WO2015145513A1 - Rubber composition and tyre - Google Patents

Rubber composition and tyre Download PDF

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Publication number
WO2015145513A1
WO2015145513A1 PCT/JP2014/006398 JP2014006398W WO2015145513A1 WO 2015145513 A1 WO2015145513 A1 WO 2015145513A1 JP 2014006398 W JP2014006398 W JP 2014006398W WO 2015145513 A1 WO2015145513 A1 WO 2015145513A1
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Prior art keywords
rubber
rubber composition
diene
tire
tan
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PCT/JP2014/006398
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French (fr)
Japanese (ja)
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貴裕 三浦
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株式会社ブリヂストン
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Publication of WO2015145513A1 publication Critical patent/WO2015145513A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • 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
    • 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
    • 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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • 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

Definitions

  • the present invention relates to a rubber composition and a tire.
  • the tire particularly its sidewall portion, is required to have both high resistance to repeated bending fatigue (high bending fatigue resistance) and high weather resistance such as ozone resistance due to its usage.
  • high bending fatigue resistance high bending fatigue resistance
  • high weather resistance such as ozone resistance due to its usage.
  • a rubber component of a rubber composition for a tire sidewall a blend rubber appropriately selected from natural rubber, rubber derived from conjugated dienes such as butadiene rubber and styrene-butadiene rubber, and the like is used. Bending fatigue resistance has been improved by use, and a method of improving weather resistance has been taken by adding a large amount of a compounding agent such as an amine-based antioxidant or a paraffinic wax to the rubber component.
  • this method has a problem that such a compounding agent blooms on the surface of the tire, and when it is exposed to ultraviolet rays, this color changes to brown and the appearance of the tire can be significantly impaired.
  • Patent Document 1 a rubber composition obtained by blending a specific ethylene-propylene-diene copolymer (EPDM) having a high ethylene content is used as the outermost layer of the sidewall portion of the tire, thereby providing high bending resistance.
  • EPDM ethylene-propylene-diene copolymer
  • JP-A-4-43106 Japanese Patent Application Laid-Open No. 2004-224952 JP 2005-272719 A
  • an object of the present invention is to provide a rubber composition having high weather resistance and crack growth resistance. Another object of the present invention is to provide a tire excellent in weather resistance and crack growth resistance using such a rubber composition.
  • the present inventor has a rubber composition having a specific viscoelastic property on condition that a specific material is blended, and has high weather resistance and crack growth resistance. As a result, the present invention has been completed.
  • the rubber composition of the present invention comprises a diene rubber, a non-diene rubber, and a reinforcing filler, and the ratio of the diene rubber in the rubber component is 40% by mass or more.
  • a composition comprising: In the plot created by taking the temperature (° C.) of the rubber composition on the horizontal axis and the loss tangent (tan ⁇ ) of the rubber composition on the vertical axis, The tan ⁇ peak appears at ⁇ 43 to ⁇ 37 ° C., The peak value of tan ⁇ is 0.90 to 1.20, and The slope (° C. ⁇ 1 ) of the line segment connecting the value of tan ⁇ at ⁇ 40 ° C. and the value of tan ⁇ at ⁇ 20 ° C. is ⁇ 0.0200 to ⁇ 0.0175.
  • Such a rubber composition has high weather resistance and crack growth resistance.
  • the tire according to the present invention is characterized in that the rubber composition is applied to at least one of the tire members, and at least one of the tire members preferably includes a sidewall.
  • Such a tire is excellent in weather resistance and crack growth resistance because the rubber composition is used.
  • the tire of the present invention preferably has a paint layer formed on the outer surface of a tire member to which the rubber composition is applied.
  • a tire is excellent in weather resistance and crack growth resistance, and can be used while maintaining its appearance for a longer period of time.
  • a rubber composition having high weather resistance and crack growth resistance can be provided.
  • the tire excellent in a weather resistance and crack growth resistance can be provided by using this rubber composition for any tire member.
  • the rubber composition of the present invention uses a diene rubber, a non-diene rubber, and a reinforcing filler as compounding materials.
  • a diene rubber is used as a rubber component.
  • the “diene rubber” is defined as a rubber other than the non-diene rubber described later, and specifically, a diene monomer in a monomer unit of natural rubber and synthetic rubber. It is defined as rubber having a unit ratio of more than 5 mol%.
  • the diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and the like.
  • examples of the non-diene monomer (non-diene monomer) constituting the synthetic rubber include ethylene, propylene, and isobutene.
  • diene rubber examples include natural rubber (NR) and diene synthetic rubber.
  • diene synthetic rubber examples include butadiene rubber (BR), styrene-butadiene rubber (SBR), isoprene rubber (IR), chloroprene rubber (CR) and the like, and those obtained by appropriately modifying these rubbers are also included in the “diene rubber”.
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • IR isoprene rubber
  • CR chloroprene rubber
  • the said diene rubber may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the ratio of the diene rubber in the rubber component is 40% by mass or more. This is because the crack growth resistance derived from the diene rubber is sufficiently secured by setting the ratio of the diene rubber in the rubber component to 40% by mass or more.
  • Non-diene rubber In the rubber composition of the present invention, a non-diene rubber is used as a rubber component.
  • “non-diene rubber” is defined as a rubber having a proportion of a unit derived from a diene monomer in a monomer unit of a synthetic rubber of 5 mol% or less.
  • Examples of the non-diene rubber include ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), butyl rubber (IIR), chlorinated butyl rubber (Cl-IIR), brominated butyl rubber (Br-IIR) and the like. It is done.
  • the rubber composition it is preferable to use ethylene-propylene-diene rubber and / or butyl rubber, more preferably to use ethylene-propylene-diene rubber and butyl rubber at the same time. From the viewpoint of property, it is preferable that the proportion of the unit derived from the diene monomer in the constituent monomer units is 0.1 mol% or more.
  • gum may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the rubber composition of the present invention is conditioned on the use of a reinforcing filler.
  • the reinforcing filler include carbon black and silica.
  • the nitrogen adsorption specific surface area (measured in accordance with N 2 SA, JIS K 6217-2: 2001) of the carbon black is not particularly limited and may be appropriately selected depending on the intended purpose.
  • 10 to 110 m 2 / g is preferable, and 20 to 90 m 2 / g is more preferable from the viewpoint of achieving both crack growth resistance and workability.
  • N 2 SA nitrogen adsorption specific surface area
  • silica examples include wet silica, dry silica, and the like. These may be used alone or in combination of two or more. Further, for example, carbon black and silica may be used in combination.
  • the total amount of the reinforcing filler is preferably 15 to 80 parts by mass, more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the rubber component.
  • the total blending amount of the reinforcing filler is 20 to 60 parts by mass, satisfactory workability can be maintained while sufficiently improving crack growth resistance.
  • components other than those described above can be used as necessary.
  • Such components include crosslinking agents (vulcanizing agents), crosslinking accelerators (vulcanization accelerators), crosslinking assistants (vulcanization assistants), vulcanization acceleration assistants (vulcanization accelerators), colorants, Examples include flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, scorch inhibitors, UV inhibitors, antistatic agents, anti-coloring agents, and other compounding agents. can do.
  • components suitable for obtaining the rubber physical properties (viscoelastic properties) of the rubber composition of the present invention will be described later.
  • the rubber composition of the present invention has specific viscoelastic properties. Hereinafter, the specific viscoelastic characteristics will be described.
  • the rubber composition of the present invention has a tan ⁇ peak of ⁇ 43 to ⁇ 37 ° C. in a plot prepared by taking the temperature (° C.) of the rubber composition on the horizontal axis and the loss tangent (tan ⁇ ) of the rubber composition on the vertical axis. It needs to appear in If the temperature at which the tan ⁇ peak appears is less than ⁇ 43 ° C., sufficient weather resistance may not be obtained, whereas if it is higher than ⁇ 37 ° C., sufficient crack growth resistance may not be obtained. There is.
  • the tan ⁇ of the rubber composition may vary with the glass transition temperature of the polymer used (T g), as a method of adjusting the temperature at which the peak of the tan ⁇ appears in, changing the type of rubber component used appropriately Is mentioned.
  • the rubber composition of the present invention requires that the tan ⁇ peak value be 0.90 to 1.20. If the tan ⁇ peak value is less than 0.90, sufficient crack growth resistance may not be obtained, whereas if it exceeds 1.20, sufficient weather resistance may not be obtained.
  • a method of adjusting (increasing) the peak value of tan ⁇ there is a method of reducing the degree of distribution of the reinforcing filler to the diene rubber used.
  • the slope (° C. ⁇ 1 ) of the line segment connecting the value of tan ⁇ at ⁇ 40 ° C. and the value of tan ⁇ at ⁇ 20 ° C. is ⁇ 0.0200 to ⁇ 0.0175. In other words, it is preferably -0.0195 to -0.0180. If the inclination is less than ⁇ 0.0200, sufficient weather resistance may not be obtained, while if it exceeds ⁇ 0.0175, sufficient crack growth resistance may not be obtained.
  • tan ⁇ is measured using a spectrometer, rheometer, or the like.
  • the diene rubber is natural rubber and / or butadiene rubber, and the diene in the rubber component is used.
  • the ratio of the base rubber is 20 to 90% by mass
  • the ratio of the natural rubber in the rubber component is 10 to 70% by mass
  • the ratio of the butadiene rubber in the rubber component is 10 to 40% by mass.
  • the amount of the reinforcing filler compounded in the primary step is 15 to 80 parts by mass with respect to 100 parts by mass of the rubber component. It is preferably 20 to 65 parts by mass.
  • the amount of the reinforcing filler blended in the primary process is 15 to 80 parts by mass with respect to 100 parts by mass of the rubber component, so that the reinforcing filler is distributed in the non-diene rubber without deteriorating workability. As a result, the crack growth resistance can be sufficiently improved.
  • A is an aromatic ring, a substituted or unsubstituted hydantoin ring, or a saturated or unsaturated linear hydrocarbon group having 1 to 18 carbon atoms, a is 0 or 1;
  • B is an aromatic group, X is a hydroxy group or an amino group, and Y is a pyridyl group or a hydrazino group].
  • Such a compound reacts with the main chain of the diene rubber and has a high affinity with carbon black, so that the effect of the diene rubber entering the non-diene rubber is enhanced, and the non-diene rubber and the diene rubber are By mixing more uniformly, the viscoelastic properties of the rubber composition can be suitably optimized.
  • Such a compound is preferably added in the step (2).
  • Examples of the compound represented by the formula (I) include phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, succinic acid dihydrazide, adipic acid dihydrazide, azelain. And acid dihydrazide, sebacic acid dihydrazide, eicosanedioic acid dihydrazide, 7,11-octadecadien-1,18-dicarbohydrazide, oxalic hydrazide and the like.
  • Examples of the compound represented by the formula (II) include anthraniloyl hydrazine, salicylic acid hydrazide, 4-hydroxybenzoic acid hydrazide, 2-hydroxy-3-naphthoic acid hydrazide, 3-hydroxy-N ′-(1,3- And dimethylbutylidene) -2-naphthoic acid hydrazide.
  • Examples of the compound represented by the formula (III) include isonicotinic acid hydrazide and carbodihydrazide.
  • isophthalic acid dihydrazide 2-hydroxy-3-naphthoic acid hydrazide, or 3-hydroxy-N ′-(1,3-dimethylbutylidene) -2-naphthoic acid
  • hydrazide it is preferred to use hydrazide.
  • the said compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount is preferably 0.1 to 5.0 parts by weight, and preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the rubber component. More preferred.
  • the compounding amount of the compound is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the rubber component, the non-diene rubber and the diene rubber are more uniformly mixed.
  • a crosslinking agent vulcanizing agent
  • the crosslinking accelerator vulcanization accelerator
  • the crosslinking aid vulcanizing aid
  • a known kneading apparatus such as a twin screw extruder, a roll, or an intensive mixer can be used.
  • the conditions are not particularly limited.
  • the secondary step the conditions are not particularly limited, but it is preferably performed at a maximum temperature of 145 ° C. or lower.
  • a crosslinking agent vulcanizing agent
  • a crosslinking accelerator vulcanization accelerator
  • a crosslinking aid vulcanization aid
  • / or a crosslinking acceleration aid vulcanization acceleration aid
  • the temperature is preferably 110 ° C. or lower.
  • the tire of the present invention is not particularly limited as long as the rubber composition of the present invention is applied to at least one of the tire members, and can be produced according to a conventional method.
  • the applicable tire member is not particularly limited and can be appropriately selected depending on the purpose.For example, a tread, a base tread, a sidewall, a side reinforcing rubber, a bead filler, and the like can be given. It is preferable to apply the rubber composition of the present invention to at least a sidewall exposed to repeated bending fatigue.
  • a pneumatic tire particularly a pneumatic tire for passenger cars is suitable, and since the rubber composition of the present invention is used, it is excellent in weather resistance and crack growth resistance.
  • the tire of the present invention preferably has a paint layer formed on the outer surface of a tire member to which the rubber composition is applied.
  • a tire is excellent in weather resistance and crack growth resistance regardless of the presence or absence of a compounding agent such as an amine-based anti-aging agent or paraffin-based wax, and thus can be used while maintaining its appearance for a longer period of time.
  • a coating material used for formation of a coating layer A well-known coating material can be selected according to the objective.
  • ⁇ Viscoelastic properties> A test piece of a rubber composition having a diameter of 6 mm and a thickness of 5 mm was prepared, and loss tangent (tan ⁇ ) in a temperature range of ⁇ 60 to 25 ° C. was measured using “ARES-G2 rheometer” manufactured by TA Instruments Japan. The measurement was performed at a temperature decrease rate of ⁇ 3 ° C./min. At this time, the measurement conditions were an initial load of 70 g, a dynamic strain of 0.1%, and a frequency of 0.1 Hz. From this measurement result, the temperature and tan ⁇ at which the value of tan ⁇ peaks are obtained, and the slope of the line segment connecting the tan ⁇ value at ⁇ 40 ° C. and the tan ⁇ value at ⁇ 20 ° C. (° C. ⁇ 1 ). Asked.
  • ⁇ Bending fatigue resistance> A test piece of a rubber composition having a length of 125 mm, a width of 25 mm, and a thickness of 5.5 mm was prepared, and bending was repeated at room temperature in accordance with JIS-K6260 “Bending crack generation test”. Then, the number of bendings until a crack of 2 mm or more occurred was measured. The number of bendings was indexed with the value of Comparative Example 1 being 100. The higher the index, the better the bending fatigue resistance.
  • ⁇ Weather resistance> A test piece of rubber composition having a length of 100 mm, a width of 10 mm, and a thickness of 2 mm is held for 96 hours in an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.) with an ozone concentration of 30 ppm and 40 ° C., and the rubber after holding The appearance of the composition was visually observed. In this appearance, the number of generated ozone cracks was measured. The reciprocal of the number of ozone cracks was indexed with the value of Comparative Example 1 being 100. It shows that it is excellent in a weather resistance, so that an index
  • the rubber compositions of the examples of the present invention having the above-mentioned specific materials and specific viscoelastic properties have high weather resistance and crack growth resistance, It turns out that it is excellent also in bending fatigue property and fracture resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Mechanical Engineering (AREA)
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Abstract

Provided is a rubber composition having high weather resistance and crack growth resistance. The rubber composition, in which a diene based rubber, a non-diene based rubber, and a reinforcing filler are combined, and in which the ratio of the diene based rubber in the rubber components is 40 mass% or more, is characterised in that in a plot created by taking the temperature (°C) of the rubber composition on the x-axis and the loss tangent (tanδ) of the rubber composition on the y-axis, the tanδ peak appears in the range of -43 to -37°C, the tanδ peak value is in the range of 0.90 to 1.20, and the incline (°C-1) of a line segment joining the tanδ value at -40°C and the tanδ value at -20°C is in the range of -0.0200 to -0.0175.

Description

ゴム組成物及びタイヤRubber composition and tire 関連出願へのクロスリファレンスCross-reference to related applications
　本出願は、日本国特許出願２０１４－０６３９９１号（２０１４年３月２６日出願）の優先権を主張するものであり、当該出願の開示全体を、ここに参照のために取り込む。 This application claims the priority of Japanese Patent Application No. 2014-063991 (filed on March 26, 2014), the entire disclosure of which is incorporated herein by reference.
　本発明は、ゴム組成物及びタイヤに関する。 The present invention relates to a rubber composition and a tire.
　タイヤ、特にそのサイドウォール部には、その使用態様から、繰り返しの屈曲疲労に対する高い耐性（高い耐屈曲疲労性）や、耐オゾン性等の耐候性が高いレベルで両立されていることが求められる。この要求を満たすため、従来より、タイヤのサイドウォール用ゴム組成物のゴム成分として、天然ゴムや、ブタジエンゴム及びスチレン－ブタジエンゴム等の共役ジエンに由来するゴム等から適宜選択されたブレンドゴムを用いることにより耐屈曲疲労性を向上させ、また、ゴム成分にアミン系老化防止剤やパラフィン系ワックス等の配合剤を多量に配合することにより、耐候性を向上させる方法が取られてきた。 The tire, particularly its sidewall portion, is required to have both high resistance to repeated bending fatigue (high bending fatigue resistance) and high weather resistance such as ozone resistance due to its usage. . In order to satisfy this requirement, conventionally, as a rubber component of a rubber composition for a tire sidewall, a blend rubber appropriately selected from natural rubber, rubber derived from conjugated dienes such as butadiene rubber and styrene-butadiene rubber, and the like is used. Bending fatigue resistance has been improved by use, and a method of improving weather resistance has been taken by adding a large amount of a compounding agent such as an amine-based antioxidant or a paraffinic wax to the rubber component.
　しかしながら、この方法では、かかる配合剤がタイヤ表面にブルームして、紫外線が当たることによってこれが茶褐色に変色し、タイヤの外観を著しく損ない得るという問題があった。 However, this method has a problem that such a compounding agent blooms on the surface of the tire, and when it is exposed to ultraviolet rays, this color changes to brown and the appearance of the tire can be significantly impaired.
　この問題への対処として、エチレン含有量が高い特定のエチレン－プロピレン－ジエン共重合体（ＥＰＤＭ）を配合してなるゴム組成物をタイヤのサイドウォール部の最外層に用いることにより、高い耐屈曲疲労性を得つつ、耐亀裂成長性を向上させるとともに、変色等による外観の悪化を改良した空気入りタイヤが提案されている（特許文献１）。また、水添スチレン－共役ジエン共重合体を配合することや、ブチルゴム、ジエン系ゴム、充填剤及び添加剤を混練してマスターバッチを作製した後にジエン系ゴムを混ぜて混練することによって、タイヤサイドウォール部の外観、耐候性や耐亀裂成長性を向上させるゴム組成物を得る方法も提案されている（特許文献２，３）。 As a countermeasure against this problem, a rubber composition obtained by blending a specific ethylene-propylene-diene copolymer (EPDM) having a high ethylene content is used as the outermost layer of the sidewall portion of the tire, thereby providing high bending resistance. There has been proposed a pneumatic tire that has improved fatigue resistance, improved crack growth resistance, and improved appearance deterioration due to discoloration (Patent Document 1). Also, by adding a hydrogenated styrene-conjugated diene copolymer, kneading butyl rubber, diene rubber, filler and additives to prepare a masterbatch, and then mixing and kneading the diene rubber, the tire There has also been proposed a method for obtaining a rubber composition that improves the appearance, weather resistance, and crack growth resistance of the sidewall portion (Patent Documents 2 and 3).
特開平４－４３１０６号公報JP-A-4-43106 特開２００４－２２４９５２号公報Japanese Patent Application Laid-Open No. 2004-224952 特開２００５－２７２７１９号公報JP 2005-272719 A
　しかしながら、上記特定のＥＰＤＭは、天然ゴムや共役ジエンに由来するゴムとの相溶性が低いため、その機能を十分には発揮することができていなかった。また、上記の各方法により得られるゴム組成物のいずれも、依然として、耐候性及び耐亀裂成長性について更なる改善の余地があった。 However, since the specific EPDM has low compatibility with natural rubber and rubber derived from conjugated dienes, it has not been able to perform its function sufficiently. In addition, any of the rubber compositions obtained by the above methods still has room for further improvement in weather resistance and crack growth resistance.
　そこで、本発明の目的は、高い耐候性及び耐亀裂成長性を有するゴム組成物を提供することにある。また、本発明の他の目的は、かかるゴム組成物を用い、耐候性及び耐亀裂成長性に優れたタイヤを提供することにある。 Therefore, an object of the present invention is to provide a rubber composition having high weather resistance and crack growth resistance. Another object of the present invention is to provide a tire excellent in weather resistance and crack growth resistance using such a rubber composition.
　本発明者は、上記目的を達成するために鋭意検討した結果、特定の材料を配合することを条件とした特定の粘弾性特性を有するゴム組成物が、高い耐候性及び耐亀裂成長性を有することを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the present inventor has a rubber composition having a specific viscoelastic property on condition that a specific material is blended, and has high weather resistance and crack growth resistance. As a result, the present invention has been completed.
　即ち、本発明のゴム組成物は、ジエン系ゴムと、非ジエン系ゴムと、補強性充填剤とを配合してなり、ゴム成分中の前記ジエン系ゴムの割合が４０質量％以上であるゴム組成物であって、
　横軸にゴム組成物の温度（℃）、縦軸にゴム組成物の損失正接（ｔａｎδ）を取って作成したプロットにおいて、
　前記ｔａｎδのピークが－４３～－３７℃に現れ、
　前記ｔａｎδのピーク値が０．９０～１．２０であり、且つ、
　－４０℃におけるｔａｎδの値と－２０℃におけるｔａｎδの値とを結んだ線分の傾き（℃-1）が－０．０２００～－０．０１７５である
ことを特徴とする。かかるゴム組成物は、高い耐候性及び耐亀裂成長性を有する。 That is, the rubber composition of the present invention comprises a diene rubber, a non-diene rubber, and a reinforcing filler, and the ratio of the diene rubber in the rubber component is 40% by mass or more. A composition comprising:
In the plot created by taking the temperature (° C.) of the rubber composition on the horizontal axis and the loss tangent (tan δ) of the rubber composition on the vertical axis,
The tan δ peak appears at −43 to −37 ° C.,
The peak value of tan δ is 0.90 to 1.20, and
The slope (° C. −1 ) of the line segment connecting the value of tan δ at −40 ° C. and the value of tan δ at −20 ° C. is −0.0200 to −0.0175. Such a rubber composition has high weather resistance and crack growth resistance.
　本発明のタイヤは、上記ゴム組成物をタイヤ部材の少なくともいずれかに適用したことを特徴とし、前記タイヤ部材の少なくともいずれかが、サイドウォールを含むことが好ましい。かかるタイヤは、上記ゴム組成物が用いられているため、耐候性及び耐亀裂成長性に優れる。 The tire according to the present invention is characterized in that the rubber composition is applied to at least one of the tire members, and at least one of the tire members preferably includes a sidewall. Such a tire is excellent in weather resistance and crack growth resistance because the rubber composition is used.
　さらに、本発明のタイヤは、上記ゴム組成物を適用したタイヤ部材の外表面に塗料層が形成されていることも好ましい。かかるタイヤは、耐候性及び耐亀裂成長性に優れ、より長期間その外観を維持して使用することが可能である。 Furthermore, the tire of the present invention preferably has a paint layer formed on the outer surface of a tire member to which the rubber composition is applied. Such a tire is excellent in weather resistance and crack growth resistance, and can be used while maintaining its appearance for a longer period of time.
　本発明によれば、高い耐候性及び耐亀裂成長性を有するゴム組成物を提供することができる。また、かかるゴム組成物をいずれかのタイヤ部材に用いることで、耐候性及び耐亀裂成長性に優れたタイヤを提供することができる。 According to the present invention, a rubber composition having high weather resistance and crack growth resistance can be provided. Moreover, the tire excellent in a weather resistance and crack growth resistance can be provided by using this rubber composition for any tire member.
　以下に、本発明を、その実施形態を例示して詳細に説明する。
　本発明のゴム組成物は、上述の通り、配合材料として、ジエン系ゴムと、非ジエン系ゴムと、補強性充填剤とを用いる。 Hereinafter, the present invention will be described in detail by illustrating its embodiments.
As described above, the rubber composition of the present invention uses a diene rubber, a non-diene rubber, and a reinforcing filler as compounding materials.
［ジエン系ゴム］
　本発明のゴム組成物には、ゴム成分としてジエン系ゴムを用いることを条件とする。ここで、本明細書で「ジエン系ゴム」は、後述する非ジエン系ゴム以外のゴムと定義し、具体的には、天然ゴム、及び、合成ゴムのうち構成するモノマー単位中のジエン系モノマー由来の単位の割合が５ｍｏｌ％を超えるゴムと定義する。前記ジエン系モノマーとしては、１，３－ブタジエン、イソプレン、１，３－ペンタジエン、２，３－ジメチルブタジエン等が挙げられる。一方、合成ゴムを構成するジエン系以外のモノマー（非ジエン系モノマー）としては、エチレン、プロピレン、イソブテン等が挙げられる。前記ジエン系ゴムとしては、天然ゴム（ＮＲ）及びジエン系合成ゴムが挙げられ、該ジエン系合成ゴムとして、具体的には、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）、クロロプレンゴム（ＣＲ）等が挙げられ、また、これらの各ゴムを適宜変性させたものも「ジエン系ゴム」に含まれるものとする。これらの中でも、ゴム組成物の耐亀裂成長性をより向上させる観点から、天然ゴム、ブタジエンゴム及び／又はスチレン－ブタジエンゴムを用いることが好ましく、天然ゴム及び／又はブタジエンゴムを用いることがより好ましい。なお、前記ジエン系ゴムは、一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。 [Diene rubber]
In the rubber composition of the present invention, a diene rubber is used as a rubber component. Here, in the present specification, the “diene rubber” is defined as a rubber other than the non-diene rubber described later, and specifically, a diene monomer in a monomer unit of natural rubber and synthetic rubber. It is defined as rubber having a unit ratio of more than 5 mol%. Examples of the diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and the like. On the other hand, examples of the non-diene monomer (non-diene monomer) constituting the synthetic rubber include ethylene, propylene, and isobutene. Examples of the diene rubber include natural rubber (NR) and diene synthetic rubber. Specific examples of the diene synthetic rubber include butadiene rubber (BR), styrene-butadiene rubber (SBR), isoprene rubber ( IR), chloroprene rubber (CR) and the like, and those obtained by appropriately modifying these rubbers are also included in the “diene rubber”. Among these, from the viewpoint of further improving the crack growth resistance of the rubber composition, it is preferable to use natural rubber, butadiene rubber and / or styrene-butadiene rubber, and it is more preferable to use natural rubber and / or butadiene rubber. . In addition, the said diene rubber may be used individually by 1 type, and may be used in combination of 2 or more type.
　また、本発明のゴム組成物においては、ゴム成分中の前記ジエン系ゴムの割合が４０質量％以上であることを条件とする。これは、ゴム成分中の前記ジエン系ゴムの割合が４０質量％以上とすることで、ジエン系ゴム由来の耐亀裂成長性を十分に確保するためである。 In the rubber composition of the present invention, the ratio of the diene rubber in the rubber component is 40% by mass or more. This is because the crack growth resistance derived from the diene rubber is sufficiently secured by setting the ratio of the diene rubber in the rubber component to 40% by mass or more.
［非ジエン系ゴム］
　本発明のゴム組成物には、ゴム成分として非ジエン系ゴムを用いることを条件とする。ここで、本発明において、「非ジエン系ゴム」は、合成ゴムのうち構成するモノマー単位中のジエン系モノマー由来の単位の割合が５ｍｏｌ％以下のゴムと定義する。前記非ジエン系ゴムとしては、エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）、エチレン－プロピレンゴム（ＥＰＭ）、ブチルゴム（ＩＩＲ）、塩素化ブチルゴム（Ｃｌ－ＩＩＲ）、臭素化ブチルゴム（Ｂｒ－ＩＩＲ）等が挙げられる。これらの中でも、ゴム組成物の耐候性をより向上させる観点から、エチレン－プロピレン－ジエンゴム及び／又はブチルゴムを用いるのが好ましく、エチレン－プロピレン－ジエンゴム及びブチルゴムを同時に用いるのがより好ましく、また、加工性の観点から、構成するモノマー単位中のジエン系モノマー由来の単位の割合は０．１ｍｏｌ％以上であることが好ましい。なお、前記非ジエン系ゴムは、一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。 [Non-diene rubber]
In the rubber composition of the present invention, a non-diene rubber is used as a rubber component. Here, in the present invention, “non-diene rubber” is defined as a rubber having a proportion of a unit derived from a diene monomer in a monomer unit of a synthetic rubber of 5 mol% or less. Examples of the non-diene rubber include ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), butyl rubber (IIR), chlorinated butyl rubber (Cl-IIR), brominated butyl rubber (Br-IIR) and the like. It is done. Among these, from the viewpoint of further improving the weather resistance of the rubber composition, it is preferable to use ethylene-propylene-diene rubber and / or butyl rubber, more preferably to use ethylene-propylene-diene rubber and butyl rubber at the same time. From the viewpoint of property, it is preferable that the proportion of the unit derived from the diene monomer in the constituent monomer units is 0.1 mol% or more. In addition, the said non-diene type rubber | gum may be used individually by 1 type, and may be used in combination of 2 or more type.
［補強性充填剤］
　本発明のゴム組成物には、補強性充填剤を用いることを条件とする。前記補強性充填剤としては、カーボンブラック、シリカ等が挙げられる。前記カーボンブラックとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ＦＥＦ、ＧＰＦ、ＳＲＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦ、などが挙げられる。これらは、一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。
　前記カーボンブラックの窒素吸着比表面積（Ｎ2ＳＡ、ＪＩＳ　Ｋ　６２１７－２：２００１に準拠して測定する）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が、ゴム組成物の耐亀裂成長性及び作業性を両立させる観点から、１０～１１０　ｍ2／ｇが好ましく、２０～９０ｍ2／ｇがより好ましい。前記カーボンブラックの窒素吸着比表面積（Ｎ2ＳＡ）が１０ｍ2／ｇ以上であると、得られるゴム組成物の耐亀裂成長性が十分に向上し、１１０ｍ2／ｇ以下であると、低ロス性を向上させつつ、作業性を良好に維持することができる。 [Reinforcing filler]
The rubber composition of the present invention is conditioned on the use of a reinforcing filler. Examples of the reinforcing filler include carbon black and silica. There is no restriction | limiting in particular as said carbon black, According to the objective, it can select suitably, For example, FEF, GPF, SRF, HAF, ISAF, SAF etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.
The nitrogen adsorption specific surface area (measured in accordance with N 2 SA, JIS K 6217-2: 2001) of the carbon black is not particularly limited and may be appropriately selected depending on the intended purpose. 10 to 110 m 2 / g is preferable, and 20 to 90 m 2 / g is more preferable from the viewpoint of achieving both crack growth resistance and workability. When the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is 10 m 2 / g or more, the crack growth resistance of the resulting rubber composition is sufficiently improved, and when it is 110 m 2 / g or less, low loss is obtained. The workability can be maintained well while improving the workability.
　前記シリカとしては、湿式シリカ、乾式シリカ等が挙げられ、これらは一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。また、例えば、カーボンブラックとシリカとを組み合わせて用いてもよい。 Examples of the silica include wet silica, dry silica, and the like. These may be used alone or in combination of two or more. Further, for example, carbon black and silica may be used in combination.
　前記補強性充填剤の総配合量は、ゴム成分１００質量部に対して１５～８０質量部であることが好ましく、２０～６０質量部であることがより好ましい。前記補強性充填剤の総配合量が２０～６０質量部であることにより、耐亀裂成長性の十分な向上を得つつ、良好な作業性を保持することができる。 The total amount of the reinforcing filler is preferably 15 to 80 parts by mass, more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the rubber component. When the total blending amount of the reinforcing filler is 20 to 60 parts by mass, satisfactory workability can be maintained while sufficiently improving crack growth resistance.
［その他の成分］
　本発明のゴム組成物には、必要に応じて、上述した成分以外の成分を用いることができる。かかる成分としては、架橋剤（加硫剤）、架橋促進剤（加硫促進剤）、架橋助剤（加硫助剤）、加硫促進助剤（加硫促進助剤）、着色剤、難燃剤、滑剤、発泡剤、可塑剤、加工助剤、酸化防止剤、スコーチ防止剤、紫外線防止剤、帯電防止剤、着色防止剤、その他の配合剤等が挙げられ、その使用目的に応じて配合することができる。
　特に、本発明のゴム組成物のゴム物性（粘弾性特性）を得るのに好適な成分については、後述する。 [Other ingredients]
In the rubber composition of the present invention, components other than those described above can be used as necessary. Such components include crosslinking agents (vulcanizing agents), crosslinking accelerators (vulcanization accelerators), crosslinking assistants (vulcanization assistants), vulcanization acceleration assistants (vulcanization accelerators), colorants, Examples include flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, scorch inhibitors, UV inhibitors, antistatic agents, anti-coloring agents, and other compounding agents. can do.
In particular, components suitable for obtaining the rubber physical properties (viscoelastic properties) of the rubber composition of the present invention will be described later.
［ゴム組成物］
　本発明のゴム組成物は、特定の粘弾性特性を有する。以下、かかる特定の粘弾性特性について述べる。 [Rubber composition]
The rubber composition of the present invention has specific viscoelastic properties. Hereinafter, the specific viscoelastic characteristics will be described.
　本発明のゴム組成物は、横軸にゴム組成物の温度（℃）、縦軸にゴム組成物の損失正接（ｔａｎδ）を取って作成したプロットにおいて、ｔａｎδのピークが－４３～－３７℃に現れることを要する。前記ｔａｎδのピークが現れる温度が、－４３℃未満であると、十分な耐候性が得られないおそれがあり、一方、－３７℃よりも高いと、十分な耐亀裂成長性が得られないおそれがある。ゴム組成物のｔａｎδは使用するポリマーのガラス転移温度（Ｔg）によって変動し得ることに鑑みれば、前記ｔａｎδのピークが現れる温度を調整する方法としては、使用するゴム成分の種類を適宜変えることが挙げられる。
　また、本発明のゴム組成物は、前記ｔａｎδのピーク値が、０．９０～１．２０であることを要する。前記ｔａｎδのピーク値が、０．９０未満であると、十分な耐亀裂成長性が得られないおそれがあり、一方、１．２０を超えると、十分な耐候性が得られないおそれがある。前記ｔａｎδのピーク値を調整する（増大させる）方法としては、使用するジエン系ゴムへの補強性充填剤の分布の度合いを低減することが挙げられる。
　さらに、本発明のゴム組成物は、－４０℃におけるｔａｎδの値と－２０℃におけるｔａｎδの値とを結んだ線分の傾き（℃-1）が、－０．０２００～－０．０１７５であることを要し、－０．０１９５～－０．０１８０であることが好ましい。前記傾きが、－０．０２００未満であると、十分な耐候性が得られないおそれがあり、一方、－０．０１７５を超えると、十分な耐亀裂成長性が得られないおそれがある。前記線分の傾きを調整する（より０に近づける）方法としては、使用する非ジエン系ゴムへの補強性充填剤の分布の度合いを増加させることが挙げられる。
　なお、ｔａｎδの測定は、スペクトロメーター、レオメーター等を用いて行うものとする。 The rubber composition of the present invention has a tan δ peak of −43 to −37 ° C. in a plot prepared by taking the temperature (° C.) of the rubber composition on the horizontal axis and the loss tangent (tan δ) of the rubber composition on the vertical axis. It needs to appear in If the temperature at which the tan δ peak appears is less than −43 ° C., sufficient weather resistance may not be obtained, whereas if it is higher than −37 ° C., sufficient crack growth resistance may not be obtained. There is. Considering that the tanδ of the rubber composition may vary with the glass transition temperature of the polymer used (T g), as a method of adjusting the temperature at which the peak of the tanδ appears in, changing the type of rubber component used appropriately Is mentioned.
In addition, the rubber composition of the present invention requires that the tan δ peak value be 0.90 to 1.20. If the tan δ peak value is less than 0.90, sufficient crack growth resistance may not be obtained, whereas if it exceeds 1.20, sufficient weather resistance may not be obtained. As a method of adjusting (increasing) the peak value of tan δ, there is a method of reducing the degree of distribution of the reinforcing filler to the diene rubber used.
Further, in the rubber composition of the present invention, the slope (° C. −1 ) of the line segment connecting the value of tan δ at −40 ° C. and the value of tan δ at −20 ° C. is −0.0200 to −0.0175. In other words, it is preferably -0.0195 to -0.0180. If the inclination is less than −0.0200, sufficient weather resistance may not be obtained, while if it exceeds −0.0175, sufficient crack growth resistance may not be obtained. As a method of adjusting the inclination of the line segment (more closer to 0), increasing the degree of distribution of the reinforcing filler to the non-diene rubber used can be mentioned.
Note that tan δ is measured using a spectrometer, rheometer, or the like.
　ここで、本発明のゴム組成物の上述したゴム物性（粘弾性特性）を得るのに好適な方法の一つとしては、ジエン系ゴムを天然ゴム及び／又はブタジエンゴムとし、ゴム成分中のジエン系ゴムの割合を２０～９０質量％とし、ゴム成分中の天然ゴムの割合を１０～７０質量％とし、且つ、ゴム成分中のブタジエンゴムの割合を１０～４０質量％とすることが挙げられる。 Here, as a suitable method for obtaining the above-described rubber physical properties (viscoelastic properties) of the rubber composition of the present invention, the diene rubber is natural rubber and / or butadiene rubber, and the diene in the rubber component is used. The ratio of the base rubber is 20 to 90% by mass, the ratio of the natural rubber in the rubber component is 10 to 70% by mass, and the ratio of the butadiene rubber in the rubber component is 10 to 40% by mass. .
　また、本発明のゴム組成物の上述したゴム物性（粘弾性特性）を得るのに好適な別の方法の一つとしては、
　（１）非ジエン系ゴムと、補強性充填剤の少なくとも一部とを混練してマスターバッチを作製する一次工程、及び
　（２）前記マスターバッチに、ジエン系ゴム、及び残りの補強性充填剤を投入して混練する二次工程
　を経てゴム組成物を製造する方法が挙げられる。
　ジエン系ゴム、非ジエン系ゴム及び補強性充填剤を用いたゴム組成物の製造において、常法に従ってこれらを一括で混練するか、又は補強性充填剤を後半段階に一括投入する場合には、補強性充填剤は親和性の高いジエン系ゴム近傍に偏在し易いという問題がある。しかしながら、あらかじめ所定量の補強性充填剤と非ジエン系ゴムとを混練する一次工程を経れば、補強性充填剤は、非ジエン系ゴム中により分布できるようになり、その後の二次工程で配合されるジエン系ゴムが前記非ジエン系ゴムに入り込んで、その補強性充填剤と親和するため、ゴム組成物の粘弾性特性の適正化を図ることができる。 As another method suitable for obtaining the above-described rubber physical properties (viscoelastic properties) of the rubber composition of the present invention,
(1) a primary step of kneading a non-diene rubber and at least a part of a reinforcing filler to produce a master batch; and (2) a diene rubber and the remaining reinforcing filler in the master batch. And a method of producing a rubber composition through a secondary step of kneading and kneading.
In the production of a rubber composition using a diene rubber, a non-diene rubber and a reinforcing filler, these are kneaded in a lump according to a conventional method, or when a reinforcing filler is collectively charged in the latter half stage, There is a problem that the reinforcing filler tends to be unevenly distributed in the vicinity of the high-affinity diene rubber. However, if a primary step of kneading a predetermined amount of reinforcing filler and non-diene rubber in advance, the reinforcing filler can be distributed in the non-diene rubber, and in the subsequent secondary step. Since the blended diene rubber enters the non-diene rubber and has an affinity with the reinforcing filler, the viscoelastic characteristics of the rubber composition can be optimized.
　本発明のゴム組成物を上記工程（１）及び（２）を経て製造する場合、一次工程で配合する補強性充填剤の量は、ゴム成分１００質量部に対して１５～８０質量部であることが好ましく、２０～６５質量部であることがより好ましい。一次工程で配合する補強性充填剤の量がゴム成分１００質量部に対して１５～８０質量部であることにより、作業性が悪化することなく、補強性充填剤が非ジエン系ゴム中により分布するようになり、耐亀裂成長性の十分な向上が得られる。 When the rubber composition of the present invention is produced through the above steps (1) and (2), the amount of the reinforcing filler compounded in the primary step is 15 to 80 parts by mass with respect to 100 parts by mass of the rubber component. It is preferably 20 to 65 parts by mass. The amount of the reinforcing filler blended in the primary process is 15 to 80 parts by mass with respect to 100 parts by mass of the rubber component, so that the reinforcing filler is distributed in the non-diene rubber without deteriorating workability. As a result, the crack growth resistance can be sufficiently improved.
　さらに、上記工程（１）及び（２）を経る場合であって、且つ、補強性充填剤としてカーボンブラックを用いる場合においては、下記式（Ｉ）～（ＩＩＩ）：
Figure JPOXMLDOC01-appb-C000001
 ［式中、Ａは芳香族環、置換され若しくは置換されていないヒダントイン環、又は炭素原子数１～１８の飽和若しくは不飽和の直鎖状炭化水素基であり、ａは０又は１であり、Ｂは芳香族基であり、Ｘはヒドロキシ基又はアミノ基であり、Ｙはピリジル基又はヒドラジノ基である］のいずれかで表される化合物をさらに配合することが好ましい。かかる化合物は、ジエン系ゴムの主鎖と反応し、また、カーボンブラックとの親和性が高いため、ジエン系ゴムが非ジエン系ゴムに入り込む効果を高め、非ジエン系ゴムとジエン系ゴムとがより均一に混和して、ゴム組成物の粘弾性特性の適正化が好適に図られ得る。
　かかる化合物は、上記工程（２）中で投入することが好ましい。 Further, in the case where the steps (1) and (2) are performed and carbon black is used as the reinforcing filler, the following formulas (I) to (III):
Figure JPOXMLDOC01-appb-C000001
 Wherein A is an aromatic ring, a substituted or unsubstituted hydantoin ring, or a saturated or unsaturated linear hydrocarbon group having 1 to 18 carbon atoms, a is 0 or 1; B is an aromatic group, X is a hydroxy group or an amino group, and Y is a pyridyl group or a hydrazino group]. Such a compound reacts with the main chain of the diene rubber and has a high affinity with carbon black, so that the effect of the diene rubber entering the non-diene rubber is enhanced, and the non-diene rubber and the diene rubber are By mixing more uniformly, the viscoelastic properties of the rubber composition can be suitably optimized.
Such a compound is preferably added in the step (2).
　式（Ｉ）で表される化合物としては、フタル酸ジヒドラジド、イソフタル酸ジヒドラジド、テレフタル酸ジヒドラジド、１，３－ビス（ヒドラジノカルボエチル）－５－イソプロピルヒダントイン、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、アゼライン酸ジヒドラジド、セバシン酸ジヒドラジド、エイコサン二酸ジヒドラジド、７，１１－オクタデカジエン－１，１８－ジカルボヒドラジド、シュウ酸ヒドラジド等が挙げられる。
　式（ＩＩ）で表される化合物としては、アントラニロイルヒドラジン、サリチル酸ヒドラジド、４－ヒドロキシベンゾイックアシドヒドラジド、２－ヒドロキシ－３－ナフトエ酸ヒドラジド、３－ヒドロキシ－Ｎ’－（１，３－ジメチルブチリデン）－２－ナフトエ酸ヒドラジド等が挙げられる。
　式（ＩＩＩ）で表される化合物としては、イソニコチン酸ヒドラジド、カルボジヒドラジド等が挙げられる。
　これらの中でも、カーボンブラックとの親和性の観点から、イソフタル酸ジヒドラジド、２－ヒドロキシ－３－ナフトエ酸ヒドラジド、又は３－ヒドロキシ－Ｎ’－（１，３－ジメチルブチリデン）－２－ナフトエ酸ヒドラジドを用いるのが好ましい。なお、前記化合物は、一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。 Examples of the compound represented by the formula (I) include phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, succinic acid dihydrazide, adipic acid dihydrazide, azelain. And acid dihydrazide, sebacic acid dihydrazide, eicosanedioic acid dihydrazide, 7,11-octadecadien-1,18-dicarbohydrazide, oxalic hydrazide and the like.
Examples of the compound represented by the formula (II) include anthraniloyl hydrazine, salicylic acid hydrazide, 4-hydroxybenzoic acid hydrazide, 2-hydroxy-3-naphthoic acid hydrazide, 3-hydroxy-N ′-(1,3- And dimethylbutylidene) -2-naphthoic acid hydrazide.
Examples of the compound represented by the formula (III) include isonicotinic acid hydrazide and carbodihydrazide.
Among these, from the viewpoint of affinity with carbon black, isophthalic acid dihydrazide, 2-hydroxy-3-naphthoic acid hydrazide, or 3-hydroxy-N ′-(1,3-dimethylbutylidene) -2-naphthoic acid It is preferred to use hydrazide. In addition, the said compound may be used individually by 1 type, and may be used in combination of 2 or more type.
　また、前記化合物を配合する場合、その配合量は、ゴム成分１００質量部に対して０．１～５．０質量部であることが好ましく、０．１～３．０質量部であることがより好ましい。前記化合物の配合量がゴム成分１００質量部に対して０．１～５．０質量部であることにより、非ジエン系ゴムとジエン系ゴムとがより一層均一に混和する。 In addition, when the compound is blended, the blending amount is preferably 0.1 to 5.0 parts by weight, and preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the rubber component. More preferred. When the compounding amount of the compound is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the rubber component, the non-diene rubber and the diene rubber are more uniformly mixed.
　なお、本発明のゴム組成物を上記工程（１）及び（２）を経て製造する場合において、架橋剤（加硫剤）と、必要に応じて用いる架橋促進剤（加硫促進剤）及び／又は架橋助剤（加硫助剤）とは、工程（２）の後に投入することが好ましい。 In addition, when manufacturing the rubber composition of this invention through the said process (1) and (2), a crosslinking agent (vulcanizing agent), the crosslinking accelerator (vulcanization accelerator) used as needed, and / or Alternatively, the crosslinking aid (vulcanizing aid) is preferably added after the step (2).
　本発明のゴム組成物の製造においては、二軸押出機、ロール、インテンシブミキサー等の公知の混練装置を使用することができる。
　前記一次工程を行う場合、その条件としては特に制限はない。
　前記二次工程を行う場合、その条件としても特に制限はないが、最高温度１４５℃以下で行うことが好ましい。
　また、架橋剤（加硫剤）と、必要に応じて架橋促進剤（加硫促進剤）、架橋助剤（加硫助剤）及び／又は架橋促進助剤（加硫促進助剤）とを用いて架橋（加硫）する場合においては、温度１１０℃以下で行うことが好ましい。 In the production of the rubber composition of the present invention, a known kneading apparatus such as a twin screw extruder, a roll, or an intensive mixer can be used.
When the primary step is performed, the conditions are not particularly limited.
When the secondary step is performed, the conditions are not particularly limited, but it is preferably performed at a maximum temperature of 145 ° C. or lower.
Further, a crosslinking agent (vulcanizing agent) and, if necessary, a crosslinking accelerator (vulcanization accelerator), a crosslinking aid (vulcanization aid) and / or a crosslinking acceleration aid (vulcanization acceleration aid). When used for crosslinking (vulcanization), the temperature is preferably 110 ° C. or lower.
［タイヤ］
　本発明のタイヤは、本発明のゴム組成物をタイヤ部材の少なくともいずれかに適用したものである限り、特に制限はなく、常法に従って製造することができる。適用可能なタイヤ部材としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、トレッド、ベーストレッド、サイドウォール、サイド補強ゴム及びビードフィラー等が挙げられるが、これらの中でも、本発明のゴム組成物を少なくとも、繰り返しの屈曲疲労にさらされるサイドウォールに適用することが好適である。本発明のタイヤとしては、空気入りタイヤ、特に乗用車用空気入りタイヤが好適であり、本発明のゴム組成物が用いられているため、耐候性及び耐亀裂成長性に優れる。
　さらに、本発明のタイヤは、上記ゴム組成物を適用したタイヤ部材の外表面に塗料層が形成されていることも好ましい。かかるタイヤは、アミン系老化防止剤やパラフィン系ワックス等の配合剤の有無にかかわらず耐候性及び耐亀裂成長性に優れるため、より長期間その外観を維持して使用することが可能である。なお、塗料層の形成に用いられる塗料としては、特に制限はされず、公知の塗料を目的に応じて選択することができる。 [tire]
The tire of the present invention is not particularly limited as long as the rubber composition of the present invention is applied to at least one of the tire members, and can be produced according to a conventional method. The applicable tire member is not particularly limited and can be appropriately selected depending on the purpose.For example, a tread, a base tread, a sidewall, a side reinforcing rubber, a bead filler, and the like can be given. It is preferable to apply the rubber composition of the present invention to at least a sidewall exposed to repeated bending fatigue. As the tire of the present invention, a pneumatic tire, particularly a pneumatic tire for passenger cars is suitable, and since the rubber composition of the present invention is used, it is excellent in weather resistance and crack growth resistance.
Furthermore, the tire of the present invention preferably has a paint layer formed on the outer surface of a tire member to which the rubber composition is applied. Such a tire is excellent in weather resistance and crack growth resistance regardless of the presence or absence of a compounding agent such as an amine-based anti-aging agent or paraffin-based wax, and thus can be used while maintaining its appearance for a longer period of time. In addition, there is no restriction | limiting in particular as a coating material used for formation of a coating layer, A well-known coating material can be selected according to the objective.
　以下、実施例を挙げて本発明をさらに詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
＜ゴム組成物の調製＞
　表１に示す配合処方（各数値は、ゴム成分１００質量部に対する質量部数である）に従って、一次工程の混練、二次工程の混練（一部の例では、１回の混練のみ）及び最終工程の加硫を行い、ゴム組成物を調製した。ここで、一次工程の条件は、温度１３０℃で３分間とし、二次工程の条件は、温度１３０℃で１．５分間とした。さらに、加硫条件は、温度１６０℃で１５分間とした。
　得られたゴム組成物を用い、下記に示す各種測定を行った。結果を表１に示す。 <Preparation of rubber composition>
According to the formulation shown in Table 1 (each numerical value is the number of parts by mass relative to 100 parts by mass of the rubber component), kneading in the primary process, kneading in the secondary process (in some cases, only one kneading) and final process Was vulcanized to prepare a rubber composition. Here, the condition of the primary process was 3 minutes at a temperature of 130 ° C., and the condition of the secondary process was 1.5 minutes at a temperature of 130 ° C. Further, the vulcanization conditions were set at a temperature of 160 ° C. for 15 minutes.
Various measurements shown below were performed using the obtained rubber composition. The results are shown in Table 1.
＜粘弾性特性＞
　直径６ｍｍ、厚さ５ｍｍのゴム組成物の試験片を準備し、ＴＡインストゥルメンツジャパン製「ＡＲＥＳ－Ｇ２レオメータ－」を用いて、－６０～２５℃の温度範囲における損失正接（ｔａｎδ）を、－３℃／分の降温速度にて測定した。このとき、初期荷重７０ｇ、動的歪０．１％、周波数０．１Ｈｚの測定条件とした。この測定結果から、ｔａｎδの値がピークとなる時の温度及びｔａｎδを求め、さらに、－４０℃におけるｔａｎδの値と－２０℃におけるｔａｎδの値とを結んだ線分の傾き（℃-1）を求めた。 <Viscoelastic properties>
A test piece of a rubber composition having a diameter of 6 mm and a thickness of 5 mm was prepared, and loss tangent (tan δ) in a temperature range of −60 to 25 ° C. was measured using “ARES-G2 rheometer” manufactured by TA Instruments Japan. The measurement was performed at a temperature decrease rate of −3 ° C./min. At this time, the measurement conditions were an initial load of 70 g, a dynamic strain of 0.1%, and a frequency of 0.1 Hz. From this measurement result, the temperature and tan δ at which the value of tan δ peaks are obtained, and the slope of the line segment connecting the tan δ value at −40 ° C. and the tan δ value at −20 ° C. (° C. −1 ). Asked.
＜耐屈曲疲労性＞
　長さ１２５ｍｍ、幅２５ｍｍ、厚さ５．５ｍｍのゴム組成物の試験片を準備し、ＪＩＳ－Ｋ６２６０「屈曲き裂発生試験」に準じて、室温で屈曲を繰り返した。そして、２ｍｍ以上の亀裂が発生したときまでの屈曲回数を測定した。かかる屈曲回数について、比較例１の値を１００として指数化した。指数が高いほど、耐屈曲疲労性に優れることを示す。 <Bending fatigue resistance>
A test piece of a rubber composition having a length of 125 mm, a width of 25 mm, and a thickness of 5.5 mm was prepared, and bending was repeated at room temperature in accordance with JIS-K6260 “Bending crack generation test”. Then, the number of bendings until a crack of 2 mm or more occurred was measured. The number of bendings was indexed with the value of Comparative Example 1 being 100. The higher the index, the better the bending fatigue resistance.
＜耐亀裂成長性＞
　初期亀裂を入れた長さ５０ｍｍ、幅１０ｍｍ、厚さ１．０ｍｍの加硫ゴムサンプルに対し、６０℃で３０％の歪をかけ、進展回数に対してどれだけ亀裂が進展するか（ｍｍ）を測定した。かかる亀裂の進展について、比較例１の値を１００として指数化した。指数が高いほど、耐亀裂成長性に優れることを示す。 <Crack growth resistance>
How much the crack progresses with respect to the number of progresses (30mm) by applying a strain of 30% at 60 ° C to a vulcanized rubber sample with an initial crack length of 50mm, width 10mm, and thickness 1.0mm. Was measured. The crack growth was indexed with the value of Comparative Example 1 being 100. The higher the index, the better the crack growth resistance.
＜耐候性＞
　オゾン濃度３０ｐｐｍ、４０℃の条件としたオゾンウェザーメーター（スガ試験機社製）内で、長さ１００ｍｍ、幅１０ｍｍ、厚さ２ｍｍのゴム組成物の試験片を９６時間保持し、保持後のゴム組成物の外観を目視により観察した。かかる外観において、発生したオゾンクラックの数を測定した。そして、かかるオゾンクラックの数の逆数について、比較例１の値を１００として指数化した。指数が高いほど、耐候性に優れることを示す。 <Weather resistance>
A test piece of rubber composition having a length of 100 mm, a width of 10 mm, and a thickness of 2 mm is held for 96 hours in an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.) with an ozone concentration of 30 ppm and 40 ° C., and the rubber after holding The appearance of the composition was visually observed. In this appearance, the number of generated ozone cracks was measured. The reciprocal of the number of ozone cracks was indexed with the value of Comparative Example 1 being 100. It shows that it is excellent in a weather resistance, so that an index | exponent is high.
＜耐破壊性＞
　ゴム組成物からＪＩＳ＃３サンプルを採取し、インストロン引張試験機により切断時伸びを測定した。かかる切断時伸びについて、比較例１の値を１００として指数化した。指数が高いほど、耐破壊性に優れることを示す。

<Destruction resistance>
A JIS # 3 sample was taken from the rubber composition, and the elongation at break was measured with an Instron tensile tester. The elongation at break was indexed with the value of Comparative Example 1 being 100. The higher the index, the better the fracture resistance.

Figure JPOXMLDOC01-appb-T000001
 ＊１　ＢＲ：ブタジエンゴム（ＪＳＲ株式会社製、ＢＲ０１、ジエン系モノマー由来の単位＝１００ｍｏｌ％）
＊２　Ｂｒ－ＩＩＲ：臭素化ブチルゴム（日本ブチル株式会社製、２２５５）
＊３　ＥＰＤＭ：エチレン－プロピレン－ジエンゴム（ＪＳＲ株式会社製、ＥＰ２５、第三成分量 ヨウ素価：１７）
＊４　カーボンブラック（東海カーボン株式会社製、シースト３００）
＊５　シリカ（東ソーシリカ株式会社製、ニップシールＡＱ）
＊６　ステアリン酸（加硫助剤）（新日本理化株式会社製、５０Ｓ）
＊７　亜鉛華（加硫促進助剤）（ハクスイテック株式会社製、酸化亜鉛華）
＊８　老化防止剤：Ｎ－（１，３－ジメチルブチル）－Ｎ’－ｐ－フェニレンジアミン（大内新興化学工業株式会社製、ノクラック６Ｃ）
＊９　ＣＢカップリング剤、３－ヒドロキシ－Ｎ’－（１，３－ジメチルブチリデン）－２－ナフトエ酸ヒドラジド（大塚化学株式会社製、ＢＭＨ）
＊１０　シランカップリング剤（信越化学株式会社製、８５６）
＊１１　硫黄（加硫剤）（細井化学工業株式会社製、普通硫黄）
＊１２　加硫促進剤：シクロヘキシルベンゾチアジルスルフェンアミド（大内新興化学工業株式会社製、ＣＺ）
Figure JPOXMLDOC01-appb-T000001
 * 1 BR: Butadiene rubber (manufactured by JSR Corporation, BR01, unit derived from diene monomer = 100 mol%)
* 2 Br-IIR: Brominated butyl rubber (Nippon Butyl Co., Ltd., 2255)
* 3 EPDM: ethylene-propylene-diene rubber (manufactured by JSR Corporation, EP25, third component amount iodine value: 17)
* 4 Carbon black (Toast Carbon Co., Ltd., Seast 300)
* 5 Silica (Tosoh Silica Co., Ltd., nip seal AQ)
* 6 Stearic acid (vulcanization aid) (manufactured by Shin Nippon Rika Co., Ltd., 50S)
* 7 Zinc Hana (Vulcanization Acceleration Auxiliary)
* 8 Anti-aging agent: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine (Ouchi Shinsei Chemical Co., Ltd., NOCRACK 6C)
* 9 CB coupling agent, 3-hydroxy-N ′-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide (manufactured by Otsuka Chemical Co., Ltd., BMH)
* 10 Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., 856)
* 11 Sulfur (vulcanizing agent) (Hosoi Chemical Co., Ltd., ordinary sulfur)
* 12 Vulcanization accelerator: Cyclohexylbenzothiazylsulfenamide (Ouchi Shinsei Chemical Co., Ltd., CZ)
　表１の結果から、上述した特定の材料を配合してなり、特定の粘弾性特性を有する本発明の実施例のゴム組成物は、高い耐候性及び耐亀裂成長性を有し、さらに、耐屈曲疲労性及び耐破壊性にも優れることが分かる。 From the results shown in Table 1, the rubber compositions of the examples of the present invention having the above-mentioned specific materials and specific viscoelastic properties have high weather resistance and crack growth resistance, It turns out that it is excellent also in bending fatigue property and fracture resistance.

Claims (4)

  1. 　ジエン系ゴムと、非ジエン系ゴムと、補強性充填剤とを配合してなり、ゴム成分中の前記ジエン系ゴムの割合が４０質量％以上であるゴム組成物であって、
    　横軸にゴム組成物の温度（℃）、縦軸にゴム組成物の損失正接（ｔａｎδ）を取って作成したプロットにおいて、
    　前記ｔａｎδのピークが－４３～－３７℃に現れ、
    　前記ｔａｎδのピーク値が０．９０～１．２０であり、且つ、
    　－４０℃におけるｔａｎδの値と－２０℃におけるｔａｎδの値とを結んだ線分の傾き（℃-1）が－０．０２００～－０．０１７５である
    　ことを特徴とする、ゴム組成物。     A rubber composition comprising a diene rubber, a non-diene rubber, and a reinforcing filler, wherein the ratio of the diene rubber in the rubber component is 40% by mass or more,
    In the plot created by taking the temperature (° C.) of the rubber composition on the horizontal axis and the loss tangent (tan δ) of the rubber composition on the vertical axis,
    The tan δ peak appears at −43 to −37 ° C.,
    The peak value of tan δ is 0.90 to 1.20, and
    A rubber composition characterized in that the slope (° C. -1 ) of a line segment connecting the value of tan δ at -40 ° C and the value of tan δ at -20 ° C is -0.0200 to -0.0175.
  2. 　請求項１に記載のゴム組成物をタイヤ部材の少なくともいずれかに適用したことを特徴とするタイヤ。 A tire characterized by applying the rubber composition according to claim 1 to at least one of tire members.
  3. 　前記タイヤ部材の少なくともいずれかが、サイドウォールを含む、請求項２に記載のタイヤ。 The tire according to claim 2, wherein at least one of the tire members includes a sidewall.
  4. 　前記ゴム組成物を適用した前記タイヤ部材の外表面に塗料層が形成された、請求項２又は３に記載のタイヤ。 The tire according to claim 2 or 3, wherein a paint layer is formed on an outer surface of the tire member to which the rubber composition is applied.
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JP2009096981A (en) * 2007-09-28 2009-05-07 Tokai Rubber Ind Ltd Method for producing vibration-proof rubber composition and vibration-proof rubber composition produced thereby and vibration-proof rubber
JP2009256579A (en) * 2008-03-27 2009-11-05 Tokai Rubber Ind Ltd Method for producing vibration-proof rubber composition and vibration-proof rubber composition produced by the same
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CN108367633A (en) * 2015-12-11 2018-08-03 株式会社普利司通 The manufacturing method of tire and tire
CN108367634A (en) * 2015-12-11 2018-08-03 株式会社普利司通 The manufacturing method of tire and tire
EP3388261A4 (en) * 2015-12-11 2018-12-05 Bridgestone Corporation Tire and method for producing tire
EP3388260A4 (en) * 2015-12-11 2018-12-05 Bridgestone Corporation Tire and method for producing tire
CN108367634B (en) * 2015-12-11 2020-05-08 株式会社普利司通 Tire and tire manufacturing method
CN108367633B (en) * 2015-12-11 2020-05-15 株式会社普利司通 Tire and tire manufacturing method

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