WO2017038724A1 - Particules de polymère enrobées, modificateur de résine, composition de caoutchouc, et pneumatique - Google Patents

Particules de polymère enrobées, modificateur de résine, composition de caoutchouc, et pneumatique Download PDF

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Publication number
WO2017038724A1
WO2017038724A1 PCT/JP2016/075087 JP2016075087W WO2017038724A1 WO 2017038724 A1 WO2017038724 A1 WO 2017038724A1 JP 2016075087 W JP2016075087 W JP 2016075087W WO 2017038724 A1 WO2017038724 A1 WO 2017038724A1
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meth
mass
polymer
coated polymer
particle
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PCT/JP2016/075087
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English (en)
Japanese (ja)
Inventor
敦 稲富
康成 梅田
大輔 香田
神原　浩
久保　敬次
社地　賢治
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株式会社クラレ
アミリス，インコーポレイティド
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Priority to JP2017537868A priority Critical patent/JP6737440B2/ja
Publication of WO2017038724A1 publication Critical patent/WO2017038724A1/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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to coated polymer particles, a resin modifier using the same, a rubber composition, and a tire. More specifically, the present invention relates to coated polymer particles useful as a resin modifier for tire applications, for example.
  • Polymer particles containing a conjugated diene polymer are known as resin modifiers.
  • resin modifiers for example, in tire applications, polymer particles made of styrene / butadiene rubber gel having a swelling index in toluene in a specific range and a particle size in a specific range are mixed with rubber to improve wear resistance and rolling. It is known that the resistance performance can be improved (see Patent Document 1).
  • the polymer particles using butadiene have a high viscosity, there is a problem that the processability of the rubber is lowered by the addition of the polymer particles.
  • the present invention has been made in view of the above situation, and in tire applications, while maintaining excellent rolling resistance performance, while suppressing deterioration of rubber processability, coated polymer particles excellent in wear resistance, and It aims at providing the resin modifier, rubber composition, and tire using this.
  • the polymer particles are coated polymer particles having particles and an outermost coating covering at least a part of the particles, and the particles are derived from farnesene.
  • the present invention has been completed by finding that the above-mentioned problems can be solved by coated polymer particles, which are polymers containing monomer units.
  • the present invention relates to the following [1] to [13].
  • Coated polymer particles having particles (x) and an outermost coating covering at least a part of the particles (x),
  • the particle (x) contains a polymer (A) containing a monomer unit derived from farnesene, Coated polymer particles, wherein the outermost coating contains a polymer (B).
  • the polymer (A) is a copolymer comprising a monomer unit derived from farnesene and a monomer unit derived from another radical polymerizable monomer (a). Coated polymer particles as described.
  • the content of the monomer unit derived from the radical polymerizable monomer (a) in the polymer (A) is 5 to 95% by mass with respect to the total mass of the polymer (A).
  • the radical polymerizable monomer (a) is a conjugated diene other than farnesene, an aromatic vinyl compound, (meth) acrylic acid and a salt thereof, (meth) acrylic acid ester, and (N-alkyl) (meth).
  • the polymer (B) is a copolymer including a monomer unit derived from a conjugated diene and a monomer unit derived from another radical polymerizable monomer (b), and the radical polymerizable property.
  • the monomer (b) is at least one selected from the group consisting of aromatic vinyl compounds, (meth) acrylic acid and salts thereof, (meth) acrylic acid esters, and (N-alkyl) (meth) acrylamides.
  • the content of the monomer unit derived from the radical polymerizable monomer (b) in the polymer (B) is 1 to 80% by mass with respect to the total mass of the polymer (B).
  • the radical polymerizable monomer (b) is (meth) acrylic acid and a salt thereof, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid N, N′—
  • polymer (A) containing a monomer unit derived from farnesene is also simply referred to as “polymer (A)”
  • radically polymerizable monomer (a) is simply referred to as “monomer (a ) "
  • radically polymerizable monomer (b) is also simply referred to as” monomer (b) ".
  • a monomer unit derived from farnesene is also simply referred to as “farnesene unit”
  • a monomer unit derived from conjugated diene is also simply referred to as “conjugated diene unit”.
  • (meth) acryl means one or two selected from “methacryl” and “acryl”, and “(N-alkyl) (meth) acrylamide” It means one or more selected from “(meth) acrylamide” and “N-alkyl (meth) acrylamide”.
  • coated polymer particles that suppress deterioration in workability of rubber and have excellent wear resistance while maintaining excellent rolling resistance performance, and a resin modifier and rubber using the same Compositions and tires can be provided.
  • the coated polymer particle of the present invention is a coated polymer particle having a particle (x) and an outermost coating film covering at least a part of the particle (x), wherein the particle (x) is a heavy polymer containing a farnesene unit.
  • a coalescence (A) is contained and this outermost film contains a polymer (B).
  • the particle (x) is a portion of the inner layer in the coated polymer particle, and the outermost coating is a portion of the outermost layer.
  • “coating” refers to a state in which the outermost coating covers at least a part of the surface of the particle (x), and preferably covers the entire surface.
  • the particles (x) in the present invention contain a polymer (A) containing farnesene units.
  • the polymer (A) is formed by polymerization of a monomer containing farnesene.
  • the polymer (A) constituting the particle (x) contains a farnesene unit, it is possible to suppress an increase in viscosity due to the addition of the coated polymer particle, improve workability, and improve wear resistance. it can.
  • Such farnesene may be ⁇ -farnesene, may be ⁇ -farnesene represented by the following formula (I), and may include ⁇ -farnesene and ⁇ -farnesene. From the viewpoint of properties, ⁇ -farnesene is preferably included.
  • the content of the monomer unit derived from ⁇ -farnesene is preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass in the farnesene unit from the viewpoint of ease of production, that is, the farnesene unit. It is more preferable that all of the above are monomer units derived from ⁇ -farnesene. Moreover, it is preferable that the farnesene unit contained in a polymer (A) is bridge
  • the content of the farnesene unit in the polymer (A) is preferably in the range of 5 to 100% by mass with respect to the total mass of the polymer (A) from the viewpoint of workability and wear resistance, and 5 to 95% by mass.
  • the range of 20 to 95% by mass is more preferable, the range of 30 to 90% by mass is still more preferable, and the range of 40 to 80% by mass is even more preferable.
  • the polymer (A) of the present invention may be a copolymer containing a farnesene unit and a monomer unit derived from a radical polymerizable monomer (a) other than farnesene.
  • Monomers (a) include conjugated dienes other than farnesene such as butadiene and isoprene; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and tert-butylstyrene; (meth) acrylic acid and salts thereof; (meth) (Meth) acrylic acid esters such as methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N- (N-alkyl) (meth) acrylamides such as ethyl (meth) acrylamide; nitriles such as (meth)
  • conjugated dienes other than farnesene aromatic vinyl compounds, (meth) acrylic acid and salts thereof, (meth) acrylic acid esters, and (N-alkyl) (meth) At least one selected from the group consisting of acrylamide is preferable, and from the viewpoint of improving rolling resistance performance, conjugated dienes other than farnesene are more preferable, butadiene is more preferable, and workability, wear resistance, and rolling resistance performance are improved. From the viewpoint, an aromatic vinyl compound is more preferable, and styrene is more preferable.
  • a monomer (a) may be used individually by 1 type, or may use 2 or more types together.
  • the content of the monomer unit derived from the monomer (a) in the polymer (A) is preferably in the range of 0 to 95% by mass with respect to the total mass of the polymer (A), and 5 to 95% by mass.
  • the range of 5 to 80% by mass is more preferable, the range of 10 to 70% by mass is still more preferable, and the range of 20 to 60% by mass is still more preferable.
  • the polymer (A) is a copolymer containing a farnesene unit and a monomer unit derived from the monomer (a)
  • the farnesene unit and the monomer unit derived from the monomer (a) is preferably 95/5 to 30/70, and preferably 90/10 to 40 from the viewpoints of workability, wear resistance and rolling resistance performance.
  • / 60 is more preferable, 80/20 to 50/50 is more preferable, and 70/30 to 60/40 is still more preferable.
  • the particles (x) may contain a plurality of types of polymers (A) having different monomer compositions, and the particles (x ′) and at least one layer covering at least a part of the particles (x ′).
  • grains which consist of several layers which have the film which becomes may be sufficient.
  • the content of the particles (x ′) in the particles (x) is preferably in the range of 1 to 50% by mass, more preferably in the range of 7 to 30% by mass, from the viewpoint of ease of production. A range is more preferred.
  • the particles (x) are composed of another polymer (A ′) containing a monomer unit having a composition different from that of the polymer (A) (hereinafter simply referred to as “polymer”). (A ′) ”) and a coating containing the polymer (A) covering at least a part of the particles (x ′) preferable.
  • Monomers that can form such other polymers (A ′) include conjugated dienes such as butadiene, isoprene, and farnesene; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, and tert-butylstyrene; (meth) acrylic Acids and salts thereof; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate; (meth) acrylamide, N- (N-alkyl) (meth) acrylamides such as methyl (meth) acrylamide and N-ethyl (meth) acrylamide; nitriles such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether;
  • the polymer (A ′) may be a copolymer containing a monomer unit derived from farnesene and a monomer unit derived from another radical polymerizable monomer (a ′).
  • the polymerizable monomer (a ′) is a conjugated diene other than farnesene, an aromatic vinyl compound, (meth) acrylic acid and its salt, (meth) acrylic acid ester, and ( N-alkyl) (meth) acrylamide is preferably selected from the group consisting of (meth) acrylamide, and from the viewpoint of workability, wear resistance and rolling resistance performance, it is selected from the group consisting of conjugated dienes other than farnesene and aromatic vinyl compounds. At least one selected from the group consisting of butadiene and styrene is more preferable. These may be used alone or in combination of two or more.
  • the content of the particles (x) in the coated polymer particles of the present invention is preferably in the range of 10 to 99.9% by mass, and 30 to 99.9% by mass with respect to the total mass of the coated polymer particles. Is more preferably in the range of 40 to 95% by mass, and still more preferably in the range of 60 to 95% by mass.
  • the outermost coating in the present invention contains the polymer (B).
  • Monomers that can form the polymer (B) of the present invention include conjugated dienes such as butadiene, isoprene and farnesene; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and tert-butylstyrene; (meth) acrylic acid And salts thereof; (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and hydroxyalkyl (meth) acrylate (Meth) acrylic acid ester such as ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid N, N′-dialkylaminoalkyl ester, (meth) acrylic acid trialkoxysilylalkyl ester; (meth)
  • conjugated dienes aromatic vinyl compounds, (meth) acrylic acid and salts thereof, (meth) acrylic acid esters, and (N-alkyl) (meta)
  • At least one selected from the group consisting of acrylamide is preferable, and at least one selected from the group consisting of conjugated dienes, aromatic vinyl compounds, (meth) acrylic acid and salts thereof, and (meth) acrylic acid esters is more preferable.
  • the conjugated diene is preferably at least one selected from the group consisting of farnesene, butadiene and isoprene, more preferably at least one selected from the group consisting of farnesene and butadiene.
  • the aromatic vinyl compound is preferably at least one selected from the group consisting of styrene and ⁇ -methylstyrene, and more preferably styrene.
  • the (meth) acrylic acid ester include (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid N, N′-dialkylaminoalkyl ester, and (meth) acrylic acid trialkoxy
  • at least one selected from the group consisting of silylalkyl esters more preferably at least one selected from the group consisting of (meth) acrylic acid hydroxyalkyl esters and (meth) acrylic acid glycidyl esters, 2-hydroxybutyl methacrylate and More preferred is at least one selected from the group consisting of glycidyl methacrylate.
  • the farnesene used in the polymer (B) may be ⁇ -farnesene, like the polymer (A), may be ⁇ -farnesene represented by the above formula (I), and ⁇ - Although it may contain farnesene and ⁇ -farnesene, it is preferable to contain ⁇ -farnesene from the viewpoint of ease of production.
  • a polymer (B) contains a farnesene unit, it is preferable that a polymer composition is not the same as a polymer (A) and a polymer (B).
  • the polymer (B) of the present invention preferably contains a conjugated diene unit from the viewpoints of workability, wear resistance and rolling resistance performance.
  • conjugated diene units are formed by polymerization of the conjugated diene described above.
  • the conjugated diene is preferably at least one selected from the group consisting of farnesene, butadiene and isoprene, from the viewpoint of wear resistance and rolling resistance performance, more preferably a combination of farnesene and another conjugated diene, and farnesene and butadiene or
  • the combined use with isoprene is more preferable, and the combined use of farnesene and butadiene is more preferable.
  • the polymer (B) may be a copolymer containing a conjugated diene unit and a monomer unit derived from another radical polymerizable monomer (b).
  • Monomer (b) is an aromatic vinyl compound, (meth) acrylic acid and its salt, (meth) acrylic acid ester, and (N-alkyl) (from the viewpoint of workability, abrasion resistance and rolling resistance performance. At least one selected from the group consisting of (meth) acrylamides is preferable, and at least one selected from the group consisting of aromatic vinyl compounds, (meth) acrylic acid and salts thereof, and (meth) acrylic acid esters is more preferable.
  • the content of the conjugated diene unit in the polymer (B) is preferably in the range of 20 to 100% by mass and preferably in the range of 20 to 99% by mass with respect to the total mass of the polymer (B). More preferably, it is in the range of 40 to 99% by mass, and further preferably in the range of 60 to 98% by mass.
  • the content of the monomer unit derived from the monomer (b) in the polymer (B) is preferably in the range of 0 to 80% by mass relative to the total mass of the polymer (B). The range of 80% by mass is more preferable, the range of 1 to 60% by mass is more preferable, and the range of 2 to 40% by mass is even more preferable.
  • the mass ratio of farnesene to other conjugated dienes is the workability and wear resistance.
  • 5/95 to 95/5 is preferable, 30/70 to 70/30 is more preferable, and 40/60 to 60/40 is still more preferable.
  • the polymer (B) is a copolymer containing a conjugated diene unit and a monomer unit derived from the monomer (b), the monomer unit derived from the conjugated diene unit and the monomer (b)
  • the mass ratio of [conjugated diene unit / monomer unit derived from monomer (b)] is preferably 98/2 to 50/50 from the viewpoints of workability, wear resistance and rolling resistance performance, 5 to 60/40 is more preferable, and 95/5 to 70/30 is still more preferable.
  • the polymer (B) forming the outermost coating preferably has a reactive functional group from the viewpoint of improving the wear resistance and rolling resistance performance.
  • the reactive functional group of the polymer (B) reacts with a filler component contained in the resin or rubber composition.
  • Such reactive functional groups include hydroxyl groups, carboxy groups, epoxy groups, amino groups, N-alkylamino groups, trialkoxysilyl groups, and the like.
  • the monomer (b) from the viewpoint of improving rolling resistance performance, (meth) acrylic acid and salts thereof; (meth) such as 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate Hydroxyalkyl esters of acrylic acid; (meth) acrylic acid glycidyl esters such as glycidyl (meth) acrylate; (meth) such as N, N′-dimethylaminoethyl (meth) acrylate and N, N′-diethylaminoethyl (meth) acrylate N, N'-dialkylaminoalkyl acrylates; (meth) acrylic acid trialkoxylates such as (meth) acrylic acid triethoxysilylpropyl, (meth) acrylic acid
  • (meth) Acrylic acid and its salts (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid N, N′-dialkylaminoalkyl ester, and (N-alkyl) (meth) acrylamide
  • At least one selected from the group is more preferable, at least one selected from the group consisting of (meth) acrylic acid and salts thereof, (meth) acrylic acid hydroxyalkyl ester and (meth) acrylic acid glycidyl ester is more preferable, Acid, glycidyl methacrylate and 2- At least one selected from the group consisting of mud carboxybutyl methacrylate is more preferred more. These may be used alone or in combination of two or more.
  • the content of the outermost coating in the coated polymer particles of the present invention is preferably in the range of 0.1 to 90% by weight, preferably 0.1 to 70% by weight, based on the total weight of the coated polymer particles.
  • the range is more preferable, the range of 5 to 60% by mass is further preferable, and the range of 5 to 40% by mass is still more preferable.
  • the content of the polymer (B) in the outermost coating is preferably in the range of 60 to 100% by mass, more preferably in the range of 80 to 100% by mass, from the viewpoint of workability, wear resistance and rolling resistance performance.
  • the range of ⁇ 100% by mass is more preferable.
  • the mass ratio of the particle (x) to the outermost coating [particle (x) / outermost coating] is in the range of 95/5 to 50/50 from the viewpoint of the balance of workability, wear resistance and rolling resistance performance. Preferably, it is in the range of 90/10 to 60/40, more preferably in the range of 80/20 to 65/35.
  • the coated polymer particle of the present invention When the coated polymer particle of the present invention is used as a resin modifier for tire applications, it is preferably crosslinked from the viewpoint of improving wear resistance.
  • the degree of crosslinking of the coated polymer particles of the present invention the toluene swelling index of the coated polymer particles can be used as an index. From the above viewpoint, the toluene swelling index is preferably 1 to 80, more preferably 1 to 60, still more preferably 6 to 40, and even more preferably 6 to 25.
  • the toluene swelling index is determined by the mass ratio ( ⁇ ) of the toluene swollen mass obtained by swelling the coated polymer particles with toluene and the mass ( ⁇ ) after drying of the toluene swollen mass by the method described in Examples. / ⁇ ) can be obtained by measuring. The lower the toluene swelling index, the higher the degree of crosslinking.
  • the average particle size of the coated polymer particles of the present invention is preferably 10 to 200 nm, more preferably 20 to 100 nm from the viewpoint of the balance between easy dispersibility and the modification effect when used as a resin modifier for tire applications. More preferably, it is 30 to 80 nm.
  • the average particle diameter is measured by embedding the coated polymer particles in a methacrylic resin, staining with osmium tetroxide, and observing the particle image with a transmission electron microscope by the method described in Examples.
  • the ratio of the average particle diameter of the particles (x) to the average thickness of the outermost coating is the workability, wear resistance and rolling resistance performance From the viewpoint, a range of 1 to 1,000 is preferable, a range of 2 to 500 is more preferable, a range of 3 to 100 is further preferable, a range of 4 to 50 is still more preferable, and a range of 5 to 30 is still more preferable. 7 to 20 is even more preferable.
  • grains (x) and the average thickness of outermost film are measured by the method as described in an Example.
  • the coated polymer particle of the present invention is an anti-aging agent, an antioxidant, a wax, a lubricant as necessary for the purpose of improving the weather resistance, heat resistance, oxidation resistance, etc., as long as the effects of the present invention are not impaired.
  • the antioxidant include hindered phenol compounds, phosphorus compounds, lactone compounds, hydroquinone compounds, and the like.
  • the antiaging agent include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds, and phosphorus compounds.
  • the coated polymer particles of the present invention can be produced, for example, by emulsion polymerization, and are preferably obtained by a production method having the following steps 1 and 2.
  • Step 1 Step of obtaining emulsion of particles (x) containing polymer (A) by emulsion polymerization of water-containing monomer forming polymer (A) in water
  • Step 2 Obtained in Step 1 A monomer for forming the polymer (B) is further added to the obtained emulsion and emulsion polymerization is carried out in water to obtain an emulsion of coated polymer particles having an outermost film containing the polymer (B).
  • Film (x) comprising polymer (A), particles (x ′) containing polymer (A ′), and film containing polymer (A) covering at least part of the particles (x ′)
  • steps 1-1 and 1-2 it is preferable to have the following steps 1-1 and 1-2 as step 1 before step 2.
  • Step 1-1 A step of emulsion-polymerizing the monomer forming the polymer (A ′) in water to obtain an emulsion of particles (x ′) containing the polymer (A ′)
  • Step 1-2 Particles having a coating film containing the polymer (A) by further adding a monomer containing farnesene that forms the polymer (A) to the emulsion obtained in step 1-1 and emulsion polymerization in water Step of Obtaining Emulsion Solution (x)
  • the coating film covering the particle (x ′) is composed of a plurality of layers, it can be produced by repeating Step 1-2.
  • the amount of water used in the emulsion polymerization is 100 masses of the sum of the monomer forming the polymer (A) and the monomer forming the polymer (B) from the viewpoint of the viscosity and stability of the emulsion.
  • the amount is preferably in the range of 50 to 1,500 parts by weight, more preferably in the range of 80 to 1,000 parts by weight, and still more preferably in the range of 100 to 800 parts by weight.
  • an emulsifier and a polymerization initiator are usually used.
  • the emulsifier used in the emulsion polymerization is preferably an anionic emulsifier such as a fatty acid salt, a rosin acid salt or an alkyl sulfate.
  • sodium, potassium or ammonium salts of aliphatic carboxylic acids such as laurate, myristate, palmitate, stearate, linoleate, linolenate; disproportionation of natural rosin Or sodium salt, potassium salt or ammonium salt of hydrogenated product; sodium salt, potassium salt or ammonium salt of aliphatic sulfate compound such as lauryl sulfate; polyoxyethylene octyl phenyl ether sulfonate, polyoxyethylene octyl phenyl ether sulfate Examples thereof include sodium salts, potassium salts, and ammonium salts of nonionic anionic emulsifiers such as ester salts.
  • a nonionic emulsifier such as polyoxyethylene octylphenyl ether or polyoxyethylene nonylphenyl ether or a protective colloid agent such as polyvinyl alcohol may be used in combination.
  • the amount of the emulsifier is not particularly limited as long as it does not impair the stability of the emulsion, but is a monomer that forms the polymer (A) from the viewpoint of removal after emulsion polymerization and environmental contamination due to waste water. And in the range of 0.01 to 15 parts by mass, preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the sum of the monomers forming the polymer (B). More preferably, it is in the range of 1 to 7 parts by mass.
  • Such an emulsifier may be usually dispersed in water from the beginning of emulsion polymerization before the monomer is added, or may be added during the polymerization reaction.
  • the polymerization initiator used in the emulsion polymerization is not particularly limited as long as it has radical polymerization initiating ability. Specifically, azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2 Azo compounds such as' -azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate; Inorganic peroxides such as sodium, potassium persulfate and hydrogen peroxide; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide and p-menthane hydroperoxide. These may be used alone or in combination of two or more. Such a polymerization initiator may be added to water from the beginning of emulsion polymerization, or may be added during the poly
  • the amount of the polymerization initiator used is 0.01 to 15 parts by mass with respect to 100 parts by mass of the sum of the monomer that forms the polymer (A) and the monomer that forms the polymer (B).
  • the range is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass.
  • a redox initiator may be used, and the redox initiator is preferably a combination of the organic peroxide and the transition metal salt.
  • transition metal salts used in combination with organic peroxides include iron (II) sulfate, iron (II) thiosulfate, iron (II) carbonate, iron (II) chloride, iron (II) bromide, and iron iodide.
  • Iron compounds such as (II), iron hydroxide (II), iron oxide (II); copper sulfate (I), copper thiosulfate (I), copper carbonate (I), copper chloride (I), copper bromide ( Copper compounds such as I), copper iodide (I), copper hydroxide (I), copper oxide (I), or hydrates thereof can be used.
  • the combined use of the organic peroxide and the iron compound is preferable, the combined use of cumene hydroperoxide and the iron compound is more preferable, and the water of cumene hydroperoxide and iron (II) sulfate is more preferable.
  • the combined use with a Japanese thing is still more preferable.
  • the amount of the organic peroxide used is 0.01 to 15 parts by mass with respect to 100 parts by mass of the sum of the monomer forming the polymer (A) and the monomer forming the polymer (B). Is preferable, and the range of 0.1 to 5 parts by mass is more preferable.
  • the amount of the transition metal salt used is 0.001 to 0.2 mass relative to 100 mass parts of the sum of the monomer forming the polymer (A) and the monomer forming the polymer (B). The range of parts is preferable, and the range of 0.005 to 0.1 parts by mass is more preferable.
  • the organic peroxide is not only used at the start of emulsion polymerization, but may be additionally used during the polymerization reaction.
  • the amount added during the polymerization reaction is not particularly limited as long as it does not impair the modification effect of the produced coated polymer particles, but from the viewpoint of the toluene swelling index of the obtained coated polymer particles, A range of 0.0001 to 0.1% by mass with respect to water at the start of polymerization is preferred.
  • a method of additional addition of the organic peroxide to the polymerization reaction system either continuous addition or intermittent addition may be used.
  • a desired amount of a reducing agent, a metal ion chelating agent, an electrolyte, or the like may be added as necessary.
  • reducing agents such as sodium hydroxymethanesulfinate and sodium ascorbate
  • metal ion chelating agents such as disodium ethylenediaminetetraacetate
  • electrolytes such as sodium chloride, sodium sulfate, and trisodium phosphate.
  • a chain transfer agent conventionally used in emulsion polymerization can be used to adjust the toluene swelling index.
  • the chain transfer agent is not particularly limited as long as it has chain transfer ability in radical polymerization of farnesene.
  • mercaptan compounds such as n-dodecyl mercaptan and t-dodecyl mercaptan; dimethylxanthogen disulfide, Examples thereof include xanthogen disulfide compounds such as diethyl xanthogen disulfide and diisopropyl xanthogen disulfide; thiuram disulfide compounds such as tetramethylthiuram disulfide and tetraethylthiuram disulfide; halogenated hydrocarbon compounds such as carbon tetrachloride.
  • chain transfer agents such as n-dodecyl mercaptan and t-dodecyl mercaptan are preferred from the viewpoint of chain transfer ability to farnesene.
  • chain transfer agents may be added to water from the beginning of emulsion polymerization or may be added during the polymerization reaction.
  • the amount of the chain transfer agent used is preferably 5 parts by mass or less with respect to 100 parts by mass of the sum of the monomer that forms the polymer (A) and the monomer that forms the polymer (B). Less than the mass part is more preferable.
  • the coated polymer particles of the present invention have a desired toluene swelling index, it can be adjusted by the addition amount of the polymerization initiator and chain transfer agent, but it can also be adjusted by adding a crosslinking agent before adding the polymerization terminator. it can.
  • the compound used for crosslinking is not particularly limited as long as it has the ability to initiate the crosslinking reaction of olefins. Specifically, hydrogen peroxide, cumene hydroperoxide, p-menthane hydroperoxide and the like are not particularly limited.
  • Oxides such as azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); sulfur And so on.
  • the emulsion polymerization is preferably performed under stirring conditions such that the environment in the system is uniform, and is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • the polymerization temperature of the emulsion polymerization is not particularly limited, but is preferably 5 to 80 ° C., more preferably 20 to 70 ° C. from the viewpoint of the polymerization rate and the stability of the emulsion.
  • the pressure condition during the emulsion polymerization depends on the vapor pressure and the amount of the compound to be used, but is appropriately selected from normal pressure to high pressure (about 1 MPa).
  • the method for adding the monomer for forming the polymer (A) is preferably intermittent addition and more preferably continuous addition from the viewpoint of emulsion stability at the time of monomer addition.
  • the monomer conversion rate is preferably 60% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. Is more preferable. This conversion rate can be confirmed by measuring the mass of the solid content precipitated from the emulsion by the method described in Examples.
  • Step 1 after producing an emulsion of particles (x) containing the polymer (A) by emulsion polymerization, in Step 2, the polymer (B) is further formed in the emulsion obtained in Step 1.
  • a monomer is added and emulsion polymerization is performed to form an outermost film covering at least a part of the particles (x).
  • the method for adding the monomer for forming the polymer (B) is preferably intermittent addition, more preferably continuous addition, from the viewpoint of the stability of the emulsion during monomer addition.
  • the monomer conversion rate is preferably 60% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. Is more preferable. This conversion rate can be confirmed by measuring the mass of the solid content precipitated from the emulsion by the method described in Examples.
  • the polymerization can be stopped by adding a polymerization terminator.
  • a polymerization terminator include amine compounds such as hydroxylamine and sodium dimethyldithiocarbamate, and phenol compounds such as hydroquinone and p-methoxyphenol. These may be used individually by 1 type, or may use 2 or more types together.
  • the addition amount of the polymerization terminator is in the range of 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of monomers usually used.
  • the polymerization terminator may be added after mixing with water to prepare an aqueous solution, suspension, emulsion or the like.
  • the coated polymer particles can be recovered by a general method of taking out the emulsion polymer such as salting out, acid precipitation, spray drying method and freezing method. You may remove a residual monomer by heating etc. before collection
  • the coated polymer particles can be recovered by using a coagulant generally used in emulsion polymerization.
  • monovalent metal salts such as sodium chloride, potassium chloride, sodium acetate, potassium acetate, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate; calcium chloride, magnesium chloride, calcium acetate, magnesium acetate, calcium sulfate
  • Divalent metal salts such as magnesium sulfate, calcium carbonate and magnesium carbonate
  • trivalent metal salts such as aluminum chloride and aluminum sulfate
  • polymer flocculants may be used alone or in combination of two or more.
  • the coated polymer particles can be recovered by using an acid compound generally used in emulsion polymerization. Specific examples include hydrochloric acid, acetic acid, sulfuric acid and the like. These acid compounds may be used alone or in combination of two or more.
  • the average dispersed particle size of the particles (x) containing the polymer (A) in the emulsion during the emulsion polymerization and the coated polymer particles in the emulsion after the completion of the emulsion polymerization is the monomer and water used in the emulsion polymerization.
  • the addition ratio, the type or amount of the emulsifier, the polymerization temperature, the type or amount of the electrolyte can be adjusted.
  • the particle size can adjust the polymerization rate and the physical properties and dispersibility of the coated polymer particles.
  • the average dispersed particle size of the coated polymer particles in the emulsion during production is 10 to 10 from the viewpoint of polymerization stability. It is preferably 200 nm, more preferably 20 to 100 nm, and even more preferably 30 to 80 nm.
  • the average dispersed particle size is measured by the method described in the examples.
  • the toluene swelling index of the particles (x) containing the polymer (A) and the coated polymer particles is the polymerization temperature, polymerization time, type or amount of polymerization initiator, type or amount of chain transfer agent when performing emulsion polymerization. It can be adjusted by the kind or amount of the monomer, the kind or amount of the crosslinking agent, and the like.
  • the resin modifier of the present invention includes the coated polymer particles and can be used by being dispersed in a resin serving as a matrix. By mixing the resin modifier of the present invention and the resin used as a matrix, it is possible to impart excellent processability to the resin composition and improve wear resistance in tire applications. A resin composition having excellent rolling resistance performance can be obtained.
  • the resin used as the matrix is not particularly limited, but various rubbers such as natural rubber, styrene-butadiene copolymer, polybutadiene, polyisoprene, isobutylene-isoprene copolymer, styrene-isoprene copolymer, styrene-isoprene- Examples thereof include a butadiene copolymer, a halogenated isobutylene-isoprene copolymer, an ethylene-propylene-diene copolymer, an acrylonitrile-butadiene copolymer, a partial hydrogenated product of an acrylonitrile-butadiene copolymer, and polychloroprene. These may be used individually by 1 type, or may use 2 or more types together.
  • a modified rubber having a functional group introduced may be used as the rubber.
  • functional groups include epoxy groups, hydroxyl groups, amino groups, alkoxysilyl groups and the like.
  • modified rubber include epoxy group-modified natural rubber, hydroxyl group-modified styrene-butadiene copolymer, amino group-modified styrene- Examples thereof include butadiene copolymers and alkoxysilyl group-modified styrene-butadiene copolymers.
  • the rubber may contain a ⁇ -farnesene homopolymer in the range of, for example, 0.1 to 50 parts by mass with respect to 100 parts by mass of the rubber.
  • the coated polymer particles of the present invention are preferably used in an amount of 0.1 to 100 parts by mass with respect to 100 parts by mass of the resin as a matrix. It is more preferable to use ⁇ 50 parts by mass, and it is more preferable to use 1 to 30 parts by mass.
  • the resin modifier of the present invention is an antioxidant, an antioxidant, a wax, a lubricant, a light stabilizer, a scorch inhibitor, a processing aid, as necessary, as long as the effects of the present invention are not impaired.
  • additives such as colorants such as pigments and dyes, flame retardants, antistatic agents, matting agents, antiblocking agents, UV absorbers, mold release agents, foaming agents, antibacterial agents, antifungal agents, and perfumes Or you may contain 2 or more types.
  • the rubber composition of the present invention is a rubber composition containing a rubber component (X) containing the above-mentioned coated polymer particles and a filler (Y), wherein the coated polymer particles in the total amount of the rubber component (X) The content is 1 to 50% by mass, and the filler (Y) is contained in an amount of 20 to 150 parts by mass with respect to 100 parts by mass of the rubber component (X).
  • examples of the rubber component (X) include natural rubber; styrene-butadiene copolymer, polybutadiene, polyisoprene, isobutylene-isoprene copolymer, styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer.
  • Halogenated isobutylene-isoprene copolymer ethylene-propylene-diene copolymer, acrylonitrile-butadiene copolymer, partially hydrogenated product of acrylonitrile-butadiene copolymer, and synthetic rubber such as polychloroprene.
  • synthetic rubber such as styrene-butadiene copolymer, polybutadiene, and polyisoprene is preferable. These rubbers may be used alone or in combination of two or more.
  • the natural rubber used as the rubber component (X) is, for example, natural rubber generally used in the tire industry such as TMR and RSS such as SMR, SIR and STR, high-purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, Examples thereof include modified natural rubbers such as hydrogenated natural rubber and grafted natural rubber.
  • TMR and RSS such as SMR, SIR and STR
  • modified natural rubbers such as hydrogenated natural rubber and grafted natural rubber.
  • SMR20, STR20, and RSS # 3 are preferable from the viewpoint of little variation in quality and easy availability.
  • These natural rubbers may be used alone or in combination of two or more. When two or more kinds of natural rubber are used in combination, the combination can be arbitrarily selected within a range not impairing the effects of the present invention, and the physical property value can be adjusted by the combination.
  • Synthetic rubber used as the rubber component (X) is styrene-butadiene copolymer, polybutadiene, polyisoprene, isobutylene-isoprene copolymer, styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer, halogenated isobutylene- At least one selected from the group consisting of an isoprene copolymer, an ethylene-propylene-diene copolymer, an acrylonitrile-butadiene copolymer, a partial hydrogenated product of an acrylonitrile-butadiene copolymer, and polychloroprene is preferable.
  • the combination can be arbitrarily selected within a range not impairing the effects of the present invention, and the physical property values can be adjusted by the combination.
  • these manufacturing methods are not specifically limited, What is marketed can be used.
  • styrene-butadiene copolymer As the styrene-butadiene copolymer, those commonly used for tire applications can be used. Specifically, those having a styrene content of 0.1 to 70% by mass are preferred, and those having a styrene content of 5 to 50% by mass. Is more preferable. Further, the butadiene monomer unit in the copolymer preferably has a bond mode content (vinyl content) of 0.1 to 60% by weight excluding 1,4 bonds, preferably 0.1 to 55% by weight. Those are more preferred.
  • the weight average molecular weight (Mw) of the styrene-butadiene copolymer is preferably 100,000 to 2,500,000, more preferably 150,000 to 2,000,000, and even more preferably 200,000 to 1,500,000. When it is within the above range, both moldability and the mechanical strength of the obtained tire can be achieved.
  • the glass transition temperature (Tg) obtained by differential thermal analysis of the styrene-butadiene copolymer used in the present invention is preferably ⁇ 95 to 0 ° C., more preferably ⁇ 95 to ⁇ 5 ° C.
  • Tg is in the above range, the rubber composition can be prevented from increasing in viscosity, and the handling becomes easy.
  • the styrene-butadiene copolymer that can be used in the present invention is obtained by copolymerizing styrene and butadiene.
  • the method for producing the styrene-butadiene copolymer and any of an emulsion polymerization method, a solution polymerization method, a gas phase polymerization method, and a bulk polymerization method can be used, and an emulsion polymerization method and a solution polymerization method are preferable.
  • the styrene-butadiene copolymer can be produced by an ordinary emulsion polymerization method, and can be obtained, for example, by emulsifying and dispersing a predetermined amount of styrene and a butadiene monomer in the presence of an emulsifier, and emulsion polymerization with a radical polymerization initiator. .
  • a chain transfer agent can also be used to adjust the molecular weight of the styrene-butadiene copolymer obtained by emulsion polymerization.
  • the copolymer can be recovered as crumb by adding the acid and coagulating the copolymer while adjusting the pH of the coagulation system to a predetermined value and then separating the dispersion solvent.
  • the crumb is washed with water, then dehydrated, and dried with a band dryer or the like to obtain the desired emulsion-polymerized styrene-butadiene copolymer.
  • a styrene-butadiene copolymer can be produced by a usual solution polymerization method.
  • an active metal capable of anion polymerization in a solvent styrene and butadiene are optionally copolymerized in the presence of a polar compound.
  • a polar compound e.g., a polar compound that is optionally copolymerized in the presence of a polar compound.
  • an anion-polymerizable active metal an alkali metal and an alkaline earth metal are preferable, an alkali metal is more preferable, and an organic alkali metal compound is further preferable.
  • organic alkali metal compound examples include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1,4- Polyfunctional organolithium compounds such as dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like.
  • organic lithium compound is preferable, and an organic monolithium compound is more preferable.
  • the amount of the organic alkali metal compound used is appropriately determined depending on the required molecular weight of the styrene-butadiene copolymer obtained by solution polymerization.
  • the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, toluene And aromatic hydrocarbons.
  • These solvents are usually preferably used in a range where the monomer concentration is 1 to 50% by mass.
  • the polar compound is not particularly limited as long as it is usually used for adjusting the microstructure of the butadiene moiety and the distribution of styrene in the copolymer chain without deactivating the reaction in anionic polymerization.
  • dibutyl ether Ether compounds such as tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.
  • the temperature of the polymerization reaction is usually in the range of ⁇ 80 to 150 ° C., preferably 0 to 100 ° C., more preferably 30 to 90 ° C.
  • the polymerization mode may be either a batch type or a continuous type.
  • the polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator.
  • a polymerization terminal modifier may be added before the polymerization terminator is added.
  • the solvent can be separated by direct drying, steam stripping or the like, and the target solution-polymerized styrene-butadiene copolymer can be recovered.
  • the polymerization solution and the extending oil may be mixed in advance and recovered as an oil-extended rubber.
  • a modified styrene-butadiene copolymer having a functional group introduced into the styrene-butadiene copolymer may be used as long as the effects of the present invention are not impaired.
  • the functional group include an amino group, an alkoxysilyl group, a hydroxyl group, an epoxy group, and a carboxyl group.
  • the position at which the functional group in the polymer is introduced may be the end of the polymer or the side chain of the polymer.
  • polyisoprene As polyisoprene, for example, a commercially available polyisoprene obtained by polymerization using a Ziegler catalyst, a lanthanoid rare earth metal catalyst, an organic alkali metal compound, or the like can be used. Among these, polyisoprene obtained by polymerization using a Ziegler catalyst is preferable from the viewpoint of a high cis isomer content. Moreover, you may use the polyisoprene of the ultra high cis body content obtained using a lanthanoid type rare earth metal catalyst.
  • the vinyl content of polyisoprene is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. When the vinyl content is 50% by mass or less, the rolling resistance performance is good. The lower limit of the vinyl content is not particularly limited.
  • the glass transition temperature (Tg) of polyisoprene varies depending on the vinyl content, but is preferably ⁇ 20 ° C. or lower, more preferably ⁇ 30 ° C. or lower.
  • the weight average molecular weight (Mw) of polyisoprene is preferably 90,000 to 2,000,000, and more preferably 150,000 to 1,500,000. When the weight average molecular weight is within the above range, the moldability and the mechanical strength of the resulting tire are good.
  • the polyisoprene is partially branched by using a polyfunctional modifier such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an amino group-containing alkoxysilane. It may have a structure or a polar functional group.
  • polybutadiene As the polybutadiene, for example, a commercially available polybutadiene obtained by polymerization using a Ziegler catalyst, a lanthanoid rare earth metal catalyst, an organic alkali metal compound, or the like can be used. Among these, polybutadiene obtained by polymerization using a Ziegler catalyst is preferable from the viewpoint of a high cis isomer content. Moreover, you may use the polybutadiene of the ultra-high cis body content obtained using a lanthanoid type rare earth metal catalyst.
  • the vinyl content of the polybutadiene is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. When the vinyl content is 50% by mass or less, the rolling resistance performance is good. The lower limit of the vinyl content is not particularly limited.
  • the glass transition temperature (Tg) of polybutadiene varies depending on the vinyl content, but is preferably ⁇ 40 ° C. or lower, more preferably ⁇ 50 ° C. or lower.
  • the weight average molecular weight (Mw) of polybutadiene is preferably 90,000 to 2,000,000, more preferably 150,000 to 1,500,000, and further preferably 250,000 to 800,000. When the weight average molecular weight is in the above range, the moldability and the mechanical strength of the resulting tire are good.
  • the polybutadiene is partially branched by using a polyfunctional modifier such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an amino group-containing alkoxysilane. Or you may have a polar functional group.
  • the rubber composition of the present invention contains 20 to 150 parts by mass of filler (Y) with respect to 100 parts by mass of rubber component (X).
  • filler (Y) physical properties such as mechanical strength, heat resistance, and weather resistance are improved, and the hardness can be adjusted and the amount of the rubber composition can be increased.
  • Fillers (Y) used in the present invention include oxides such as silica and titanium oxide; silicates such as clay, talc, mica, glass fiber and glass balloon; carbonates such as calcium carbonate and magnesium carbonate; magnesium hydroxide And hydroxides such as aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate; inorganic fillers such as carbons such as carbon black and carbon fiber; organic fillers such as resin particles, wood powder and cork powder. . These may be used alone or in combination of two or more.
  • the content of the coated polymer particles in the rubber composition is 1 to 50% by mass, preferably 2 to 30% by mass, and more preferably 3 to 10% by mass in the total amount of the rubber component (X).
  • the content of the filler (Y) in the rubber composition is 20 to 150 parts by weight, preferably 25 to 130 parts by weight, and more preferably 30 to 110 parts by weight with respect to 100 parts by weight of the rubber component (X). .
  • the content of the filler (Y) is in the above range, molding processability, braking performance, mechanical strength, and wear resistance are improved.
  • the rubber composition of the present invention preferably contains a silane coupling agent.
  • the silane coupling agent include sulfide compounds, mercapto compounds, vinyl compounds, amino compounds, glycidoxy compounds, nitro compounds, and chloro compounds.
  • sulfide compounds include bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (2-trimethoxysilyl).
  • Ethyl) tetrasulfide bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N, N Examples include dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxys
  • Examples of the mercapto compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and the like.
  • Examples of the vinyl compound include vinyl triethoxysilane and vinyl trimethoxysilane.
  • Examples of amino compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, and 3- (2-aminoethyl) aminopropyltrimethoxy. Silane etc. are mentioned.
  • Examples of glycidoxy compounds include ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -glycidoxypropylmethyldimethoxysilane.
  • Examples of the nitro compound include 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.
  • Examples of the chloro compound include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, and 2-chloroethyltriethoxysilane.
  • sulfide compounds and mercapto compounds are preferable from the viewpoint of the effect of addition and cost, and bis (3-triethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) tetrasulfide, and 3-mercapto are preferred. More preferred is propyltrimethoxysilane.
  • the content of the silane coupling agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the filler (Y). 1 to 15 parts by mass is more preferable.
  • the content of the silane coupling agent is within the above range, dispersibility, coupling effect, reinforcement, and tire wear resistance are improved.
  • the rubber composition of the present invention is preferably used after being crosslinked (vulcanized) by adding a crosslinking agent.
  • the crosslinking agent include sulfur and sulfur compounds, oxygen, organic peroxides, phenol resins and amino resins, quinones and quinone dioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, metal halides and organometallic halogens.
  • silane compounds other than silane coupling agents are preferred. These may be used alone or in combination of two or more.
  • the content of the crosslinking agent is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, and still more preferably 0.8 to 5 parts by weight with respect to 100 parts by weight of the rubber component (X). .
  • the rubber composition of the present invention can be vulcanized and used as a vulcanized rubber.
  • the vulcanization conditions and method it is preferably carried out using a vulcanization mold under pressure and heating conditions of a vulcanization temperature of 120 to 200 ° C. and a vulcanization pressure of 0.5 to 2.0 MPa.
  • the rubber composition of the present invention may contain a vulcanization accelerator.
  • the vulcanization accelerator include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamic acid compounds, aldehyde-amine compounds or aldehyde-ammonia compounds, imidazoline compounds. Compounds, xanthate compounds, and the like. These may be used alone or in combination of two or more.
  • the content thereof is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component (X).
  • the rubber composition of the present invention may further contain a vulcanization aid.
  • a vulcanization aid include fatty acids such as stearic acid; metal oxides such as zinc white; and fatty acid metal salts such as zinc stearate. These may be used alone or in combination of two or more.
  • the content thereof is preferably 0.1 to 15 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the rubber component (X).
  • the rubber composition of the present invention is intended to improve molding processability, fluidity, etc. within a range that does not impair the effects of the invention, and if necessary, silicon oil, aroma oil, TDAE (Treated Distilled Aromatic Extracts), MES ( Mild Extracted Solvates), RAE (Residual Aromatic Extracts), process oils such as paraffin oil and naphthenic oil, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, C9 resins, rosin resins, coumarone-indene resins, Resin components such as phenol resins, liquid polymers such as low molecular weight polybutadiene, low molecular weight polyisoprene, low molecular weight styrene-butadiene copolymer, and low molecular weight styrene-isoprene copolymer can be used as a softening agent as appropriate. .
  • the copolymer may be in any polymerization form such
  • the rubber composition of the present invention is an anti-aging agent, an antioxidant, a wax, a lubricant, a light as needed for the purpose of improving the weather resistance, heat resistance, oxidation resistance, etc., as long as the effects of the invention are not impaired.
  • One or more additives such as an agent and a fragrance may be contained.
  • the antioxidant include hindered phenol compounds, phosphorus compounds, lactone compounds, and hydroquinone compounds.
  • the anti-aging agent include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds, and phosphorus compounds.
  • the method for producing the rubber composition of the present invention is not particularly limited, and the components may be mixed uniformly.
  • the uniform mixing method include a tangential or meshing closed kneader such as a kneader ruder, a brabender, a banbury mixer, an internal mixer, a single screw extruder, a twin screw extruder, a mixing roll, and a roller. Usually, it can be carried out in a temperature range of 70 to 270 ° C.
  • the tire of the present invention is a tire using at least a part of the rubber composition. Therefore, workability, wear resistance, and rolling resistance performance are good.
  • the rubber composition of the present invention can be used for various members of tires, and can be suitably used particularly as tire treads for passenger cars, truck buses, motorcycles and industrial vehicles.
  • a tire using the rubber composition of the present invention or a crosslinked product of the rubber composition of the present invention can maintain characteristics such as wear resistance and rolling resistance performance even when used for a long time.
  • a tire made of a rubber composition containing the coated polymer particles of the present invention is excellent in wear resistance and rolling resistance performance.
  • a mixture of the emulsion (0.1 ml) and ion-exchanged water (10 ml) sampled before the addition of the polymerization terminator is used as a dynamic light scattering measurement device (device).
  • FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.
  • the particle size distribution of the particles was measured on a volume basis, and the median diameter was measured as the average dispersed particle size.
  • the emulsion was sampled after the monomer mixture (ii) was added and before the polymerization terminator was added.
  • the average particle diameter of the particles (x) is measured by the same method as above except that the emulsion of the particles (x) is used in place of the coated polymer particles or the emulsion of polymer particles, and the above measurement is performed. The average thickness was obtained from the difference from the average particle diameter of the coated polymer particles.
  • Toluene swelling index The coated polymer particles or polymer particles immersed in toluene were shaken for 24 hours so that the solid concentration was about 1% by mass to obtain a toluene solution containing a toluene swell.
  • the toluene solution containing the swollen body was treated at 20,000 rpm for 1 hour using a centrifuge (device name: hymac CR 22GII, manufactured by Hitachi Koki Co., Ltd.), and solid-liquid separation was performed. Subsequently, after taking out the solid layer containing the swollen body and measuring the mass ( ⁇ ), it was vacuum-dried under the conditions of 0.1 kPa and 60 ° C. using the vacuum dryer until the mass change of the swollen body disappeared, and toluene The toluene swelling index ( ⁇ / ⁇ ) was calculated from the ratio of the mass before drying ( ⁇ ) and the mass after drying ( ⁇ ).
  • Example 1 (Preparation of initiator emulsion) An emulsion containing 3.45 g of cumene hydroperoxide as a polymerization initiator, 3.75 g of sodium lauryl sulfate as an emulsifier, and 150 g of ion-exchanged water was subjected to deoxygenation to obtain an initiator emulsion.
  • the addition of the monomer mixture (iii) when it was confirmed that the total monomer conversion calculated by the above method exceeded 95% by mass, the addition of the initiator emulsion was stopped, and the polymerization terminator A hydroquinone deoxygenated aqueous solution was added.
  • the polymerization tank was cooled to 25 ° C., and the emulsion of the coated polymer particles of the present invention was taken out.
  • the polymerization time from the start of polymerization to the addition of the polymerization terminator was 10 hours.
  • Examples 2 to 6 (Production of coated polymer particles (1-2) to (1-6) and rubber composition) Using the monomer mixture shown in Table 1, coated polymer particles (1-2) to (1-6) were obtained in the same manner as in Example 1, and then the blending ratio (parts by mass) shown in Table 3 Thus, a rubber composition was obtained in the same manner as in Example 1. Each of the obtained coated polymer particles and the rubber composition was evaluated by the above method. The results are shown in Table 4.
  • Example 7 (Preparation of initiator emulsion) An initiator emulsion was obtained in the same manner as in the preparation of the initiator emulsion in Example 1. (Production of coated polymer particles (1-7)) (Step 1-1) In a dried 0.5 L pressure-resistant polymerization tank, 200 g of ion-exchanged water, 5 g of sodium lauryl sulfate, 0.032 g of iron (II) sulfate (7 hydrate), 0.02 g of disodium ethylenediaminetetraacetate, 0% of sodium chloride After adding 2 g, deoxygenation was performed by bubbling with nitrogen gas for 30 minutes to obtain an aqueous solution.
  • Step 1-1 In a dried 0.5 L pressure-resistant polymerization tank, 200 g of ion-exchanged water, 5 g of sodium lauryl sulfate, 0.032 g of iron (II) sulfate (7 hydrate), 0.02 g of disodium ethylened
  • Step 1-2 After confirming that the total monomer conversion calculated by the above method exceeded 95% by mass, the initiator emulsion was added to the emulsion obtained in Step 1-1 at a rate of 0.02 ml / min.
  • the monomer mixture (ii) shown in Table 1 was deoxygenated while being fed at 0, and then continuously added at a rate of 1.7 ml / min to obtain an emulsion of particles (x).
  • Process 2 After the addition of the monomer mixture (ii), when it was confirmed that the total monomer conversion calculated by the above method exceeded 95% by mass, the monomer mixture (iii) shown in Table 1 was removed. After oxygen treatment, it was continuously added at a rate of 1.7 ml / min.
  • the addition of the monomer mixture (iii) when it was confirmed that the total monomer conversion calculated by the above method exceeded 95% by mass, the addition of the initiator emulsion was stopped, and the polymerization terminator A hydroquinone deoxygenated aqueous solution was added. Thereafter, the polymerization tank was cooled to 25 ° C., and the emulsion of the coated polymer particles of the present invention was taken out. The polymerization time from the start of polymerization to the addition of the polymerization terminator was 10 hours.
  • Examples 8-10 (Production of coated polymer particles (1-8) to (1-10) and a rubber composition) Using the monomer mixture shown in Table 1, coated polymer particles (1-8) to (1-10) were obtained in the same manner as in Example 7, and then the blending ratio (parts by mass) shown in Table 3 Thus, a rubber composition was obtained in the same manner as in Example 1. Each of the obtained coated polymer particles and the rubber composition was evaluated by the above method. The results are shown in Table 4.
  • Comparative Examples 1 and 2 (Production of coated polymer particles (2-1) and (2-2)) Using the monomer mixture shown in Table 2, coated polymer particles (2-1) and (2-2) were obtained in the same manner as in Example 1. Each of the obtained coated polymer particles was analyzed by the above method. The results are shown in Table 4. (Manufacture of rubber composition) According to the compounding ratio (parts by mass) shown in Table 3, a rubber composition was obtained in the same manner as in Example 1. Each rubber composition obtained was evaluated by the above method. The results are shown in Table 4.
  • the monomer mixture (ii) shown in Table 2 was deoxygenated and then added.
  • the polymerization was started by continuously adding the initiator emulsion at a rate of 0.02 ml / min.
  • the addition of the initiator emulsion was stopped, and a deoxygenated aqueous solution of hydroquinone as a polymerization terminator was added.
  • the polymerization tank was cooled to 25 ° C., and an emulsion of polymer particles was taken out.
  • the polymerization time from the start of polymerization to the addition of the polymerization terminator was 10 hours.
  • Table 4 Each notation in Table 4 is as follows. * 1: Numerical values in parentheses in Table 4 indicate the content (% by mass) of each monomer in each polymer. * 2: Indicates the average particle diameter of the coated polymer particles or polymer particles. * 3: Indicates the ratio between the average particle diameter of the particles (x) and the average thickness of the outermost coating.
  • the rubber compositions using the coated polymer particles of Examples 1 to 10 are excellent in workability and wear resistance while maintaining excellent rolling resistance performance as compared with Comparative Examples 1 to 4. This shows that the rolling resistance performance is compatible with workability and wear resistance.
  • coated polymer particles of the present invention are useful as a resin modifier capable of suppressing deterioration in processability of rubber and improving wear resistance while maintaining excellent rolling resistance performance in tire applications.
  • a rubber composition containing coalesced particles can be suitably used as a rubber composition for a tire or the like having excellent processability and excellent wear resistance and rolling resistance performance.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Tires In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne des particules de polymère enrobées comprenant des particules (x) et un film d'enrobage le plus externe enrobant au moins une partie des particules (x), les particules de polymère enrobées contenant des particules (x) contenant un polymère (A) comportant des motifs monomères dérivés du farnésène, et le film d'enrobage le plus externe contenant un polymère (B) ; et un modificateur de résine, une composition de caoutchouc, ainsi qu'un pneumatique l'utilisant.
PCT/JP2016/075087 2015-08-31 2016-08-26 Particules de polymère enrobées, modificateur de résine, composition de caoutchouc, et pneumatique WO2017038724A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020067414A1 (fr) * 2018-09-28 2020-04-02 株式会社カネカ Composition de caoutchouc pour bandages, bandage et corps moulé
WO2022130771A1 (fr) * 2020-12-15 2022-06-23 株式会社ブリヂストン Composition de caoutchouc pour pneu, et pneu
US20230192934A1 (en) * 2021-12-20 2023-06-22 Korea Kumho Petrochemical Co., Ltd. Copolymer, method of preparing the same, and rubber composition including the same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020203301A1 (fr) * 2019-03-29 2020-10-08
KR102446296B1 (ko) * 2020-12-15 2022-09-22 한화토탈에너지스 주식회사 고무 조성물의 제조방법, 이의 방법으로 제조된 고무 조성물 및 이를 이용하여 제조된 타이어

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0971620A (ja) * 1995-06-26 1997-03-18 Kuraray Co Ltd 酢酸ビニル系重合体の製法、酢酸ビニル系重合体ケン化物の製法および樹脂組成物
JP2012514079A (ja) * 2008-12-29 2012-06-21 フイナ・テクノロジー・インコーポレーテツド 光過酸化法を使用する重合体組成物および重合開始剤
WO2013125496A1 (fr) * 2012-02-24 2013-08-29 株式会社クラレ Composition de caoutchouc et pneu
WO2013151069A1 (fr) * 2012-04-04 2013-10-10 株式会社クラレ Copolymère, composition de caoutchouc mettant en œuvre celui-ci, et pneumatique
WO2013151068A1 (fr) * 2012-04-04 2013-10-10 株式会社クラレ Copolymère, composition de caoutchouc mettant en œuvre celui-ci, et pneumatique
WO2013151067A1 (fr) * 2012-04-04 2013-10-10 株式会社クラレ Copolymère, composition de caoutchouc mettant en œuvre celui-ci, et pneumatique
JP2015067805A (ja) * 2013-09-30 2015-04-13 株式会社クラレ 樹脂組成物、これを硬化させた硬化物及びこの樹脂組成物を含む光学用粘着剤
JP2015511266A (ja) * 2012-02-22 2015-04-16 アムイリス， インコーポレイテッド ファルネセンを含む組成物の重合

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5868915B2 (ja) * 2013-09-06 2016-02-24 株式会社ユニバーサルエンターテインメント 遊技機

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0971620A (ja) * 1995-06-26 1997-03-18 Kuraray Co Ltd 酢酸ビニル系重合体の製法、酢酸ビニル系重合体ケン化物の製法および樹脂組成物
JP2012514079A (ja) * 2008-12-29 2012-06-21 フイナ・テクノロジー・インコーポレーテツド 光過酸化法を使用する重合体組成物および重合開始剤
JP2015511266A (ja) * 2012-02-22 2015-04-16 アムイリス， インコーポレイテッド ファルネセンを含む組成物の重合
WO2013125496A1 (fr) * 2012-02-24 2013-08-29 株式会社クラレ Composition de caoutchouc et pneu
WO2013151069A1 (fr) * 2012-04-04 2013-10-10 株式会社クラレ Copolymère, composition de caoutchouc mettant en œuvre celui-ci, et pneumatique
WO2013151068A1 (fr) * 2012-04-04 2013-10-10 株式会社クラレ Copolymère, composition de caoutchouc mettant en œuvre celui-ci, et pneumatique
WO2013151067A1 (fr) * 2012-04-04 2013-10-10 株式会社クラレ Copolymère, composition de caoutchouc mettant en œuvre celui-ci, et pneumatique
JP2015067805A (ja) * 2013-09-30 2015-04-13 株式会社クラレ 樹脂組成物、これを硬化させた硬化物及びこの樹脂組成物を含む光学用粘着剤

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020067414A1 (fr) * 2018-09-28 2020-04-02 株式会社カネカ Composition de caoutchouc pour bandages, bandage et corps moulé
JPWO2020067414A1 (ja) * 2018-09-28 2021-09-16 株式会社カネカ タイヤ用ゴム組成物、タイヤおよび成形体
JP7299908B2 (ja) 2018-09-28 2023-06-28 株式会社カネカ タイヤ用ゴム組成物、タイヤおよび成形体
WO2022130771A1 (fr) * 2020-12-15 2022-06-23 株式会社ブリヂストン Composition de caoutchouc pour pneu, et pneu
US20230192934A1 (en) * 2021-12-20 2023-06-22 Korea Kumho Petrochemical Co., Ltd. Copolymer, method of preparing the same, and rubber composition including the same
US11820847B2 (en) * 2021-12-20 2023-11-21 Korea Kumho Petrochemical Co., Ltd. Copolymer, method of preparing the same, and rubber composition including the same

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