WO2022130772A1 - Composition de caoutchouc pour pneu, et pneu - Google Patents

Composition de caoutchouc pour pneu, et pneu Download PDF

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Publication number
WO2022130772A1
WO2022130772A1 PCT/JP2021/038525 JP2021038525W WO2022130772A1 WO 2022130772 A1 WO2022130772 A1 WO 2022130772A1 JP 2021038525 W JP2021038525 W JP 2021038525W WO 2022130772 A1 WO2022130772 A1 WO 2022130772A1
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Prior art keywords
rubber
rubber composition
acrylate
meth
mol
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PCT/JP2021/038525
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English (en)
Japanese (ja)
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彩花 ▲高▼橋
繁希 田島
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株式会社ブリヂストン
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Priority to JP2022569739A priority Critical patent/JPWO2022130772A1/ja
Publication of WO2022130772A1 publication Critical patent/WO2022130772A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • 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
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a rubber composition for a tire and a tire.
  • Patent Document 2 discloses a rubber composition containing a silyl group-terminated (meth) acrylate-based polymer and a (meth) acrylamide-based polymer as a crosslinkable oligomer or polymer.
  • Patent Document 2 by forming an aggregate of the copolymer and the white filler, the aggregate is effectively dispersed in the diene rubber, and the performance on ice and the wear resistance are improved.
  • Patent Document 1 In the method exemplified in Patent Document 1, the water film can be taken in as the surface roughness increases, but the area that can come into contact with the ice top surface decreases. Therefore, it can be said that there is a limit to the effect of improving the performance on ice due to the surface roughness. Further, when a foaming agent, a heat-expandable microcapsule, or the like is blended, there is a problem that the fracture resistance property of the tread rubber is deteriorated. In the rubber composition of Patent Document 2, although the performance on ice was improved, the fracture resistance and rolling resistance were not evaluated. Further, since the oligomer or polymer added in Patent Document 2 is in a liquid state, there is also a problem that weighing and feeding into a mixer are complicated.
  • the present invention has been made in view of the above circumstances, and provides a rubber composition for a tire which is excellent in fuel efficiency and on-ice performance and has good fracture resistance when used for a tire.
  • Another object of the present invention is to provide a tire which is excellent in fuel efficiency and on-ice performance and also exhibits good fracture resistance by using the rubber composition.
  • the present invention provides the following [1] to [15].
  • [1] A rubber composition for a tire containing a rubber component and a copolymer obtained by polymerizing a monomer component containing glycidyl (meth) acrylate and stearyl (meth) acrylate.
  • [2] The tire according to [1], wherein the ratio of the glycidyl (meth) acrylate in the monomer component is 5 to 98 mol%, and the ratio of the stearyl (meth) acrylate is 2% by mass to 95% by mass. Rubber composition.
  • [14] A tire using the vulcanized product of the rubber composition for a tire according to any one of [1] to [13].
  • [15] The tire according to [14], wherein the tread rubber is a vulcanized product of the rubber composition for a tire according to any one of [1] to [13].
  • the present invention it is possible to provide a rubber composition for a tire which is excellent in fuel efficiency and on-ice performance and has good fracture resistance when used for a tire. Further, by using the rubber composition, it is possible to provide a tire which is excellent in fuel efficiency and on-ice performance and also exhibits good fracture resistance.
  • the rubber composition for a tire of the present invention contains a rubber component and a copolymer obtained by polymerizing a monomer component containing glycidyl (meth) acrylate and stearyl (meth) acrylate.
  • the rubber composition of the present invention contains a copolymer obtained by polymerizing a monomer component containing glycidyl (meth) acrylate and stearyl (meth) acrylate, thereby ensuring good grip on ice and snow road surfaces and excellent on ice. In addition to having performance, rolling resistance can be reduced to make a tire with excellent fuel efficiency. Further, by using the rubber composition of the present invention, a tire exhibiting good fracture resistance can be obtained.
  • the rubber composition of the present invention is particularly effective when applied to a rubber composition for tread.
  • the type of rubber is not particularly limited.
  • natural rubber NR
  • polyisoprene rubber IR
  • polybutadiene rubber BR
  • styrene-butadiene copolymer rubber SBR
  • butyl rubber IIR
  • EPDM ethylene-propylene-diene copolymer
  • NBR butadiene copolymer
  • the rubber component preferably contains natural rubber, polybutadiene rubber, and styrene-butadiene copolymer rubber.
  • the rubber component has a ratio of natural rubber of 20 to 60% by mass, a ratio of polybutadiene rubber of 20 to 60% by mass, and a ratio of styrene butadiene rubber of 10 to 40% by mass.
  • the polybutadiene rubber may be a modified butadiene rubber or an unmodified butadiene rubber, but a modified butadiene rubber is more preferable.
  • the styrene-butadiene copolymer rubber may be a modified styrene-butadiene copolymer rubber or an unmodified styrene-butadiene copolymer rubber, but may be a modified styrene-butadiene copolymer rubber. It is more preferable to have.
  • the modified conjugated diene polymer described in International Publication No. 2019/146323 can be applied.
  • the copolymer added to the rubber composition for a tire of the present invention is formed by polymerizing a monomer component containing glycidyl (meth) acrylate and stearyl (meth) acrylate as the monomer component.
  • the glycidyl (meth) acrylate refers to glycidyl methacrylate or glycidyl acrylate.
  • the present invention includes not only the case where glycidyl methacrylate or glycidyl acrylate is contained alone, but also the case where a mixture of glycidyl methacrylate and glycidyl acrylate is contained.
  • the stearyl (meth) acrylate refers to stearyl methacrylate or stearyl acrylate.
  • the present invention includes not only the case where stearyl methacrylate or stearyl acrylate is contained alone, but also the case where a mixture of stearyl methacrylate and stearyl acrylate is contained.
  • the copolymer preferably contains glycidyl methacrylate (GMA) and stearyl methacrylate (SMA) as monomer components. Examples of such a copolymer include a binary copolymer obtained by polymerizing glycidyl methacrylate (GMA) and stearyl methacrylate (SMA) as monomer components.
  • the proportion of glycidyl (meth) acrylate is preferably 5 to 98 mol%, the proportion of stearyl (meth) acrylate is preferably 2 to 95 mol%, and the proportion of glycidyl (meth) acrylate is 5 to 50 mol% in the monomer component.
  • the proportion of stearyl (meth) acrylate is more preferably 50 to 95 mol%, the proportion of glycidyl (meth) acrylate is 5 to 25 mol%, and the proportion of stearyl (meth) acrylate is 75 to 95 mol%. It is more preferable to have.
  • the ratio of glycidyl methacrylate is 5 to 98 mol%
  • the ratio of stearyl methacrylate is particularly preferably 2 to 95 mol%
  • the ratio of glycidyl methacrylate is 5 to 50 mol%
  • the ratio of stearyl methacrylate is 50 to 95 mol. % Is more particularly preferable.
  • the copolymer is preferably formed by further polymerizing a monomer component containing 2-hydroxyethyl (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate refers to 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate.
  • the present invention includes not only the case where 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate is contained alone, but also the case where a mixture of 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate is contained.
  • the copolymer is formed by polymerizing a monomer component containing 2-hydroxyethyl (meth) acrylate, the fracture resistance can be particularly improved.
  • the copolymer is formed by polymerizing a monomer component containing 2-hydroxyethyl methacrylate (HEMA).
  • the copolymer is more preferably formed by polymerizing a monomer component containing glycidyl methacrylate (GMA), stearyl methacrylate (SMA), and 2-hydroxyethyl methacrylate (HEMA).
  • GMA glycidyl methacrylate
  • SMA stearyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • Examples of such a copolymer include a ternary copolymer obtained by polymerizing glycidyl methacrylate (GMA), stearyl methacrylate (SMA), and 2-hydroxyethyl methacrylate (HEMA) as monomer components. Be done.
  • the copolymer is obtained by polymerizing a monomer component further containing 2-hydroxyethyl (meth) acrylate
  • the proportion of glycidyl (meth) acrylate in the monomer component is 4 to 51 mol%, and stearyl (meth) acrylate.
  • the proportion of 2-hydroxyethyl (meth) acrylate is preferably 2 to 35 mol%, the proportion of 2-hydroxyethyl (meth) acrylate is preferably 27 to 94 mol%, the proportion of glycidyl (meth) acrylate is 10 to 40 mol%, and the proportion of stearyl (meth) is
  • the proportion of acrylate is preferably 10 to 32 mol%, the proportion of 2-hydroxyethyl (meth) acrylate is preferably 35 to 80 mol%, the proportion of glycidyl (meth) acrylate is 20 to 30 mol%, and the proportion of stearyl (meth).
  • the proportion of acrylate is 20 to 30 mol%, and the proportion of 2-hydroxyethyl (meth) acrylate is more preferably 40 to 60 mol%.
  • the ratio of glycidyl methacrylate is preferably 4 to 51 mol%
  • the ratio of stearyl methacrylate is 2 to 35 mol%
  • the ratio of 2-hydroxyethyl methacrylate is preferably 27 to 94 mol%
  • the ratio of glycidyl methacrylate is 10. It is particularly preferable that the proportion is about 40 mol%
  • the proportion of stearyl methacrylate is 10 to 32 mol%
  • the proportion of 2-hydroxyethyl methacrylate is 35 to 80 mol%.
  • the copolymer may be obtained by further polymerizing a monomer component containing methyl (meth) acrylate.
  • the methyl (meth) acrylate refers to methyl methacrylate or methyl acrylate.
  • the present invention includes not only the case where methyl methacrylate or methyl acrylate is contained alone, but also the case where a mixture of methyl methacrylate and methyl acrylate is contained.
  • the melting point of the copolymer can be increased by polymerizing the monomer component containing methyl (meth) acrylate as the monomer component. As a result of being able to raise the melting point of the copolymer, as will be described later, it is easy to handle because it is weighed as a solid at the manufacturing stage.
  • the copolymer is formed by polymerizing a monomer component containing methyl methacrylate (MMA).
  • the copolymer may be obtained by polymerizing a monomer component containing glycidyl methacrylate (GMA), stearyl methacrylate (SMA), 2-hydroxyethyl methacrylate (HEMA), and methyl methacrylate (MMA). More preferred.
  • GMA glycidyl methacrylate
  • SMA stearyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • MMA methyl methacrylate
  • a quaternary copolymer can be mentioned.
  • the proportion of glycidyl (meth) acrylate in the monomer component is 4 to 46 mol%
  • the proportion of stearyl (meth) acrylate is It is preferably 1 to 20 mol%, preferably 20 to 87 mol% of 2-hydroxyethyl (meth) acrylate, 6 to 44 mol% of methyl (meth) acrylate, and preferably 6 to 44 mol% of glycidyl (meth) acrylate.
  • the proportion of stearyl (meth) acrylate is 5 to 17 mol%
  • the proportion of 2-hydroxyethyl (meth) acrylate is 30 to 75 mol%
  • the proportion of methyl (meth) acrylate is 8. It is more preferably to 35 mol%
  • the proportion of glycidyl (meth) acrylate is 20 to 35 mol%
  • the proportion of stearyl (meth) acrylate is 7 to 15 mol%
  • the proportion of 2-hydroxyethyl (meth) acrylate is 40 to 63 mol%
  • the proportion of methyl (meth) acrylate is more preferably 10 to 20 mol%.
  • the ratio of glycidyl methacrylate is 4 to 46 mol%
  • the ratio of stearyl methacrylate is 1 to 20 mol%
  • the ratio of 2-hydroxyethyl methacrylate is 20 to 87 mol%
  • the ratio of methyl methacrylate is 6 to 44 mol%.
  • the proportion of glycidyl methacrylate is 10 to 40 mol%
  • the proportion of stearyl methacrylate is 5 to 17 mol%
  • the proportion of 2-hydroxyethyl methacrylate is 30 to 75 mol%
  • the proportion of methyl methacrylate is more preferably 8 to 35 mol%.
  • the copolymer may be in any form such as a random copolymer, a block copolymer, or an alternating copolymer.
  • a random copolymer is suitable.
  • the copolymer is preferably solid at room temperature.
  • a copolymer facilitates weighing of the copolymer at the stage of producing the rubber composition. Further, in the kneading stage of the rubber composition, it becomes easy to put the copolymer into the mixer. Further, since it is possible to suppress fluctuations in the amount of the copolymer charged into the rubber composition between batches, there is also an advantage that fluctuations in the composition between batches can be suppressed.
  • the form of the copolymer is not particularly limited as long as it is in the solid state, and it can be used for kneading the rubber composition in the form of granules, powder or the like. In the present invention, "room temperature" means 25 ⁇ 5 ° C.
  • the polystyrene-equivalent weight average molecular weight of the copolymer is preferably 2,000 to 20,000.
  • the polystyrene-equivalent weight average molecular weight is 2,000 or more, the copolymer becomes solid at room temperature.
  • the rubber composition is mixed with the rubber component, it is possible to obtain a tire having excellent on-ice performance and fracture resistance without impairing fuel efficiency.
  • the polystyrene-equivalent weight average molecular weight of the copolymer is more preferably 2,300 or more, and further preferably 2,500 or more.
  • the polystyrene-equivalent weight average molecular weight of the copolymer is more preferably 20,000 or less, further preferably 18,000 or less, and 15,000 or less. It is particularly preferable to have.
  • the content of the copolymer is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
  • the content of the copolymer is 1 part by mass or more, it becomes possible to obtain a tire having excellent on-ice performance and fracture resistance.
  • the content of the copolymer with respect to 100 parts by mass of the rubber component is preferably 20 parts by mass or less.
  • the rubber composition of the present invention contains a filler that reinforces the rubber composition.
  • the strength of the vulcanized rubber portion vulcanized by the rubber composition can be increased.
  • the type of silica is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. Among these, wet silica is used. preferable. These silicas may be used alone or in combination of two or more.
  • the specific surface area (CTAB) of the cetyltrimethylammonium bromide of silica used in the present invention is not particularly limited.
  • the specific surface area (CTAB) of cetyltrimethylammonium bromide (CTAB) of silica is preferably 40 to 350 m 2 / g, and more preferably 100 to 250 m 2 / g.
  • the CTAB specific surface area of silica is a value measured by a method based on the method of ASTM-D3765-80.
  • the content of silica in the rubber composition is not particularly limited and can be appropriately selected according to the required performance.
  • the silica content may be 5 to 120 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of achieving both fracture resistance and on-ice performance at a higher level while suppressing deterioration of low heat generation. It is preferably 15 to 100 parts by mass, and more preferably 15 to 100 parts by mass.
  • the rubber composition for tires of the present invention preferably further contains carbon black as a filler.
  • carbon black as a filler.
  • the rubber composition for tires of the present invention may contain, for example, an inorganic filler such as clay, talc, calcium carbonate, or aluminum hydroxide.
  • the carbon black is not particularly limited, and examples thereof include GPF, FEF, HAF, ISAF, and SAF grade carbon black. These carbon blacks may be used alone or in combination of two or more.
  • the content of carbon black in the rubber composition is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. Further, from the viewpoint of reducing rolling resistance, the content of carbon black in the rubber composition is preferably 70 parts by mass or less and 50 parts by mass or less with respect to 100 parts by mass of the rubber component. Is more preferable.
  • the total of the silica content and the carbon black content is preferably 25 to 130 parts by mass, more preferably 50 to 90 parts by mass.
  • the rubber composition for a tire of the present invention contains at least one void-introducing agent selected from the group consisting of a foaming agent, heat-expanding microcapsules, a metal sulfate, porous cellulose particles, and a lignin derivative.
  • the rubber composition for a tire contains a foaming agent
  • bubbles are generated in the vulcanized rubber by the foaming agent during vulcanization of the rubber composition, and the vulcanized rubber can be used as the foamed rubber.
  • the rubber composition for a tire contains heat-expanding microcapsules
  • bubbles are generated in the vulcanized rubber by the heat-expanding microcapsules during vulcanization of the rubber composition, and the vulcanized rubber can be made into foam rubber. Since the foamed rubber has flexibility, the tire surface using the vulcanized rubber easily adheres to the icy road surface.
  • air bubbles generate holes (foam holes) derived from air bubbles on the surface of the vulcanized rubber and the surface of the tire, and function as a water channel for draining water.
  • Metal sulfate has the property of dissolving vulcanized rubber when it comes into contact with water. Therefore, when the rubber composition for a tire contains a metal sulfate, if the metal sulfate is exposed on the tire surface obtained by vulcanizing the rubber composition, water on an ice-snow road surface causes voids in the tire. The water between the tire and the road surface can be removed.
  • the rubber composition for a tire contains porous cellulose particles
  • water on an ice-snow road surface is absorbed by the porous cellulose particles when the porous cellulose particles are exposed on the tire surface obtained by vulcanizing the rubber composition. And the water between the tire and the road surface can be removed.
  • cellulose which is a polysaccharide, causes the interaction between the tire and water on the ice and snow road surface, so that the interaction between the tire and water due to the modified polyoxyalkylene glycol can be further enhanced.
  • the rubber composition for a tire contains a lignin derivative, the effect of improving the performance on ice can be enhanced.
  • the foaming agent, the heat-expanding microcapsules, the metal sulfate, the porous cellulose particles, and the lignin derivative are contained in the rubber composition for a tire of the present invention to obtain a sulfide rubber and a tire.
  • the voids include bubbles that are spaces as a closed system generated in the vulcanized rubber and pores that are spaces as an open system, and the pores may be penetrated or one. The part may be closed.
  • the effervescent agent include azodicarboxylic amide (ADCA), dinitrosopentamethylenetetramine (DPT), dinitrosopentastyrenetetramine, benzenesulfonylhydrazide derivative, and p, p'-oxybisbenzenesulfonyl hydrazide (. OBSH), ammonium bicarbonate that generates carbon dioxide, sodium bicarbonate, ammonium carbonate, nitrososulfonylazo compound that generates nitrogen, N, N'-dimethyl-N, N'-dinitrosophthalamide, toluenesulfonyl hydrazide, p.
  • ADCA azodicarboxylic amide
  • DPT dinitrosopentamethylenetetramine
  • DPT dinitrosopentastyrenetetramine
  • benzenesulfonylhydrazide derivative and p, p'-oxybisbenzene
  • -Toluenesulfonyl semicarbazide p, p'-oxybisbenzenesulfonyl semicarbazide and the like can be mentioned.
  • azodicarbonamide (ADCA) and dinitrosopentamethylenetetramine (DPT) are preferable from the viewpoint of manufacturing processability.
  • These foaming agents may be used alone or in combination of two or more.
  • the content of the foaming agent in the rubber composition for a tire is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. preferable.
  • the rubber composition for tires may further use urea, zinc stearate, zinc benzenesulfinate, zinc oxide, or the like as a foaming aid. These may be used alone or in combination of two or more. By using a foaming aid in combination, it is possible to promote the foaming reaction, increase the degree of completion of the reaction, and suppress unnecessary deterioration over time.
  • the heat-expandable microcapsules are composed of a shell material made of a thermoplastic resin containing a heat-expandable substance.
  • the shell material of the heat-expandable microcapsules can be formed of a nitrile-based polymer.
  • the heat-expandable substance contained in the shell material of the microcapsules has a property of being vaporized or expanded by heat, and for example, at least one kind selected from the group consisting of hydrocarbons such as isoalkane and normalalkane is exemplified.
  • isoalkanes examples include isobutane, isopentane, 2-methylpentane, 2-methylhexane, 2,2,4-trimethylpentane, and examples of normal alkanes include n-butane, n-propane, and n-hexane. Examples thereof include n-heptane and n-octane.
  • These hydrocarbons may be used alone or in combination of two or more.
  • a hydrocarbon obtained by dissolving a gaseous hydrocarbon at room temperature in a liquid hydrocarbon at room temperature is preferable.
  • heat-expandable microcapsules include the trade name "EXPANCEL 091DU-80" or “EXPANCEL 092DU-120” manufactured by EXPANCEL, Sweden, or the trade name "Matsumoto Micros” manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. "Fair F-85D” or “Matsumoto Microsphere F-100D” or the like can be used.
  • the content of the heat-expandable microcapsules in the rubber composition for a tire is not particularly limited, but is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the rubber component. preferable.
  • the metal sulfate examples include magnesium sulfate, potassium sulfate, calcium sulfate and the like. These metal sulfates may be used alone or in combination of two or more.
  • the content of the metal sulfate in the rubber composition for a tire is not particularly limited, but is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the rubber component. ..
  • Porous cellulose particles are cellulose particles having voids due to their porous structure.
  • the particle size of the porous cellulose particles is not particularly limited, but from the viewpoint of wear resistance, those having an average particle size of 1000 ⁇ m or less are preferable. These porous cellulose particles may be used alone or in combination of two or more. As such porous cellulose particles, the trade name "Viscopearl" manufactured by Rengo Co., Ltd. can be used.
  • the content of the porous cellulose particles in the rubber composition for a tire is not particularly limited, but is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the rubber component. preferable.
  • lignin sulfonate is preferably used as the lignin derivative.
  • the lignin sulfonate include an alkali metal salt of lignin sulfonic acid, an alkaline earth metal salt, an ammonium salt, an alcohol amine salt and the like, and at least one of these can be used.
  • alkali metal salts and / or alkaline earth metal salts of lignin sulfonic acid and examples thereof include potassium salt, sodium salt, calcium salt, magnesium salt, lithium salt, barium salt and the like, and a mixed salt thereof may also be used. good.
  • the content of the lignin derivative in the rubber composition for a tire is not particularly limited, but is preferably 0.1 to 40 parts by mass, more preferably 0.3 to 20 parts by mass with respect to 100 parts by mass of the rubber component. preferable.
  • the foaming ratio is usually 1 to 50%, preferably 5. ⁇ 40%.
  • the foaming rate is 50% or less, so that the voids on the rubber surface do not become too large, a sufficient ground contact area can be secured, and the formation of bubbles that effectively function as drainage ditches can be secured. Since the amount of air bubbles can be appropriately maintained, there is no risk of impairing durability.
  • the foaming rate of the vulcanized rubber means the average foaming rate Vs, and specifically, means the value calculated by the following formula (1).
  • Vs ( ⁇ 0 / ⁇ 1-1) ⁇ 100 (%) ( 1 )
  • ⁇ 1 indicates the density (g / cm 3 ) of the vulcanized rubber (foam rubber)
  • ⁇ 0 indicates the density (g / cm 3 ) of the solid phase portion of the vulcanized rubber (foam rubber).
  • the density of the vulcanized rubber and the density of the solid phase portion of the vulcanized rubber are calculated from the mass in ethanol and the mass in air. Further, the foaming rate can be appropriately changed depending on the type, amount and the like of the foaming agent and the foaming aid.
  • the rubber composition for a tire of the present invention may contain an organic acid, if necessary.
  • the organic acid has the effect of improving the foaming rate of the vulcanized rubber by balancing the rate of decomposition and foaming reaction of the above-mentioned foaming agent with the rate of the vulcanization reaction of the rubber composition during vulcanization of the rubber composition.
  • the SP value (solubility parameter) of the organic acid is preferably 9.15 to 16.0 (cal / cm 3 ) 1/2 .
  • the SP value of the organic acid is 9.15 (cal / cm 3 ) 1/2 or more, the decomposition of the foaming agent can be sufficiently promoted.
  • the SP value of the organic acid is 16.0 (cal / cm 3 ) 1/2 or less, the rubber composition adheres to the manufacturing equipment such as a roll at the time of manufacturing the rubber composition, and the rubber composition is formed. It is possible to prevent the workability of the object from deteriorating.
  • the SP value of the organic acid is more preferably 10.5 to 14.3 (cal / cm 3 ) 1/2 . In this specification, the SP value of the organic acid is calculated according to the Fedors method.
  • the organic acid may be any of monocarboxylic acid, dicarboxylic acid, tricarboxylic acid and the like, and may be aliphatic or aromatic.
  • the organic acid may further have a functional group other than the carboxyl group, such as a hydroxyl group, a ketone group and an ethylenically unsaturated group.
  • the organic acid one having an aromatic ring (aromatic) is preferable, and a monocarboxylic acid is preferable.
  • the organic acid has an aromatic ring, the adhesion of the rubber composition to the manufacturing equipment can be further reduced, and the workability of the rubber composition can be further improved.
  • the SP value of stearic acid which is widely used as a vulcanization aid in rubber compositions, is 9.12 (cal / cm 3 ) 1/2 , and the effect of promoting the decomposition of the foaming agent is low.
  • the aliphatic monocarboxylic acid include palmitic acid and the like.
  • the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like.
  • the aromatic monocarboxylic acid include benzoic acid and salicylic acid.
  • Examples of the aromatic dicarboxylic acid include phthalic acid and the like.
  • organic acid having a functional group other than the carboxyl group examples include tartrate acid, malic acid, maleic acid, glycolic acid, ⁇ -ketoglutaric acid and the like.
  • the organic acid may be used alone or in combination of two or more.
  • benzoic acid When benzoic acid is added to the rubber composition, the adhesion of the rubber composition to the manufacturing equipment can be further reduced, and the workability of the rubber composition can be further improved.
  • the content of the organic acid is preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of the workability of the rubber composition, the foaming rate of the vulcanized rubber and the performance on ice of the tire. , 1.5 to 7 parts by mass, more preferably 3 to 7 parts by mass.
  • the total content of the foaming agent and the organic acid is preferably 3 parts by mass or more and less than 15 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of the foaming rate of the vulgarized rubber and the performance on ice of the tire.
  • the range of 5 parts by mass or more and less than 15 parts by mass is more preferable, and the range of 7 parts by mass or more and less than 15 parts by mass is further preferable.
  • the mass ratio of the foaming agent to the organic acid may be in the range of 1: 0.5 to 1: 1.5 from the viewpoint of the foaming rate of the vulture rubber and the performance on ice of the tire. It is more preferably in the range of 1: 0.7 to 1: 1.3.
  • the rubber composition for a tire of the present invention may contain hydrophilic short fibers.
  • hydrophilic short fibers long bubbles are present in the tire (particularly the tread) after vulcanization of the rubber composition, and the long bubbles are generated on the tire surface due to the wear of the tire.
  • a cavity is formed by being exposed to the tire, and it is easy to function as a drainage channel for efficient drainage.
  • the cavity may have any shape of a hole, a depression, or a groove.
  • the staple fibers are hydrophilic, the cavities derived from the staple fibers formed on the tire surface can easily absorb water.
  • the hydrophilic staple fiber means a staple fiber having a contact angle with water of 5 to 80 degrees.
  • For the contact angle of the hydrophilic short fibers with water prepare a test piece obtained by molding the hydrophilic short fibers into a smooth plate shape, and use an automatic contact angle meter DM-301 manufactured by Kyowa Surface Chemistry Co., Ltd. at 25 ° C. Obtained by measuring the angle formed by the straight line formed by the surface of the test piece and the tangent line formed by the surface of the water droplet when water is dropped on the surface of the test piece under the condition of relative humidity of 55% and immediately after that, when observed from the side. be able to.
  • a resin having a hydrophilic group in the molecule (sometimes referred to as a hydrophilic resin) can be used, and specifically, it is selected from an oxygen atom, a nitrogen atom, and a sulfur atom.
  • a resin containing at least one is preferable.
  • a resin containing at least one substituent selected from the group consisting of -OH, -COOH, -OCOR (R is an alkyl group), -NH 2 , -NCO, and -SH can be mentioned.
  • substituents -OH, -COOH, -OCOR, -NH 2 and -NCO are preferable.
  • the hydrophilic resin preferably has a small contact angle with water and has an affinity for water, but the hydrophilic resin is preferably insoluble in water. Since the hydrophilic resin is insoluble in water, it is possible to prevent the hydrophilic resin from dissolving in the water when water adheres to the surface of the vulcanized rubber and the tire surface, and the water absorption of the cavity derived from the short fiber can be prevented. Can hold force.
  • hydrophilic resin having a large contact angle with water and being insoluble in water as described above, more specifically, an ethylene-vinyl alcohol copolymer, a vinyl alcohol homopolymer, and a poly (meth).
  • examples thereof include acrylic acid resin or an ester resin thereof, polyamide resin, polyethylene glycol resin, carboxyvinyl copolymer, styrene-maleic acid copolymer, polyvinylpyrrolidone resin, vinylpyrrolidone-vinyl acetate copolymer, mercaptoethanol and the like.
  • ethylene-vinyl alcohol copolymer vinyl alcohol homopolymer, poly (meth) acrylic acid resin, polyamide resin, aliphatic polyamide resin, aromatic polyamide resin, polyester resin, polyolefin resin, polyvinyl alcohol resin.
  • acrylic resins at least one selected from the group consisting of acrylic resins is preferable, and an ethylene-vinyl alcohol copolymer is more preferable.
  • the shape of the short fibers is not particularly limited and may be appropriately selected depending on the intended purpose, but as a micro drainage groove in the vulcanized rubber obtained by vulcanizing the rubber composition for a tire containing the short fibers.
  • the average value of 100 short fibers is preferably 0.1 mm to 10 mm in the long axis direction, and is preferably 0.5 mm to 5 mm. Is more preferable.
  • the average diameter (D) of the staple fibers is preferably 10 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 100 ⁇ m, as the average value of 100 staple fibers.
  • the content of the staple fibers in the rubber composition for a tire is preferably 0.2 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the rubber component.
  • the rubber composition for a tire in the present invention includes various components usually used in the rubber industry, such as stearic acid, an antioxidant, a silane coupling agent, and zinc oxide, if necessary.
  • Zinc oxide a vulcanization accelerator, a vulcanization agent, a work improving agent, a resin, a wax, an oil and the like may be appropriately selected and contained within a range that does not impair the object of the present invention.
  • the rubber composition for a tire of the present invention can be produced by blending each of the above-mentioned components and kneading them using a kneading machine such as a Banbury mixer, a roll, or an internal mixer.
  • the blending amount of each component is the same as the amount described above as the content in the rubber composition for tires.
  • the kneading of each component may be carried out in one step, but it is preferably carried out in two or more steps. When kneading is performed in two or more steps, at least the rubber component, the above-mentioned copolymer, and silica are kneaded in the first step of kneading.
  • the tire of the present invention is a vulcanized rubber obtained by vulcanizing the rubber composition for a tire of the present invention, and has excellent on-ice performance and fracture resistance, and has low fuel consumption.
  • the rubber composition for tires of the present invention is particularly preferably used for tread rubber.
  • Rubber component NR Natural rubber (RSS # 3)
  • BR Modified polybutadiene rubber obtained by the following manufacturing method
  • SBR Modified styrene-butadiene copolymer rubber obtained by the following manufacturing method 2.
  • Copolymer Copolymer 1 Methacrylic acid-based random copolymer obtained by polymerizing monomer components having GMA 10 mol% and SMA 90 mol%, polystyrene-equivalent weight average molecular weight 11,000, granular (room temperature).
  • Copolymer 2 Methacrylic acid-based random copolymer obtained by polymerizing monomer components of GMA 25 mol%, SMA 25 mol%, and HEMA 50 mol%, polystyrene-equivalent weight average molecular weight 5,000, granular (room temperature).
  • Copolymer 3 Methacrylic acid-based random copolymer obtained by polymerizing monomer components of GMA 25 mol%, SMA 12.5 mol%, HEMA 50 mol%, MMA 12.5 mol%, polystyrene-equivalent weight average molecular weight 5,200, granular (room temperature).
  • Copolymer 4 Methacrylic acid-based random copolymer obtained by polymerizing monomer components of GMA 25 mol%, SMA 12.5 mol%, HEMA 50 mol%, MMA 12.5 mol%, polystyrene-equivalent weight average molecular weight 13,400, granular (room temperature).
  • the weight average molecular weight is determined by gel permeation chromatography [GPC: HLC-8121GPC / HT manufactured by Tosoh Corporation, column: GMH HR -H (S) HT manufactured by Tosoh Corporation x 2, detector: differential refractometer (differential refractometer).
  • the bonded styrene content was 10% by mass
  • the vinyl content of the butadiene portion was 40%
  • the polystyrene-equivalent peak molecular weight obtained by gel permeation chromatography. was 200,000.
  • the tire using the rubber composition of Example 1 had the same fracture resistance as that of Comparative Example 1, but the results showed that it was excellent in on-ice performance and fuel efficiency.
  • the tires using the rubber compositions of Examples 2 to 4 were excellent in all of on-ice performance, fuel efficiency, and fracture resistance as compared with Comparative Examples.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne une composition de caoutchouc qui est destinée à un pneu et confère un excellent rendement de carburant et une excellente performance sur glace lorsqu'elle est utilisée pour un pneu, et à partir de laquelle de bonnes caractéristiques de résistance à la rupture peuvent être obtenues ; et un pneu utilisant cette composition de caoutchouc et qui confère un excellent rendement de carburant et une excellente performance sur glace, et présente de bonnes caractéristiques de résistance à la fracture. La composition de caoutchouc pour pneu comprend un composant de caoutchouc et un copolymère obtenu par polymérisation de composants monomères comprenant du (méth)acrylate de glycidyle et du (méth)acrylate de stéaryle.
PCT/JP2021/038525 2020-12-15 2021-10-19 Composition de caoutchouc pour pneu, et pneu WO2022130772A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024005029A1 (fr) * 2022-07-01 2024-01-04 株式会社ブリヂストン Composition de caoutchouc vulcanisé pour pneus et pneu

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104774580A (zh) * 2015-03-31 2015-07-15 山东天鼎丰非织造布有限公司 乳液胶黏剂和胎基布
US20170027168A1 (en) * 2015-07-27 2017-02-02 Stephan HEATH Methods, products, and systems relating to making, providing, and using nanocrystalline (nc) products comprising nanocrystalline cellulose (ncc), nanocrystalline (nc) polymers and/or nanocrystalline (nc) plastics or other nanocrystals of cellulose composites or structures, in combination with other materials
KR20190059073A (ko) * 2017-11-22 2019-05-30 주식회사 워솔 타이어용 미끄럼방지 조성물

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104774580A (zh) * 2015-03-31 2015-07-15 山东天鼎丰非织造布有限公司 乳液胶黏剂和胎基布
US20170027168A1 (en) * 2015-07-27 2017-02-02 Stephan HEATH Methods, products, and systems relating to making, providing, and using nanocrystalline (nc) products comprising nanocrystalline cellulose (ncc), nanocrystalline (nc) polymers and/or nanocrystalline (nc) plastics or other nanocrystals of cellulose composites or structures, in combination with other materials
KR20190059073A (ko) * 2017-11-22 2019-05-30 주식회사 워솔 타이어용 미끄럼방지 조성물

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024005029A1 (fr) * 2022-07-01 2024-01-04 株式会社ブリヂストン Composition de caoutchouc vulcanisé pour pneus et pneu

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