838A1 (en) * | 2007-12-17 | 2009-06-18 | Erik Paul Sandstrom | Tire containing an internal cord reinforced rubber component |
| DE102009003720B4 (en) | 2009-04-01 | 2024-01-18 | Continental Reifen Deutschland Gmbh | Rubber mixture and its use |
| WO2011030792A1 (en) | 2009-09-08 | 2011-03-17 | Ｊｘ日鉱日石エネルギー株式会社 | Vinyl ether compound, vinyl ether polymer, and method for producing vinyl ether compound |
| WO2013151072A1 (en) * | 2012-04-03 | 2013-10-10 | 株式会社ブリヂストン | Process for producing rubber composition |
| JP6182419B2 (en) * | 2013-10-15 | 2017-08-16 | 株式会社ブリヂストン | Method for producing rubber composition |
| JP6784066B2 (en) | 2016-06-08 | 2020-11-11 | 住友ゴム工業株式会社 | Pneumatic tires |
-
1997
- 1997-09-12 JP JP24831797A patent/JP3410938B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1180433A (en) | 1999-03-26 |
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