JP2015183057A - Rubber composition and pneumatic tire using the same - Google Patents
Rubber composition and pneumatic tire using the same Download PDFInfo
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- JP2015183057A JP2015183057A JP2014059588A JP2014059588A JP2015183057A JP 2015183057 A JP2015183057 A JP 2015183057A JP 2014059588 A JP2014059588 A JP 2014059588A JP 2014059588 A JP2014059588 A JP 2014059588A JP 2015183057 A JP2015183057 A JP 2015183057A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 67
- 239000005060 rubber Substances 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 7
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 7
- -1 disulfide compound Chemical class 0.000 claims description 23
- 239000006229 carbon black Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000004073 vulcanization Methods 0.000 claims description 15
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 claims description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 4
- 229960002447 thiram Drugs 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 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
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 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
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001993 wax 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
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
Description
本発明は、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、ゴム組成物の粘度を低下させ、優れた加工性を有し、破断伸びおよび耐摩耗性に優れた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。 The present invention relates to a rubber composition and a pneumatic tire using the same, and more specifically, a rubber having a reduced viscosity of the rubber composition, excellent workability, and excellent elongation at break and wear resistance. The present invention relates to a composition and a pneumatic tire using the composition.
タイヤ用ゴムの製造においては、ゴムの粘度を低下させる必要がある。これにより、優れたゴムの押出し性、シート加工性等が得られる。
一方、地球環境上の観点から自動車に対する低燃費化の要求が高まっており、良好な転がり抵抗性を有するタイヤの開発が望まれている。そこで、ジエン系ゴムにシリカやシランカップリング剤を配合する技術が数多く提案されているが、このようなゴムは高粘度化に伴う加工性の悪化が課題となっている。
また、タイヤには一般的に優れた耐破壊性や耐摩耗性に代表される耐久性が求められている。そのため硫黄や充填剤を増量する手法が採られるが、発熱性や破断伸び（とくに高温破断伸び）が悪化するという問題点がある。
以上から、ゴム組成物における加工性、耐摩耗性、破断伸びをいずれも向上させることは当業界では困難な事項とされていた。
In the production of tire rubber, it is necessary to reduce the viscosity of the rubber. Thereby, excellent extrudability of rubber, sheet processability and the like can be obtained.
On the other hand, from the viewpoint of the global environment, there is an increasing demand for lower fuel consumption for automobiles, and the development of tires with good rolling resistance is desired. Therefore, many techniques for blending silica or a silane coupling agent with diene rubber have been proposed. However, such rubber has a problem of deterioration of workability due to increase in viscosity.
Further, tires are generally required to have durability represented by excellent fracture resistance and wear resistance. For this reason, a method of increasing the amount of sulfur or filler is employed, but there is a problem that exothermic properties and elongation at break (especially high temperature elongation at break) deteriorate.
From the above, it has been considered difficult in the art to improve all of the workability, wear resistance, and elongation at break in the rubber composition.
なお、下記特許文献１には、ジエン系ゴムに、硫黄と、特定の官能基を有するジスルフィド化合物とを配合し、シリカを配合せずに、混練り機を用いて１４０℃以上の温度で予備混合し、得られた予備混合物にシリカを配合し混合するゴム組成物の製造方法が開示され、得られたゴムは低発熱性に優れるとされている。
しかし、この従来技術でも、製造時にゴム組成物が高粘度化し、押出し性、シート加工性等のゴムの加工性が悪化するという問題点があった。また、耐摩耗性、破断伸びにも改善の余地がある。
In Patent Document 1 below, a diene rubber is compounded with sulfur and a disulfide compound having a specific functional group, and is preliminarily prepared at a temperature of 140 ° C. or higher using a kneader without compounding silica. A method for producing a rubber composition in which silica is mixed and mixed with the resulting premix is disclosed, and the obtained rubber is said to be excellent in low heat build-up.
However, this prior art also has a problem that the rubber composition has a high viscosity at the time of production, and the rubber processability such as extrudability and sheet processability deteriorates. There is also room for improvement in wear resistance and elongation at break.
したがって本発明の目的は、ゴム組成物の粘度を低下させ、優れた加工性を有し、破断伸び（とくに高温破断伸び）および耐摩耗性に優れた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。 Accordingly, an object of the present invention is to reduce the viscosity of the rubber composition, have excellent processability, and have a rubber composition excellent in breaking elongation (particularly, high temperature breaking elongation) and wear resistance, and a pneumatic tire using the same. Is to provide.
本発明者は鋭意研究を重ねた結果、特定の組成のジエン系ゴムに対し、特定のジスルフィド化合物を特定量で配合することにより、前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通りである。
As a result of extensive research, the present inventor has found that the above-mentioned problems can be solved by blending a specific amount of a specific disulfide compound with a specific amount of a diene rubber, and the present invention can be completed. It was.
That is, the present invention is as follows.
１．スチレン−ブタジエン共重合体ゴムとブタジエンゴムとの合計が５０質量部以上であるジエン系ゴム成分１００質量部に対し、下記一般式（１）で表されるジスルフィド化合物を０．１〜５質量部配合してなることを特徴とするゴム組成物。 1. The disulfide compound represented by the following general formula (1) is added in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the diene rubber component in which the total of styrene-butadiene copolymer rubber and butadiene rubber is 50 parts by mass or more. A rubber composition characterized by being compounded.
一般式（１）中、Ｒ３およびＲ４はそれぞれ独立して、単結合または炭素数１〜３のアルキレン基を表す。Ａ１およびＡ２はそれぞれ独立して、下記式で表される基を表す。 In general formula (1), R3 and R4 each independently represent a single bond or an alkylene group having 1 to 3 carbon atoms. A1 and A2 each independently represent a group represented by the following formula.
前記式中、Ｒ５は水素または炭素数１〜６のアルキル基を表す。
２．前記一般式（１）で表される化合物が、下記式で表されるジフェニルジスルフィドであることを特徴とする前記１に記載のゴム組成物。
In the above formula, R5 represents hydrogen or an alkyl group having 1 to 6 carbon atoms.
2. 2. The rubber composition as described in 1 above, wherein the compound represented by the general formula (1) is diphenyl disulfide represented by the following formula.
３．前記一般式（１）で表される化合物が、下記式で表されるジベンジルジスルフィドであることを特徴とする前記１に記載のゴム組成物。 3. 2. The rubber composition as described in 1 above, wherein the compound represented by the general formula (1) is dibenzyl disulfide represented by the following formula.
４．前記ジエン系ゴム成分１００質量部に対して、カーボンブラックおよび／またはシリカを４０〜１２０質量部配合してなることを特徴とする前記１〜３のいずれかに記載のゴム組成物。
５．前記ジエン系ゴム成分１００質量部に対して、チウラム系加硫促進剤を０．１〜５質量部配合してなることを特徴とする前記１〜４のいずれかに記載のゴム組成物。
６．前記ゴム組成物がシリカを含み、前記シリカに対して、メルカプト基を有するシランカップリング剤を０．５〜１０質量％配合してなることを特徴とする前記４に記載のゴム組成物。
７．前記ジエン系ゴム成分１００質量部に対し、加硫系配合物を配合せずかつカーボンブラックおよび／またはシリカは実質上配合せずに、前記一般式（１）で表されるジスルフィド化合物を０．１〜５質量部を配合し、１００℃以下の温度で混合する予備混合工程を経て製造されてなる前記１〜６のいずれかに記載のゴム組成物。
８．前記１〜７のいずれかに記載のゴム組成物を使用してなる空気入りタイヤ。
4). 4. The rubber composition according to any one of 1 to 3, wherein 40 to 120 parts by mass of carbon black and / or silica is blended with 100 parts by mass of the diene rubber component.
5. 5. The rubber composition as described in any one of 1 to 4 above, wherein 0.1 to 5 parts by mass of a thiuram vulcanization accelerator is blended with 100 parts by mass of the diene rubber component.
6). 5. The rubber composition as described in 4 above, wherein the rubber composition contains silica, and 0.5 to 10% by mass of a silane coupling agent having a mercapto group is blended with the silica.
7). With respect to 100 parts by mass of the diene rubber component, the disulfide compound represented by the above general formula (1) is added to the compound in an amount of 0.1% without adding a vulcanized compound and substantially not containing carbon black and / or silica. The rubber composition according to any one of 1 to 6 above, which is produced through a premixing step in which 1 to 5 parts by mass are blended and mixed at a temperature of 100 ° C or lower.
8). A pneumatic tire using the rubber composition according to any one of 1 to 7 above.
本発明のゴム組成物は、特定の組成のジエン系ゴムに対し、特定のジスルフィド化合物を特定量で配合したので、ゴム組成物の粘度を低下させ、優れた加工性を有し、破断伸び（とくに高温破断伸び）および耐摩耗性に優れた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。
また該効果は、前記ジエン系ゴム成分１００質量部に対し、加硫系配合物を配合せずかつカーボンブラックおよび／またはシリカは実質上配合せずに、前記一般式（１）で表されるジスルフィド化合物を０．１〜５質量部を配合し、１００℃以下の温度で混合する予備混合工程を経てゴム組成物を製造することにより、さらに向上する。
In the rubber composition of the present invention, a specific disulfide compound is blended in a specific amount with respect to a diene rubber having a specific composition, so that the viscosity of the rubber composition is reduced, the processability is excellent, and the elongation at break ( In particular, it is possible to provide a rubber composition excellent in high temperature breaking elongation) and wear resistance and a pneumatic tire using the rubber composition.
The effect is expressed by the general formula (1) without adding a vulcanized compound and substantially not containing carbon black and / or silica to 100 parts by mass of the diene rubber component. It improves further by manufacturing a rubber composition through the premixing process which mix | blends 0.1-5 mass parts of disulfide compounds, and mixes at the temperature of 100 degrees C or less.
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.
（ジエン系ゴム成分）
本発明で使用されるジエン系ゴム成分は、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）とブタジエンゴム（ＢＲ）との合計が５０質量部以上である。このようなジエン系ゴム成分の配合においては、高粘度化の課題の解決が当業界でとくに求められ、また破断伸び（とくに高温破断伸び）および耐摩耗性の向上も求められている。
なお本発明では、ＳＢＲおよびＢＲ以外の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）アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）等を必要に応じて使用することもできる。ジエン系ゴム成分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。
(Diene rubber component)
The diene rubber component used in the present invention has a total of 50 parts by mass or more of styrene-butadiene copolymer rubber (SBR) and butadiene rubber (BR). In the blending of such a diene rubber component, a solution to the problem of increasing the viscosity is particularly required in the industry, and an improvement in breaking elongation (particularly, high temperature breaking elongation) and wear resistance is also required.
In the present invention, any rubber other than SBR and BR can be used. For example, natural rubber (NR), isoprene rubber (IR) acrylonitrile-butadiene copolymer rubber (NBR) or the like is used as necessary. You can also The molecular weight and microstructure of the diene rubber component are not particularly limited, and may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or epoxidized.
（ジスルフィド化合物）
本発明では、ゴムの粘度を低下させ、優れた加工性を付与し得るという効果を奏するために、ジスルフィド化合物の使用が必須である。
ジスルフィド化合物は、下記一般式（１）で表される。
(Disulfide compound)
In the present invention, it is essential to use a disulfide compound in order to reduce the viscosity of the rubber and to provide excellent processability.
The disulfide compound is represented by the following general formula (1).
一般式（１）中、Ｒ３およびＲ４はそれぞれ独立して、単結合または炭素数１〜３のアルキレン基を表す。Ａ１およびＡ２はそれぞれ独立して、下記式で表される基を表す。 In general formula (1), R3 and R4 each independently represent a single bond or an alkylene group having 1 to 3 carbon atoms. A1 and A2 each independently represent a group represented by the following formula.
前記式中、Ｒ５は水素または炭素数１〜６のアルキル基を表す。 In the above formula, R5 represents hydrogen or an alkyl group having 1 to 6 carbon atoms.
また、本発明の効果が向上するという観点から、前記一般式（１）で表される化合物は、下記式で表されるジフェニルジスルフィドであることがとくに好ましい。 From the viewpoint of improving the effect of the present invention, the compound represented by the general formula (1) is particularly preferably diphenyl disulfide represented by the following formula.
これとは別に、本発明の効果が向上するという観点から、前記一般式（１）で表される化合物は、下記式で表されるジベンジルジスルフィドであることがとくに好ましい。 Apart from this, from the viewpoint of improving the effect of the present invention, the compound represented by the general formula (1) is particularly preferably dibenzyl disulfide represented by the following formula.
（ジスルフィド化合物の配合割合）
前記一般式（１）で表されるジスルフィド化合物は、ジエン系ゴム成分１００質量部に対し、０．１〜５質量部を配合される。０．１質量部未満では、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５質量部を超えると、発熱性が悪化が悪化する。さらに好ましい前記ジスルフィド化合物の配合量は、ジエン系ゴム成分１００質量部に対し、０．３〜２質量部である。
(Compounding ratio of disulfide compound)
The disulfide compound represented by the general formula (1) is blended in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the diene rubber component. If the amount is less than 0.1 parts by mass, the blending amount is too small to achieve the effects of the present invention. Conversely, when it exceeds 5 mass parts, exothermicity will deteriorate. A more preferable blending amount of the disulfide compound is 0.3 to 2 parts by mass with respect to 100 parts by mass of the diene rubber component.
（カーボンブラックおよび／またはシリカ）
本発明のゴム組成物は、カーボンブラックおよび／またはシリカを配合することが好ましい。これらの充填剤を配合することにより、耐破壊性や耐摩耗性に代表される耐久性を高めることができる。なお従来技術では、カーボンブラックやシリカを増量すると発熱性や破断伸び（とくに高温破断伸び）が悪化するという問題点を有していたが、本発明では上記特定のジスルフィド化合物を特定量で配合しているので、このような問題点は生じない。
カーボンブラックおよび／またはシリカは、ジエン系ゴム成分１００質量部に対して、４０〜１２０質量部の範囲で配合することが好ましい。この範囲によれば、発熱性や破断伸び（とくに高温破断伸び）を悪化させることなく、耐破壊性や耐摩耗性に代表される耐久性をさらに向上できるという効果を奏する。なおカーボンブラックおよびシリカの両方を配合する場合、ジエン系ゴム成分１００質量部に対し、カーボンブラックは２〜８０質量部、シリカは１０〜１００質量部配合するのが好ましい。
なお、本発明において、カーボンブラックの窒素吸着比表面積（Ｎ２ＳＡ）は、３０〜２００ｍ２／ｇであるのが好ましく、シリカのＢＥＴ比表面積は、１００〜２２０ｍ２／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り、ＢＥＴ比表面積は、ＩＳＯ５７９４／１に準拠して求めた値である。
(Carbon black and / or silica)
The rubber composition of the present invention preferably contains carbon black and / or silica. By blending these fillers, durability typified by fracture resistance and wear resistance can be enhanced. In the prior art, there is a problem that exothermicity and elongation at break (especially high temperature elongation at break) deteriorate when carbon black and silica are increased, but in the present invention, the above specific disulfide compound is blended in a specific amount. Therefore, such a problem does not occur.
Carbon black and / or silica is preferably blended in the range of 40 to 120 parts by mass with respect to 100 parts by mass of the diene rubber component. According to this range, there is an effect that durability represented by fracture resistance and wear resistance can be further improved without deteriorating exothermic property and elongation at break (particularly high temperature elongation at break). When both carbon black and silica are blended, it is preferable to blend 2 to 80 parts by mass of carbon black and 10 to 100 parts by mass of silica with respect to 100 parts by mass of the diene rubber component.
In the present invention, the nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably from 30 to 200 m 2 / g, BET specific surface area of silica is preferably from 100~220m 2 / g .
The nitrogen adsorption specific surface area (N 2 SA) is a value determined in accordance with JIS K6217-2, and the BET specific surface area is a value determined in accordance with ISO 5794/1.
（シランカップリング剤）
本発明のゴム組成物がシリカを含む場合、前記シリカに対して、メルカプト基を有するシランカップリング剤を０．５〜１５質量％配合するのが好ましい。メルカプト基を有するシランカップリング剤を配合することにより、ジエン系ゴム成分中でシリカの分散性が高まり、破断伸び（とくに高温破断伸び）および耐摩耗性をさらに高めることができる。なお、従来技術では一般的にメルカプト基を有するシランカップリング剤を配合すると、押出性等の加工性や破断伸びが悪化する傾向にあるが、本発明では上記特定のジスルフィド化合物を特定量で配合しているので、このような問題点を軽減できる。
なおメルカプト基を有するシランカップリング剤のさらに好ましい前記配合量は、１〜１０質量％である。また必要に応じてメルカプト基を有するシランカップリング剤以外のシランカップリング剤を使用することもできる。
(Silane coupling agent)
When the rubber composition of this invention contains a silica, it is preferable to mix | blend 0.5-15 mass% of silane coupling agents which have a mercapto group with respect to the said silica. By blending a silane coupling agent having a mercapto group, the dispersibility of silica in the diene rubber component is increased, and the elongation at break (especially high temperature elongation at break) and wear resistance can be further increased. In general, when a silane coupling agent having a mercapto group is blended in the prior art, processability such as extrudability and elongation at break tend to deteriorate, but in the present invention, the above specific disulfide compound is blended in a specific amount. This can alleviate these problems.
In addition, the said more preferable compounding quantity of the silane coupling agent which has a mercapto group is 1-10 mass%. Moreover, silane coupling agents other than the silane coupling agent which has a mercapto group can also be used as needed.
（加硫促進剤）
本発明のゴム組成物は、加硫促進剤を配合するのが好ましい。加硫促進剤としては、従来から公知のものがいずれも使用可能であり、例えば、チウラム系加硫促進剤、スルフェンアミド系加硫促進剤、グアニジン系加硫促進剤、チアゾール系加硫促進剤、等が挙げられ、中でも本発明の効果が向上するという観点から、好ましくはチウラム系加硫促進剤である。
(Vulcanization accelerator)
The rubber composition of the present invention preferably contains a vulcanization accelerator. Any conventionally known vulcanization accelerator can be used. For example, thiuram vulcanization accelerator, sulfenamide vulcanization accelerator, guanidine vulcanization accelerator, thiazole vulcanization accelerator. Among them, a thiuram vulcanization accelerator is preferable from the viewpoint of improving the effect of the present invention.
本発明のゴム組成物は、ジエン系ゴム成分１００質量部に対し、加硫系配合物を配合せずかつカーボンブラックおよび／またはシリカは実質上配合せずに、前記一般式（１）で表されるジスルフィド化合物を０．１〜５質量部を配合し、１００℃以下の温度で混合する予備混合工程を経て製造されることが好ましい。なお加硫系配合物とは、硫黄のような加硫剤や加硫促進剤を意味する。
また、カーボンブラックおよび／またはシリカを「実質上配合しない」とは、カーボンブラックおよび／またはシリカを、ジエン系ゴム成分１００質量部に対して０〜５質量部の範囲であれば配合してもよいことを意味する。
この予備混合工程によって、分断されたジエン系ゴム成分の分子末端とジスルフィド化合物とが相互作用し、分断されたジエン系ゴム成分の分子同士の再結合が抑制され、結果としてゴムの粘度が低下するものと考えられる。また、破断伸び（とくに高温破断伸び）および耐摩耗性も良化する。なお予備混合工程で、カーボンブラックおよび／またはシリカを０〜５質量部の範囲で混合すると、混合発熱性を抑制できるという点で有利であるが、５質量部を超えて配合すると、混合発熱温度が高くなり、ジスルフィド化合物がフィラーに吸着し効果が低減するという理由で好ましくない。
予備混合工程は、１００℃以下の混合温度で行われるのがよい。１００℃以下の温度で予備混合工程が行われることにより、分断されたジエン系ゴム成分の分子同士の再結合が抑制され、好ましい。さらに好ましい予備混合工程の温度は、７０〜９５℃である。予備混合工程は、従来公知の各種ミキサーを用いて実施することができ、ヒータ等によってミキサー内の温度、すなわち予備混合工程の混合温度を制御することができる。
予備混合工程における混合時間としては、例えば１分〜５分である。
ここで予備混合工程において加硫系配合物を配合しないことにより、前記と同様に、分断されたジエン系ゴム成分の分子同士の再結合が抑制され、好ましい。
また予備混合工程は、加硫系配合物、カーボンブラックおよびシリカ以外にも、白色充填剤を配合しないことが好ましく、ジエン系ゴム成分およびジスルフィド化合物のみを配合して実施するのがとくに好ましい。
The rubber composition of the present invention is represented by the above general formula (1) with 100 parts by mass of the diene rubber component and no vulcanized compound and substantially no carbon black and / or silica. The disulfide compound is preferably produced through a premixing step in which 0.1 to 5 parts by mass of the disulfide compound is blended and mixed at a temperature of 100 ° C. or less. The vulcanized compound means a vulcanizing agent such as sulfur or a vulcanization accelerator.
Further, “substantially not compounding” carbon black and / or silica means that carbon black and / or silica may be compounded in the range of 0 to 5 parts by mass with respect to 100 parts by mass of the diene rubber component. Means good.
By this premixing step, the molecular ends of the separated diene rubber component interact with the disulfide compound, and recombination of the molecules of the separated diene rubber component is suppressed, resulting in a decrease in the viscosity of the rubber. It is considered a thing. Further, the elongation at break (particularly the high temperature elongation at break) and the wear resistance are improved. In addition, when carbon black and / or silica is mixed in the range of 0 to 5 parts by mass in the preliminary mixing step, it is advantageous in that mixing exothermic property can be suppressed. And the disulfide compound is adsorbed on the filler and the effect is reduced, which is not preferable.
The premixing step may be performed at a mixing temperature of 100 ° C. or lower. By performing the premixing step at a temperature of 100 ° C. or lower, recombination of the separated diene rubber component molecules is suppressed, which is preferable. The temperature of the more preferable premixing process is 70-95 degreeC. The premixing step can be carried out using various conventionally known mixers, and the temperature in the mixer, that is, the mixing temperature in the premixing step can be controlled by a heater or the like.
The mixing time in the preliminary mixing step is, for example, 1 minute to 5 minutes.
Here, by not blending the vulcanized compound in the preliminary mixing step, recombination of molecules of the divided diene rubber component is suppressed as described above, which is preferable.
Moreover, it is preferable not to mix | blend a white filler other than a vulcanization-type compound, carbon black, and a silica, and it is especially preferable to implement a pre-mixing process by mix | blending only a diene rubber component and a disulfide compound.
なお予備混合工程の実施前に、ジエン系ゴム成分のみを素練りする素練り工程を行なってもよい。また、予備混合工程は、配合物を分割して複数回行なってもよい。
予備混合工程の実施後は、配合設計に基づき、予備混合工程で配合しなかったその他の配合材料を予備混合物に配合し、本混合を行うことができる。本混合の条件は、とくに制限されず、公知の方法により行うことができる。
In addition, you may perform the mastication process of masticating only a diene rubber component before implementation of a pre-mixing process. Further, the premixing step may be performed a plurality of times by dividing the blend.
After the premixing step, based on the blending design, other blending materials that were not blended in the premixing step can be blended into the premixed mixture to perform the main mixing. The conditions for this mixing are not particularly limited and can be carried out by a known method.
なお、本発明において、ゴム中には、前記した成分に加えて無機充填剤、老化防止剤、可塑剤などのゴム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。
また本発明で製造されたゴムは、タイヤ用途に有用であり、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 the present invention, in addition to the above-described components, various additives that are generally blended in rubbers such as inorganic fillers, anti-aging agents, and plasticizers can be blended in the rubber. 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 produced in the present invention is useful for tire applications and 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１〜６および比較例１〜３
表１に示す配合（質量部）において、ジエン系ゴム成分およびジスルフィド化合物を１．７リットルの密閉式バンバリーミキサーに入れ、混合時の温度が８０〜９０℃となるように１分間混練した（予備混合工程）。続いて、カーボンブラック、シリカおよびその他の配合物を加え、１３０〜１５０℃で８分混合した（本混合工程）。さらに加硫系配合物を加え、オープンロールで８０〜１１０℃で３分混合した。
次に得られたゴム組成物を所定の金型中で１７０℃で１０分間プレス加硫して加硫ゴム試験片を調製した。得られたゴム組成物および加硫ゴム試験片について以下に示す試験法で物性を測定した。
結果を表１に示す。
Examples 1-6 and Comparative Examples 1-3
In the composition (parts by mass) shown in Table 1, the diene rubber component and the disulfide compound were placed in a 1.7 liter closed Banbury mixer and kneaded for 1 minute so that the temperature during mixing was 80 to 90 ° C. (preliminary) Mixing step). Subsequently, carbon black, silica and other blends were added and mixed at 130 to 150 ° C. for 8 minutes (main mixing step). Further, the vulcanized compound was added and mixed with an open roll at 80 to 110 ° C. for 3 minutes.
Next, the obtained rubber composition was press vulcanized at 170 ° C. for 10 minutes in a predetermined mold to prepare a vulcanized rubber test piece. The physical properties of the obtained rubber composition and vulcanized rubber test piece were measured by the following test methods.
The results are shown in Table 1.
粘度：ＪＩＳ ６３００に従い、１００℃におけるムーニー粘度を測定した。結果は比較例１または２の値を１００として指数表示した。この値が低いほど粘度が低く、加工性が良好であることを示す。
押出性：ガーベダイテストを行い、以下の評価基準で押出性を評価した。
○：押出し後のゴム平面部が平滑で、エッジのゴム薄部も連続性がある
△：押出し後のゴム平面部にやや凹凸があり、エッジ部のギザギザが少し見られる
×：押出し後のゴム平面部に凹凸があり、エッジ部にギザギザがある
破断伸び：ＪＩＳ Ｋ ６２５１（ＪＩＳ ３号ダンベル）に準拠して、２５℃および１００℃にて引張試験を実施し、切断時伸び（ＥＢ）を測定した。結果は比較例１または２の値を１００として指数表示した。指数が大きいほど破断伸びに優れることを示す。
耐摩耗性：ＪＩＳ Ｋ６２６４に準拠して、ランボーン摩耗試験機（岩本製作所（株）製）を使用して、荷重４９Ｎ、スリップ率２５％、時間４分、室温において測定した。結果は、実施例１〜４に関しては比較例１の値を１００として、実施例５〜６および比較例３に関しては比較例２の値を１００として指数表示した。指数が大きいほど、耐摩耗性が良好であることを意味する。
Viscosity: Mooney viscosity at 100 ° C. was measured according to JIS 6300. The results are shown as an index with the value of Comparative Example 1 or 2 as 100. The lower this value, the lower the viscosity and the better the workability.
Extrudability: A garbage die test was performed, and extrudability was evaluated according to the following evaluation criteria.
○: The flat rubber portion after extrusion is smooth and the thin rubber portion of the edge is continuous. Δ: The flat surface of the rubber after extrusion is slightly uneven, and there are some jagged edges. ×: Rubber after extrusion There are irregularities in the flat part, and there are jagged edges. Elongation at break: In accordance with JIS K 6251 (JIS No. 3 dumbbell), a tensile test is performed at 25 ° C. and 100 ° C., and the elongation at break (EB) is It was measured. The results are shown as an index with the value of Comparative Example 1 or 2 as 100. The larger the index, the better the elongation at break.
Abrasion resistance: Measured according to JIS K6264 using a Lambourn abrasion tester (manufactured by Iwamoto Seisakusho Co., Ltd.) with a load of 49 N, a slip rate of 25%, a time of 4 minutes, and room temperature. The results are shown as an index with the value of Comparative Example 1 as 100 for Examples 1 to 4, and the value of Comparative Example 2 as 100 for Examples 5 to 6 and Comparative Example 3. A larger index means better wear resistance.
＊１：ＳＢＲ（日本ゼオン（株）製Ｎｉｐｏｌ １５０２）
＊２：ＢＲ（日本ゼオン（株）製Ｎｉｐｏｌ ＢＲ１２２０）
＊３：ジスルフィド化合物−１（関東化学（株）製ジベンジルジスルフィド）
＊４：ジスルフィド化合物−２（関東化学（株）製ジフェニルジスルフィド）
＊５：シリカ（UNITED SILICA INDUSTRIAL社製ULTRASIL VN-3G、ＢＥＴ比表面積＝１７０ｍ２／ｇ）
＊６：カーボンブラック（東海カーボン（株）製シーストＫＨ、窒素吸着比表面積（Ｎ２ＳＡ）＝９３ｍ２／ｇ）
＊７：シランカップリング剤−１（エボニックデグッサジャパン（株）製Ｓｉ６９）
＊８：シランカップリング剤−２（エボニックデグッサジャパン（株）製Ｓｉ３６３。メルカプト基を有するシランカップリング剤）
＊９：加硫促進剤−１（大内新興化学工業（株）製テトラキス（２−エチルヘキシル）チウラムジスルフィド）
＊１０：加硫促進剤−２（大内新興化学工業（株）製テトラベンジルチウラムジスルフィド）
＊１１：ステアリン酸（日油(株)製ビーズステアリン酸ＹＲ）
＊１２：老化防止剤（フレキシス社製サントフレックス６ＰＰＤ）
＊１３：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊１４：ワックス（大内新興化学工業（株）製パラフィンワックス）
＊１５：オイル（昭和シェル石油（株）製エキストラクト４号Ｓ）
＊１６：加硫促進剤−３（大内新興化学工業（株）製ノクセラーＣＺ）
＊１７：加硫促進剤−４（住友化学(株)製ソクシノールＤＧ）
＊１８：硫黄（四国化成工業（株）製ミュークロンＯＴ−２０）
* 1: SBR (Nipol 1502 manufactured by Nippon Zeon Co., Ltd.)
* 2: BR (Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.)
* 3: Disulfide compound-1 (dibenzyl disulfide manufactured by Kanto Chemical Co., Inc.)
* 4: Disulfide compound-2 (diphenyl disulfide manufactured by Kanto Chemical Co., Inc.)
* 5: Silica (ULTRASIL VN-3G manufactured by UNITED SILICA INDUSTRIAL, BET specific surface area = 170 m 2 / g)
* 6: Carbon black (Toast Carbon Co., Ltd. Seast KH, Nitrogen adsorption specific surface area (N 2 SA) = 93 m 2 / g)
* 7: Silane coupling agent-1 (Si69 manufactured by Evonik Degussa Japan Co., Ltd.)
* 8: Silane coupling agent-2 (Si363 manufactured by Evonik Degussa Japan Co., Ltd. Silane coupling agent having a mercapto group)
* 9: Vulcanization accelerator-1 (Tetrakis (2-ethylhexyl) thiuram disulfide manufactured by Ouchi Shinsei Chemical Co., Ltd.)
* 10: Vulcanization accelerator-2 (Tetrabenzylthiuram disulfide manufactured by Ouchi Shinsei Chemical Co., Ltd.)
* 11: Stearic acid (beef stearic acid YR manufactured by NOF Corporation)
* 12: Anti-aging agent (Santflex 6PPD manufactured by Flexis)
* 13: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 14: Wax (paraffin wax manufactured by Ouchi Shinsei Chemical Co., Ltd.)
* 15: Oil (Extract No. 4 S manufactured by Showa Shell Sekiyu KK)
* 16: Vulcanization accelerator-3 (Noxeller CZ manufactured by Ouchi Shinsei Chemical Co., Ltd.)
* 17: Vulcanization accelerator-4 (Soxinol DG manufactured by Sumitomo Chemical Co., Ltd.)
* 18: Sulfur (Muklon OT-20, manufactured by Shikoku Chemicals Co., Ltd.)
上記の表１から明らかなように、実施例１〜６で調製されたタイヤ用ゴム組成物は、特定の組成のジエン系ゴムに対し、特定のジスルフィド化合物を特定量で配合したので、比較例１または２の従来のゴム組成物と比較すると、ゴム組成物の粘度が低下し、優れた加工性を有し、破断伸び（とくに高温破断伸び）および耐摩耗性に優れることが分かった。
比較例３は、ジスルフィド化合物の配合量が本発明で規定する上限を超えているので、押出性が悪化した。
As is clear from Table 1 above, the tire rubber compositions prepared in Examples 1 to 6 were blended with a specific amount of a specific disulfide compound with respect to a diene rubber having a specific composition. As compared with the conventional rubber composition 1 or 2, it was found that the viscosity of the rubber composition was lowered, the processability was excellent, and the elongation at break (particularly high temperature elongation at break) and the abrasion resistance was excellent.
In Comparative Example 3, since the compounding amount of the disulfide compound exceeds the upper limit specified in the present invention, the extrudability deteriorated.
Claims (8)
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| JP2014059588A Active JP6331544B2 (en) | 2014-03-24 | 2014-03-24 | Rubber composition, method for producing the same, and pneumatic tire using the same |
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Cited By (3)
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| JP2015183060A (en) * | 2014-03-24 | 2015-10-22 | 横浜ゴム株式会社 | Method for manufacturing rubber |
| KR20180090815A (en) * | 2015-12-07 | 2018-08-13 | 스미토모 세이카 가부시키가이샤 | Composition comprising anti-caking agent |
| JP2020158709A (en) * | 2019-03-27 | 2020-10-01 | 住友ゴム工業株式会社 | Rubber composition for tire tread and tire |
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| JP7242003B2 (en) | 2019-03-27 | 2023-03-20 | 住友ゴム工業株式会社 | Rubber composition for tire tread and tire |
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| JP6331544B2 (en) | 2018-05-30 |
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