WO2013046845A1 - Rubber composition for tire outer layer, and pneumatic tire - Google Patents

Rubber composition for tire outer layer, and pneumatic tire Download PDF

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Publication number
WO2013046845A1
WO2013046845A1 PCT/JP2012/067145 JP2012067145W WO2013046845A1 WO 2013046845 A1 WO2013046845 A1 WO 2013046845A1 JP 2012067145 W JP2012067145 W JP 2012067145W WO 2013046845 A1 WO2013046845 A1 WO 2013046845A1
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Prior art keywords
mass
parts
rubber composition
tire
less
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PCT/JP2012/067145
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French (fr)
Japanese (ja)
Inventor
達也 宮崎
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住友ゴム工業株式会社
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Application filed by 住友ゴム工業株式会社 filed Critical 住友ゴム工業株式会社
Priority to CN201280046056.XA priority Critical patent/CN103814074B/en
Priority to KR1020147003249A priority patent/KR20140068870A/en
Priority to BR112014007054A priority patent/BR112014007054A2/en
Publication of WO2013046845A1 publication Critical patent/WO2013046845A1/en

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    • 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
    • B60C1/0016—Compositions of the tread
    • 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
    • B60C1/0025—Compositions of the sidewalls
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C08K5/08—Quinones
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • 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
    • B60C2001/005—Compositions of the bead portions, e.g. clinch or chafer rubber or cushion rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes

Definitions

  • the present invention relates to a rubber composition for an outer layer of a tire, and a pneumatic tire using the same.
  • a wax etc. are mix
  • the blended wax soaks out to the rubber surface, and by stretching the film on the rubber surface, it is possible to physically protect the rubber from the stimulation of ozone, oxygen and harmful gases.
  • the volume of the tread rubber shrinks easily after vulcanization and cooling to room temperature as compared with the state during vulcanization in the mold, and before the tire use air pressure is filled in the tread groove bottom. After being filled, it tends to cause tensile strain. When the rubber is pulled, it becomes susceptible to ozone attack, and tread groove cracks (TGC) tend to occur. Therefore, it is important to achieve both ozone resistance and white discoloration.
  • a method to improve ozone resistance a method using anti-aging agent 3PPD is known, but it is easier to bloom than 6PPD and 6QDI, and ozone resistance in a low temperature environment can be improved, but volatility It is difficult to secure ozone resistance for a long period of time because it is high and decreases quickly.
  • Patent Document 1 proposes that a specific wax be blended, there is a large room for improvement in ozone resistance in the low temperature area and the temperate area winter, and while obtaining excellent ozone resistance in a wide temperature area, There is a need for a technology that can suppress discoloration.
  • the present invention solves the above-mentioned problems and provides a rubber composition for an outer layer of a tire capable of satisfactorily suppressing discoloration while obtaining excellent ozone resistance in a wide environmental temperature range, and a pneumatic tire using the same. With the goal.
  • the present invention comprises each normal alkane having a carbon number of 20 to 32 and a phenylenediamine based antioxidant and / or a quinone based antioxidant, and the carbon number is 20 to 32 with respect to 100 parts by mass of a diene rubber component.
  • the total content of each normal alkane is 0.7 to 3.5 parts by mass, and the total content of the phenylenediamine based antioxidant and the quinone based antioxidant is 1.5 to 3 parts by mass It relates to a rubber composition.
  • the rubber composition for a tire outer layer contains a total of 0.1 parts by mass or less of each normal alkane having a carbon number of 48 or more with respect to 100 parts by mass of the diene rubber component.
  • the total content of each normal alkane having 20 to 32 carbon atoms is preferably 0.9 to 2.4 parts by mass with respect to 100 parts by mass of the diene rubber component. It is preferable to contain 15 parts by mass or less of process oil with respect to 100 parts by mass of the diene rubber component.
  • the tire outer layer rubber composition is preferably used as at least one selected from the group consisting of a tread, a sidewall, a wing, and a clinch apex.
  • the present invention also relates to a pneumatic tire produced using the rubber composition.
  • the total content of each normal alkane having 20 to 32 carbon atoms which contains each normal alkane having 20 to 32 carbon atoms, and a phenylenediamine based antioxidant and / or a quinone based antioxidant, is Since it is a rubber composition for a tire outer layer which is a specific amount, and the total content of the phenylenediamine anti-aging agent and the quinone-based anti-aging agent is also a specific amount, excellent ozone resistance in a wide environmental temperature range While being obtained, color change can be favorably suppressed.
  • the rubber composition for the outer layer of a tire according to the present invention comprises each normal alkane having 20 to 32 carbon atoms, a phenylenediamine based antioxidant and / or a quinone based antioxidant, and the above-mentioned carbon number for the diene based rubber component is 20 to
  • the total content of each of the 32 normal alkanes is a specific amount, and the total content of the phenylenediamine anti-aging agent and the quinone anti-aging agent is also a specific amount.
  • the rubber composition of the present invention is used for tire outer layer members such as treads, sidewalls, wings and clinch apexes.
  • diene rubber components include natural rubber (NR), highly purified natural rubber (Highly purified NR), epoxidized natural rubber (ENR), butadiene rubber (BR), styrene butadiene rubber (SBR), isoprene rubber ( IR), butyl rubber (IIR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), styrene isoprene butadiene rubber (SIBR), styrene isoprene rubber, isoprene butadiene rubber and the like, and these may be used alone. Two or more may be used in combination.
  • SBR or BR when applied to the tread, it is preferable to use SBR or BR because grip performance and breaking strength can be obtained well.
  • BR When applied to side walls and clinchapex, it is preferable to use BR because isoprene rubber such as NR and IR and crack growth are excellent because fracture strength is obtained well.
  • the SBR is not particularly limited, and for example, those modified with a conventionally known modifying agent (modified SBR) can be suitably used.
  • the bound styrene content of SBR is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of improving grip performance. On the other hand, the content is preferably 45% by mass or less, more preferably 40% by mass or less, from the viewpoint of improving the wear resistance. In the present invention, the styrene content of SBR is calculated by H 1 -NMR measurement.
  • the content of SBR in 100% by mass of the diene rubber component is preferably 20% by mass or more, more preferably 60% by mass or more. If the amount is less than 20% by mass, grip performance may not be sufficiently obtained.
  • the content is preferably 90% by mass or less, more preferably 80% by mass or less. When it exceeds 90% by mass, sufficient abrasion resistance may not be obtained.
  • the BR is not particularly limited, but preferred is BR (hysis BR) in which the cis content of the double bond portion is 95 mol% or more.
  • the content of BR in 100% by mass of the diene rubber component is preferably 10% by mass or more, more preferably 20% by mass or more. If the amount is less than 10% by mass, sufficient abrasion resistance may not be obtained.
  • the content is preferably 80% by mass or less, more preferably 40% by mass or less. If it exceeds 80% by mass, sufficient grip performance may not be obtained.
  • the content of BR in 100% by mass of the diene rubber component is preferably 10% by mass or more, more preferably 30% by mass or more. If it is less than 10% by mass, crack growth and reversion resistance tend to be deteriorated.
  • the content is preferably 80% by mass or less, more preferably 50% by mass or less. If it exceeds 80% by mass, sufficient elongation at break and tearability may not be obtained.
  • the NR is not particularly limited.
  • common ones in the tire industry such as SIR20, RSS # 3, TSR20 and ENR25 can be used.
  • IR What is common in the tire industry can be used.
  • the content of isoprene-based rubber in 100% by mass of diene-based rubber component is preferably 20% by mass or more, more preferably 50% by mass or more. is there. If it is less than 20% by mass, mechanical strength may not be sufficiently obtained.
  • the content is preferably 90% by mass or less, more preferably 70% by mass or less. If it exceeds 90% by mass, crack growth may be deteriorated.
  • the rubber composition of the present invention contains each normal alkane having 20 to 32 carbon atoms. Thereby, ozone resistance in a temperature range of about 0 to 20 ° C. can be obtained well.
  • the total content of C20-32 normal alkanes is at least 0.7 parts by mass, preferably at least 0.9 parts by mass, per 100 parts by mass of the diene rubber component. If it is less than 0.7 parts by mass, sufficient ozone resistance may not be obtained in a temperature range of 20 ° C. or less.
  • the total content is 3.5 parts by mass or less, preferably 2.4 parts by mass or less. If the amount is more than 3.5 parts by mass, the discoloration resistance and the adhesiveness during molding may be reduced.
  • the rubber composition of the present invention usually contains each normal alkane having 33 to 44 carbon atoms. Thereby, ozone resistance in a temperature range of about 40 to 50 ° C. can be obtained well.
  • the total content of each normal alkane having a carbon number of 33 to 44 is preferably at least 0.45 parts by mass, more preferably at least 0.5 parts by mass, per 100 parts by mass of the diene rubber component. If the amount is less than 0.45 parts by mass, ozone resistance in a temperature range of about 40 to 50 ° C. may not be sufficiently obtained. Further, the total content is preferably 1.7 parts by mass or less, more preferably 1.6 parts by mass or less. If the amount is more than 1.7 parts by mass, the amount of the Bloom-deposited amount of the normal alkane having 33 to 44 carbon atoms in the temperature range of about 40 to 50 ° C. tends to be white.
  • the rubber composition of the present invention usually contains 45 to 47 carbons of each normal alkane, for convenience of the purification and production process of the wax described later.
  • the total content of the normal alkanes having 45 to 47 carbon atoms is preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the diene rubber component. If the amount is less than 0.01 parts by mass, the crack resistance in a temperature range of about 60 ° C. tends to be slightly deteriorated.
  • the total content is preferably 1 part by mass or less, more preferably 0.15 parts by mass or less. If the amount is more than 1 part by mass, discoloration resistance (white discoloration) in a temperature range of about 60 ° C. tends to be deteriorated.
  • the rubber composition of the present invention preferably contains 0.1 parts by mass or less of a normal alkane having 48 or more carbon atoms with respect to 100 parts by mass of the diene rubber component.
  • a normal alkane having 48 or more carbon atoms with respect to 100 parts by mass of the diene rubber component.
  • the content of the normal alkane having a carbon number of 48 or more is more preferably 0.08 parts by mass or less with respect to 100 parts by mass of the diene rubber component. If the amount is more than 0.1 parts by mass, white discoloration may occur.
  • the total content of each normal alkane having 25 to 27 carbon atoms is preferably a specified amount.
  • the total content of each normal alkane having 25 to 27 carbon atoms is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the diene rubber component. If the amount is less than 0.2 parts by mass, sufficient ozone resistance may not be obtained in a temperature range of about 10 ° C. Further, the total content is preferably 2 parts by mass or less, more preferably 1.8 parts by mass or less. If it exceeds 2 parts by mass, it tends to discolor.
  • a wax containing each C20-32 normal alkane may be blended.
  • the wax containing each normal alkane having 20 to 32 carbon atoms is not particularly limited, and a wax containing each normal alkane having 20 to 55 carbon atoms can be used. Among them, one having a content of 70% by mass or more of normal alkane in 100% by mass of wax can be suitably used because an excellent ozone resistance can be obtained, and one having a content of 80% by mass or more is more suitably used. it can.
  • the total content of each normal alkane having 20 to 32 carbon atoms in 100% by mass of the wax is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more. If it is less than 30% by mass, ozone resistance may not be sufficiently obtained in a low temperature range of about 0 to 20 ° C. 90 mass% or less is preferable, and, as for this content, 65 mass% or less is more preferable. If it exceeds 90% by mass, white discoloration tends to occur in a low temperature range of about 0 to 20 ° C.
  • each normal alkane having 25 to 27 carbon atoms in the above 100% by mass wax is preferably 4.1% by mass or more, and more preferably 5% by mass or more. If it is less than 4.1 mass, the effect of improving the ozone resistance in a temperature range of about 10 ° C. may not be sufficiently obtained. Although the upper limit of this content is not specifically limited, 50 mass% or less is preferable, and 45 mass% or less is more preferable. If it exceeds 50% by mass, white discoloration tends to easily occur in a temperature range of about 10 ° C. In addition, there is a possibility that the ozone resistance in the temperature range of about 30 to 50 ° C. can not be sufficiently obtained.
  • the wax containing each normal alkane having the carbon number distribution as described above can be prepared, for example, by appropriately mixing known waxes.
  • phenylenediamine based antioxidants and / or quinone based antioxidants are used.
  • a specific amount of each of the specific antiaging agent and the normal alkane having a specific carbon number it is possible to obtain excellent ozone resistance in a wide temperature range and to well suppress the color change.
  • other anti-aging agents such as TMQ, although the color of the anti-aging agent itself is thin and discoloration does not become a major problem, there is a tendency that improvement effects such as ozone resistance can not be sufficiently obtained.
  • phenylenediamine-based antioxidants include N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N, N'-diphenyl -P-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N, N'-bis (1-methylheptyl) -p -Phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N-4- Methyl-2-pentyl-N'-phenyl-p-phenylenediamine
  • quinone anti-aging agent examples include benzoquinones, hydroquinones, catechols, quinone diimines, quinomethanes, quinodimethane anti-aging agents and the like. Among them, quinone diimine anti-aging agents are preferable.
  • N- (1,3-dimethylbutyl) -N'-phenylquinone diimine (6QDI) is preferable.
  • the total content of the phenylenediamine based antioxidant and the quinone based antioxidant is 1.5 parts by mass or more, preferably 2 parts by mass or more, with respect to 100 parts by mass of the diene rubber component. If the amount is less than 1.5 parts by mass, sufficient ozone resistance may not be obtained.
  • the content is 3 parts by mass or less, preferably 2.8 parts by mass or less. If it exceeds 3 parts by mass, it tends to discolor (brown).
  • the rubber composition of the present invention preferably contains carbon black. Thereby, the reinforcing effect and the ultraviolet ray preventing effect can be obtained, and the effect of the present invention can be obtained well.
  • the content of carbon black is preferably 0.2 to 20 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of a diene rubber component. is there. Within the above range, the reinforcing effect and the ultraviolet ray preventing effect can be obtained, and the effect of the present invention can be obtained well.
  • the content of carbon black is preferably 10 to 50 parts by mass with respect to 100 parts by mass of the diene rubber component.
  • a reinforcement effect is acquired as it is in the said range, and the effect of this invention is acquired favorably.
  • the rubber composition of the present invention preferably contains silica. Thereby, good fuel economy can be obtained.
  • the silica is not particularly limited, and, for example, dry method silica (anhydrous silica), wet method silica (hydrous silica) and the like can be used.
  • dry method silica anhydrous silica
  • wet method silica hydrophilic silica
  • hydrophilic silica hydrophilic silica
  • the content of silica is preferably 20 parts by mass or more, more preferably 60 parts by mass or more, with respect to 100 parts by mass of a diene rubber component.
  • the content is preferably 120 parts by mass or less, more preferably 80 parts by mass or less.
  • the lower limit of the content of silica is not particularly limited, but preferably 0.1 parts by mass or more with respect to 100 parts by mass of the diene rubber component. is there.
  • the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less. When the content is in the above range, good elongation at break, low fuel consumption and processability can be obtained.
  • silica when silica is used, it is preferable to use a silane coupling agent.
  • the rubber composition of the present invention can be suitably used particularly as a silica-containing rubber composition in terms of TGC and the like, for example, when the rubber composition is applied to a tread, 100% by mass in total of silica and carbon black
  • the content ratio of silica is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass or more.
  • an upper limit is not specifically limited, 100 mass% may be sufficient.
  • the content of silica in the total 100% by mass of silica and carbon black is preferably 5% by mass or more, more preferably 10% by mass. It is above.
  • the upper limit is not particularly limited, but is preferably 40% by mass or less, more preferably 20% by mass or less.
  • a process oil may be blended.
  • the process oil for example, paraffin-based process oil, aroma-based process oil, naphthene-based process oil and the like can be used.
  • the content of the process oil is preferably 15 parts by mass or less with respect to 100 parts by mass of the diene rubber component. If it exceeds 15 parts by mass, it tends to be discolored.
  • the lower limit of the content is not particularly limited, but is preferably 2 parts by mass or more, more preferably 5 parts by mass or more. If the amount is less than 2 parts by mass, processability may be degraded.
  • compounding agents generally used in the production of rubber compositions such as C5 petroleum resin, coumarone indene resin, ⁇ -methylstyrene and / or styrene are polymerized.
  • An aromatic vinyl polymer, stearic acid, zinc oxide, a vulcanizing agent, a vulcanization accelerator and the like obtained by
  • the above-mentioned components are kneaded using a rubber kneading apparatus such as an open roll or a Banbury mixer and then vulcanized. It can be manufactured.
  • a rubber kneading apparatus such as an open roll or a Banbury mixer
  • the rubber composition of the present invention can be used without particular limitation as long as it is an outer layer member of a tire, but as described above, can be suitably used for a tread, a sidewall, a wing, and a clinch apex.
  • the pneumatic tire of the present invention can be produced by the usual method using the above rubber composition. That is, the above rubber composition is extruded at the unvulcanized stage according to the shape of each outer layer member (tread, sidewall, wing, clinchapex, etc.) of the tire, and the usual method is carried out on the tire molding machine It can be molded and bonded together with other tire members to form an unvulcanized tire.
  • the unvulcanized tire can be heated and pressurized in a vulcanizer to produce a tire.
  • High cis BR (CB25): BUNA-CB25 manufactured by LANXESS (BR synthesized using Nd catalyst, cis content: 96%) Modified SSBR (HPR 355): HPR 355 (modified S-SBR, styrene content: 27% by mass, vinyl content 55% by mass) manufactured by JSR Corporation TSR20: NR (TSR20) Carbon black (N220): Show black N220 (N 2 SA: 120 m 2 / g, DBP oil absorption: 115 ml / 100 g) manufactured by Cabot Japan Ltd.
  • SA 85 Aromatic vinyl polymer
  • SA 85 SYLVARES SA 85 (copolymer of ⁇ -methylstyrene and styrene, softening point: 85 ° C., Mw: 1000) manufactured by Arizona chemical Process oil: H & R vivatec 500 (TDAE)
  • Stearic acid Stearic acid "Nuka” manufactured by NOF Corporation
  • Zinc flower Ginkgo R manufactured by Toho Zinc Co., Ltd.
  • Silane coupling agent Si75 (bis (3-triethoxysilylpropyl) disulfide) manufactured by Evonik Degussa Powdered sulfur containing 5% oil: HK-200-5 (5% oil content) manufactured by Hosoi Chemical Industry Co., Ltd. 10% oil-containing insoluble sulfur: Seimi Sulfur (60% insoluble in carbon disulfide, 10% oil) manufactured by Nippon Denryo Kogyo Co., Ltd.
  • Vulcanization accelerator Noxceler D (N, N'-diphenyl guanidine) manufactured by Ouchi Emerging Chemical Industry Co., Ltd.
  • Wax 1 Prototype 1 (normal alkane content: 85% by mass on average)
  • Wax 2 Prototype 2 (normal alkane content: average 87% by mass)
  • Wax 3 Prototype 3 (normal alkane content: 81% by mass on average)
  • Wax 4 sorbitan monostearate (Lonza Chemical Company manufactured Glycomul S TM)
  • 6PPD Antigen 6C (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
  • 6QDI 6QDI (N- (1,3-dimethylbutyl) -N'-phenylquinonediimine) manufactured by Flexis.
  • TMQ Nouchi 224 manufactured by Ouchi Emerging Chemical Industry Co., Ltd. (2,2,4-trimethyl-1,2-dihydroquinoline polymer)
  • the carbon number distribution of the wax was measured by the following method. The results are shown in FIG. 1 and Table 4.
  • Example and Comparative Example According to the formulation shown in the upper part of Tables 1 to 3, chemicals other than sulfur and a vulcanization accelerator were kneaded using a 1.7 L Banbury mixer manufactured by Kobe Steel, Ltd. Next, using an open roll, sulfur and a vulcanization accelerator were added to the obtained kneaded product and kneaded to obtain an unvulcanized rubber composition. Using the obtained unvulcanized rubber composition, members to be the tread portion, the sidewall portion and the clinch apex are produced to produce a green tire, which is vulcanized at 170 ° C. to test a tire (205 / 65R15) was obtained. The performance of the obtained test tire was evaluated by the following test.

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Abstract

Provided are: a rubber composition for a tire outer layer, whereby excellent ozone resistance is obtained in a wide range of environment temperatures, and whereby discoloration can be satisfactorily suppressed; and a pneumatic tire that uses the rubber composition for a tire outer layer. The present invention relates to a rubber composition for a tire outer layer, comprising C20-32 normal alkanes and a phenylene-diamine-based antioxidant and/or quinone-based antioxidant, the total content of the C20-32 normal alkanes being 0.7-3.5 parts by mass, and the total content of the phenylene-diamine-based antioxidant and/or quinone-based antioxidant being 1.5-3 parts by mass with respect to 100 parts by mass of diene-based rubber components.

Description

タイヤ外層用ゴム組成物及び空気入りタイヤRubber composition for tire outer layer and pneumatic tire
本発明は、タイヤ外層用ゴム組成物、及びそれを用いた空気入りタイヤに関する。 The present invention relates to a rubber composition for an outer layer of a tire, and a pneumatic tire using the same.
タイヤのトレッドやサイドウォールなどのゴム組成物には、オゾン劣化や酸化劣化、熱分解劣化を防止するために、ワックスなどが配合されている。配合されたワックスは、ゴム表面へ染みだし、ゴム表面に膜を張ることで、物理的にオゾン、酸素、有害気体の刺激からゴムを守ることができる。 In order to prevent ozone deterioration, oxidation deterioration, thermal degradation deterioration, a wax etc. are mix | blended with rubber compositions, such as a tread and a sidewall, of a tire. The blended wax soaks out to the rubber surface, and by stretching the film on the rubber surface, it is possible to physically protect the rubber from the stimulation of ozone, oxygen and harmful gases.
低温地域や温帯地域では、ワックスがブルームしにくく、耐オゾン性を確保することが難しい。このため、従来公知のワックスを変色の抑制が可能な量で配合すると、温帯冬季など低温環境での耐オゾン性が不足する場合がある。一方、高温地域では、ゴムの分子運動が活発であるため、ワックスがブルームしやすく耐オゾン性を確保し易いが、タイヤ表面が白変色し易い。このように、寒帯～熱帯という広い温度域で、優れた耐オゾン性を得ながら、白変色を抑制することは困難である。 In low temperature areas and temperate areas, it is difficult for the wax to bloom and it is difficult to secure ozone resistance. For this reason, when the conventionally well-known wax is mix | blended in the quantity which can suppress discoloration, ozone resistance in low temperature environments, such as temperate winter, may be insufficient. On the other hand, in a high temperature area, since the molecular motion of rubber is active, the wax is likely to bloom and ozone resistance is easily secured, but the tire surface is likely to be discolored to white. As described above, it is difficult to suppress white discoloration while obtaining excellent ozone resistance in a wide temperature range from the cold zone to the tropics.
特にシリカ配合トレッドゴムの場合、金型内での加硫中の状態に比べ、加硫、常温への冷却後、トレッドゴムが体積収縮し易く、トレッド溝底に、タイヤ使用空気圧を充填する前、或いは充填した後で、引張り歪が生じ易い。ゴムが引っ張られた状態になると、オゾンアタックを受けやすい状態となり、トレッドグルーブクラック（ＴＧＣ）が発生しやすい。ゆえに、耐オゾン性、白変色性を両立させることが重要である。 In particular, in the case of silica-containing tread rubber, the volume of the tread rubber shrinks easily after vulcanization and cooling to room temperature as compared with the state during vulcanization in the mold, and before the tire use air pressure is filled in the tread groove bottom. After being filled, it tends to cause tensile strain. When the rubber is pulled, it becomes susceptible to ozone attack, and tread groove cracks (TGC) tend to occur. Therefore, it is important to achieve both ozone resistance and white discoloration.
また、耐オゾン性を改善する方法として、老化防止剤３ＰＰＤを使用する方法が知られているが、６ＰＰＤや６ＱＤＩに比べブルームし易く、低温環境での耐オゾン性を改善できるが、揮発性が高くすぐに減ってしまうため、耐オゾン性を長期間確保することが困難である。 In addition, as a method to improve ozone resistance, a method using anti-aging agent 3PPD is known, but it is easier to bloom than 6PPD and 6QDI, and ozone resistance in a low temperature environment can be improved, but volatility It is difficult to secure ozone resistance for a long period of time because it is high and decreases quickly.
特許文献１では、特定のワックスを配合することが提案されているが、低温地域や温帯地域冬季における耐オゾン性については改善の余地が大きく、広い温度域で優れた耐オゾン性を得ながら、変色を抑制できる技術が要求されている。 Although Patent Document 1 proposes that a specific wax be blended, there is a large room for improvement in ozone resistance in the low temperature area and the temperate area winter, and while obtaining excellent ozone resistance in a wide temperature area, There is a need for a technology that can suppress discoloration.
特開２０１１－１１６８４７号公報JP 2011-116847 A
本発明は、前記課題を解決し、広い環境温度域で優れた耐オゾン性が得られるとともに、変色を良好に抑制できるタイヤ外層用ゴム組成物、及びこれを用いた空気入りタイヤを提供することを目的とする。 The present invention solves the above-mentioned problems and provides a rubber composition for an outer layer of a tire capable of satisfactorily suppressing discoloration while obtaining excellent ozone resistance in a wide environmental temperature range, and a pneumatic tire using the same. With the goal.
本発明は、炭素数２０～３２の各ノルマルアルカンと、フェニレンジアミン系老化防止剤及び／又はキノン系老化防止剤とを含み、ジエン系ゴム成分１００質量部に対して、前記炭素数２０～３２の各ノルマルアルカンの合計含有量が０．７～３．５質量部、前記フェニレンジアミン系老化防止剤及び前記キノン系老化防止剤の合計含有量が１．５～３質量部であるタイヤ外層用ゴム組成物に関する。 The present invention comprises each normal alkane having a carbon number of 20 to 32 and a phenylenediamine based antioxidant and / or a quinone based antioxidant, and the carbon number is 20 to 32 with respect to 100 parts by mass of a diene rubber component. For the outer layer of the tire, wherein the total content of each normal alkane is 0.7 to 3.5 parts by mass, and the total content of the phenylenediamine based antioxidant and the quinone based antioxidant is 1.5 to 3 parts by mass It relates to a rubber composition.
前記タイヤ外層用ゴム組成物は、前記ジエン系ゴム成分１００質量部に対して、炭素数４８以上の各ノルマルアルカンを合計０．１質量部以下含むことが好ましい。
前記ジエン系ゴム成分１００質量部に対して、前記炭素数２０～３２の各ノルマルアルカンの合計含有量が０．９～２．４質量部であることが好ましい。前記ジエン系ゴム成分１００質量部に対して、プロセスオイルを１５質量部以下含むことが好ましい。 It is preferable that the rubber composition for a tire outer layer contains a total of 0.1 parts by mass or less of each normal alkane having a carbon number of 48 or more with respect to 100 parts by mass of the diene rubber component.
The total content of each normal alkane having 20 to 32 carbon atoms is preferably 0.9 to 2.4 parts by mass with respect to 100 parts by mass of the diene rubber component. It is preferable to contain 15 parts by mass or less of process oil with respect to 100 parts by mass of the diene rubber component.
前記タイヤ外層用ゴム組成物は、トレッド、サイドウォール、ウイング及びクリンチエイペックスからなる群より選択される少なくとも１種として使用されることが好ましい。
本発明はまた、前記ゴム組成物を用いて作製した空気入りタイヤに関する。 The tire outer layer rubber composition is preferably used as at least one selected from the group consisting of a tread, a sidewall, a wing, and a clinch apex.
The present invention also relates to a pneumatic tire produced using the rubber composition.
本発明によれば、炭素数２０～３２の各ノルマルアルカンと、フェニレンジアミン系老化防止剤及び／又はキノン系老化防止剤とを含み、前記炭素数２０～３２の各ノルマルアルカンの合計含有量が特定量であり、かつ前記フェニレンジアミン系老化防止剤及び前記キノン系老化防止剤の合計含有量も特定量であるタイヤ外層用ゴム組成物であるので、広い環境温度域で優れた耐オゾン性が得られるとともに、変色を良好に抑制できる。 According to the present invention, the total content of each normal alkane having 20 to 32 carbon atoms, which contains each normal alkane having 20 to 32 carbon atoms, and a phenylenediamine based antioxidant and / or a quinone based antioxidant, is Since it is a rubber composition for a tire outer layer which is a specific amount, and the total content of the phenylenediamine anti-aging agent and the quinone-based anti-aging agent is also a specific amount, excellent ozone resistance in a wide environmental temperature range While being obtained, color change can be favorably suppressed.
ワックスの炭素数分布を示す図である。It is a figure which shows carbon number distribution of a wax.
本発明のタイヤ外層用ゴム組成物は、炭素数２０～３２の各ノルマルアルカンと、フェニレンジアミン系老化防止剤及び／又はキノン系老化防止剤とを含み、ジエン系ゴム成分に対する前記炭素数２０～３２の各ノルマルアルカンの合計含有量が特定量であり、かつ前記フェニレンジアミン系老化防止剤及び前記キノン系老化防止剤の合計含有量も特定量である。 The rubber composition for the outer layer of a tire according to the present invention comprises each normal alkane having 20 to 32 carbon atoms, a phenylenediamine based antioxidant and / or a quinone based antioxidant, and the above-mentioned carbon number for the diene based rubber component is 20 to The total content of each of the 32 normal alkanes is a specific amount, and the total content of the phenylenediamine anti-aging agent and the quinone anti-aging agent is also a specific amount.
本発明のゴム組成物は、トレッド、サイドウォール、ウイング、クリンチエイペックスなどのタイヤ外層部材に使用される。 The rubber composition of the present invention is used for tire outer layer members such as treads, sidewalls, wings and clinch apexes.
ジエン系ゴム成分としては、たとえば、天然ゴム（ＮＲ）、高純度化天然ゴム（Ｈｉｇｈｌｙ　ｐｕｒｉｆｉｅｄ　ＮＲ）、エポキシ化天然ゴム（ＥＮＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、イソプレンゴム（ＩＲ）、ブチルゴム（ＩＩＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、スチレンイソプレンブタジエンゴム（ＳＩＢＲ）、スチレンイソプレンゴム、イソプレンブタジエンゴムなどが挙げられ、これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。
なかでも、トレッドに適用する場合、グリップ性能、破断強度が良好に得られるという理由から、ＳＢＲ、ＢＲを使用することが好ましい。サイドウォール及びクリンチエイペックスに適用する場合、破断強度が良好に得られるという理由から、ＮＲ、ＩＲなどのイソプレン系ゴム、亀裂成長性に優れるという理由から、ＢＲを使用することが好ましい。 Examples of diene rubber components include natural rubber (NR), highly purified natural rubber (Highly purified NR), epoxidized natural rubber (ENR), butadiene rubber (BR), styrene butadiene rubber (SBR), isoprene rubber ( IR), butyl rubber (IIR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), styrene isoprene butadiene rubber (SIBR), styrene isoprene rubber, isoprene butadiene rubber and the like, and these may be used alone. Two or more may be used in combination.
Among them, when applied to the tread, it is preferable to use SBR or BR because grip performance and breaking strength can be obtained well. When applied to side walls and clinchapex, it is preferable to use BR because isoprene rubber such as NR and IR and crack growth are excellent because fracture strength is obtained well.
ＳＢＲとしては特に限定されず、例えば、従来公知の変性剤で変性されたもの（変性ＳＢＲ）などを好適に使用できる。 The SBR is not particularly limited, and for example, those modified with a conventionally known modifying agent (modified SBR) can be suitably used.
ＳＢＲの結合スチレン量は、グリップ性能向上という点から、好ましくは１０質量％以上、より好ましくは２０質量％以上である。一方、耐摩耗性向上という点から、好ましくは４５質量％以下、より好ましくは４０質量％以下である。
なお、本発明において、ＳＢＲのスチレン量は、Ｈ１－ＮＭＲ測定により算出される。 The bound styrene content of SBR is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of improving grip performance. On the other hand, the content is preferably 45% by mass or less, more preferably 40% by mass or less, from the viewpoint of improving the wear resistance.
In the present invention, the styrene content of SBR is calculated by H 1 -NMR measurement.
本発明のゴム組成物をトレッドに適用する場合、ジエン系ゴム成分１００質量％中のＳＢＲの含有量は、好ましくは２０質量％以上、より好ましくは６０質量％以上である。２０質量％未満であると、グリップ性能が充分に得られないおそれがある。該含有量は、好ましくは９０質量％以下、より好ましくは８０質量％以下である。９０質量％を超えると、充分な耐摩耗性が得られないおそれがある。 When the rubber composition of the present invention is applied to a tread, the content of SBR in 100% by mass of the diene rubber component is preferably 20% by mass or more, more preferably 60% by mass or more. If the amount is less than 20% by mass, grip performance may not be sufficiently obtained. The content is preferably 90% by mass or less, more preferably 80% by mass or less. When it exceeds 90% by mass, sufficient abrasion resistance may not be obtained.
ＢＲとしては特に限定されないが、二重結合部分のシス含量が９５モル％以上のＢＲ（ハイシスＢＲ）が好ましい。 The BR is not particularly limited, but preferred is BR (hysis BR) in which the cis content of the double bond portion is 95 mol% or more.
本発明のゴム組成物をトレッドに適用する場合、ジエン系ゴム成分１００質量％中のＢＲの含有量は、好ましくは１０質量％以上、より好ましくは２０質量％以上である。１０質量％未満であると、充分な耐摩耗性が得られないおそれがある。該含有量は、好ましくは８０質量％以下、より好ましくは４０質量％以下である。８０質量％を超えると、充分なグリップ性能が得られないおそれがある。 When the rubber composition of the present invention is applied to a tread, the content of BR in 100% by mass of the diene rubber component is preferably 10% by mass or more, more preferably 20% by mass or more. If the amount is less than 10% by mass, sufficient abrasion resistance may not be obtained. The content is preferably 80% by mass or less, more preferably 40% by mass or less. If it exceeds 80% by mass, sufficient grip performance may not be obtained.
本発明のゴム組成物をサイドウォール及びクリンチエイペックスに適用する場合、ジエン系ゴム成分１００質量％中のＢＲの含有量は、好ましくは１０質量％以上、より好ましくは３０質量％以上である。１０質量％未満であると、亀裂成長性、加硫戻り性が悪化する傾向がある。該含有量は、好ましくは８０質量％以下、より好ましくは５０質量％以下である。８０質量％を超えると、充分な破断時伸び、引き裂き性が得られないおそれがある。 When the rubber composition of the present invention is applied to side walls and clinchapex, the content of BR in 100% by mass of the diene rubber component is preferably 10% by mass or more, more preferably 30% by mass or more. If it is less than 10% by mass, crack growth and reversion resistance tend to be deteriorated. The content is preferably 80% by mass or less, more preferably 50% by mass or less. If it exceeds 80% by mass, sufficient elongation at break and tearability may not be obtained.
ＮＲとしては特に限定されず、例えば、ＳＩＲ２０、ＲＳＳ♯３、ＴＳＲ２０、ＥＮＲ２５など、タイヤ工業において一般的なものを使用できる。また、ＩＲとしては特に限定されず、タイヤ工業において一般的なものを使用できる。 The NR is not particularly limited. For example, common ones in the tire industry such as SIR20, RSS # 3, TSR20 and ENR25 can be used. Moreover, it does not specifically limit as IR, What is common in the tire industry can be used.
本発明のゴム組成物をサイドウォール及びクリンチエイペックスに適用する場合、ジエン系ゴム成分１００質量％中のイソプレン系ゴムの含有量は、好ましくは２０質量％以上、より好ましくは５０質量％以上である。２０質量％未満であると、機械的強度が充分に得られないおそれがある。該含有量は、好ましくは９０質量％以下、より好ましくは７０質量％以下である。９０質量％を超えると、亀裂成長性などが低下するおそれがある。 When the rubber composition of the present invention is applied to side walls and clinchapex, the content of isoprene-based rubber in 100% by mass of diene-based rubber component is preferably 20% by mass or more, more preferably 50% by mass or more. is there. If it is less than 20% by mass, mechanical strength may not be sufficiently obtained. The content is preferably 90% by mass or less, more preferably 70% by mass or less. If it exceeds 90% by mass, crack growth may be deteriorated.
本発明のゴム組成物は、炭素数２０～３２の各ノルマルアルカンを含む。これにより、０～２０℃程度の温度域での耐オゾン性が良好に得られる。
炭素数２０～３２の各ノルマルアルカンの合計含有量は、ジエン系ゴム成分１００質量部に対して、０．７質量部以上、好ましくは０．９質量部以上である。０．７質量部未満であると、２０℃以下の温度域で充分な耐オゾン性が得られないそれがある。また、該合計含有量は、３．５質量部以下、好ましくは２．４質量部以下である。３．５質量部を超えると、耐変色性、成型時粘着性が低下するおそれがある。 The rubber composition of the present invention contains each normal alkane having 20 to 32 carbon atoms. Thereby, ozone resistance in a temperature range of about 0 to 20 ° C. can be obtained well.
The total content of C20-32 normal alkanes is at least 0.7 parts by mass, preferably at least 0.9 parts by mass, per 100 parts by mass of the diene rubber component. If it is less than 0.7 parts by mass, sufficient ozone resistance may not be obtained in a temperature range of 20 ° C. or less. The total content is 3.5 parts by mass or less, preferably 2.4 parts by mass or less. If the amount is more than 3.5 parts by mass, the discoloration resistance and the adhesiveness during molding may be reduced.
本発明のゴム組成物は、通常、炭素数３３～４４の各ノルマルアルカンを含む。これにより、４０～５０℃程度の温度域での耐オゾン性が良好に得られる。
炭素数３３～４４の各ノルマルアルカンの合計含有量は、ジエン系ゴム成分１００質量部に対して、好ましくは０．４５質量部以上、より好ましくは０．５質量部以上である。０．４５質量部未満であると、４０～５０℃程度の温度域での耐オゾン性が充分に得られないおそれがある。また、該合計含有量は、好ましくは１．７質量部以下、より好ましくは１．６質量部以下である。１．７質量部を超えると、４０～５０℃程度の温度域で炭素数３３～４４のノルマルアルカンのブルーム析出量が多く、白変色する傾向がある。 The rubber composition of the present invention usually contains each normal alkane having 33 to 44 carbon atoms. Thereby, ozone resistance in a temperature range of about 40 to 50 ° C. can be obtained well.
The total content of each normal alkane having a carbon number of 33 to 44 is preferably at least 0.45 parts by mass, more preferably at least 0.5 parts by mass, per 100 parts by mass of the diene rubber component. If the amount is less than 0.45 parts by mass, ozone resistance in a temperature range of about 40 to 50 ° C. may not be sufficiently obtained. Further, the total content is preferably 1.7 parts by mass or less, more preferably 1.6 parts by mass or less. If the amount is more than 1.7 parts by mass, the amount of the Bloom-deposited amount of the normal alkane having 33 to 44 carbon atoms in the temperature range of about 40 to 50 ° C. tends to be white.
本発明のゴム組成物は、後述するワックスの精製、製造工程の都合上、通常、炭素数４５～４７の各ノルマルアルカンを含む。
炭素数４５～４７の各ノルマルアルカンの合計含有量は、ジエン系ゴム成分１００質量部に対して、好ましくは０．０１質量部以上、より好ましくは０．０５質量部以上である。０．０１質量部未満であると、６０℃程度の温度域の耐クラック性が若干悪化する傾向がある。また、該合計含有量は、好ましくは１質量部以下、より好ましくは０．１５質量部以下である。１質量部を超えると、６０℃程度の温度域の耐変色性（白変色）が悪化する傾向がある。 The rubber composition of the present invention usually contains 45 to 47 carbons of each normal alkane, for convenience of the purification and production process of the wax described later.
The total content of the normal alkanes having 45 to 47 carbon atoms is preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the diene rubber component. If the amount is less than 0.01 parts by mass, the crack resistance in a temperature range of about 60 ° C. tends to be slightly deteriorated. The total content is preferably 1 part by mass or less, more preferably 0.15 parts by mass or less. If the amount is more than 1 part by mass, discoloration resistance (white discoloration) in a temperature range of about 60 ° C. tends to be deteriorated.
本発明のゴム組成物は、ジエン系ゴム成分１００質量部に対して、炭素数４８以上のノルマルアルカンを０．１質量部以下含むことが好ましい。これにより、６０℃以上の温度域での耐変色性（白変色）が良好に得られる。炭素数４８以上のノルマルアルカンの含有量は、ジエン系ゴム成分１００質量部に対して、より好ましくは０．０８質量部以下である。０．１質量部を超えると、白変色するおそれがある。 The rubber composition of the present invention preferably contains 0.1 parts by mass or less of a normal alkane having 48 or more carbon atoms with respect to 100 parts by mass of the diene rubber component. Thereby, discoloration resistance (white discoloration) in a temperature range of 60 ° C. or higher can be obtained favorably. The content of the normal alkane having a carbon number of 48 or more is more preferably 0.08 parts by mass or less with respect to 100 parts by mass of the diene rubber component. If the amount is more than 0.1 parts by mass, white discoloration may occur.
また、本発明では、炭素数２５～２７の各ノルマルアルカンの合計含有量が特定量であることが好ましい。炭素数２５～２７の各ノルマルアルカンの合計含有量は、ジエン系ゴム成分１００質量部に対して、好ましくは０．２質量部以上、より好ましくは０．５質量部以上である。０．２質量部未満であると、１０℃程度の温度域で充分な耐オゾン性が得られないおそれがある。また、該合計含有量は、好ましくは２質量部以下、より好ましくは１．８質量部以下である。２質量部を超えると、変色する傾向がある。 In the present invention, the total content of each normal alkane having 25 to 27 carbon atoms is preferably a specified amount. The total content of each normal alkane having 25 to 27 carbon atoms is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the diene rubber component. If the amount is less than 0.2 parts by mass, sufficient ozone resistance may not be obtained in a temperature range of about 10 ° C. Further, the total content is preferably 2 parts by mass or less, more preferably 1.8 parts by mass or less. If it exceeds 2 parts by mass, it tends to discolor.
炭素数２０～３２の各ノルマルアルカンの合計含有量を特定量とするには、例えば、炭素数２０～３２の各ノルマルアルカンを含むワックスを配合すればよい。 In order to set the total content of the C20-32 normal alkanes to a specific amount, for example, a wax containing each C20-32 normal alkane may be blended.
炭素数２０～３２の各ノルマルアルカンを含むワックスとしては特に限定されず、炭素数２０～５５の各ノルマルアルカンを含むワックスなどを使用できる。なかでも、優れた耐オゾン性が得られるという理由から、ワックス１００質量％中のノルマルアルカンの含有量が７０質量％以上のものを好適に使用でき、８０質量％以上のものをより好適に使用できる。 The wax containing each normal alkane having 20 to 32 carbon atoms is not particularly limited, and a wax containing each normal alkane having 20 to 55 carbon atoms can be used. Among them, one having a content of 70% by mass or more of normal alkane in 100% by mass of wax can be suitably used because an excellent ozone resistance can be obtained, and one having a content of 80% by mass or more is more suitably used. it can.
上記ワックス１００質量％中、炭素数２０～３２の各ノルマルアルカンの合計含有量は３０質量％以上が好ましく、３５質量％以上がより好ましく、４０質量％以上が更に好ましい。３０質量％未満であると、０～２０℃程度の低温域での耐オゾン性が充分に得られないおそれがある。該含有量は、９０質量％以下が好ましく、６５質量％以下がより好ましい。９０質量％を超えると、０～２０℃程度の低温域で、白変色しやすくなる傾向がある。 The total content of each normal alkane having 20 to 32 carbon atoms in 100% by mass of the wax is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more. If it is less than 30% by mass, ozone resistance may not be sufficiently obtained in a low temperature range of about 0 to 20 ° C. 90 mass% or less is preferable, and, as for this content, 65 mass% or less is more preferable. If it exceeds 90% by mass, white discoloration tends to occur in a low temperature range of about 0 to 20 ° C.
上記ワックス１００質量％中、炭素数２５～２７の各ノルマルアルカンの含有量はそれぞれ４．１質量％以上が好ましく、５質量％以上がより好ましい。４．１質量未満であると、１０℃程度の温度域での耐オゾン性の改善効果が充分に得られないおそれがある。該含有量の上限は特に限定されないが、５０質量％以下が好ましく、４５質量％以下がより好ましい。５０質量％を超えると、１０℃程度の温度域で白変色しやすい傾向がある。また、相対的に３０～５０℃程度の温度域での耐オゾン性が充分に得られないおそれがある。 The content of each normal alkane having 25 to 27 carbon atoms in the above 100% by mass wax is preferably 4.1% by mass or more, and more preferably 5% by mass or more. If it is less than 4.1 mass, the effect of improving the ozone resistance in a temperature range of about 10 ° C. may not be sufficiently obtained. Although the upper limit of this content is not specifically limited, 50 mass% or less is preferable, and 45 mass% or less is more preferable. If it exceeds 50% by mass, white discoloration tends to easily occur in a temperature range of about 10 ° C. In addition, there is a possibility that the ozone resistance in the temperature range of about 30 to 50 ° C. can not be sufficiently obtained.
以上のような炭素数分布を有する各ノルマルアルカンを含むワックスは、例えば、公知のワックスを適宜混合することなどによって調製できる。 The wax containing each normal alkane having the carbon number distribution as described above can be prepared, for example, by appropriately mixing known waxes.
本発明では、フェニレンジアミン系老化防止剤及び／又はキノン系老化防止剤が使用される。これら特定の老化防止剤と特定炭素数のノルマルアルカンとをそれぞれ特定量配合することで、広い温度域で優れた耐オゾン性が得られるとともに、変色を良好に抑制できる。一方、ＴＭＱなどの他の老化防止剤では、老化防止剤自体の色が薄く変色が大きな問題とならないが、耐オゾン性などの改善効果が充分に得られない傾向がある。 In the present invention, phenylenediamine based antioxidants and / or quinone based antioxidants are used. By blending a specific amount of each of the specific antiaging agent and the normal alkane having a specific carbon number, it is possible to obtain excellent ozone resistance in a wide temperature range and to well suppress the color change. On the other hand, with other anti-aging agents such as TMQ, although the color of the anti-aging agent itself is thin and discoloration does not become a major problem, there is a tendency that improvement effects such as ozone resistance can not be sufficiently obtained.
フェニレンジアミン系老化防止剤としては、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニル－ｐ－フェニレンジアミン、Ｎ－イソプロピル－Ｎ’－フェニル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジフェニル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミン、Ｎ－シクロヘキシル－Ｎ’－フェニル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ビス（１－メチルヘプチル）－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ビス（１，４－ジメチルペンチル）－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ビス（１－エチル－３－メチルペンチル）－ｐ－フェニレンジアミン、Ｎ－４－メチル－２－ペンチル－Ｎ’－フェニル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジアリール－ｐ－フェニレンジアミン、ヒンダードジアリール－ｐ－フェニレンジアミン、フェニルヘキシル－ｐ－フェニレンジアミン、フェニルオクチル－ｐ－フェニレンジアミンなどが挙げられる。なかでも、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニル－ｐ－フェニレンジアミンが好ましい。 Examples of phenylenediamine-based antioxidants include N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N, N'-diphenyl -P-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N, N'-bis (1-methylheptyl) -p -Phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N-4- Methyl-2-pentyl-N'-phenyl-p-phenylenediamine, N, N'-diaryl-p-phenylenediamine, hindered diaryl -p- phenylenediamine, phenyl hexyl -p- phenylenediamine, and the like phenyloctyl -p- phenylenediamine. Among them, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine is preferable.
キノン系老化防止剤としては、ベンゾキノン系、ヒドロキノン系、カテコール系、キノンジイミン系、キノメタン系、キノジメタン系老化防止剤などが挙げられ、なかでも、キノンジイミン系老化防止剤が好ましい。 Examples of the quinone anti-aging agent include benzoquinones, hydroquinones, catechols, quinone diimines, quinomethanes, quinodimethane anti-aging agents and the like. Among them, quinone diimine anti-aging agents are preferable.
キノンジイミン系老化防止剤としては、Ｎ－イソプロピル－Ｎ’－フェニル－ｐ－キノンジイミン、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニルキノンジイミン、Ｎ，Ｎ’－ジフェニル－ｐ－キノンジイミン、Ｎ－シクロヘキシル－Ｎ’－フェニル－ｐ－キノンジイミン、Ｎ－ｎヘキシル－Ｎ’－フェニル－ｐ－キノンジイミン、Ｎ，Ｎ’－ジオクチル－ｐ－キノンジイミンなどが挙げられる。なかでも、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニルキノンジイミン（６ＱＤＩ）が好ましい。 N-isopropyl-N'-phenyl-p-quinonediimine, N- (1,3-dimethylbutyl) -N'-phenylquinonediimine, N, N'-diphenyl-p-quinonediimine as a quinone diimine anti-aging agent And N-cyclohexyl-N'-phenyl-p-quinonediimine, Nn-hexyl-N'-phenyl-p-quinonediimine, N, N'-dioctyl-p-quinonediimine and the like. Among them, N- (1,3-dimethylbutyl) -N'-phenylquinone diimine (6QDI) is preferable.
フェニレンジアミン系老化防止剤及びキノン系老化防止剤の合計含有量は、ジエン系ゴム成分１００質量部に対して、１．５質量部以上、好ましくは２質量部以上である。１．５質量部未満であると、充分な耐オゾン性が得られないおそれがある。また、該含有量は、３質量部以下、好ましくは２．８質量部以下である。３質量部を超えると、変色（茶変色）する傾向がある。 The total content of the phenylenediamine based antioxidant and the quinone based antioxidant is 1.5 parts by mass or more, preferably 2 parts by mass or more, with respect to 100 parts by mass of the diene rubber component. If the amount is less than 1.5 parts by mass, sufficient ozone resistance may not be obtained. The content is 3 parts by mass or less, preferably 2.8 parts by mass or less. If it exceeds 3 parts by mass, it tends to discolor (brown).
本発明のゴム組成物はカーボンブラックを含むことが好ましい。これにより、補強効果、紫外線防止効果が得られ、本発明の効果が良好に得られる。 The rubber composition of the present invention preferably contains carbon black. Thereby, the reinforcing effect and the ultraviolet ray preventing effect can be obtained, and the effect of the present invention can be obtained well.
本発明のゴム組成物をトレッドに適用する場合、カーボンブラックの含有量は、ジエン系ゴム成分１００質量部に対して、好ましくは０．２～２０質量部、より好ましくは２～２０質量部である。上記範囲内であると、補強効果、紫外線防止効果が得られ、本発明の効果が良好に得られる。 When the rubber composition of the present invention is applied to a tread, the content of carbon black is preferably 0.2 to 20 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of a diene rubber component. is there. Within the above range, the reinforcing effect and the ultraviolet ray preventing effect can be obtained, and the effect of the present invention can be obtained well.
また、本発明のゴム組成物をサイドウォール及びクリンチエイペックスに適用する場合、カーボンブラックの含有量は、ジエン系ゴム成分１００質量部に対して、好ましくは１０～５０質量部である。上記範囲内であると、補強効果が得られ、本発明の効果が良好に得られる。 When the rubber composition of the present invention is applied to side walls and clinchapex, the content of carbon black is preferably 10 to 50 parts by mass with respect to 100 parts by mass of the diene rubber component. A reinforcement effect is acquired as it is in the said range, and the effect of this invention is acquired favorably.
本発明のゴム組成物はシリカを含むことが好ましい。これにより、良好な低燃費性が得られる。 The rubber composition of the present invention preferably contains silica. Thereby, good fuel economy can be obtained.
シリカとしては特に限定されず、例えば、乾式法シリカ（無水シリカ）、湿式法シリカ（含水シリカ）などを用いることができる。シラノール基が多いという理由から、湿式法シリカ（含水シリカ）が好ましい。 The silica is not particularly limited, and, for example, dry method silica (anhydrous silica), wet method silica (hydrous silica) and the like can be used. Wet method silica (hydrous silica) is preferable because it has many silanol groups.
本発明のゴム組成物をトレッドに適用する場合、シリカの含有量は、ジエン系ゴム成分１００質量部に対して、好ましくは２０質量部以上、より好ましくは６０質量部以上である。該含有量は、好ましくは１２０質量部以下、より好ましくは８０質量部以下である。該含有量が上記範囲内であると、良好な低燃費性、加工性が得られる。 When the rubber composition of the present invention is applied to a tread, the content of silica is preferably 20 parts by mass or more, more preferably 60 parts by mass or more, with respect to 100 parts by mass of a diene rubber component. The content is preferably 120 parts by mass or less, more preferably 80 parts by mass or less. When the content is in the above range, good fuel economy and processability can be obtained.
本発明のゴム組成物をサイドウォール及びクリンチエイペックスに適用する場合、シリカの含有量の下限は特に限定されないが、ジエン系ゴム成分１００質量部に対して、好ましくは０．１質量部以上である。該含有量は、好ましくは３０質量部以下、より好ましくは２０質量部以下である。該含有量が上記範囲内であると、良好な破断伸び、低燃費性、加工性が得られる。
なお、本発明では、シリカを使用する場合、シランカップリング剤を使用することが好ましい。 When the rubber composition of the present invention is applied to the side wall and clinchapex, the lower limit of the content of silica is not particularly limited, but preferably 0.1 parts by mass or more with respect to 100 parts by mass of the diene rubber component. is there. The content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less. When the content is in the above range, good elongation at break, low fuel consumption and processability can be obtained.
In the present invention, when silica is used, it is preferable to use a silane coupling agent.
ＴＧＣなどの点から、本発明のゴム組成物は、特にシリカ配合ゴム組成物として好適に使用できるが、例えば、該ゴム組成物をトレッドに適用する場合、シリカ及びカーボンブラックの合計１００質量％中のシリカの含有率は、好ましくは６０質量％以上、より好ましくは６５質量％以上、更に好ましくは７０質量％以上である。なお、上限は特に限定されず、１００質量％でもよい。 Although the rubber composition of the present invention can be suitably used particularly as a silica-containing rubber composition in terms of TGC and the like, for example, when the rubber composition is applied to a tread, 100% by mass in total of silica and carbon black The content ratio of silica is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass or more. In addition, an upper limit is not specifically limited, 100 mass% may be sufficient.
また、本発明のゴム組成物をサイドウォール及びクリンチエイペックスに適用する場合、シリカ及びカーボンブラックの合計１００質量％中のシリカの含有率は、好ましくは５質量％以上、より好ましくは１０質量％以上である。上限は特に限定されないが、好ましくは４０質量％以下、より好ましくは２０質量％以下である。 When the rubber composition of the present invention is applied to side walls and clinchapex, the content of silica in the total 100% by mass of silica and carbon black is preferably 5% by mass or more, more preferably 10% by mass. It is above. The upper limit is not particularly limited, but is preferably 40% by mass or less, more preferably 20% by mass or less.
本発明ではプロセスオイルを配合してもよい。プロセスオイルとしては、例えば、パラフィン系プロセスオイル、アロマ系プロセスオイル、ナフテン系プロセスオイルなどを用いることができる。 In the present invention, a process oil may be blended. As the process oil, for example, paraffin-based process oil, aroma-based process oil, naphthene-based process oil and the like can be used.
プロセスオイルの含有量は、ジエン系ゴム成分１００質量部に対して、好ましくは１５質量部以下である。１５質量部を超えると、変色し易い傾向がある。該含有量の下限は特に限定されないが、好ましくは２質量部以上、より好ましくは５質量部以上である。２質量部未満では、加工性が悪化するおそれがある。 The content of the process oil is preferably 15 parts by mass or less with respect to 100 parts by mass of the diene rubber component. If it exceeds 15 parts by mass, it tends to be discolored. The lower limit of the content is not particularly limited, but is preferably 2 parts by mass or more, more preferably 5 parts by mass or more. If the amount is less than 2 parts by mass, processability may be degraded.
本発明のゴム組成物には、前記成分以外にも、ゴム組成物の製造に一般に使用される配合剤、例えば、Ｃ５系石油樹脂、クマロンインデン樹脂、α－メチルスチレン及び／又はスチレンを重合して得られる芳香族ビニル重合体、ステアリン酸、酸化亜鉛、加硫剤、加硫促進剤などを適宜配合できる。 In the rubber composition of the present invention, in addition to the above components, compounding agents generally used in the production of rubber compositions, such as C5 petroleum resin, coumarone indene resin, α-methylstyrene and / or styrene are polymerized. An aromatic vinyl polymer, stearic acid, zinc oxide, a vulcanizing agent, a vulcanization accelerator and the like obtained by
本発明のゴム組成物の製造方法としては、公知の方法を用いることができ、例えば、前記各成分をオープンロール、バンバリーミキサーなどのゴム混練装置を用いて混練し、その後加硫する方法などにより製造できる。 As a method for producing the rubber composition of the present invention, a known method can be used. For example, the above-mentioned components are kneaded using a rubber kneading apparatus such as an open roll or a Banbury mixer and then vulcanized. It can be manufactured.
本発明のゴム組成物は、タイヤの外層部材であれば特に制限なく使用できるが、前述のとおり、トレッド、サイドウォール、ウイング、クリンチエイペックスに好適に使用できる。 The rubber composition of the present invention can be used without particular limitation as long as it is an outer layer member of a tire, but as described above, can be suitably used for a tread, a sidewall, a wing, and a clinch apex.
本発明の空気入りタイヤは、上記ゴム組成物を用いて通常の方法によって製造できる。すなわち、上記ゴム組成物を未加硫の段階でタイヤの各外層部材（トレッド、サイドウォール、ウイング、クリンチエイペックスなど）の形状に合わせて押し出し加工し、タイヤ成形機上にて通常の方法にて成形し、他のタイヤ部材とともに貼り合わせ、未加硫タイヤを形成できる。この未加硫タイヤを加硫機中で加熱加圧してタイヤを製造できる。 The pneumatic tire of the present invention can be produced by the usual method using the above rubber composition. That is, the above rubber composition is extruded at the unvulcanized stage according to the shape of each outer layer member (tread, sidewall, wing, clinchapex, etc.) of the tire, and the usual method is carried out on the tire molding machine It can be molded and bonded together with other tire members to form an unvulcanized tire. The unvulcanized tire can be heated and pressurized in a vulcanizer to produce a tire.
実施例に基づいて、本発明を具体的に説明するが、本発明はこれらのみに限定されるものではない。 Although the present invention will be specifically described based on examples, the present invention is not limited to these.
以下、実施例及び比較例で用いた各種薬品について説明する。
ハイシスＢＲ（ＣＢ２５）：ランクセス社製のＢＵＮＡ－ＣＢ２５（Ｎｄ系触媒を用いて合成したＢＲ、シス含量：９６％）
変性ＳＳＢＲ（ＨＰＲ３５５）：ＪＳＲ（株）製のＨＰＲ３５５（変性Ｓ－ＳＢＲ、スチレン含量：２７質量％、ビニル含量５５質量％）
ＴＳＲ２０：ＮＲ（ＴＳＲ２０）
カーボンブラック（Ｎ２２０）：キャボットジャパン（株）製のショウブラックＮ２２０（Ｎ２ＳＡ：１２０ｍ２／ｇ、ＤＢＰ吸油量：１１５ｍｌ／１００ｇ）
カーボンブラック（Ｎ５５０）：キャボットジャパン（株）製のショウブラックＮ５５０（Ｎ２ＳＡ：４２ｍ２／ｇ、ＤＢＰ吸油量：１１５ｍｌ／１００ｇ）
シリカ：エボニックデグッサ社製のウルトラシルＶＮ３（Ｎ２ＳＡ：１７５ｍ２／ｇ）
クマロンインデン樹脂：Ｒｕｔｇｅｒｓ　Ｃｈｅｍｉｃａｌｓ社製のＮＯＶＡＲＥＳ　Ｃ１０（クマロンインデン樹脂、軟化点：５～１５℃）
Ｃ５系石油樹脂：丸善石油化学（株）製のマルカレッツＴ－１００ＡＳ（Ｃ５系石油樹脂：ナフサ分解によって得られるＣ５留分中のオレフィン、ジオレフィン類を主原料とする脂肪族系石油樹脂）（軟化点：１０２℃）
芳香族ビニル重合体（ＳＡ８５）：Ａｒｉｚｏｎａ　ｃｈｅｍｉｃａｌ社製のＳＹＬＶＡＲＥＳ　ＳＡ８５（α－メチルスチレンとスチレンとの共重合体、軟化点：８５℃、Ｍｗ：１０００）
プロセスオイル：Ｈ＆Ｒ社製のｖｉｖａｔｅｃ５００（ＴＤＡＥ）
ステアリン酸：日油（株）製のステアリン酸「椿」
亜鉛華：東邦亜鉛（株）製の銀嶺Ｒ
シランカップリング剤：エボニックデグッサ社製のＳｉ７５（ビス（３－トリエトキシシリルプロピル）ジスルフィド）
５％オイル含有粉末硫黄：細井化学工業（株）製のＨＫ－２００－５（オイル分５％）
１０％オイル含有不溶性硫黄：日本乾溜工業（株）製のセイミサルファー（２硫化炭素による不溶分６０％、オイル分１０％）
加硫促進剤（ＴＢＢＳ）：大内新興化学工業（株）製のノクセラーＮＳ（Ｎ－ｔｅｒｔ－ブチル－２－ベンゾチアゾリルスルフェンアミド）
加硫促進剤（ＤＰＧ）：大内新興化学工業（株）製のノクセラーＤ（Ｎ，Ｎ’－ジフェニルグアニジン）
ワックス１：試作品１（ノルマルアルカン分：平均８５質量％）
ワックス２：試作品２（ノルマルアルカン分：平均８７質量％）
ワックス３：試作品３（ノルマルアルカン分：平均８１質量％）
ワックス４：ソルビタンモノステアレート（Ｌｏｎｚａ　Ｃｈｅｍｉｃａｌ　Ｃｏｍｐａｎｙ製のＧｌｙｃｏｍｕｌ　ＳＴＭ）
６ＰＰＤ：住友化学（株）製のアンチゲン６Ｃ（Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニル－ｐ－フェニレンジアミン）
６ＱＤＩ：フレキシス社製の６ＱＤＩ（Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニルキノンジイミン）
ＴＭＱ：大内新興化学工業（株）製ノクラック２２４（２，２，４－トリメチル－１，２－ジヒドロキノリン重合体） Hereinafter, various medicines used by an example and a comparative example are explained.
High cis BR (CB25): BUNA-CB25 manufactured by LANXESS (BR synthesized using Nd catalyst, cis content: 96%)
Modified SSBR (HPR 355): HPR 355 (modified S-SBR, styrene content: 27% by mass, vinyl content 55% by mass) manufactured by JSR Corporation
TSR20: NR (TSR20)
Carbon black (N220): Show black N220 (N 2 SA: 120 m 2 / g, DBP oil absorption: 115 ml / 100 g) manufactured by Cabot Japan Ltd.
Carbon black (N 550): Show black N 550 (N 2 SA: 42 m 2 / g, DBP oil absorption: 115 ml / 100 g) manufactured by Cabot Japan Ltd.
Silica: Ultrasil VN3 (N 2 SA: 175 m 2 / g) manufactured by Evonik Degussa
Coumarone-indene resin: NOVARES C10 (Coumarone-indene resin, softening point: 5 to 15 ° C.) manufactured by Rutgers Chemicals
C5 petroleum resin: Marcalez T-100 AS (C5 petroleum resin: an aliphatic petroleum resin whose main raw material is an olefin or diolefin in the C5 fraction obtained by naphtha decomposition) manufactured by Maruzen Petrochemical Co., Ltd. Softening point: 102 ° C)
Aromatic vinyl polymer (SA 85): SYLVARES SA 85 (copolymer of α-methylstyrene and styrene, softening point: 85 ° C., Mw: 1000) manufactured by Arizona chemical
Process oil: H & R vivatec 500 (TDAE)
Stearic acid: Stearic acid "Nuka" manufactured by NOF Corporation
Zinc flower: Ginkgo R manufactured by Toho Zinc Co., Ltd.
Silane coupling agent: Si75 (bis (3-triethoxysilylpropyl) disulfide) manufactured by Evonik Degussa
Powdered sulfur containing 5% oil: HK-200-5 (5% oil content) manufactured by Hosoi Chemical Industry Co., Ltd.
10% oil-containing insoluble sulfur: Seimi Sulfur (60% insoluble in carbon disulfide, 10% oil) manufactured by Nippon Denryo Kogyo Co., Ltd.
Vulcanization accelerator (TBBS): Noccellar NS (N-tert-butyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Emerging Chemical Industry Co., Ltd.
Vulcanization accelerator (DPG): Noxceler D (N, N'-diphenyl guanidine) manufactured by Ouchi Emerging Chemical Industry Co., Ltd.
Wax 1: Prototype 1 (normal alkane content: 85% by mass on average)
Wax 2: Prototype 2 (normal alkane content: average 87% by mass)
Wax 3: Prototype 3 (normal alkane content: 81% by mass on average)
Wax 4: sorbitan monostearate (Lonza Chemical Company manufactured Glycomul S TM)
6PPD: Antigen 6C (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
6QDI: 6QDI (N- (1,3-dimethylbutyl) -N'-phenylquinonediimine) manufactured by Flexis.
TMQ: Nouchi 224 manufactured by Ouchi Emerging Chemical Industry Co., Ltd. (2,2,4-trimethyl-1,2-dihydroquinoline polymer)
ワックスの炭素数分布は、以下の方法により測定した。結果を図１及び表４に示す。 The carbon number distribution of the wax was measured by the following method. The results are shown in FIG. 1 and Table 4.
測定装置としてキャピラリーＧＣ、カラムとしてアルミニウムコーティングされたキャピラリーカラムを用い、キャリアガスヘリウム、流量４ｍｌ／分、カラム温度１８０～３９０℃、昇温速度１５℃／分の条件にて測定した。 Using a capillary GC as a measurement apparatus and a capillary column coated with aluminum as a column, measurement was carried out under the conditions of carrier gas helium, flow rate 4 ml / min, column temperature 180 to 390 ° C., temperature rise rate 15 ° C./min.
（実施例及び比較例）
表１～３の上段に示す配合処方にしたがい、（株）神戸製鋼所製１．７Ｌバンバリーミキサーを用いて、硫黄及び加硫促進剤以外の薬品を混練りした。次に、オープンロールを用いて、得られた混練り物に硫黄及び加硫促進剤を添加して練り込み、未加硫ゴム組成物を得た。
得られた未加硫ゴム組成物を用いて、トレッド部、サイドウォール部及びクリンチエイペックス部となる部材を作製して、生タイヤを製造し、１７０℃で加硫して試験用タイヤ（２０５／６５Ｒ１５）を得た。得られた試験用タイヤの性能を以下の試験により評価した。 (Example and Comparative Example)
According to the formulation shown in the upper part of Tables 1 to 3, chemicals other than sulfur and a vulcanization accelerator were kneaded using a 1.7 L Banbury mixer manufactured by Kobe Steel, Ltd. Next, using an open roll, sulfur and a vulcanization accelerator were added to the obtained kneaded product and kneaded to obtain an unvulcanized rubber composition.
Using the obtained unvulcanized rubber composition, members to be the tread portion, the sidewall portion and the clinch apex are produced to produce a green tire, which is vulcanized at 170 ° C. to test a tire (205 / 65R15) was obtained. The performance of the obtained test tire was evaluated by the following test.
（クラック試験）
高温地域は中近東アラブ首長国連邦で約１年間（夏を含む）、亜寒冷地域は北海道で約１年間（冬を含む）ロードテストを行ない、発生したクラックの度合いを、以下の基準にしたがって評価した。数字が大きいほど、耐クラック性能に優れている。 (Crack test)
The high temperature area is subjected to road tests in the Middle East and the UAE for about 1 year (including summer), and the sub cold area is about 1 year (including winter) in Hokkaido. evaluated. The larger the number, the better the crack resistance.
（基準）
１：３ｍｍ以上の亀裂または切断が見られる。
２：１ｍｍ以上３ｍｍ未満の深い亀裂が見られる。
３：１ｍｍ未満の深くて比較的大きな亀裂が見られる。
４：肉眼では、やっとのことで亀裂または切断が確認できる。
５：肉眼では確認できないが、拡大鏡（１０倍）では亀裂または切断が確認できる。 (Standard)
Cracks or cuts of 1: 3 mm or more are observed.
A deep crack of 2: 1 mm or more and less than 3 mm is observed.
Deep and relatively large cracks of less than 3: 1 mm can be seen.
4: With the naked eye, cracking or cutting can be confirmed at last.
5: Although it can not be confirmed with the naked eye, cracks or cuts can be confirmed with a magnifying glass (10 times).
（変色試験）
屋外：茶変色評価
神戸にて、タイヤを屋外の日の当たる場所に６カ月間（冬～夏）放置し、色差度計を用いて、ａ*、ｂ*を測定し、その値により、以下の基準にしたがって５段階に分けて評価した。数字が大きいほど、茶変色の度合いが小さい。 (Color change test)
Outdoor: Tea discoloration evaluation In Kobe, leave the tire in an outdoor sunny place for 6 months (winter to summer), use a color difference meter to measure a * and b *. The evaluation was divided into five stages according to the criteria of The higher the number, the smaller the degree of browning.
（基準）
１：－（ａ*＋ｂ*）×１０≦－３０
２：－３０＜－（ａ*＋ｂ*）×１０≦－２０
３：－２０＜－（ａ*＋ｂ*）×１０≦－１０
４：－１０＜－（ａ*＋ｂ*）×１０≦０
５：－（ａ*＋ｂ*）×１０＞０
屋内：白変色評価
神戸にて、タイヤを屋内の倉庫に６カ月間（冬～夏）放置し、色差度計を用いて、Ｌ*を測定し、その値により、以下の基準にしたがって５段階に分けて評価した。数字が大きいほど、白変色の度合いが小さい。 (Standard)
1:-(a * + b * ) x 10 <-30
2: -30 <-(a * + b * ) x 10 <-20
3: -20 <-(a * + b * ) x 10 <-10
4:-10 <-(a * + b * ) x 10 <0
5:-(a * + b * ) x 10> 0
Indoor: White discoloration evaluation In Kobe, the tire is left in an indoor warehouse for 6 months (winter to summer), L * is measured using a colorimeter, and according to the value, it is five steps according to the following criteria It divided into and evaluated. The higher the number, the smaller the degree of white discoloration.
（基準）
１：１００－Ｌ*≦６０
２：６０＜１００－Ｌ*≦６５
３：６５＜１００－Ｌ*≦７０
４：７０＜１００－Ｌ*≦７５
５：１００－Ｌ*＞７５ (Standard)
1: 100-L * ≦ 60
2: 60 <100-L * ≦ 65
3: 65 <100-L * ≦ 70
4: 70 <100-L * ≦ 75
5: 100-L * > 75
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
炭素数２０～３２の各ノルマルアルカンと、フェニレンジアミン系老化防止剤及び／又はキノン系老化防止剤とをそれぞれ特定量配合した実施例では、広い温度域で優れた耐オゾン性が得られた。また、変色を良好に抑制できた。
特に、フェニレンジアミン系老化防止剤及びキノン系老化防止剤を多量に含む比較例５～８、１０、１４では、茶変色してしまった。なお、これら老化防止剤の配合量を減量すると耐オゾン性が低下する傾向があった（実施例９～１１、２２）。 In the examples in which specific amounts of each normal alkane having a carbon number of 20 to 32 and a phenylenediamine-based antioxidant and / or a quinone-based antioxidant were blended, excellent ozone resistance was obtained in a wide temperature range. In addition, the color change could be suppressed well.
In particular, in Comparative Examples 5 to 8 and 10 and 14 containing a large amount of phenylenediamine based antioxidant and quinone based antioxidant, brown discoloration occurred. The ozone resistance tended to decrease when the blending amount of these antioxidants was decreased (Examples 9 to 11 and 22).

Claims (6)

  1. 炭素数２０～３２の各ノルマルアルカンと、フェニレンジアミン系老化防止剤及び／又はキノン系老化防止剤とを含み、
    ジエン系ゴム成分１００質量部に対して、前記炭素数２０～３２の各ノルマルアルカンの合計含有量が０．７～３．５質量部、前記フェニレンジアミン系老化防止剤及び前記キノン系老化防止剤の合計含有量が１．５～３質量部であるタイヤ外層用ゴム組成物。     And each alkane having a carbon number of 20 to 32 and a phenylenediamine antidegradant and / or a quinone antidegradant,
    The total content of each normal alkane having a carbon number of 20 to 32 is 0.7 to 3.5 parts by mass with respect to 100 parts by mass of a diene rubber component, the phenylenediamine based antioxidant and the quinone based antioxidant The rubber composition for the outer layer of a tire, wherein the total content thereof is 1.5 to 3 parts by mass.
  2. 前記ジエン系ゴム成分１００質量部に対して、炭素数４８以上のノルマルアルカンを０．１質量部以下含む請求項１記載のタイヤ外層用ゴム組成物。 The rubber composition for a tire outer layer according to claim 1, containing 0.1 part by mass or less of a normal alkane having 48 or more carbon atoms with respect to 100 parts by mass of the diene rubber component.
  3. 前記ジエン系ゴム成分１００質量部に対して、前記炭素数２０～３２の各ノルマルアルカンの合計含有量が０．９～２．４質量部である請求項１又は２記載のタイヤ外層用ゴム組成物。 The rubber composition for the tire outer layer according to claim 1 or 2, wherein the total content of each normal alkane having 20 to 32 carbon atoms is 0.9 to 2.4 parts by mass with respect to 100 parts by mass of the diene rubber component. object.
  4. 前記ジエン系ゴム成分１００質量部に対して、プロセスオイルを１５質量部以下含む請求項１～３のいずれかに記載のタイヤ外層用ゴム組成物。 The tire outer layer rubber composition according to any one of claims 1 to 3, which contains 15 parts by mass or less of a process oil with respect to 100 parts by mass of the diene rubber component.
  5. トレッド、サイドウォール、ウイング及びクリンチエイペックスからなる群より選択される少なくとも１種として使用される請求項１～４のいずれかに記載のタイヤ外層用ゴム組成物。 The tire outer layer rubber composition according to any one of claims 1 to 4, which is used as at least one selected from the group consisting of a tread, a sidewall, a wing and a clinch apex.
  6. 請求項１～５のいずれかに記載のゴム組成物を用いて作製した空気入りタイヤ。 A pneumatic tire produced using the rubber composition according to any one of claims 1 to 5.
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JP2013082884A (en) 2013-05-09
BR112014007054A2 (en) 2017-03-28

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