JP2024027444A - Rubber composition, manufacturing method thereof and tire product - Google Patents
Rubber composition, manufacturing method thereof and tire product Download PDFInfo
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- JP2024027444A JP2024027444A JP2022130232A JP2022130232A JP2024027444A JP 2024027444 A JP2024027444 A JP 2024027444A JP 2022130232 A JP2022130232 A JP 2022130232A JP 2022130232 A JP2022130232 A JP 2022130232A JP 2024027444 A JP2024027444 A JP 2024027444A
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- Prior art keywords
- rubber
- sulfur
- rubber composition
- hydrocarbon polymer
- mass
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 206
- 239000005060 rubber Substances 0.000 title claims abstract description 200
- 239000000203 mixture Substances 0.000 title claims abstract description 88
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 85
- 239000011593 sulfur Substances 0.000 claims abstract description 85
- 229920000642 polymer Polymers 0.000 claims abstract description 72
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 66
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- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- LVMTVPFRTKXRPH-UHFFFAOYSA-N penta-1,2-diene Chemical compound CCC=C=C LVMTVPFRTKXRPH-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 229920002743 polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- WDHVIZKSFZNHJB-UHFFFAOYSA-L zinc;butanoate Chemical compound [Zn+2].CCCC([O-])=O.CCCC([O-])=O WDHVIZKSFZNHJB-UHFFFAOYSA-L 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、ゴム組成物およびその製造方法に関する。また、本発明は、該ゴム組成物を用いて製造されたタイヤ製品に関する。 TECHNICAL FIELD The present invention relates to a rubber composition and a method for producing the same. The present invention also relates to tire products manufactured using the rubber composition.
従来、タイヤは、加硫を担う加硫剤、カーボンブラックやシリカなどの充填剤、品質劣化を抑制する老化防止剤やワックスなどを含むゴム組成物から製造されており、それぞれの成分について改良がなされてきた。 Traditionally, tires have been manufactured from rubber compositions that include a vulcanizing agent for vulcanization, fillers such as carbon black and silica, and anti-aging agents and wax to suppress quality deterioration. It has been done.
近年、タイヤには、ウェットグリップ性および耐摩耗性等の様々な性能が求められている。例えば、タイヤのウェットグリップ性およびドライグリップ性の総合性能を改善するために、水によって可逆的に動的弾性率Ｅ＊が変化し、特定の式（水湿潤時の動的弾性率Ｅ＊／乾燥時の動的弾性率Ｅ＊×１００％≦９０％）を満たすゴム組成物が提案されている（特許文献１参照）。しかし、特許文献１に記載の発明では、タイヤの耐摩耗性は十分に検討されていなかった。 In recent years, tires are required to have various performances such as wet grip properties and wear resistance. For example, in order to improve the overall wet grip performance and dry grip performance of a tire, the dynamic elastic modulus E* is reversibly changed by water, and a specific formula (dynamic elastic modulus E*/ A rubber composition has been proposed that satisfies the dynamic elastic modulus E*×100%≦90% upon drying (see Patent Document 1). However, in the invention described in Patent Document 1, the wear resistance of the tire was not sufficiently studied.
ところで、タイヤ用ゴム組成物に、ウェットグリップ性能の向上を目的として、ガラス転移温度が高いゴム成分を用いた場合や、石油樹脂のようなゴム成分のガラス転移温度を上げる添加剤を配合した場合には、タイヤの耐摩耗性が悪化する傾向にある。そのため、ガラス転移温度が高いゴム成分を用いた場合であっても、タイヤの耐摩耗性を向上させるタイヤ用ゴム組成物が求められている。 By the way, when a rubber component with a high glass transition temperature is used in a tire rubber composition for the purpose of improving wet grip performance, or when an additive such as a petroleum resin that increases the glass transition temperature of the rubber component is blended. In this case, the wear resistance of tires tends to deteriorate. Therefore, there is a need for a rubber composition for tires that improves the wear resistance of tires even when a rubber component with a high glass transition temperature is used.
そこで、本発明者らは、上記課題を解決するために鋭意検討を行った結果、驚くべきことに、特定の含硫黄炭化水素重合体を含むゴム用添加剤を、特定のゴム成分に配合して得られたゴム組成物を用いて製造したタイヤは、耐摩耗性が向上し、さらにウェットグリップ性、操縦安定性、および氷雪路走行性が向上することを知見した。本発明者らは、かかる知見に基づいて、本発明を完成するに至った。 Therefore, the present inventors conducted intensive studies to solve the above problem, and surprisingly, they found that a rubber additive containing a specific sulfur-containing hydrocarbon polymer was blended into a specific rubber component. It has been found that tires manufactured using the rubber composition obtained in this manner have improved abrasion resistance, and further improved wet grip, steering stability, and driving performance on icy and snowy roads. The present inventors have completed the present invention based on such knowledge.
すなわち、本発明によれば、以下の発明が提供される。
［１］ ガラス転移温度が－１００℃以上－５５℃未満であるゴム成分と、
含硫黄炭化水素重合体を含むゴム用添加剤と、
を含み、
前記ゴム成分が、芳香族ビニル－共役ジエン共重合体ゴムおよびブタジエンゴムの少なくとも１種を含み、
前記芳香族ビニル－共役ジエン共重合体ゴムおよび前記ブタジエンゴムの合計含有量が、前記ゴム成分全体の７０質量％以上であり、
前記含硫黄炭化水素重合体が、不飽和炭化水素重合体と硫黄との反応生成物であり、前記不飽和炭化水素が脂環式不飽和化合物を含み、
前記含硫黄炭化水素重合体の重量平均分子量が５００以上４０００以下である、ゴム組成物。
［２］ 前記脂環式不飽和炭化水素が、ノルボルネン骨格を有する化合物を含む、［１］に記載のゴム組成物。
［３］ 前記ノルボルネン骨格を有する化合物が、ジシクロペンタジエンを含む、［２］に記載のゴム組成物。
［４］ 前記ノルボルネン骨格中の不飽和結合が硫黄と反応してなる、［２］に記載のゴム組成物。
［５］ 前記ゴム成分のガラス転移温度が－９０℃以上－５７℃以下である、［１］～［４］のいずれかに記載のゴム組成物。
［６］ 前記含硫黄炭化水素重合体の重量平均分子量が７００以上２０００以下である、［１］～［５］のいずれかに記載のゴム組成物。
［７］ 充填剤をさらに含む、［１］～［６］のいずれかに記載のゴム組成物。
［８］ 前記充填剤が、シリカおよびカーボンブラックからなる群から選択される少なくとも１種を含む、［７］に記載のゴム組成物。
［９］ 前記充填剤の含有量は、前記ゴム成分１００質量部に対して８０質量部以上２００質量部未満である、［７］または［８］に記載のゴム組成物。
［１０］ 前記ゴム用添加剤が、タイヤの耐摩耗性向上剤である、［１］～［９］のいずれかに記載のゴム組成物。
［１１］ タイヤ用である、［１］～［１０］のいずれかに記載のゴム組成物。
［１２］ 少なくともゴム成分とゴム用添加剤とを混練する工程を含む、ゴム組成物の製造方法であって、
前記ゴム成分が、芳香族ビニル－共役ジエン共重合体ゴムおよびブタジエンゴムの少なくとも１種を含み、
前記芳香族ビニル－共役ジエン共重合体ゴムおよび前記ブタジエンゴムの合計含有量が、前記ゴム成分全体の７０質量％以上であり、
前記ゴム用添加剤が、含硫黄炭化水素重合体を含み、
前記含硫黄炭化水素重合体が、不飽和炭化水素重合体と硫黄との反応生成物であり、前記炭化水素が脂環式不飽和化合物を含み、
前記含硫黄炭化水素重合体の重量平均分子量が５００以上４０００以下である、ゴム組成物の製造方法。
［１３］ ［１］～［１１］のいずれかに記載のゴム組成物を用いて製造されたタイヤ。
［１４］ 前記タイヤが冬用タイヤである、［１３］に記載のタイヤ。
［１５］ 前記冬用タイヤがスタッドレスタイヤである、［１４］に記載のタイヤ。
That is, according to the present invention, the following inventions are provided.
[1] A rubber component having a glass transition temperature of -100°C or more and less than -55°C,
A rubber additive containing a sulfur-containing hydrocarbon polymer,
including;
The rubber component includes at least one of aromatic vinyl-conjugated diene copolymer rubber and butadiene rubber,
The total content of the aromatic vinyl-conjugated diene copolymer rubber and the butadiene rubber is 70% by mass or more of the entire rubber component,
The sulfur-containing hydrocarbon polymer is a reaction product of an unsaturated hydrocarbon polymer and sulfur, and the unsaturated hydrocarbon contains an alicyclic unsaturated compound,
A rubber composition, wherein the sulfur-containing hydrocarbon polymer has a weight average molecular weight of 500 or more and 4,000 or less.
[2] The rubber composition according to [1], wherein the alicyclic unsaturated hydrocarbon includes a compound having a norbornene skeleton.
[3] The rubber composition according to [2], wherein the compound having a norbornene skeleton contains dicyclopentadiene.
[4] The rubber composition according to [2], wherein the unsaturated bond in the norbornene skeleton reacts with sulfur.
[5] The rubber composition according to any one of [1] to [4], wherein the rubber component has a glass transition temperature of -90°C or higher and -57°C or lower.
[6] The rubber composition according to any one of [1] to [5], wherein the sulfur-containing hydrocarbon polymer has a weight average molecular weight of 700 or more and 2,000 or less.
[7] The rubber composition according to any one of [1] to [6], further comprising a filler.
[8] The rubber composition according to [7], wherein the filler contains at least one selected from the group consisting of silica and carbon black.
[9] The rubber composition according to [7] or [8], wherein the content of the filler is 80 parts by mass or more and less than 200 parts by mass based on 100 parts by mass of the rubber component.
[10] The rubber composition according to any one of [1] to [9], wherein the rubber additive is a tire wear resistance improver.
[11] The rubber composition according to any one of [1] to [10], which is used for tires.
[12] A method for producing a rubber composition, comprising at least a step of kneading a rubber component and a rubber additive,
The rubber component includes at least one of aromatic vinyl-conjugated diene copolymer rubber and butadiene rubber,
The total content of the aromatic vinyl-conjugated diene copolymer rubber and the butadiene rubber is 70% by mass or more of the entire rubber component,
The rubber additive contains a sulfur-containing hydrocarbon polymer,
The sulfur-containing hydrocarbon polymer is a reaction product of an unsaturated hydrocarbon polymer and sulfur, and the hydrocarbon contains an alicyclic unsaturated compound,
A method for producing a rubber composition, wherein the sulfur-containing hydrocarbon polymer has a weight average molecular weight of 500 or more and 4,000 or less.
[13] A tire manufactured using the rubber composition according to any one of [1] to [11].
[14] The tire according to [13], wherein the tire is a winter tire.
[15] The tire according to [14], wherein the winter tire is a studless tire.
本発明によれば、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性に優れるタイヤを製造するためのゴム組成物を提供することができる。さらに、本発明によれば、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性に優れるタイヤを製造することができる。 According to the present invention, it is possible to provide a rubber composition for producing a tire that is excellent in wear resistance, wet grip performance, steering stability, and running performance on ice and snow. Further, according to the present invention, it is possible to manufacture a tire that is excellent in wear resistance, wet grip performance, steering stability, and running performance on icy and snowy roads.
［ゴム組成物］
本発明のゴム組成物は、ゴム成分と、ゴム用添加剤とを含み、充填剤をさらに含んでもよい。本発明のゴム組成物を用いて製造したタイヤは、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性に優れる。ゴム成分の含有量は、ゴム組成物の固形分質量全体に対して、好ましくは２０質量％以上７０質量％以下であり、より好ましくは２５質量％以上６５質量％以下であり、さらに好ましくは３０質量％以上６０質量％以下である。ゴム用添加剤の含有量は、ゴム成分１００質量部に対して好ましくは１質量部以上３０質量部以下であり、より好ましくは３質量部以上２５質量部以下であり、さらに好ましくは５質量部以上２０質量部以下である。充填剤の含有量は、ゴム成分１００質量部に対して、好ましくは８０質量部以上２００質量部未満であり、より好ましくは８５質量部以上１８０質量部以下であり、さらに好ましくは９０質量部以上１６０質量部以下である。
[Rubber composition]
The rubber composition of the present invention includes a rubber component and a rubber additive, and may further include a filler. Tires manufactured using the rubber composition of the present invention have excellent wear resistance, wet grip, steering stability, and running performance on icy and snowy roads. The content of the rubber component is preferably 20% by mass or more and 70% by mass or less, more preferably 25% by mass or more and 65% by mass or less, and even more preferably 30% by mass or less, based on the entire solid mass of the rubber composition. It is not less than 60% by mass and not more than 60% by mass. The content of the rubber additive is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 25 parts by mass or less, and even more preferably 5 parts by mass, based on 100 parts by mass of the rubber component. The amount is 20 parts by mass or less. The content of the filler is preferably 80 parts by mass or more and less than 200 parts by mass, more preferably 85 parts by mass or more and 180 parts by mass or less, and even more preferably 90 parts by mass or more, based on 100 parts by mass of the rubber component. It is 160 parts by mass or less.
（ゴム成分）
ゴム組成物に用いるゴム成分は、ガラス転移温度（Ｔｇ）が、－１００℃以上－５５℃未満であり、好ましくは－９０℃以上－５７℃以下であり、より好ましくは－８０℃以上－５９℃以下であり、さらに好ましくは－７５℃以上－６０℃以下である。ガラス転移温度（Ｔｇ）が上記数値範囲内のゴム成分を用いたタイヤは、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性に優れているために好ましい。特にガラス転移温度（Ｔｇ）が上記数値範囲内のゴム成分を用い、かつ、特定量（ゴム成分１００質量部に対して８０質量部以上２００質量部未満）の充填剤を含有させたタイヤは、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性が特に優れるため、冬用タイヤとして好適であり、特にスタッドレスタイヤとして好適である。
ゴム成分として２種以上のゴムを用いる場合には、混合後のゴム成分のＴｇが上記範囲内であれば良い。
なお、ゴム成分のＴｇは、従来公知の方法により測定することができる。例えば、ゴム成分のＴｇは、示差熱分析（ＤＴＡ）や示差走査熱量測定（ＤＳＣ）により測定することができる。
(rubber component)
The rubber component used in the rubber composition has a glass transition temperature (Tg) of -100°C or more and less than -55°C, preferably -90°C or more and -57°C or less, more preferably -80°C or more and -59°C. ℃ or less, more preferably -75°C or more and -60°C or less. A tire using a rubber component having a glass transition temperature (Tg) within the above numerical range is preferable because it has excellent wear resistance, wet grip, steering stability, and running performance on ice and snow. In particular, a tire that uses a rubber component whose glass transition temperature (Tg) is within the above numerical range and contains a specific amount of filler (80 parts by mass or more and less than 200 parts by mass per 100 parts by mass of the rubber component), Since it has particularly excellent wear resistance, wet grip, steering stability, and running performance on ice and snow, it is suitable as a winter tire, and particularly suitable as a studless tire.
When two or more types of rubber are used as the rubber component, the Tg of the rubber components after mixing may be within the above range.
Note that the Tg of the rubber component can be measured by a conventionally known method. For example, the Tg of the rubber component can be measured by differential thermal analysis (DTA) or differential scanning calorimetry (DSC).
ゴム成分としては、上記のＴｇを満たすものであれば特に限定されないが、ジエン系ゴムを含むことが好ましい。下記の含硫黄炭化水素重合体は、一般的な不飽和炭化水素重合体である不飽和石油樹脂（硫黄を含有しないもの）に比べて、ジエン系ゴムに対する反応性が高く、ゴム分子鎖に反応し易い。 The rubber component is not particularly limited as long as it satisfies the above Tg, but preferably includes diene rubber. The sulfur-containing hydrocarbon polymers listed below have higher reactivity with diene rubber than unsaturated petroleum resins (which do not contain sulfur), which are common unsaturated hydrocarbon polymers, and react with rubber molecular chains. Easy to do.
ジエン系ゴムとしては、芳香族ビニル－共役ジエン共重合体ゴムおよびブタジエンゴム（ＢＲ）の少なくとも１種を用いることが好ましく、芳香族ビニル－共役ジエン共重合体ゴムおよびブタジエンゴムの両方を用いることがより好ましい。特に、ブタジエンゴムは、凡庸ゴムの中でもガラス転移温度が低く、耐寒性に優れているため、氷雪路上走行性を向上させることができる。芳香族ビニル－共役ジエン共重合体ゴムとしては、スチレン－ブタジエンゴム（ＳＢＲ）、スチレン－イソプレン－ブタジエンゴム、スチレン－イソプレンゴム、およびスチレン－α－メチルスチレン－ブタジエンゴム等が挙げられる。これらの中でも、スチレン－ブタジエンゴムを用いることが好ましい。さらに、これらの変性ジエン系ゴムを用いることもできる。変性ジエン系ゴムには、主鎖変性、片末端変性、両末端変性、水素添加等の変性手法によるジエン系ゴムが包含される。ここで、変性合成ジエン系ゴムの変性官能基としては、エポキシ基、アミノ基、アルコキシシリル基、水酸基等の各種官能基が挙げられ、これら官能基は１種又は２種以上が変性合成ジエン系ゴムに含まれていてもよい。 As the diene rubber, it is preferable to use at least one of aromatic vinyl-conjugated diene copolymer rubber and butadiene rubber (BR), and it is preferable to use both aromatic vinyl-conjugated diene copolymer rubber and butadiene rubber. is more preferable. In particular, butadiene rubber has a low glass transition temperature among ordinary rubbers and is excellent in cold resistance, so it can improve running performance on ice and snow. Examples of the aromatic vinyl-conjugated diene copolymer rubber include styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber, styrene-isoprene rubber, and styrene-α-methylstyrene-butadiene rubber. Among these, it is preferable to use styrene-butadiene rubber. Furthermore, these modified diene rubbers can also be used. The modified diene rubber includes diene rubbers obtained by modification methods such as main chain modification, one end modification, both end modification, and hydrogenation. Here, the modified functional groups of the modified synthetic diene rubber include various functional groups such as epoxy groups, amino groups, alkoxysilyl groups, and hydroxyl groups, and one or more of these functional groups are present in the modified synthetic diene rubber. May be included in rubber.
ジエン系ゴムの製造方法は、特に制限はなく、乳化重合、溶液重合、ラジカル重合、アニオン重合、カチオン重合等が挙げられる。 The method for producing diene rubber is not particularly limited, and examples include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, and cationic polymerization.
また、ジエン系ゴムの二重結合部のシス／トランス／ビニルの比率は、特に制限はなく、いずれの比率においても好適に用いることができる。また、ジエン系ゴムの数平均分子量および分子量分布は、特に制限はないが、数平均分子量は５００～３００００００、分子量分布は１．５～１５が好ましい。 Further, the ratio of cis/trans/vinyl in the double bond portion of the diene rubber is not particularly limited, and any ratio can be suitably used. Further, the number average molecular weight and molecular weight distribution of the diene rubber are not particularly limited, but the number average molecular weight is preferably 500 to 3,000,000, and the molecular weight distribution is preferably 1.5 to 15.
ゴム成分中の芳香族ビニル－共役ジエン共重合体ゴムおよびブタジエンゴムの合計含有量は、ゴム成分の全量に対して、好ましくは５０質量％以上であり、より好ましくは７０質量％以上であり、さらに好ましくは９０質量％以上であり、また、１００質量％であってもよい。芳香族ビニル－共役ジエン共重合体ゴムおよびブタジエンゴムの合計含有量が上記数値範囲内であれば、ゴム成分のＴｇを上述の数値範囲内に調節し易く、タイヤの耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性をバランス良く向上できるタイヤ用ゴム組成物が得られる。 The total content of aromatic vinyl-conjugated diene copolymer rubber and butadiene rubber in the rubber component is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total amount of the rubber component, More preferably, it is 90% by mass or more, and may be 100% by mass. If the total content of aromatic vinyl-conjugated diene copolymer rubber and butadiene rubber is within the above numerical range, it is easy to adjust the Tg of the rubber component within the above numerical range, and the tire wear resistance and wet grip properties are improved. A rubber composition for a tire is obtained which can improve steering stability and driving performance on ice and snow roads in a well-balanced manner.
また、本発明のゴム組成物には、その機能を損なわない範囲で、上記のゴム成分以外にもエラストマーを配合することもできる。エラストマーとしては、スチレン－イソプレン－スチレン三元ブロック共重合体（ＳＩＳ）、スチレン－ブタジエン－スチレン三元ブロック共重合体（ＳＢＳ）、それらの水添物（ＳＥＢＳ，ＳＥＰＳ，ＳＥＥＰＳ）等のポリスチレン系エラストマー性ポリマー、ポリオレフィン系エラストマー、ポリ塩化ビニル系エラストマー、ポリウレタン系エラストマー、ポリエステル系エラストマー、及び、ポリアミド系エラストマーのからなる群より選択される熱可塑性エラストマーが挙げられる。 Further, the rubber composition of the present invention may contain an elastomer other than the above-mentioned rubber components within a range that does not impair its functions. Examples of elastomers include polystyrene-based elastomers such as styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene-styrene triblock copolymer (SBS), and hydrogenated products thereof (SEBS, SEPS, SEEPS). Examples include thermoplastic elastomers selected from the group consisting of elastomeric polymers, polyolefin elastomers, polyvinyl chloride elastomers, polyurethane elastomers, polyester elastomers, and polyamide elastomers.
（ゴム用添加剤）
ゴム組成物に用いるゴム用添加剤は、下記の含硫黄炭化水素重合体を含む。上記のガラス転移温度が高いゴム成分に、従来公知の石油樹脂のようなゴム成分のガラス転移温度を上げる添加剤を配合した場合には、得られたゴム組成物を用いて製造したタイヤの耐摩耗性は悪化する。一方、本発明においては、上記のガラス転移温度が高いゴム成分に、下記の含硫黄炭化水素重合体を含むゴム用添加剤を配合することで、得られたゴム組成物を用いて製造したタイヤの耐摩耗性を向上することができる。そのため、下記の含硫黄炭化水素重合体は、タイヤの耐摩耗性向上剤として用いることができる。
(Rubber additive)
The rubber additive used in the rubber composition includes the following sulfur-containing hydrocarbon polymer. When the above-mentioned rubber component with a high glass transition temperature is blended with an additive that increases the glass transition temperature of the rubber component, such as a conventionally known petroleum resin, the durability of tires manufactured using the obtained rubber composition is Abrasion properties worsen. On the other hand, in the present invention, a tire manufactured using a rubber composition obtained by blending a rubber additive containing the following sulfur-containing hydrocarbon polymer with the above-mentioned rubber component having a high glass transition temperature. can improve the wear resistance of Therefore, the following sulfur-containing hydrocarbon polymer can be used as a tire wear resistance improver.
（含硫黄炭化水素重合体）
含硫黄炭化水素重合体は、不飽和炭化水素の重合体と硫黄との反応生成物である。具体的には、含硫黄炭化水素重合体は、不飽和炭化水素の重合体の不飽和結合に硫黄を反応させて得た反応生成物であることが好ましい。
(Sulfur-containing hydrocarbon polymer)
A sulfur-containing hydrocarbon polymer is a reaction product of an unsaturated hydrocarbon polymer and sulfur. Specifically, the sulfur-containing hydrocarbon polymer is preferably a reaction product obtained by reacting sulfur with the unsaturated bonds of an unsaturated hydrocarbon polymer.
含硫黄炭化水素重合体の重量平均分子量（Ｍｗ）は、５００以上４０００以下であり、下限値は好ましくは６００以上であり、より好ましくは７００以上であり、さらに好ましくは８００以上であり、また、上限値は好ましくは３０００以下であり、より好ましくは２０００以下であり、さらに好ましくは１５００以下である。特に、含硫黄炭化水素重合体の重量平均分子量（Ｍｗ）は、好ましくは６００以上３０００以下であり、より好ましくは７００以上２０００以下であり、さらに好ましくは８００以上１５００以下である。含硫黄炭化水素重合体の重量平均分子量を小さくすることで、含硫黄炭化水素重合体同士が硫黄を介して結合するのを抑制し、ゴム成分と結合する硫黄量を増大させ、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性をより向上させることができる。
また、含硫黄炭化水素重合体の分子量分布（Ｍｗ／数平均分子量（Ｍｎ））は、好ましくは１．０以上５．０以下であり、より好ましくは１．０以上４．０以下であり、さらに好ましくは１．０以上３．０以下であり、さらにより好ましくは１．０以上２．５以下である。
なお、重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）は、従来公知のＧＰＣ（ゲルパーミエーションクロマトグラフィー）解析の方法によって測定することができる。
The weight average molecular weight (Mw) of the sulfur-containing hydrocarbon polymer is 500 or more and 4000 or less, and the lower limit is preferably 600 or more, more preferably 700 or more, still more preferably 800 or more, and The upper limit is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,500 or less. In particular, the weight average molecular weight (Mw) of the sulfur-containing hydrocarbon polymer is preferably 600 or more and 3000 or less, more preferably 700 or more and 2000 or less, and even more preferably 800 or more and 1500 or less. By reducing the weight average molecular weight of the sulfur-containing hydrocarbon polymer, it is possible to prevent the sulfur-containing hydrocarbon polymers from bonding with each other through sulfur, increase the amount of sulfur that bonds with the rubber component, and improve wear resistance. Wet grip performance, steering stability, and driving performance on icy and snowy roads can be further improved.
Further, the molecular weight distribution (Mw/number average molecular weight (Mn)) of the sulfur-containing hydrocarbon polymer is preferably 1.0 or more and 5.0 or less, more preferably 1.0 or more and 4.0 or less, More preferably, it is 1.0 or more and 3.0 or less, and even more preferably 1.0 or more and 2.5 or less.
Note that the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) can be measured by a conventionally known method of GPC (gel permeation chromatography) analysis.
本発明においては、重合体の原料として、少なくとも、硫黄と反応させるための不飽和結合を有する炭化水素を用いる。不飽和炭化水素は脂環式不飽和化合物を含むものであり、脂環式不飽和炭化水素はノルボルネン骨格を有する化合物であることが好ましい。ノルボルネン骨格の二重結合の構造がひずみを持ち、硫黄との反応性が良いためである。脂環式不飽和化合物の不飽和結合は硫黄との反応後に残存してもよく、全て消費されてもよい。脂環式不飽和化合物の不飽和結合としては、ノルボルネン骨格に存在する不飽和結合とシクロペンテン骨格に存在する不飽和結合があるが、タイヤの耐摩耗性向上の観点からは、ノルボルネン骨格の不飽和結合は全て消費されていることがより好ましい。 In the present invention, a hydrocarbon having at least an unsaturated bond for reaction with sulfur is used as a raw material for the polymer. The unsaturated hydrocarbon includes an alicyclic unsaturated compound, and the alicyclic unsaturated hydrocarbon is preferably a compound having a norbornene skeleton. This is because the double bond structure of the norbornene skeleton is strained and has good reactivity with sulfur. The unsaturated bonds of the alicyclic unsaturated compound may remain after the reaction with sulfur or may be completely consumed. Unsaturated bonds in alicyclic unsaturated compounds include unsaturated bonds present in the norbornene skeleton and unsaturated bonds present in the cyclopentene skeleton, but from the perspective of improving tire wear resistance, unsaturated bonds in the norbornene skeleton More preferably, all bonds are consumed.
本発明の一実施形態においては、不飽和炭化水素の重合体として、工業的な製造の観点から、ナフサを熱分解して得た留分のうち、エチレン、プロピレンおよびブタジエン等の有用な化合物を取り去った残りの留分を、混合状態のまま重合して得られた樹脂（以下、「石油樹脂」という）を用いることができる。石油樹脂としては、一般的には、Ｃ５留分を（共）重合して得られる脂肪族系石油樹脂（Ｃ５系石油樹脂）、ナフサの熱分解によって得られるＣ９留分を（共）重合して得られる芳香族系石油樹脂（Ｃ９系石油樹脂）、前記Ｃ５留分とＣ９留分を共重合して得られる共重合系石油樹脂（Ｃ５／Ｃ９系石油樹脂）が挙げられる。なお、石油樹脂は、原料中のオレフィン含有量によって生成する樹脂の性質が異なるが、分子量２００～８０００、軟化点５～１８０℃の透明な淡黄色ないし黄褐色の松脂（まつやに）状の樹脂である。 In one embodiment of the present invention, from the viewpoint of industrial production, useful compounds such as ethylene, propylene and butadiene are used as unsaturated hydrocarbon polymers from the fraction obtained by thermally decomposing naphtha. A resin obtained by polymerizing the remaining distillate in a mixed state (hereinafter referred to as "petroleum resin") can be used. Petroleum resins are generally aliphatic petroleum resins (C5 petroleum resins) obtained by (co)polymerizing C5 fractions, and (co)polymerizing C9 fractions obtained by thermal decomposition of naphtha. Examples include aromatic petroleum resins (C9 petroleum resins) obtained by copolymerization of the C5 fraction and C9 fraction (C5/C9 petroleum resins). Petroleum resins are transparent pale yellow to yellowish brown pine resin-like resins with a molecular weight of 200 to 8,000 and a softening point of 5 to 180°C, although the properties of the resin produced vary depending on the olefin content in the raw materials. It is.
本発明においては、石油樹脂の中でも、脂環式不飽和炭化水素を含む留分を（共）重合して得られる石油樹脂（以下、「脂環式不飽和炭化水素系石油樹脂」という）を用いる。脂環式不飽和炭化水素系石油樹脂は、例えば、Ｃ５留分中に含まれるシクロペンタジエン類を２量体化してジシクロペンタジエン類とし、蒸留して他のＣ５留分と分離し、加熱してディールス・アルダー反応により重合させたものを含む。シクロペンタジエン類とは、例えば、シクロペンタジエン、メチルシクロペンタジエン等が挙げられる。また、ジシクロペンタジエン類とは、例えば、ジシクロペンタジエン（ＤＣＰＤ）、メチルジシクロペンタジエン等があげられ、特にジシクロペンタジエンが好ましい。 In the present invention, among petroleum resins, petroleum resins obtained by (co)polymerizing fractions containing alicyclic unsaturated hydrocarbons (hereinafter referred to as "alicyclic unsaturated hydrocarbon petroleum resins") are used. use Alicyclic unsaturated hydrocarbon petroleum resins are produced by, for example, dimerizing cyclopentadiene contained in the C5 fraction to form dicyclopentadiene, distilling it to separate it from other C5 fractions, and heating it. Including those polymerized by Diels-Alder reaction. Examples of cyclopentadiene include cyclopentadiene, methylcyclopentadiene, and the like. Examples of dicyclopentadiene include dicyclopentadiene (DCPD) and methyldicyclopentadiene, with dicyclopentadiene being particularly preferred.
脂環式不飽和炭化水素系石油樹脂には、シクロペンタジエン類以外のＣ５留分やＣ９留分が含まれていてもよい。 The alicyclic unsaturated hydrocarbon petroleum resin may contain C5 fractions and C9 fractions other than cyclopentadienes.
Ｃ５留分は、一般的には、石油類の熱分解により得られる留分のうち、沸点範囲が２０～１１０℃程度の留分が用いられる。シクロペンタジエン類以外のＣ５留分としては、例えば、１－ペンテン、２－ペンテン、２－メチル－１－ブテン、２－メチル－２－ブテン、３－メチル－１－ブテン等のオレフィン系炭化水素、２－メチル－１，３－ブタジエン、１，２－ペンタジエン、１，３－ペンタジエン、３－メチル－１，２－ブタジエン等のジオレフィン系炭化水素が挙げられる。 As the C5 fraction, a fraction with a boiling point range of about 20 to 110° C. is generally used among fractions obtained by thermal decomposition of petroleum. Examples of C5 fractions other than cyclopentadiene include olefinic hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene. , 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene.
Ｃ９留分は、一般的には、石油類の熱分解により得られる留分のうち、沸点範囲が１００～２８０℃程度の留分が用いられる。Ｃ９留分としては、例えば、α－メチルスチレン、β－メチルスチレン、γ－メチルスチレン等のスチレン同族体やインデン、クマロン等のインデン同族体等が挙げられる。 As the C9 fraction, a fraction with a boiling point range of about 100 to 280° C. is generally used among fractions obtained by thermal decomposition of petroleum. Examples of the C9 fraction include styrene analogs such as α-methylstyrene, β-methylstyrene, and γ-methylstyrene, and indene analogs such as indene and coumaron.
一般的なＣ５系石油樹脂、Ｃ９系石油樹脂、Ｃ５／Ｃ９系石油樹脂の製造方法は以下の通りである。原料油に対して０．０１～５重量％のフリーデルクラフツ型触媒を添加し、重合反応を行う。反応終了後、アルカリを用いてフリーデルクラフツ型触媒を分解除去し、最後に蒸留等により未反応油および低分子重合物を除去する。一般的にフリーデルクラフツ型触媒としては、例えば三塩化アルミニウム、三臭化アルミニウム、三フッ化ホウ素あるいはそのフェノール錯体、ブタノール錯体等が挙げられる。中でも三塩化アルミニウム、三フッ化ホウ素のフェノール錯体、三フッ化ホウ素のブタノール錯体が好ましい。重合温度は０～１００℃が好ましく、特に好ましくは０～８０℃である。また、触媒量及び重合時間は、原料油１００質量部に対して触媒０．１～２．０質量部のとき、０．１～１０時間であることが好ましい。反応圧力は大気圧～１ＭＰａが好ましい。 The general manufacturing method of C5 petroleum resin, C9 petroleum resin, and C5/C9 petroleum resin is as follows. A Friedel-Crafts type catalyst is added in an amount of 0.01 to 5% by weight based on the raw material oil to carry out a polymerization reaction. After the reaction is completed, the Friedel-Crafts type catalyst is decomposed and removed using an alkali, and finally, unreacted oil and low-molecular polymers are removed by distillation or the like. Generally, Friedel-Crafts type catalysts include, for example, aluminum trichloride, aluminum tribromide, boron trifluoride, or their phenol complexes and butanol complexes. Among these, aluminum trichloride, a phenol complex of boron trifluoride, and a butanol complex of boron trifluoride are preferred. The polymerization temperature is preferably 0 to 100°C, particularly preferably 0 to 80°C. Further, the catalyst amount and polymerization time are preferably 0.1 to 10 hours when the catalyst is 0.1 to 2.0 parts by mass relative to 100 parts by mass of the raw oil. The reaction pressure is preferably atmospheric pressure to 1 MPa.
石油樹脂は一部に種々の官能基を有する化合物が重合していてもよい。官能基の例としては、水酸基を有するアルコール化合物やフェノール化合物が挙げられる。アルコール化合物の具体例としては、アリルアルコール、２－ブテン－１，４－ジオール等の二重結合を有するアルコール化合物が挙げられる。フェノール化合物としては、フェノール、クレゾール、キシレノール、ｐ－ｔ－ブチルフェノール、ｐ－オクチルフェノール、ｐ－ノニルフェノール等のアルキルフェノール類を使用できる。これらの水酸基を有する化合物は、単独で用いてもよく、二種以上を併用してもよい。 A part of the petroleum resin may be polymerized with compounds having various functional groups. Examples of the functional group include alcohol compounds and phenol compounds having hydroxyl groups. Specific examples of alcohol compounds include alcohol compounds having a double bond such as allyl alcohol and 2-butene-1,4-diol. As the phenol compound, alkylphenols such as phenol, cresol, xylenol, pt-butylphenol, p-octylphenol, and p-nonylphenol can be used. These hydroxyl group-containing compounds may be used alone or in combination of two or more.
また、水酸基含有石油樹脂は、石油留分と共に（メタ）アクリル酸アルキルエステル等を熱重合して石油樹脂中にエステル基を導入した後、該エステル基を還元する方法や、石油樹脂中に残存又は導入した二重結合を水和する方法等によっても製造できる。本発明では、水酸基含有石油樹脂として、上記のような各種方法により得られるものが使用できるが、性能及び製造の観点から、フェノール変性石油樹脂等を使用するのが好ましい。 In addition, hydroxyl group-containing petroleum resins can be produced by thermally polymerizing (meth)acrylic acid alkyl esters together with petroleum fractions to introduce ester groups into petroleum resins, and then reducing the ester groups. Alternatively, it can be produced by a method of hydrating the introduced double bond. In the present invention, as the hydroxyl group-containing petroleum resin, those obtained by the various methods described above can be used, but from the viewpoint of performance and production, it is preferable to use a phenol-modified petroleum resin or the like.
該フェノール変性石油樹脂は、Ｃ９留分をフェノールの存在下でカチオン重合して得られ、変性が容易である。 The phenol-modified petroleum resin is obtained by cationic polymerization of a C9 fraction in the presence of phenol, and is easily modified.
重合の方法は、特に限定されず、例えば、上述のディールス・アルダー反応等の１５０～３００℃程度で１～１０時間程度の加熱を行う熱重合反応や、上述のフリーデルクラフツ型反応などから選択できる。 The polymerization method is not particularly limited, and may be selected from, for example, the above-mentioned Diels-Alder reaction, a thermal polymerization reaction in which heating is performed at about 150 to 300°C for about 1 to 10 hours, and the above-mentioned Friedel-Crafts type reaction. can.
上述のこれらの樹脂は、軟化点が２００℃以下（測定法：ＡＳＴＭ Ｅ２８－５８－Ｔ）であることが好ましく、更に好ましくは、４５～１６０℃が望ましい。 The above-mentioned resins preferably have a softening point of 200°C or less (measurement method: ASTM E28-58-T), more preferably 45 to 160°C.
本発明においては、上述の石油樹脂中の二重結合の一部を水素添加した部分水添石油樹脂を使用することもできる。水素添加の条件は任意であるが、常圧での沸点が１４０～２８０℃の飽和鎖状炭化水素、飽和脂環式炭化水素、芳香族炭化水素より選ばれた１種以上の溶剤と石油樹脂とを混合し、ニッケル、モリブデン、コバルト、パラジウム、白金等を含む一般的な水素化触媒を使用し、反応温度１５０～３２０℃、反応圧力３～３０ＭＰａ、反応時間１～１０時間の条件で反応を行う。 In the present invention, a partially hydrogenated petroleum resin obtained by hydrogenating some of the double bonds in the petroleum resin described above can also be used. The conditions for hydrogenation are arbitrary, but one or more solvents selected from saturated chain hydrocarbons, saturated alicyclic hydrocarbons, and aromatic hydrocarbons with a boiling point of 140 to 280°C at normal pressure and petroleum resin. Using a general hydrogenation catalyst containing nickel, molybdenum, cobalt, palladium, platinum, etc., the reaction temperature is 150 to 320°C, the reaction pressure is 3 to 30 MPa, and the reaction time is 1 to 10 hours. I do.
分子内に二重結合を有するＣ５系、Ｃ９系、Ｃ５／Ｃ９系石油樹脂の市販品としては、ＥＮＥＯＳ（株）製ネオレジンＥＰ－１４０ （軟化点：１４０℃）、丸善石油化学（株）製マルカレッツＭ－８９０Ａ （軟化点：１０５℃）、丸善石油化学（株）製マルカレッツＭ－８４５Ａ （軟化点：１４５℃）ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ ＲＢ０９３（軟化点：９２℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ ＲＢ１００（軟化点：９８℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ ＲＣ０９３（軟化点：９３℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ ＲＣ１００（軟化点：９７℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ ＲＣ１１５（軟化点：１１２℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ ＲＤ１０４（軟化点：１０２℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ ＰＲ８０２（軟化点：８９℃）、日本ゼオン（株）製 Ｑｕｉｎｔｏｎｅ Ｂ１７０（軟化点：７０℃）、日本ゼオン（株）製 Ｑｕｉｎｔｏｎｅ Ｍ１００（軟化点：９５℃）、日本ゼオン（株）製 Ｑｕｉｎｔｏｎｅ Ｒ１００（軟化点：９６℃）、日本ゼオン（株）製 Ｑｕｉｎｔｏｎｅ Ａ１００（軟化点：１００℃）、日本ゼオン（株）製 Ｑｕｉｎｔｏｎｅ ＲＸ１１０（軟化点：１１０℃）、Ｅｘｘｏｎ Ｍｏｂｉｌ Ｃｈｅｍｉｃａｌ製 Ｅｓｃｏｒｅｚ １１０２（軟化点：１００℃）、Ｅｘｘｏｎ Ｍｏｂｉｌ Ｃｈｅｍｉｃａｌ製 Ｅｓｃｏｒｅｚ １３０４（軟化点：９４℃）、Ｅｘｘｏｎ Ｍｏｂｉｌ Ｃｈｅｍｉｃａｌ製 Ｅｓｃｏｒｅｚ １３１０ＬＣ（軟化点：１００℃）、Ｅｘｘｏｎ Ｍｏｂｉｌ Ｃｈｅｍｉｃａｌ製 Ｅｓｃｏｒｅｚ １３１５（軟化点：１１５℃）、ＫＯＬＯＮ Ｉｎｄｕｔｒｉｅｓ製 ＨＩＫＯＲＥＺ Ａ－１１００（軟化点：９８℃）、ＫＯＬＯＮ Ｉｎｄｕｔｒｉｅｓ製 ＨＩＫＯＲＥＺ Ａ－１１１５（軟化点：１１２℃）、ＫＯＬＯＮ Ｉｎｄｕｔｒｉｅｓ製 ＨＩＫＯＲＥＺ Ａ－２１１５（軟化点：１１２℃）、ＫＯＬＯＮ Ｉｎｄｕｔｒｉｅｓ製 ＨＩＫＯＲＥＺ Ｃ－１１００（軟化点：９８℃）等が挙げられる。 Commercially available C5, C9, and C5/C9 petroleum resins with double bonds in the molecule include Neoresin EP-140 (softening point: 140°C) manufactured by ENEOS Co., Ltd. and Maruzen Petrochemical Co., Ltd. Marukarez M-890A (softening point: 105°C), Marukarez M-845A manufactured by Maruzen Petrochemical Co., Ltd. (softening point: 145°C), T-REZ RB093 manufactured by ENEOS Co., Ltd. (softening point: 92°C), ENEOS Co., Ltd. ) manufactured by T-REZ RB100 (softening point: 98°C), T-REZ RC093 manufactured by ENEOS Corporation (softening point: 93°C), T-REZ RC100 manufactured by ENEOS Corporation (softening point: 97°C), ENEOS ( T-REZ RC115 manufactured by ENEOS Co., Ltd. (softening point: 112°C), T-REZ RD104 manufactured by ENEOS Co., Ltd. (softening point: 102°C), T-REZ PR802 manufactured by ENEOS Co., Ltd. (softening point: 89°C), Japan Quintone B170 (softening point: 70°C) manufactured by Zeon Co., Ltd., Quintone M100 (softening point: 95°C) manufactured by Nippon Zeon Co., Ltd., Quintone R100 (softening point: 96°C) manufactured by Nippon Zeon Co., Ltd. Quintone A100 (softening point: 100°C) manufactured by Zeon Co., Ltd., Quintone RX110 (softening point: 110°C) manufactured by Zeon Co., Ltd., Escorez 1102 (softening point: 100°C) manufactured by Exxon Mobil Chemical, Exxon Mobil Che Escorez 1304 made by mical ( Softening point: 94°C), Escorez 1310LC manufactured by Exxon Mobil Chemical (softening point: 100°C), Escorez 1315 manufactured by Exxon Mobil Chemical (softening point: 115°C), H manufactured by KOLON Industries. IKOREZ A-1100 (softening point: 98°C), HIKOREZ A-1115 manufactured by KOLON Industries (softening point: 112°C), HIKOREZ A-2115 manufactured by KOLON Industries (softening point: 112°C), HIKOREZ C-1100 manufactured by KOLON Industries (softening point: 112°C) temperature: 98°C).
（含硫黄炭化水素重合体の製造方法）
含硫黄炭化水素重合体は、不飽和炭化水素を無溶媒下で加熱しながら溶融状態で硫黄と反応させることにより製造することができる。加熱反応を溶媒中ではなく無溶媒下で行うことで、含硫黄炭化水素重合体の重量平均分子量を小さくしながら、分子量のばらつきを小さくすることができる。また、加熱反応の条件は、特に限定されず適宜設定することができるが、好ましくは９０～１６０℃で、より好ましくは１００～１５０℃で、さらに好ましくは１００～１４０℃で、反応時間は好ましくは０．５～１０時間、より好ましくは１～８時間である。なお、加熱反応の条件を調節することで、含硫黄炭化水素重合体の重量平均分子量を調節することができる。
(Method for producing sulfur-containing hydrocarbon polymer)
The sulfur-containing hydrocarbon polymer can be produced by reacting an unsaturated hydrocarbon with sulfur in a molten state while heating in the absence of a solvent. By performing the heating reaction not in a solvent but without a solvent, it is possible to reduce the variation in molecular weight while reducing the weight average molecular weight of the sulfur-containing hydrocarbon polymer. Further, the conditions for the heating reaction are not particularly limited and can be set appropriately, but the temperature is preferably 90 to 160°C, more preferably 100 to 150°C, even more preferably 100 to 140°C, and the reaction time is preferably is 0.5 to 10 hours, more preferably 1 to 8 hours. Note that the weight average molecular weight of the sulfur-containing hydrocarbon polymer can be adjusted by adjusting the heating reaction conditions.
上記の製造方法によれば、副反応を抑制することができるため、含硫黄炭化水素重合体の収率が向上し、精製工程を経ずにそのままゴム用組成物に配合することができる。 According to the above production method, since side reactions can be suppressed, the yield of the sulfur-containing hydrocarbon polymer is improved, and it can be blended into a rubber composition as it is without going through a purification step.
石油樹脂に対する硫黄の添加量は特に限定されないが、不飽和炭化水素の不飽和結合（二重結合）当たり、０．１当量以上、好ましくは０．３～５当量の割合であることが好ましい。 The amount of sulfur added to the petroleum resin is not particularly limited, but it is preferably 0.1 equivalent or more, preferably 0.3 to 5 equivalents, per unsaturated bond (double bond) of the unsaturated hydrocarbon.
本発明においては、不飽和脂環式炭化水素としてノルボルネン骨格を有する化合物、特にジシクロペンタジエンを用いることが好ましい。さらに、ジシクロペンタジエンのノルボルネン骨格上の二重結合が硫黄と反応することが好ましく、ノルボルネン骨格上の二重結合のみが硫黄と反応することがより好ましい。ノルボルネン骨格上の二重結合が硫黄と反応して消費されたことは、１Ｈ－ＮＭＲにより確認することができる。 In the present invention, it is preferable to use a compound having a norbornene skeleton, particularly dicyclopentadiene, as the unsaturated alicyclic hydrocarbon. Furthermore, it is preferable that the double bond on the norbornene skeleton of dicyclopentadiene reacts with sulfur, and it is more preferable that only the double bond on the norbornene skeleton reacts with sulfur. It can be confirmed by 1 H-NMR that the double bond on the norbornene skeleton was consumed by reacting with sulfur.
（充填剤）
充填剤としては、シリカ、カーボンブラック、および硫酸バリウム等が挙げられ、シリカおよびカーボンブラックの少なくとも１種を用いることが好ましく、シリカを用いることがより好ましい。
(filler)
Examples of the filler include silica, carbon black, and barium sulfate. It is preferable to use at least one of silica and carbon black, and it is more preferable to use silica.
（シリカ）
シリカとしては、特に限定されないが、例えば、乾式法シリカ、湿式法シリカ、コロイダルシリカ、および沈降シリカ等が挙げられる。これらの中でも、含水ケイ酸を主成分とする湿式法シリカが好ましい。これらのシリカは、それぞれ単独でまたは２種以上を組み合わせて用いることができる。
(silica)
Silica is not particularly limited, and examples thereof include dry process silica, wet process silica, colloidal silica, and precipitated silica. Among these, wet process silica containing hydrous silicic acid as a main component is preferred. These silicas can be used alone or in combination of two or more.
シリカの比表面積は、特に制限されないが、窒素吸着比表面積（ＢＥＴ法）で通常１０～４００ｍ２／ｇ、好ましくは２０～３００ｍ２／ｇ、更に好ましくは１２０～１９０ｍ２／ｇの範囲である。シリカの比表面積が上記数値範囲内であれば、機械的特性等を向上させることができる。ここで、窒素吸着比表面積は、ＡＳＴＭ Ｄ３０３７－８１に準じ、ＢＥＴ法で測定される値である。 The specific surface area of silica is not particularly limited, but is usually in the range of 10 to 400 m 2 /g, preferably 20 to 300 m 2 /g, and more preferably 120 to 190 m 2 /g, as measured by nitrogen adsorption specific surface area (BET method). . If the specific surface area of silica is within the above numerical range, mechanical properties etc. can be improved. Here, the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTM D3037-81.
（シランカップリング剤）
シリカを配合する場合には、シランカップリング剤を配合することが好ましい。シランカップリング剤としては、公知のシランカップリング剤を用いることができる。例えば、ビス［３－（トリエトキシシリル）プロピル］テトラスルフィド、ビス［３－（トリエトキシシリル）プロピル］ジスルフィド、３－オクタノイルチオ－１－プロピルトリエトキシシラン(3-octanoylthio-1-propyltriethoxysilane)）およびその単独縮合物もしくは３－メルカプトプロピルトリエトキシシランとの共縮合物が挙げられる。ビス［３－（トリエトキシシリル）プロピル］テトラスルフィドは、市販されているものを使用してもよく、例えば、エボニック社製のＳｉ－６９が挙げられる。また、ビス［３－（トリエトキシシリル）プロピル］ジスルフィドについても、市販されているものを使用してもよく、例えば、エボニック社製のＳｉ－７５が挙げられる。また、３－オクタノイルチオ－１－プロピルトリエトキシシラン(3-octanoylthio-1-propyltriethoxysilane)）は、市販されているものを使用してもよく、例えば、モメンティブ社製のＮＸＴ－シランが挙げられる。また、３－オクタノイルチオ－１－プロピルトリエトキシシラン(3-octanoylthio-1-propyltriethoxysilane)）の縮合物は、市販されているものを使用してもよく、例えば、モメンティブ社製のＮＸＴ－Ｚ４５シランが挙げられる。シランカップリング剤の含有量は、シリカ量の１～２０質量％が好ましく、２～１０質量％がより好ましい。
(Silane coupling agent)
When blending silica, it is preferable to blend a silane coupling agent. As the silane coupling agent, a known silane coupling agent can be used. For example, bis[3-(triethoxysilyl)propyl]tetrasulfide, bis[3-(triethoxysilyl)propyl]disulfide, 3-octanoylthio-1-propyltriethoxysilane) and Examples thereof include a single condensate thereof or a co-condensate thereof with 3-mercaptopropyltriethoxysilane. As bis[3-(triethoxysilyl)propyl]tetrasulfide, commercially available products may be used, such as Si-69 manufactured by Evonik. Furthermore, commercially available bis[3-(triethoxysilyl)propyl]disulfide may be used, such as Si-75 manufactured by Evonik. Furthermore, commercially available 3-octanoylthio-1-propyltriethoxysilane may be used, such as NXT-silane manufactured by Momentive. In addition, a commercially available condensate of 3-octanoylthio-1-propyltriethoxysilane may be used, such as NXT-Z45 silane manufactured by Momentive. Can be mentioned. The content of the silane coupling agent is preferably 1 to 20% by weight, more preferably 2 to 10% by weight based on the amount of silica.
（その他の加工助剤）
本発明のゴム組成物は、その機能を損なわない範囲で、加硫剤、加硫促進剤、加硫促進助剤、老化防止剤、軟化剤、酸化防止剤、及び着色剤等のその他の加工助剤を含んでいてもよい。
(Other processing aids)
The rubber composition of the present invention may be subjected to other processing such as a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerating aid, an antiaging agent, a softening agent, an antioxidant, and a coloring agent to the extent that its functions are not impaired. It may also contain auxiliary agents.
加硫剤としては、粉末硫黄、沈降性硫黄、高分散性硫黄、表面処理硫黄、不溶性硫黄、ジモルフォリンジサルファイド、アルキルフェノールジサルファイド等の硫黄系加硫剤や、酸化亜鉛、酸化マグネシウム、リサージ、ｐ－キノンジオキシム、ｐ－ジベンゾイルキノンジオキシム、テトラクロロ－ｐ－ベンゾキノン、ポリ－ｐ－ジニトロベンゼン、メチレンジアニリン、フェノール樹脂、臭素化アルキルフェノール樹脂、塩素化アルキルフェノール樹脂等が挙げられる。加硫剤の含有量は、ゴム成分１００質量部に対して好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Vulcanizing agents include sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersed sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, zinc oxide, magnesium oxide, litharge, Examples include p-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylene dianiline, phenol resin, brominated alkylphenol resin, chlorinated alkylphenol resin, and the like. The content of the vulcanizing agent is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the rubber component.
加硫促進剤としては、テトラメチルチウラムジスルフィド（ＴＭＴＤ）、テトラエチルチウラムジスルフィド（ＴＥＴＤ）、テトラメチルチウラムモノスルフィド（ＴＭＴＭ）等のチウラム系、ヘキサメチレンテトラミン等のアルデヒド・アンモニア系、ジフェニルグアニジン（ＤＰＧ）等のグアニジン系、２－メルカプトベンゾチアゾール（ＭＢＴ）、ジベンゾチアジルジサルファイド（ＤＭ）等のチアゾール系、Ｎ－シクロヘキシル－２－ベンゾチアジルスルフェンアマイド（ＣＢＳ）、Ｎ－ｔ－ブチル－２－ベンゾチアジルスルフェンアマイド（ＢＢＳ）等のスルフェンアミド系、ジメチルジチオカルバミン酸亜鉛（ＺｎＰＤＣ）等のジチオカルバミン酸塩系挙げられる。加硫促進剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Examples of vulcanization accelerators include thiuram-based agents such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM), aldehyde/ammonia-based agents such as hexamethylenetetramine, and diphenylguanidine (DPG). guanidine series such as 2-mercaptobenzothiazole (MBT), thiazole series such as dibenzothiazyl disulfide (DM), N-cyclohexyl-2-benzothiazyl sulfenamide (CBS), N-t-butyl-2 - Examples include sulfenamides such as benzothiazylsulfenamide (BBS) and dithiocarbamates such as zinc dimethyldithiocarbamate (ZnPDC). The content of the vulcanization accelerator is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the rubber component.
加硫促進助剤としては、酢酸、プロピオン酸、ブタン酸、ステアリン酸、アクリル酸、マレイン酸等の脂肪酸、酢酸亜鉛、プロピオン酸亜鉛、酪酸亜鉛、ステアリン酸亜鉛、アクリル酸亜鉛、マレイン酸亜鉛等の脂肪酸亜鉛、およびそれらの塩である脂肪酸亜鉛塩、ならびに酸化亜鉛等が挙げられる。加硫促進助剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Examples of vulcanization accelerators include fatty acids such as acetic acid, propionic acid, butanoic acid, stearic acid, acrylic acid, maleic acid, zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc acrylate, zinc maleate, etc. Examples include fatty acid zinc, fatty acid zinc salts thereof, and zinc oxide. The content of the vulcanization accelerator is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the rubber component.
老化防止剤としては、例えば、脂肪族および芳香族のヒンダードアミン系、ヒンダードフェノール系等の化合物が挙げられる。老化防止剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Examples of anti-aging agents include aliphatic and aromatic hindered amine compounds, hindered phenol compounds, and the like. The content of the anti-aging agent is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the rubber component.
酸化防止剤としては、例えば、ブチルヒドロキシトルエン（ＢＨＴ）、ブチルヒドロキシアニソール（ＢＨＡ）等が挙げられる。酸化防止剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Examples of the antioxidant include butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), and the like. The content of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the rubber component.
軟化剤としては、従来公知のものを用いることができ、特に制限されるものではないが、アロマオイル、パラフィンオイル、ナフテンオイル等の石油系軟化剤や、パーム油、ひまし油、綿実油、大豆油等の植物系軟化剤等が挙げられる。使用の際にはこれらの中から１種単独で又は２種以上を適宜選択使用すればよい。軟化剤を含有する場合には、取り扱い容易性の観点から、上述した軟化剤の中でも、２５℃等の常温で液体であるもの、例えば、アロマオイル、パラフィンオイル、ナフテンオイル等の石油系軟化剤を含有することが好ましく、特にアロマオイルが好ましい。軟化剤の含有量は、ゴム成分１００質量部に対して好ましくは１０～２００質量部であり、より好ましくは２０～１００質量部である。 As the softening agent, conventionally known ones can be used, and there are no particular limitations, but petroleum-based softening agents such as aroma oil, paraffin oil, naphthenic oil, palm oil, castor oil, cottonseed oil, soybean oil, etc. Examples include plant-based softeners. When used, one type may be used alone or two or more types may be selected and used as appropriate. When containing a softener, from the viewpoint of ease of handling, among the above-mentioned softeners, one that is liquid at room temperature such as 25 ° C, for example, a petroleum-based softener such as aroma oil, paraffin oil, naphthenic oil, etc. It is preferable to contain aroma oil, and aroma oil is particularly preferable. The content of the softener is preferably 10 to 200 parts by mass, more preferably 20 to 100 parts by mass, per 100 parts by mass of the rubber component.
着色剤としては、二酸化チタン、酸化亜鉛、群青、ベンガラ、リトポン、鉛、カドミウム、鉄、コバルト、アルミニウム、塩酸塩、硫酸塩等の無機顔料、アゾ顔料、銅フタロシアニン顔料等が挙げられる。着色剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Examples of the coloring agent include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate, azo pigments, and copper phthalocyanine pigments. The content of the colorant is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the rubber component.
その他の加工助剤は、公知のゴム用混練機、例えば、ロール、バンバリーミキサー、ニーダー等でゴム成分と混練し、任意の条件で加硫してゴム組成物として使用することができる。その他の加工助剤の添加量は、本発明の目的に反しない限り、従来の一般的な含有量とすることができる。 Other processing aids can be used as a rubber composition by kneading the rubber component with a known rubber kneading machine such as a roll, Banbury mixer, or kneader, and vulcanizing the mixture under arbitrary conditions. The amounts of other processing aids to be added can be set to conventional and common amounts as long as they do not contradict the purpose of the present invention.
［ゴム組成物の製造方法］
本発明のゴム組成物の製造方法は、少なくとも上記のゴム成分と上記のゴム用添加剤とを混練する工程を含んでなる。ゴム組成物の製造方法は、好ましくは、さらに上記の加硫剤を混練する工程を含んでなるものであってもよい。より好ましくは、さらに該加硫剤と上記の加硫促進剤を混練する工程を含んでなるものであってもよい。
[Method for producing rubber composition]
The method for producing a rubber composition of the present invention includes at least the step of kneading the above-mentioned rubber component and the above-mentioned rubber additive. The method for producing a rubber composition may preferably further include the step of kneading the above-mentioned vulcanizing agent. More preferably, the method may further include a step of kneading the vulcanizing agent and the above-mentioned vulcanization accelerator.
また、ゴム組成物の製造方法は、ゴム組成物の機能を損なわない範囲で、上記のその他の加工助剤を適宜配合して、混練することができる。 In addition, in the method for producing the rubber composition, the other processing aids mentioned above can be appropriately blended and kneaded within a range that does not impair the functions of the rubber composition.
ゴム組成物の製造には、従来公知の混練装置を用いることができ、混練温度や時間、配合順序等を適宜選択することができる。 A conventionally known kneading device can be used to manufacture the rubber composition, and the kneading temperature, time, blending order, etc. can be selected as appropriate.
［タイヤ製品］
本発明のゴム組成物を用いて、従来公知の方法および当業者に広く知られた技術常識によりタイヤ製品を製造することができる。タイヤ製品としては、タイヤやその他の関連部材が挙げられる。例えば、ゴム組成物を押し出し、次いで、タイヤ成型機を用いて成形した後、加硫機を用いて加熱、加圧することにより架橋が形成され、タイヤを製造することができる。本発明のゴム組成物を用いて製造したタイヤは耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性に優れる。
[Tire products]
Using the rubber composition of the present invention, tire products can be manufactured by conventionally known methods and common technical knowledge widely known to those skilled in the art. Tire products include tires and other related parts. For example, a rubber composition is extruded, then molded using a tire molding machine, and then heated and pressurized using a vulcanizer to form crosslinks, thereby producing a tire. Tires manufactured using the rubber composition of the present invention have excellent wear resistance, wet grip, steering stability, and running performance on icy and snowy roads.
タイヤの用途としては、特に制限はなく、例えば、乗用車用タイヤ、重荷重用タイヤ、モーターサイクル（自動二輪車）用タイヤ、冬用タイヤ等が挙げられる。これらの中でも、冬用タイヤに好適に使用でき、特にスタッドレスタイヤに好適に使用できる。 The use of the tire is not particularly limited, and examples include tires for passenger cars, tires for heavy loads, tires for motorcycles, winter tires, and the like. Among these, it can be suitably used for winter tires, and particularly for studless tires.
タイヤの形状、構造、大きさ及び材質としては、特に制限はなく、目的に応じて適宜選択することができる。また、本発明のゴム組成物はタイヤの各部に適用することができる。タイヤの適用部としては、特に制限はなく、タイヤのトレッド、カーカス、サイドウォール、インナーライナー、アンダートレッド、ベルト部など、目的に応じて適宜選択することができる。 The shape, structure, size, and material of the tire are not particularly limited and can be appropriately selected depending on the purpose. Further, the rubber composition of the present invention can be applied to various parts of a tire. There are no particular restrictions on the applicable part of the tire, and it can be appropriately selected depending on the purpose, such as the tire tread, carcass, sidewall, inner liner, undertread, and belt part.
［ゴム製品］
本発明のゴム組成物を用いて、タイヤ製品以外のゴム製品を製造することもできる。タイヤ以外のゴム製品としては、自動車用ゴム部品（外装、内装、ウェザーストリップ類、ブーツ類、マウント類、シール類、シーラー類、ガスケット類）、ホース、ベルト、シート、防振ゴム、ローラー、ライニング、ゴム引布、シール材、手袋、防舷材、医療用ゴム（シリンジガスケット、チューブ、カテーテル）、ガスケット（家電用、建築用）、アスファルト改質剤、グリップ類、玩具、靴、サンダル、キーパッド、ギア、ペットボトルキャプライナー等が挙げられる。
[Rubber product]
Rubber products other than tire products can also be manufactured using the rubber composition of the present invention. Rubber products other than tires include automotive rubber parts (exterior, interior, weather strips, boots, mounts, seals, sealers, gaskets), hoses, belts, seats, anti-vibration rubber, rollers, linings. , rubberized cloth, sealing materials, gloves, fender materials, medical rubber (syringe gaskets, tubes, catheters), gaskets (for home appliances, construction), asphalt modifiers, grips, toys, shoes, sandals, keys Examples include pads, gears, and plastic bottle cap liners.
以下に実施例および比較例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
（調製例１）
・含硫黄炭化水素重合体Ａの合成
３００ｍｌ二口ナスフラスコに、石油樹脂Ａ（Ｍｗ：８１０、Ｍｗ／Ｍｎ：１．７４、軟化点８５℃、ヨウ素価（ＪＩＳ Ｋ００７０準拠）：１８５．０、ＤＣＰＤ含有不飽和炭化水素の重合体）９０ｇを入れて、１３０℃に加熱し、溶融状態とした。次に、フラスコ内に硫黄８．７ｇを入れて、３時間撹拌した。反応完了後、反応物をアルミ皿に流し出し自然放冷した。
(Preparation example 1)
・Synthesis of sulfur-containing hydrocarbon polymer A In a 300 ml two-necked eggplant flask, petroleum resin A (Mw: 810, Mw/Mn: 1.74, softening point 85°C, iodine value (according to JIS K0070): 185.0, 90 g of DCPD-containing unsaturated hydrocarbon polymer) was added and heated to 130°C to make it into a molten state. Next, 8.7 g of sulfur was put into the flask and stirred for 3 hours. After the reaction was completed, the reaction product was poured into an aluminum dish and allowed to cool naturally.
その後、得られた反応物の１Ｈ－ＮＭＲ解析を行い、５．８ｐｐｍ付近のノルボルネン骨格上の二重結合の消費を確認した。また、反応物をＧＰＣ解析した結果、Ｍｗ：１，２２０、Ｍｗ／Ｍｎ：２．１０であった。元素分析の結果、硫黄量は８．９質量％であり、ノルボルネン骨格上の二重結合量当たり３．０１個の硫黄分子の導入を確認した。 Thereafter, 1 H-NMR analysis of the obtained reaction product was performed, and it was confirmed that the double bond on the norbornene skeleton was consumed at around 5.8 ppm. Further, as a result of GPC analysis of the reaction product, Mw: 1,220, Mw/Mn: 2.10. As a result of elemental analysis, the amount of sulfur was 8.9% by mass, and it was confirmed that 3.01 sulfur molecules were introduced per amount of double bonds on the norbornene skeleton.
（調製例２）
・炭化水素重合体Ｂの合成
ナフサクラッカーから得られるＣ５留分およびＣ９留分を原料モノマーとして、酸触媒による重合工程、残触媒の中和工程、軽質分の除去工程を経て、芳香族分１２％、軟化点９０℃、Ｍｗ１３００の石油樹脂を得た。
(Preparation example 2)
・Synthesis of hydrocarbon polymer B Using the C5 fraction and C9 fraction obtained from a naphtha cracker as raw material monomers, the aromatic content 12 %, a softening point of 90° C., and a Mw of 1300.
［実施例１］
以下の各成分を、２５０ｍＬニーダー（東洋精機社製ラボプラストミル）を用いて混練し、ゴム組成物を得た。実施した混練操作の詳細は以下の（ｉ）～（ｉｉｉ）の通りである。
（ｉ）ミキサー混練：１３０℃に加熱した密閉式加圧ニーダーへゴム成分を投入し、３０ｒｐｍで１分間素練りを行った後、シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物の１／２量を測り取ったものと、シランカップリング剤１の全量および含硫黄炭化水素重合体Ａの全量を投入し、５０ｒｐｍに回転数を上げて１分３０秒間混練を行った。さらに残りの１／２量の前記シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物を加えて、５分３０秒間混練を行い、放出した。
（ｉｉ）リミル：シリカの分散をよくするために、１２０℃に加熱した密閉式加圧ニーダーへ放出して十分温度が下がった混練物を、さらに５０ｒｐｍで２分間混練を行った後、放出した。
（ｉｉｉ）ロール混練（加硫系添加）：放出して十分温度が下がった後、２本ロールで上述の混練物に硫黄、加硫促進剤等を加え、混練し、ゴム組成物を得た。
・ゴム（ＳＢＲ（Ｂ）、Ｔｇ：－６０℃） ７０質量部
・ゴム（ＢＲ、Ｔｇ：－１００℃） ３０質量部
・シリカＡＱ（東ソー社製、商品名：ニップシールＡＱ） １００質量部
・酸化亜鉛３号（東邦亜鉛社製、商品名：銀嶺Ｒ） ３質量部
・ステアリン酸（新日本理化製、商品名：ステアリン酸３００） １質量部
・老化防止剤（大内新興化学社製、商品名：ノクラック６Ｃ） １質量部
・シランカップリング剤１（エボニック社製、商品名：Ｓｉ６９） ５．６質量部
・含硫黄炭化水素重合体Ａ １５質量部
・硫黄（細井化学社製、５％油処理硫黄） １質量部
・加硫促進剤１（大内新興化学社製、商品名：ノクセラーＣＺ） ２．３質量部
・加硫促進剤２（大内新興化学社製、商品名：ノクセラーＤ） １質量部
[Example 1]
The following components were kneaded using a 250 mL kneader (Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. The details of the kneading operation carried out are as follows (i) to (iii).
(i) Mixer kneading: After putting the rubber component into a closed pressure kneader heated to 130°C and masticating at 30 rpm for 1 minute, 1 of the mixture of silica, zinc oxide, stearic acid, and anti-aging agent was mixed. The total amount of silane coupling agent 1 and the total amount of sulfur-containing hydrocarbon polymer A were added, and the rotation speed was increased to 50 rpm to perform kneading for 1 minute and 30 seconds. Further, the remaining 1/2 amount of the mixture of silica, zinc oxide, stearic acid, and anti-aging agent was added, kneaded for 5 minutes and 30 seconds, and then released.
(ii) Remilling: In order to improve the dispersion of silica, the kneaded material was discharged into a closed pressurized kneader heated to 120°C, and the temperature was sufficiently lowered, and the kneaded material was further kneaded at 50 rpm for 2 minutes, and then discharged. .
(iii) Roll kneading (addition of vulcanization system): After the temperature was sufficiently lowered after release, sulfur, vulcanization accelerator, etc. were added to the above-mentioned kneaded product using two rolls, and the mixture was kneaded to obtain a rubber composition. .
・Rubber (SBR (B), Tg: -60℃) 70 parts by mass ・Rubber (BR, Tg: -100℃) 30 parts by mass ・Silica AQ (manufactured by Tosoh Corporation, product name: Nip Seal AQ) 100 parts by mass ・Oxidation Zinc No. 3 (manufactured by Toho Zinc Co., Ltd., product name: Ginrei R) 3 parts by mass Stearic acid (manufactured by Shin Nippon Chemical Co., Ltd., product name: Stearic Acid 300) 1 part by mass / Anti-aging agent (manufactured by Ouchi Shinko Kagaku Co., Ltd., product Name: NOCRAC 6C) 1 part by mass Silane coupling agent 1 (manufactured by Evonik, product name: Si69) 5.6 parts by mass Sulfur-containing hydrocarbon polymer A 15 parts by mass Sulfur (manufactured by Hosoi Chemical Co., Ltd., 5% Oil treatment sulfur) 1 part by mass, vulcanization accelerator 1 (manufactured by Ouchi Shinko Kagaku Co., Ltd., product name: Noxeler CZ) 2.3 parts by mass, vulcanization accelerator 2 (manufactured by Ouchi Shinko Kagaku Co., Ltd., product name: Noxeler) D) 1 part by mass
［比較例１］
含硫黄炭化水素重合体Ａの代わりに炭化水素重合体Ｂ（硫黄非含有）１５質量部を添加し、硫黄の添加量を１．５質量部に変更した以外は実施例１と同様にして、ゴム組成物を得た。
[Comparative example 1]
In the same manner as in Example 1, except that 15 parts by mass of hydrocarbon polymer B (sulfur-free) was added instead of sulfur-containing hydrocarbon polymer A, and the amount of sulfur added was changed to 1.5 parts by mass, A rubber composition was obtained.
［実施例２］
シランカップリング剤１（Ｓｉ６９）の代わりにシランカップリング剤２（エボニック社製、商品名：Ｓｉ－７５）５．６質量部を添加した以外は実施例１と同様にして、ゴム組成物を得た。
[Example 2]
A rubber composition was prepared in the same manner as in Example 1, except that 5.6 parts by mass of Silane Coupling Agent 2 (manufactured by Evonik, trade name: Si-75) was added instead of Silane Coupling Agent 1 (Si69). Obtained.
［実施例３］
シランカップリング剤１（Ｓｉ６９）の代わりにシランカップリング剤３（エボニック社製、商品名：Ｓｉ－３６３）５．６質量部を添加した以外は実施例１と同様にして、ゴム組成物を得た。
[Example 3]
A rubber composition was prepared in the same manner as in Example 1, except that 5.6 parts by mass of Silane Coupling Agent 3 (manufactured by Evonik, trade name: Si-363) was added instead of Silane Coupling Agent 1 (Si69). Obtained.
［実施例４］
シランカップリング剤１（Ｓｉ６９）の代わりにシランカップリング剤４（モメンティブ社製、商品名：ＮＸＴ－シラン）５．６質量部を添加した以外は実施例１と同様にして、ゴム組成物を得た。
[Example 4]
A rubber composition was prepared in the same manner as in Example 1, except that 5.6 parts by mass of silane coupling agent 4 (manufactured by Momentive, trade name: NXT-silane) was added instead of silane coupling agent 1 (Si69). Obtained.
［実施例５］
シランカップリング剤１（Ｓｉ６９）の代わりにシランカップリング剤５（モメンティブ社製、商品名：ＮＸＴ－Ｚ４５シラン）５．６質量部を添加した以外は実施例１と同様にして、ゴム組成物を得た。
[Example 5]
A rubber composition was prepared in the same manner as in Example 1, except that 5.6 parts by mass of silane coupling agent 5 (manufactured by Momentive, trade name: NXT-Z45 silane) was added instead of silane coupling agent 1 (Si69). I got it.
［比較例２］
ゴム成分としてＳＢＲ（Ｂ）（Ｔｇ：－６０℃）の代わりにＳＢＲ（Ａ）（Ｔｇ：－２７℃）７０質量部を添加した以外は比較例１と同様にして、ゴム組成物を得た。
[Comparative example 2]
A rubber composition was obtained in the same manner as in Comparative Example 1, except that 70 parts by mass of SBR(A) (Tg: -27°C) was added instead of SBR(B) (Tg: -60°C) as a rubber component. .
［比較例３］
炭化水素重合体Ｂの代わりに含硫黄炭化水素重合体Ａ１５質量部を添加し、硫黄の添加量を１質量部に変更した以外は比較例２と同様にして、ゴム組成物を得た。
[Comparative example 3]
A rubber composition was obtained in the same manner as in Comparative Example 2, except that 15 parts by mass of sulfur-containing hydrocarbon polymer A was added instead of hydrocarbon polymer B, and the amount of sulfur added was changed to 1 part by mass.
［実施例６］
シリカの添加量を９０質量部に変更し、カーボンブラック（ＡＳＴＭコード：Ｎ３３９、東海カーボン社製、商品名：シ―ストＫＨ）１０質量部を添加した以外は実施例１と同様にして、ゴム組成物を得た。
[Example 6]
Rubber was prepared in the same manner as in Example 1, except that the amount of silica added was changed to 90 parts by mass, and 10 parts by mass of carbon black (ASTM code: N339, manufactured by Tokai Carbon Co., Ltd., trade name: SEAST KH) was added. A composition was obtained.
［比較例４］
含硫黄炭化水素重合体Ａの代わりに炭化水素重合体Ｂ１５質量部を添加し、硫黄の添加量を１．５質量部に変更した以外は実施例６と同様にして、ゴム組成物を得た。
[Comparative example 4]
A rubber composition was obtained in the same manner as in Example 6, except that 15 parts by mass of hydrocarbon polymer B was added instead of sulfur-containing hydrocarbon polymer A, and the amount of sulfur added was changed to 1.5 parts by mass. .
［実施例７］
シリカの添加量を１５０質量部に変更した以外は実施例１と同様にして、ゴム組成物を得た。
[Example 7]
A rubber composition was obtained in the same manner as in Example 1 except that the amount of silica added was changed to 150 parts by mass.
［比較例５］
含硫黄炭化水素重合体Ａの代わりに炭化水素重合体Ｂ１５質量部を添加し、硫黄の添加量を１．５質量部に変更した以外は実施例７と同様にして、ゴム組成物を得た。
[Comparative example 5]
A rubber composition was obtained in the same manner as in Example 7, except that 15 parts by mass of hydrocarbon polymer B was added instead of sulfur-containing hydrocarbon polymer A, and the amount of sulfur added was changed to 1.5 parts by mass. .
［実施例８］
ゴム成分としてＢＲを添加せず、ＳＢＲ（Ｂ）の添加量を１００質量部に変更した以外は実施例１と同様にして、ゴム組成物を得た。
[Example 8]
A rubber composition was obtained in the same manner as in Example 1, except that BR was not added as a rubber component and the amount of SBR (B) added was changed to 100 parts by mass.
［比較例６］
含硫黄炭化水素重合体Ａの代わりに炭化水素重合体Ｂ１５質量部を添加し、硫黄の添加量を１．５質量部に変更した以外は実施例８と同様にして、ゴム組成物を得た。
[Comparative example 6]
A rubber composition was obtained in the same manner as in Example 8, except that 15 parts by mass of hydrocarbon polymer B was added instead of sulfur-containing hydrocarbon polymer A, and the amount of sulfur added was changed to 1.5 parts by mass. .
［実施例９］
ゴム成分として、天然ゴム（ＮＲ、Ｔｇ：－７０℃）２０質量部を添加し、ＳＢＲ（Ｂ）の添加量を６０質量部に変更し、ＢＲの添加量を２０質量部に変更した以外は実施例１と同様にして、ゴム組成物を得た。
[Example 9]
As a rubber component, 20 parts by mass of natural rubber (NR, Tg: -70°C) was added, the amount of SBR (B) added was changed to 60 parts by mass, and the amount of BR added was changed to 20 parts by mass. A rubber composition was obtained in the same manner as in Example 1.
［比較例７］
含硫黄炭化水素重合体Ａの代わりに炭化水素重合体Ｂ１５質量部を添加し、硫黄の添加量を１．５質量部に変更した以外は実施例９と同様にして、ゴム組成物を得た。
[Comparative Example 7]
A rubber composition was obtained in the same manner as in Example 9, except that 15 parts by mass of hydrocarbon polymer B was added instead of sulfur-containing hydrocarbon polymer A, and the amount of sulfur added was changed to 1.5 parts by mass. .
［物性評価］
実施例１～９および比較例１～７で得られたゴム組成物を用いて、下記の測定を行った。なお、各ゴム成分のＴｇは、示差走査熱量測定装置（ＤＳＣ、日立ハイテクサイエンス製、型番：ＤＳＣ７０００Ｘ）を用いて、サンプル量：約１０ｍｇ、流通条件：窒素ガス４０ｍｌ／分、昇温速度：２０℃／分の条件で測定した値である。
[Evaluation of the physical properties]
The following measurements were performed using the rubber compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 7. The Tg of each rubber component was determined using a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science, model number: DSC7000X): sample amount: approximately 10 mg, flow conditions: nitrogen gas 40 ml/min, temperature increase rate: 20 This is a value measured under conditions of °C/min.
（引張強度）
各ゴム組成物４２ｇを金型（１５０ｍｍ×１５０ｍｍ×１ｍｍ）に入れて、１６０℃、２０ＭＰａの条件で、４０分間加熱加圧して、１ｍｍ厚のゴムシート（厚さ１ｍｍ、縦１５０ｍｍ、横１５０ｍｍ）を得た。各ゴムシートから３号ダンベル状の試験片を打ち抜き、引張速度５００ｍｍ／分での引張試験をＪＩＳ Ｋ６２５１（２０１０年発行）に準拠して行い、１００％モジュラス［ＭＰａ］を室温（２５℃）にて測定した。なお、各実施例および各比較例では、各ゴムシートの架橋密度の指標である１００％モジュラスの値を概ね近い値になるように調節した上で他の物性を確認した。
(Tensile strength)
42g of each rubber composition was placed in a mold (150mm x 150mm x 1mm) and heated and pressed at 160°C and 20MPa for 40 minutes to form a 1mm thick rubber sheet (1mm thick, 150mm long, 150mm wide). I got it. A No. 3 dumbbell-shaped test piece was punched out from each rubber sheet, and a tensile test was performed at a tensile speed of 500 mm/min in accordance with JIS K6251 (published in 2010), and the 100% modulus [MPa] was measured at room temperature (25°C). It was measured using In addition, in each Example and each Comparative Example, the value of 100% modulus, which is an index of the crosslinking density of each rubber sheet, was adjusted to approximately a similar value, and other physical properties were checked.
（摩耗量）
各ゴム組成物１５ｇを、直径１６．０ｍｍ、厚さ８ｍｍの円盤状の試料となるようにそれぞれ成型した。次に、得られた円盤状の試料をそれぞれ用いて、ＪＩＳ Ｋ６２６４－２（２００５年発行）に準拠して、ＤＩＮ摩耗試験機（回転円筒型摩耗試験機：安田精機社製の商品名「ＤＩＮ摩耗試験機」）を用いて、温度：室温（２５℃）、荷重：２．５Ｎ、ドラム回転速度：４０ｒｐｍ、試料横送り速度：２．８ｍｍ／ｓｅｃの条件で耐摩耗試験を行って、摩耗量（体積基準：摩耗前の総体積に対する試験により摩耗した体積の割合（体積％））を測定した。なお、摩耗量が少ない方が、耐摩耗性に優れることを示す。
(amount of wear)
15 g of each rubber composition was molded into a disk-shaped sample with a diameter of 16.0 mm and a thickness of 8 mm. Next, using each of the obtained disc-shaped samples, a DIN abrasion tester (rotating cylindrical abrasion tester: trade name "DIN An abrasion test was conducted using an abrasion tester (temperature: room temperature (25°C), load: 2.5N, drum rotation speed: 40 rpm, sample traversal speed: 2.8 mm/sec). The amount (volume basis: ratio of the volume worn by the test to the total volume before wear (volume %)) was measured. Note that the smaller the amount of wear, the better the wear resistance.
（ウェットグリップ性）
上記で得られた各ゴムシートについて、粘弾性測定装置（ＵＢＭ社製ＲＥＯＧＥＬ Ｅ－４０００）を用い、ＪＩＳ Ｋ ６３９４に準拠して、引張モードで、歪約０．１％、周波数１０Ｈｚの条件下において、測定温度０℃におけるｔａｎδを測定した。ｔａｎδ（０℃）の値が高い方がウェットグリップ性に優れることを示す。
(Wet grip)
Each of the rubber sheets obtained above was measured using a viscoelasticity measuring device (REOGEL E-4000 manufactured by UBM) in tensile mode at a strain of approximately 0.1% and a frequency of 10 Hz in accordance with JIS K 6394. The tan δ was measured at a measurement temperature of 0°C. A higher value of tan δ (0° C.) indicates better wet grip properties.
（操縦安定性・氷雪路上走行性）
上記で得られた各ゴムシートについて、粘弾性測定装置（ＵＢＭ社製ＲＥＯＧＥＬ Ｅ－４０００）を用い、ＪＩＳ Ｋ ６３９４に準拠して、引張モードで、歪約０．１％、周波数１０Ｈｚの条件下において、測定温度３０℃における弾性率Ｅ’（３０℃）および測定温度－１０℃における弾性率Ｅ’（ －１０℃）を測定した。弾性率Ｅ’（３０℃）の値が高い方が、操縦安定性に優れることを示す。また、弾性率Ｅ’（ －１０℃）の値が小さい方が、氷雪路上走行性（氷雪グリップ性）が優れることを意味する。
(Driving stability/drivability on ice and snow)
Each of the rubber sheets obtained above was measured using a viscoelasticity measuring device (REOGEL E-4000 manufactured by UBM) in tensile mode at a strain of approximately 0.1% and a frequency of 10 Hz in accordance with JIS K 6394. The elastic modulus E' (30°C) at a measurement temperature of 30°C and the elastic modulus E' (-10°C) at a measurement temperature of -10°C were measured. A higher value of elastic modulus E' (30° C.) indicates better handling stability. Furthermore, the smaller the value of the elastic modulus E' (-10°C), the better the running properties on ice and snow (ice and snow grip properties).
以上の測定結果を表１および２に表す。なお、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路上走行性の各結果について、実施例１～５は比較例１における各値を１００とした場合の相対値として記載し、比較例３は比較例２における各値を１００とした場合の相対値として記載し、実施例６は比較例４における各値を１００とした場合の相対値として記載し、実施例７は比較例５における各値を１００とした場合の相対値として記載し、実施例８は比較例６における各値を１００とした場合の相対値として記載し、実施例９は比較例７における各値を１００とした場合の相対値として記載した。 The above measurement results are shown in Tables 1 and 2. Regarding the results of abrasion resistance, wet grip performance, steering stability, and running performance on ice and snow, Examples 1 to 5 are described as relative values when each value in Comparative Example 1 is set as 100, and Comparative Example 3 is described as a relative value when each value in Comparative Example 2 is set to 100, Example 6 is described as a relative value when each value in Comparative Example 4 is set to 100, and Example 7 is described as a relative value when each value in Comparative Example 5 is set to 100. Each value is described as a relative value when each value is set to 100, Example 8 is described as a relative value when each value in Comparative Example 6 is set to 100, and Example 9 is described as a relative value when each value in Comparative Example 7 is set to 100. It is stated as a relative value for each case.
実施例１～５および比較例１の結果、実施例６および比較例４の結果、ならびに実施例７および比較例５の結果から、ガラス転移温度が－７２℃であるゴム成分に対して硫黄非含有の炭化水素重合体Ｂの代わりに含硫黄炭化水素重合体Ａを添加することで、得られたゴムシートは、タイヤの耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性が非常に優れていた。
比較例２および比較例３の結果から、ガラス転移温度が－４９℃のゴム成分に対して硫黄非含有の炭化水素重合体Ｂの代わりに含硫黄炭化水素重合体Ａを添加したところ、得られたゴムシートは、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性がバランス良く改善しなかった。
実施例８および比較例６の結果から、ガラス転移温度が－６０℃であるゴム成分に対して硫黄非含有の炭化水素重合体Ｂの代わりに含硫黄炭化水素重合体Ａを添加することで、得られたゴムシートは、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性が非常に優れていた。
実施例９および比較例７の結果から、ガラス転移温度が－７０℃であるゴム成分に対して硫黄非含有の炭化水素重合体Ｂの代わりに含硫黄炭化水素重合体Ａを添加することで、得られたゴムシートは、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性が非常に優れていた。
よって、本発明のゴム組成物を用いることで、耐摩耗性、ウェットグリップ性、操縦安定性、および氷雪路走行性に優れたタイヤを製造できることが判明した。
From the results of Examples 1 to 5 and Comparative Example 1, the results of Example 6 and Comparative Example 4, and the results of Example 7 and Comparative Example 5, sulfur-free By adding sulfur-containing hydrocarbon polymer A in place of hydrocarbon polymer B, the resulting rubber sheet has improved tire wear resistance, wet grip, steering stability, and icy road performance. It was very good.
From the results of Comparative Example 2 and Comparative Example 3, when sulfur-containing hydrocarbon polymer A was added instead of sulfur-free hydrocarbon polymer B to a rubber component with a glass transition temperature of -49°C, the following results were obtained: The rubber sheet obtained did not improve the wear resistance, wet grip, steering stability, and driving performance on ice and snow in a well-balanced manner.
From the results of Example 8 and Comparative Example 6, by adding sulfur-containing hydrocarbon polymer A instead of sulfur-free hydrocarbon polymer B to a rubber component whose glass transition temperature is -60 ° C. The obtained rubber sheet had excellent abrasion resistance, wet grip, steering stability, and running performance on ice and snow.
From the results of Example 9 and Comparative Example 7, by adding sulfur-containing hydrocarbon polymer A instead of sulfur-free hydrocarbon polymer B to a rubber component whose glass transition temperature is -70 ° C. The obtained rubber sheet had excellent abrasion resistance, wet grip, steering stability, and running performance on ice and snow.
Therefore, it has been found that by using the rubber composition of the present invention, a tire with excellent wear resistance, wet grip performance, steering stability, and running performance on ice and snow roads can be manufactured.
Claims (15)
含硫黄炭化水素重合体を含むゴム用添加剤と、
を含み、
前記ゴム成分が、芳香族ビニル－共役ジエン共重合体ゴムおよびブタジエンゴムの少なくとも１種を含み、
前記芳香族ビニル－共役ジエン共重合体ゴムおよび前記ブタジエンゴムの合計含有量が、前記ゴム成分全体の７０質量％以上であり、
前記含硫黄炭化水素重合体が、不飽和炭化水素重合体と硫黄との反応生成物であり、前記不飽和炭化水素が脂環式不飽和化合物を含み、
前記含硫黄炭化水素重合体の重量平均分子量が５００以上４０００以下である、ゴム組成物。 A rubber component having a glass transition temperature of -100°C or more and less than -55°C;
A rubber additive containing a sulfur-containing hydrocarbon polymer,
including;
The rubber component includes at least one of aromatic vinyl-conjugated diene copolymer rubber and butadiene rubber,
The total content of the aromatic vinyl-conjugated diene copolymer rubber and the butadiene rubber is 70% by mass or more of the entire rubber component,
The sulfur-containing hydrocarbon polymer is a reaction product of an unsaturated hydrocarbon polymer and sulfur, and the unsaturated hydrocarbon contains an alicyclic unsaturated compound,
A rubber composition, wherein the sulfur-containing hydrocarbon polymer has a weight average molecular weight of 500 or more and 4,000 or less.
前記ゴム成分が、芳香族ビニル－共役ジエン共重合体ゴムおよびブタジエンゴムの少なくとも１種を含み、
前記芳香族ビニル－共役ジエン共重合体ゴムおよび前記ブタジエンゴムの合計含有量が、前記ゴム成分全体の７０質量％以上であり、
前記ゴム用添加剤が、含硫黄炭化水素重合体を含み、
前記含硫黄炭化水素重合体が、不飽和炭化水素重合体と硫黄との反応生成物であり、前記炭化水素が脂環式不飽和化合物を含み、
前記含硫黄炭化水素重合体の重量平均分子量が５００以上４０００以下である、ゴム組成物の製造方法。 A method for producing a rubber composition, comprising at least a step of kneading a rubber component and a rubber additive,
The rubber component includes at least one of aromatic vinyl-conjugated diene copolymer rubber and butadiene rubber,
The total content of the aromatic vinyl-conjugated diene copolymer rubber and the butadiene rubber is 70% by mass or more of the entire rubber component,
The rubber additive contains a sulfur-containing hydrocarbon polymer,
The sulfur-containing hydrocarbon polymer is a reaction product of an unsaturated hydrocarbon polymer and sulfur, and the hydrocarbon contains an alicyclic unsaturated compound,
A method for producing a rubber composition, wherein the sulfur-containing hydrocarbon polymer has a weight average molecular weight of 500 or more and 4,000 or less.
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| JP2022130232A JP2024027444A (en) | 2022-08-17 | 2022-08-17 | Rubber composition, manufacturing method thereof and tire product |
| PCT/JP2023/029624 WO2024038880A1 (en) | 2022-08-17 | 2023-08-16 | Rubber composition, production method therefor, and tire product |
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| JPS52777B2 (en) * | 1973-04-28 | 1977-01-10 | ||
| JPS63301244A (en) * | 1987-06-02 | 1988-12-08 | Bridgestone Corp | Rubber composition |
| WO2018189878A1 (en) * | 2017-04-14 | 2018-10-18 | 四国化成工業株式会社 | Vulcanizing agent composition and rubber composition containing same |
| JP6508254B2 (en) * | 2017-04-28 | 2019-05-08 | 横浜ゴム株式会社 | Stud tire |
| JP7346158B2 (en) * | 2019-08-22 | 2023-09-19 | Ｅｎｅｏｓ株式会社 | Sulfur-containing unsaturated hydrocarbon polymer and its production method, rubber additive, rubber composition, and tire |
| CN117836363A (en) * | 2021-08-30 | 2024-04-05 | 引能仕株式会社 | Rubber composition, method for producing same, and tire product |
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2022
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