WO2005040267A1 - Rubber composition for footwear - Google Patents

Rubber composition for footwear Download PDF

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Publication number
WO2005040267A1
WO2005040267A1 PCT/JP2004/016465 JP2004016465W WO2005040267A1 WO 2005040267 A1 WO2005040267 A1 WO 2005040267A1 JP 2004016465 W JP2004016465 W JP 2004016465W WO 2005040267 A1 WO2005040267 A1 WO 2005040267A1
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WIPO (PCT)
Prior art keywords
group
weight
modified polymer
parts
polymer
Prior art date
Application number
PCT/JP2004/016465
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French (fr)
Japanese (ja)
Inventor
Haruo Yamada
Hiroshi Fusamae
Takaaki Matsuda
Original Assignee
Asahi Kasei Chemicals Corporation
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Application filed by Asahi Kasei Chemicals Corporation filed Critical Asahi Kasei Chemicals Corporation
Priority to JP2005515070A priority Critical patent/JP4721900B2/en
Priority to CN2004800322692A priority patent/CN1875063B/en
Publication of WO2005040267A1 publication Critical patent/WO2005040267A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2421/00—Characterised by the use of unspecified rubbers

Definitions

  • the present invention relates to a rubber-like polymer composition
  • a rubber-like polymer composition comprising a modified polymer in which a rubber-like polymer component and a functional group-containing atomic group are combined, and a masterbatch component in which an inorganic filler is mixed in advance.
  • the present invention relates to a novel rubber composition for footwear having excellent abrasion resistance and adhesiveness.
  • rubber-like polymers have been used in various footwear applications as raw materials for footwear.
  • a rubber composition containing a rubber-like polymer as a main component and further blending various inorganic fillers, additives, coloring agents, and the like is used as a raw material.
  • a white filler such as silica is widely used as a reinforcing agent to improve the appearance of the product.
  • silica is used as a reinforcing filler, the affinity for rubber is lower than that of conventional carbon black, and the dispersibility of silica in rubber is not always good. This tends to result in a decrease in mechanical properties and mechanical strength.
  • silica is incorporated into a rubber composition by using a silane coupling agent represented by bis- (3-triethoxysilylpropyl) tetrasulfide. Improving variances has forced product costs to rise.
  • Patent Document 1 discloses a shoe sole having excellent coloring and abrasion resistance by limiting silica and a silane coupling agent and mixing a rubber with a thermoplastic resin.
  • Patent Document 2 discloses a lightweight, wear-resistant shoe sole material made of high-cis polybutadiene, styrene resin, and silica.
  • Patent Document 3 discloses a rubber composition for footwear in which a specific polysiloxane compound is used to improve abrasion resistance.
  • Patent Document 4 discloses a rubber composition for footwear having excellent abrasion resistance and anti-skid resistance by combining a modified polymer having a specific structure with silica. A rubber composition having excellent adhesive strength when used has not been obtained.
  • Patent Documents 5 and 6 disclose a rubber composition using a masterbatch comprising a modified polymer and a reinforcing filler, but the adhesive strength, which is an important property as a rubber composition for footwear, is described. There is no.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2000-236905
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2002-191401
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2002-2849 31
  • Patent Document 5 Japanese Patent Application Laid-Open No. 8-23 1766
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2000-136269 discloses the invention
  • the present invention provides a rubber composition obtained from a rubbery polymer and an inorganic filler, wherein a masterbatch of a modified polymer having a functional group-containing atomic group bonded thereto and an inorganic filler is produced, and the masterbatch and the rubbery polymer are prepared.
  • An object of the present invention is to provide a rubber composition for footwear which has excellent tear strength, abrasion resistance and adhesiveness and can improve the working environment of a shoe factory by using a rubber composition containing
  • the present inventors have proposed that a conjugated gen-based polymer or a vinyl aromatic hydrocarbon and a conjugated gen-based
  • a rubber composition containing a rubbery polymer and an inorganic filler was produced.
  • a masterbatch in which a modified polymer having a specific functional group and an inorganic filler are kneaded in advance, a rubber composition for footwear with excellent tear strength, abrasion resistance and adhesion can be obtained. Heading, the present invention has been completed.
  • the present invention is as follows.
  • the component (2) is charged with 20 to 80% by weight of the inorganic filler in a kneader in advance and kneaded, then the modified polymer is added, and the remaining amount of the inorganic filler is added to the kneaded mass.
  • modified polymer is a modified polymer in which at least one atomic group selected from the following formulas (1) to (14) is bonded.
  • N is a nitrogen atom
  • Si is a silicon atom
  • O is an oxygen atom
  • C is a carbon atom
  • H is a hydrogen atom
  • R 1 and R 2 are each independently Represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms
  • each of the hydrocarbon groups independently has a hydroxyl group, an epoxy group, an amino group, or a hydrocarbon group having 1 to 24 carbon atoms, if desired. It may have at least one functional group selected from the group consisting of an imino group, a silanol group and an alkoxysilane group having 1 to 24 carbon atoms
  • each R 3 is independently a group having 1 to 48 carbon atoms.
  • Each R 4 may have at least one functional group selected from the group consisting of alkoxysilane groups. Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.
  • the compound (4) having a reactivity with a functional group bonded to the modified polymer is further added to the modified polymer by 100 wt. 2.
  • Component (2) Force The compound (4) having a reactivity with the functional group bonded to the modified polymer is added to the kneaded product of the modified polymer and the inorganic filler at 100 wt.
  • the modified polymer used for the component (2) may be a compound (4) having a reactivity with a functional group bound to the modified polymer. 2.
  • Masterbatch obtained by kneading A method for producing a rubber composition for footwear, including a step of kneading 1 to 150 parts by weight.
  • the shoe for footwear according to the above item 12 which is a master batch obtained by dividing the component (2) by 5 to 300 parts by weight of the inorganic filler two or more times and putting into a kneading machine to be kneaded sequentially.
  • a method for producing a composition which is a master batch obtained by dividing the component (2) by 5 to 300 parts by weight of the inorganic filler two or more times and putting into a kneading machine to be kneaded sequentially.
  • the rubber composition for footwear of the present invention manufactured using a modified polymer having a specific functional group-containing atomic group bonded thereto and a master batch of an inorganic filler has a tear strength, abrasion resistance, and water-based adhesion. It is a rubber composition that has excellent adhesiveness and can improve the working environment of a shoe factory.
  • the type of the rubbery polymer which is the component (1) constituting the rubber composition for footwear of the present invention is not particularly limited, but may be a conjugated polymer or a hydrogenated product thereof, a conjugated monomer and a vinyl aromatic. Random copolymers of hydrocarbons or hydrogenated products thereof, block copolymers of conjugated diene monomers and butyl aromatic hydrocarbons or hydrogenated products thereof, non-gen-based polymers, natural rubber, etc. can give.
  • butadiene rubber or its hydrogenated product isoprene rubber or its hydrogenated product
  • styrene-butadiene Styrene-based elastomer such as styrene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof, styrene-isoprene block copolymer or hydrogenated product thereof, at court tri-butadiene rubber or hydrogenated product thereof
  • non-gen-based polymers such as ethylene-propylene rubber, ethylene-propylene-gen rubber, ethylene-butene-gen rubber, ethylene-butene rubber, ethen-hexene rubber, and ethylene-butene rubber.
  • Olefin elastomer butyl rubber, brominated butyl rubber, acryl rubber, fluoro rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, ⁇ , j3_unsaturated nitrile-acrylic acid ester-conjugated gen copolymer rubber, Urethane rubber, etc. And the like.
  • These rubbery polymers may be modified rubbers having a functional group.
  • the rubbery polymer can be used alone or as a mixture of two or more rubbery polymers.
  • the component (2) constituting the rubber composition for footwear of the present invention contains a functional group in a conjugated gen-based polymer or a copolymer composed of a conjugated gen-based monomer and butyl aromatic hydrocarbon or a hydrogenated product thereof.
  • a rubber composition obtained by kneading at least one modified polymer selected from modified polymers having at least one atomic group and an inorganic filler in advance and forming a master batch.
  • the modified conjugated gen-based polymer or modified copolymer comprising a conjugated gen-based monomer and a butyl aromatic hydrocarbon used in the component (2) of the present invention comprises at least one conjugated gen-based monomer and at least one conjugated-gen monomer. It can be produced by solution polymerization of one kind of vinyl aromatic aromatic hydrocarbon in the presence of an organic lithium catalyst. As for the method for producing the modified polymer of the present invention, any production method can be adopted as long as a polymer having the structure of the present invention can be obtained.
  • the conjugated diene monomer in the present invention is a diolefin having a pair of conjugated double bonds, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3- Dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like can be mentioned, and particularly common ones are 1,3-butadiene and isoprene. These are the only ones in the production of polymers Alternatively, two or more kinds may be used.
  • butyl aromatic hydrocarbons examples include styrene, 0-methylstyrene, -methylstyrene, -tert-butynolestyrene, 1,3-dimethylstyrene, a-methylstyrene, vinylinalephthalene, and vinylanthracene.
  • styrene and methyl styrene are particularly common. These may be used alone or in combination of two or more in the production of the polymer.
  • Solvents used in the production of the modified polymer include butane, pentane, hexane, isopentane, heptane, octane, isooctane, and other aliphatic hydrocarbons, cyclopentane, methinoresic pentane, cyclohexane, methinoresic hexane, Hydrocarbon solvents such as alicyclic hydrocarbons such as ethylcyclohexane or aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or in combination of two or more.
  • the organic lithium compound used in the production of the modified polymer is a compound in which one or more lithium atoms are bonded in a molecule, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec- Butyllithium, tert-butyllithium, hexamethylenedilithium, butageninoresitium lithium, isoprenyldilithium and the like.
  • Organic metal compounds such as amide lithium disclosed in U.S. Pat. These may be used alone or in combination of two or more.
  • the organolithium compound may be dividedly added one or more times during the polymerization in the production of the polymer.
  • a polar compound / randomizing agent can be used for adjustment or the like.
  • the polar compound and the randomizing agent include ethers, amines, thioethers, phosphoramides, potassium or sodium salts of alkylbenzenesulfonic acids, and alkoxides of potassium or sodium.
  • Examples of the ethers include dimethyl ether, getyl ether, diphenyl ether phenol, tetrahydrofuran, diethylene glycol dimethyl methino ole ether, and jeti lendarichol dibutyl ether.
  • Examples of the amines include tertiary amines, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines.
  • Examples of phosphines and phosphoramides include triphenylphosphine, hexamethylphosphoramide and the like.
  • the polymerization temperature in producing the polymer is preferably ⁇ 10 to 150 ° C., and more preferably 30 to 120 ° C.
  • the time required for the polymerization varies depending on the conditions, but is preferably within 48 hours, particularly preferably 0.5 to 10 hours.
  • the polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas.
  • the pressure of the polymerization system may be in a range of a pressure sufficient to maintain the monomer and the solvent in a liquid phase within the above-mentioned polymerization temperature range, and is not particularly limited, but is usually 0.2 to 2 MPa. Yes, preferably 0.3 to 1.5 MPa.
  • the reaction temperature is preferably in the range of 0 to 150 ° C, more preferably 20 to 120 ° C, and still more preferably 50 to 100 ° C. Further, it is preferable that impurities such as water, oxygen, and carbon dioxide gas which inactivate the catalyst and the living polymer are not mixed in the polymerization system.
  • the modified polymer of the conjugated gen-based polymer or its hydrogenated product used in the component (2) of the present invention is a conjugated gen-based monomer homopolymer or a conjugated polymer having a vinyl aromatic hydrocarbon content of less than 5 wt%. It is a modified polymer of a gen-based polymer.
  • the structure of the conjugated gen-based polymer or its hydrogenated product may be linear or branched, or may be an arbitrary mixture thereof.
  • the copolymer comprising a conjugated diene monomer and a vinyl aromatic hydrocarbon or a hydrogenated product thereof may be a random copolymer or a block copolymer.
  • the structure of the modified copolymer or the hydrogenated product thereof may be linear, branched, or an arbitrary mixture thereof.
  • the random copolymer comprising the conjugated diene monomer and the vinyl aromatic hydrocarbon used in the component (2) of the present invention or the hydrogenated product thereof usually has a vinyl aromatic hydrocarbon content of 5 to 95 wt °. / o, preferably from 10 to 90 wt%, more preferably 15 885 wt%.
  • the conjugated diene polymer block or its water One or more additives may be present.
  • a modified polymer of a conjugated gen-based polymer / a modified copolymer of a random copolymer can be obtained by subjecting a living terminal of a conjugated gen-based polymer / random copolymer to a modification agent described later by an addition reaction.
  • the block copolymer comprising a conjugated diene monomer and a vinyl aromatic hydrocarbon used in the component (2) of the present invention or a hydrogenated product thereof generally has a vinyl aromatic hydrocarbon content of 5 to 95 wt. %, More preferably from 10 to 90 wt% / 0 , even more preferably from 15 to 85 wt%. If the block copolymer or its hydrogenated product has a Bull aromatic hydrocarbon content of at least 60 wt%, preferably at least 65 wt%, it has resinous properties and is less than 60 wt%, preferably Has sexual properties when it is less than 55 wt%.
  • Examples of the method include the methods described in Japanese Patent Application Laid-Open No. 1666518 and Japanese Patent Application Laid-Open No. 60-185677.
  • a modified polymer of the block copolymer used in the present invention can be obtained by adding and reacting a modifying agent described below to the living terminal of the block copolymer obtained by these methods, and is represented by the following general formula, for example. Having a structure.
  • A is a polymer block mainly composed of vinyl aromatic hydrocarbon
  • B is a polymer block mainly composed of conjugated diene monomer. Boundary between A block and block Need not be clearly distinguished, and n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11.
  • X is Indicates the residue of the modifier to which an atomic group having a functional group described below is bonded When X is added by a metallation reaction described below, it is bonded to the side chain of the A block and / or B block. ing
  • the polymer block A mainly composed of vinyl aromatic hydrocarbon preferably contains 50% by weight or more, more preferably 70% by weight or more of butyl aromatic hydrocarbon.
  • the polymer block B mainly containing a conjugated diene monomer is preferably 50 wt. /. It is a copolymer block of a co-gen monomer and a vinyl aromatic hydrocarbon containing more than 60 wt% or more, and more preferably a homopolymer block of a conjugated j-mon monomer.
  • modified block copolymer a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions where vinyl aromatic hydrocarbons are distributed in a tapered shape may coexist.
  • the modified block copolymer used in the present invention may be any mixture of the modified block copolymer represented by the above general formula.
  • the proportion of the vinyl aromatic hydrocarbon polymer block incorporated in the modified block copolymer (referred to as the vinyl aromatic hydrocarbon block rate) is less than 5 ° wt% when wear resistance is important, and preferably less than 5%.
  • the proportion of the vinyl aromatic hydrocarbon polymer block incorporated in the modified block copolymer is less than 5 ° wt% when wear resistance is important, and preferably less than 5%.
  • the modified conjugated polymer or conjugated gen (Weight of vinyl aromatic hydrocarbon polymer block in block copolymer) / weight of total vinyl aromatic hydrocarbon in block copolymer) X 100
  • the microstructure (ratio of cis, trans, and vinyl) of the conjugated gen moiety in the modified copolymer composed of a vinyl monomer and a vinyl aromatic hydrocarbon can be arbitrarily changed by using a polar compound described below. Can be.
  • the content of the Bull bond is not particularly limited, but when 1,3-butadiene is used as the conjugated diene monomer, the vinyl bond content is preferably 5 to 90%, more preferably 10 to 80%, When isoprene is used as the conjugated diene monomer or when 1,3-butadiene and isoprene are used in combination, the number of butyl bonds, which is the sum of 1,2-vinyl bonds and 3,4-butyl bonds, is preferable. Is 3 to 80%, and more preferably 5 to 70%.
  • the vinyl bond content refers to the conjugated diene monomer incorporated in the polymer in a 1,2_ bond, 3,4-linkage, and 1,4-linkage bond mode.
  • the vinyl bonds in the modified polymer may be uniformly distributed in the polymer chain, may be tapered, or may have two or more polymer blocks having different Bull bonds.
  • the Bull bond content can be arbitrarily changed by using a polar compound described below.
  • a hydrogenated product of a modified block copolymer when used, its microstructure is preferably from 10 to 80 when 1,3-butadiene is used as a syngeneic monomer. %, More preferably 25 to 75 ° / 0 , when isoprene is used as the conjugated diene monomer or when 1,3-butadiene and isoprene are used.
  • the total amount of vinyl bonds which is the sum of 1,2-vinyl bonds and 3,4-vinyl bonds, be 5 to 70 ° / 0 .
  • the vinyl bond content based on the conjugated diene monomer in the modified polymer can be known by using a nuclear magnetic resonance apparatus (NMR). '
  • the weight ratio of 1,3-butadiene is preferably 95/5 to 5/95, more preferably 90 to 10/90, and even more preferably 85 to 105/85.
  • the weight ratio of isoprene to 1,3-butadiene is preferably 49/5 1 to 5/95, more preferably 45/55 to 10Z90, and still more preferably. Is recommended to be between 40/60 and 15/85.
  • the modified polymer can be produced by reacting a functional group-containing modifying agent with a living terminal of a polymer obtained using an organolithium compound as a polymerization catalyst and adding a functional group-containing atomic group.
  • the functional group-containing atomic group is bonded to at least one polymer chain terminal of the polymer.
  • Examples of functional groups of the functional group-containing atomic group bonded to the modified polymer include a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carbonyl group, a thiocarboxylic acid group, and an aldehyde.
  • Group thioaldehyde group, carboxylic ester group, amide group, sulfonic acid group, sulfonic ester group, phosphoric acid group, phosphoric ester group, amino group, imino group, cyano group, pyridyl group, quinoline group, Selected from the group consisting of an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilane group, a tin halide group, an alkoxytin group, and a phenyltin group. At least one functional group.
  • a hydroxyl group, an epoxy group, an amino group, an amino group, a silanol group, and an alkoxysilane group are particularly preferred.
  • Preferred examples of the atomic group having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, an imino group, a silanol group, and an alkoxysilane group include those represented by the following formulas (1) to (14). At least one kind represented by a formula selected from the group consisting of:
  • N is a nitrogen atom
  • Si is a silicon atom
  • O is an oxygen atom
  • C is a carbon atom
  • H is a hydrogen atom
  • R 1 and R 2 are each independently Represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and each of the hydrocarbon groups may be independently a hydroxyl group, an epoxy group, an amino group, a hydrocarbon group having 1 to 24 carbon atoms, if desired.
  • each R 3 independently has 1 carbon atom ⁇ 48 divalent hydrocarbon groups, and, if desired, each independently represents a hydroxyl group, an epoxy group, an amino group, an imino group having a hydrocarbon group having 1 to 24 carbon atoms, a silanol group, and It may have at least one functional group selected from the group consisting of alkoxysilane groups having 1 to 24 carbon atoms,
  • Each R 4 is independently a hydrogen atom or carbon number 1 to
  • a known compound having the above functional group and / or a known compound having the above functional group can be formed.
  • Known compounds can be used. For example, Tokuhei 41
  • the terminal modifying agent described in Japanese Patent No. 39495/95 can be used, and specific examples include the following.
  • Examples of the modifying agents having the functional groups represented by the above formulas (1) to (6) include tetraglycidyl metaxylene diamine, tetraglycidyl 1,3-bisaminomethylcyclohexane, and tetraglycidyl p-phenylene diamine.
  • Examples of the modifier having a functional group represented by the above formula (7) include ⁇ -force prolatatone, ⁇
  • modifying agent having the functional group of the above formula (8) examples include 4-methoxybenzophenone, 4-ethoxybenzophenone, 4,4,1-bis (methoxy) benzophenone, 4,4, -bis (Ethoxy) benzophenone, ⁇ -glycidoxyshethyltrimethoxysilane, and -glycidoxypropyltrimethoxysilane.
  • Examples of the modifying agents having the functional groups of the above formulas (9) and (10) include ⁇ -glycidoxybutyltrimethoxysilane, ⁇ -daricidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltripropoxy. Silane and y-glycidoxypropyl tributoxy silane.
  • Examples of the modifying agent having a functional group represented by the above formula (11) include 1,3-dimethyl-21-imidazolidinone and 1,3-getyl-12-imidazolidinone.
  • Examples of the modifying agent having a functional group represented by the above formula (12) include N, N, 1-dimethylpyrene perylene, N-methylpyrrolidone, and the like.
  • the modified polymer having an atomic group having a functional group represented by the above formula (13) or (14) is a non-aqueous polymer having an atomic group having a functional group represented by the above formula (11) or (12), respectively. It is obtained by hydrogenating the addition-modified polymer.
  • the hydrogenated product of the modified polymer used in the component (2) of the present invention can be produced by modifying the polymer and then hydrogenating it.
  • the hydrogenated polymer is modified after hydrogenation.
  • a modified polymer is obtained by reacting the living terminal of the polymer obtained using an organic lithium compound as a polymerization catalyst with the above-mentioned modifying agent to obtain a modified polymer.
  • a hydrogenated modified polymer is obtained.
  • an organic alkali metal compound such as an organolithium compound is reacted with the polymer (metallation reaction) to obtain an organic alkali metal compound.
  • metalation reaction a method in which an added polymer is obtained and the above-mentioned modifier is subjected to an addition reaction.
  • a hydrogenated product of the polymer may be obtained and then subjected to a metalation reaction, and the above-mentioned modifier may be reacted to obtain a modified polymer of the hydrogenated product.
  • the hydroxyl group, amino group, etc. may be It may be an organic metal salt, but in such a case, it can be converted to a hydroxyl group or a amino group by treating with a compound having active hydrogen such as water or alcohol.
  • the reaction pressure at the time of performing the denaturation reaction is not particularly limited, but is usually 0.2 to 2 MPa, preferably 0.3 to 1 MPa.
  • the reaction temperature is preferably in the range of 0 to 150 ° C, more preferably 20 to 120 ° C, and even more preferably 50 to 100 ° C.
  • the time required for the denaturation reaction generally depends on the reaction temperature during the adjustment, but is in the range of 1 second to 10 hours, preferably in the range of 1 second to 3 hours.
  • a polymer that has not been modified after reacting a modifying agent with the polymer may be mixed with the modified polymer.
  • the amount of the unmodified polymer mixed in the modified polymer is preferably 70% by weight based on the weight of the modified polymer. / 0 or less, more preferably 60% by weight or less, further preferably 50% by weight or less.
  • a hydrogenated product of the modified polymer is obtained by hydrogenating the modified polymer obtained above.
  • the hydrogenation catalyst is not particularly limited, and is conventionally known.
  • a homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh and Zr is used.
  • the hydrogenation catalyst examples include JP-B-42-8704, JP-B-43-636, JP-B-63-4841, JP-B-1-37970, and JP-B
  • the hydrogenation catalysts described in Japanese Patent Application Laid-Open Nos. 1-53851 and 2-9041 can be used.
  • Preferred hydrogenation catalysts include mixtures with titanocene compounds and Z or reducing organometallic compounds.
  • the titanocene compound compounds described in JP-A-8-10992 can be used. Specific examples thereof include biscyclopentadiene / retitanium dichloride and monopentamethinoresic compound.
  • Compounds having at least one ligand having a (substituted) cyclopentagel skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as pentagenenyl titanium trichloride may be mentioned.
  • the reducing organic metal compound include organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds, and organic zinc compounds.
  • the hydrogenation reaction is preferably carried out in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C.
  • the pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to: L0 MPa, and still more preferably ⁇ 3 to 5 MPa.
  • the hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.
  • the hydrogenation reaction can be used in a batch process, a continuous process, or a combination thereof.
  • the total hydrogenation rate of the unsaturated double bond based on the conjugated diene monomer unit can be arbitrarily selected according to the purpose, and is not particularly limited.
  • an unsaturated double bond based on a conjugated diene monomer unit in the modified polymer is 70. /.
  • only a part may be hydrogenated.
  • the hydrogenation ratio is preferably 10% or more and less than 70%, or 15% or more and less than 65%, and if desired, 20% or more and less than 60%.
  • the hydrogenation rate of the Bull bond based on the conjugated diene monomer before hydrogenation is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. It is recommended for obtaining a rubber composition having excellent thermal stability.
  • the hydrogenation rate of vinyl bonds refers to the ratio of hydrogenated vinyl bonds to vinyl bonds based on the conjugated gen-based monomer before hydrogenation incorporated in the modified polymer.
  • the hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the modified random copolymer or modified block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30%. Or less, more preferably 20% or less is recommended.
  • the hydrogenation rate can be determined by a nuclear magnetic resonance apparatus (NMR).
  • a secondary modified polymer obtained by reacting a compound (4) having reactivity with a functional group bonded to the modified polymer used in the preparation of the masterbatch can also be used.
  • the secondary modified polymer is obtained by reacting a secondary modifier, which is the compound (4), with the modified polymer of the present invention, and the secondary modified agent has a functional group of the modified polymer.
  • Preferred examples of the functional group of the secondary modifier as the compound (4) include at least one selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group.
  • Particularly preferred are secondary modifiers having at least two of the above functional groups.
  • the functional group is an acid anhydride group
  • a secondary modifier having only one acid anhydride group is also particularly preferred.
  • the amount of the secondary modifier is usually 0.3 to 10 mol, preferably 0.4, per equivalent of the functional group bonded to the modified polymer. -5 mol, more preferably 0.5-4 mol.
  • the method of reacting the modified polymer with the secondary modifier is not particularly limited, but a known method can be used. For example, a melt kneading method described later, a method in which each component is dissolved or dispersed and mixed in a solvent or the like, and the reaction is performed are exemplified.
  • the solvent is not particularly limited as long as it dissolves or disperses each component.
  • Aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic In addition to hydrocarbon solvents such as group hydrocarbons, halogen-containing solvents, ester solvents, ether solvents and the like can be used.
  • the temperature at which the modified polymer is reacted with the secondary modifier is usually 110 to 150 ° C, preferably 30 to 120 ° C.
  • the time required for the reaction generally depends on the reaction temperature at the time of adjustment, but is usually within 3 hours, and preferably several seconds to 1 hour.
  • a particularly preferred method is a method of obtaining a secondary modified polymer by adding a secondary modifier to a solution of the produced modified polymer and reacting.
  • Examples of the secondary modifier having a carboxyl group include maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, levalilic acid, and cyclohexanedicarboxylic acid. Acids, aliphatic carboxylic acids such as cyclopentanedicarboxylic acid; aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid and pyromellitic acid; No.
  • Examples of the secondary modifier having an acid anhydride group include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-1,4-cyclohexane-1,1,2-dicarboxylic anhydride, 1,2, 4,5-benzenetetracarboxylic dianhydride, 5- (2,5-dihydroxytetratetra-3-furaninole) -1,3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Can be
  • Examples of the secondary modifier having an isocyanate group include tolylene diisocyanate, diphenylmethane diisocyanate, and a polyfunctional aromatic isocyanate (that is, when three or more isocyanate groups are aromatic). Compound bonded to an aromatic ring).
  • Examples of the secondary modifier having an epoxy group include tetradaridyl-1,3-bisaminomethylcyclohexane, tetraglycidyl m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene dalicol diglycidyl, terephthal. Acid diglycidyl ester acrylate and the like.
  • Examples of the secondary modifier having a silanol group include a hydrolyzate of the above-mentioned alkoxysilane compound described as a modifier used for obtaining a modified polymer.
  • Examples of the secondary modifier having an alkoxysilane group include bis- (3-triethoxysilylpropyl) -tetrasulfan, bis- (3-triethoxysilylpropyl) pill, di-sulfane, and ethoxysiloxane oligomer. No.
  • a reactive functional oligomer can also be used as the secondary modifier.
  • the functional group of the functional oligomer is not particularly limited as long as it has a reactivity with the functional group bonded to the modified polymer.
  • Preferred examples of the functional oligomer include at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a hydroxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group.
  • Functional oligomers are usually at least 300 and less than 3,000, preferably at least 50,000 and less than 15,500, more preferably at least 1,000 and more than 20,000.
  • the functional oligomer include a butadiene oligomer having at least one functional group or a hydrogenated product thereof, an isoprene oligomer having at least one functional group or a hydrogenated product thereof, and at least one of the above functional groups.
  • Ethylene oligomer having one, propylene oligomer having at least one of the above functional groups, ethylene oxide oligomer, propylene oxide oligomer, ethylene oxide propylene oxide copolymerization oligomer, styrene-maleic anhydride copolymer Examples include a coalesced oligomer and a saponified product of an ethylene-vinyl acetate copolymer oligomer.
  • Particularly preferred examples of the secondary modifier in the present invention include a carboxylic acid having two or more carboxylic acid groups or an acid anhydride thereof, or an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, or an alkoxysilane group.
  • Modifiers such as maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, tetraglycidyl
  • maleic anhydride pyromellitic anhydride
  • 1,2,4,5-benzenetetracarboxylic dianhydride 1,2,4,5-benzenetetracarboxylic dianhydride
  • toluylene diisocyanate tetraglycidyl
  • tetraglycidyl examples thereof include 1,3-bisaminomethylcyclohexane, bis- (3-to.riethoxysilylpropyl) -tetranoslephane, and a styrene-monomaleic anhydride copolymer oligomer.
  • a secondary modifier which is the compound (4), can be added in addition to the modified polymer and the inorganic filler.
  • the amount of the secondary modifier is 0.01 to 20 parts by weight, preferably 0.02 to 10 parts by weight, more preferably 0.02 to 100 parts by weight based on 100 parts by weight of the modified polymer. It is in the range of 5 to 7 parts by weight.
  • the weight average molecular weight of the modified polymer or the secondary modified polymer used in the component (2) of the present invention is 30,000 or more from the viewpoint of the mechanical strength and abrasion resistance of the rubber composition, and 1 or more from the viewpoint of processability. It is preferably 200,000 or less, more preferably 50,000 to 100,000, and still more preferably 10 to 800,000.
  • the weight-average molecular weight of the modified polymer was measured by gel permeation chromatography (GPC), and the molecular weight of the peak in the chromatogram was determined from a calibration curve (standard (Created using the peak molecular weight of polystyrene). From the solution of the modified polymer obtained as described above, the catalyst residue can be removed as necessary, and the modified polymer can be separated from the solution.
  • GPC gel permeation chromatography
  • a method for separating the solvent for example, a method of adding a polar solvent which is a poor solvent for the polymer such as acetone or alcohol to the solution after polymerization or hydrogenation to precipitate and recover the polymer, a solution of the modified polymer, Into the boiling water with stirring and removing the solvent by steam stripping to recover the solvent, or directly heating the polymer solution to distill off the solvent.
  • the modified polymer or its hydrogenated product used in the present invention may contain various phenol-based stabilizers, phosphorus-based stabilizers, zeo-based stabilizers, and amine-based stabilizers. it can.
  • the inorganic filler used as a raw material of the master batch of the component (2) or the inorganic filler of the component (3) may be a known reinforcing filler, for example, a natural silicic acid, a wet method or a dry method.
  • Preferred inorganic fillers include silica-based inorganic fillers, metal oxides, metal hydroxides, and carbon. The above-mentioned inorganic fillers may be used alone or in combination of two or more.
  • Silica-based inorganic filler refers to solid particles whose main component is the chemical formula SiO 2, for example, silica, clay, talc, Mai force, diatomaceous earth, wollastonite, montmorillonite, zeolite, glass fiber, etc.
  • An inorganic fibrous substance or the like can be used.
  • a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica-based inorganic filler can also be used.
  • Force is preferred.
  • Silicas such as dry-process white carbon, wet-process white carbon, synthetic silicate-based white carbon, and colloidal silica can be used.
  • the average dispersed particle diameter is preferably 0.05 to 1 ⁇ , more preferably 0.05. ⁇ 0.5 im.
  • a metal oxide is a solid particle mainly composed of a structural unit represented by the formula MxOy (M is a metal atom, x and y are each an integer of 1 to 6), such as alumina and titanium oxide. , Magnesium oxide, zinc oxide and the like can be used. Also, a mixture of a metal oxide and an inorganic filler other than the metal oxide can be used.
  • the metal hydroxide used in the present invention is aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, aluminum silicate hydrate, magnesium silicate hydrate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide. Hydrate of tin oxide, hydrate of inorganic metal compounds such as borax, etc., are hydrated inorganic fillers, among which magnesium hydroxide and aluminum hydroxide are preferable.
  • the amount of the inorganic filler used for preparing the master batch of the component (2) is 5 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 100 parts by weight of the modified polymer. Ranges from 10 to 150 parts by weight. If the amount of the inorganic filler exceeds 300 parts by weight, the dispersibility of the inorganic filler is inferior, and the workability of the master batch becomes poor. On the other hand, when the amount is less than 5 parts by weight, the adhesiveness as an effect of the present invention is inferior.
  • the compounding amount of the inorganic filler of the component (3) is 0.1 to 150 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the rubbery polymer of the component (1). Preferably it is 5 to 50 parts by weight. If the amount of the inorganic filler exceeds 150 parts by weight, the dispersibility of the inorganic filler is poor, and the processability and the mechanical strength are poor.
  • Coupling agents can be used.
  • the silane coupling agent is for tightening the interaction between the rubber-like polymer and the inorganic filler, and has an affinity or binding group for the rubber-like polymer and the inorganic filler, respectively.
  • Things Specifically, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- (triethoxysilyl) -Ethyl]-tetrasulfide, 3-mercaptopropyl-trimethoxysilane, vinyltrimethoxysilane, butyltriethoxysilane and the like.
  • Preferred silane coupling agents are those that have an alkoxysilane and a polysulfide bond in which two or more sulfur atoms are linked, such as bis- [3- (triethoxysilyl) -propyl] -tetrasulfide. And bis- [3- (triethoxysilyl) -propyl] -disulfide.
  • the amount of the silane coupling agent is from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight, based on the reinforcing filler.
  • the functional group present on the surface of the inorganic filler and the modified polymer can be used.
  • a physical interaction such as a chemical bond or a hydrogen bond is effectively developed with the union, and a rubber composition for footwear excellent in tear strength, abrasion resistance and adhesiveness can be obtained.
  • the method for producing the masterbatch which is the component (2) of the present invention is not particularly limited, and a known method can be used.
  • a kneading method using a general mixer such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, a roll, etc.
  • a method of removing the solvent by heating or the like is used.
  • a preferred method is to knead each component with a Banbury mixer and a coadar.
  • the kneading temperature at the time of manufacturing the master batch is generally from 80 to 30 in order to promote the deterioration of the modified polymer and the interaction between the modified polymer and the inorganic filler and to obtain a master batch with good dispersibility of the inorganic filler.
  • the temperature is preferably 0 ° C, more preferably from 130 to 250 ° C, and still more preferably from 150 to 220 ° C.
  • the kneading time is generally preferably from 0.2 to 60 minutes, more preferably from 0.5 to 30 minutes, from the viewpoint of the dispersibility of the inorganic filler, the productivity of the masterbatch, and the deterioration of the modified polymer. It is more preferably in the range of 1 to 20 minutes.
  • a particularly preferred method is a method in which the entire amount of the inorganic filler is previously kneaded in a kneader and kneaded, and then the modified polymer is added and kneaded, and the inorganic filler is divided into two or more portions and put into the kneader. This is a method in which a modified polymer and an inorganic filler are kneaded and produced.
  • the inorganic filler As a method of dividing the inorganic filler into the kneader twice or more, it is preferable to add the inorganic filler in 2 to 10 times, considering the complexity of the process of manufacturing the master batch. In particular, a method of adding in 2 to 5 portions is preferable. Specifically, 20 to 80 weight of the inorganic filler. /. Preferably, 30 to 80% by weight, more preferably 40 to 80% by weight, is previously charged into the kneader, and the kneading time is 1 second to 60 minutes, preferably 0.5 minute to 30 minutes.
  • a kneading time of 1 second to 60 minutes, preferably 20 seconds to 30 minutes, more preferably Kneading is carried out for 1 minute to 20 minutes, and then the remaining inorganic filler is added, and the kneading time is 1 second to 60 minutes, preferably 0.5 minute to 30 minutes, more preferably 1 minute to 2 minutes.
  • the entire amount of the inorganic filler is previously charged into a kneader, and the kneading time is 1 second to 60 minutes, preferably 0.5 minute to 30 minutes, more preferably 1 minute to 20 minutes.
  • kneading time is 1 second to 60 minutes, preferably 0.5 minute to 30 minutes, more preferably 1 minute to 20
  • the most important factor in preparing a particularly preferred form of masterbatch is Filler 5 to 300 parts by weight at least 20 parts by weight. /.
  • the above is put in a kneader in advance, and the temperature is kneaded in the range of 50 to 300 ° C, preferably 70 to 250 ° C, more preferably 100 to 200 ° C, and then the remaining components are mixed and kneaded. Adjusting the batch.
  • the rubber composition for footwear of the present invention comprises a rubbery polymer (component 1) and a masterbatch (component 2), or a rubbery polymer (component 1) and a masterbatch (component 2) and an inorganic filler (component 3). ).
  • the amount of the masterbatch is in the range of 1 to 150 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 70 parts by weight, per 100 parts by weight of the rubbery polymer (component 1).
  • the method for producing the rubber composition for footwear of the present invention is not particularly limited, and a known method can be used.
  • a kneading method using a general kneader such as a Banbury mixer, a single screw extruder, a two-screw extruder, a coneder, a multi-screw extruder, or the like is used.
  • the components (1), (2) and (3) are put into a kneader at a time and kneaded.
  • a method can be adopted in which any components are premixed and then the remaining components are added.
  • the kneading temperature is preferably from 50 to 300 ° C, more preferably from 70 to 250 ° C, further preferably from 100 to 200 ° C, from the viewpoint of thermal deterioration of the rubbery polymer or the modified polymer.
  • the kneading time is generally preferably from 0.2 to 60 minutes, more preferably from 0.2 to 60 minutes, in view of the dispersibility of the inorganic filler, the productivity of the rubber composition, the deterioration of the modified polymer and the rubbery polymer, and the like.
  • the range is 5 to 30 minutes, more preferably 1 to 20 minutes.
  • the rubber composition for footwear of the present invention is characterized by using a masterbatch excellent in dispersibility of an inorganic filler obtained by kneading a modified polymer and an inorganic filler by the above-mentioned specific production method.
  • the dispersibility of the inorganic filler is improved, thereby improving the resistance.
  • a rubber composition for footwear having excellent abrasion and adhesion can be obtained.
  • the dispersibility of the inorganic filler in the rubber composition can be confirmed by using a transmission electron microscope, a scanning prop microscope, or the like.
  • additives can be blended as required.
  • the type of additive is not particularly limited as long as it is generally used for compounding a rubber-like polymer.
  • GPC (apparatus: LC10 manufactured by Shimadzu Corporation, column: Shimpac GPC805 + GPC804 + GPC804 + GPC803 manufactured by Shimadzu Corporation) was used. Tetrahydrofuran was used as a solvent, and the measurement was performed at a temperature of 35 ° C.
  • the molecular weight is obtained by measuring the molecular weight of the peak in the chromatogram from the measurement of commercially available standard polystyrene. It is the weight average molecular weight obtained using the calibration curve (created using the peak molecular weight of standard polystyrene).
  • a sample solution was prepared by dissolving 10 mg of the modified polymer and lOmg of low-molecular-weight internal standard polystyrene having a weight average molecular weight of 8000 in 20 ml of tetrahydrofuran.
  • GPC measurement was performed on the sample solution in the same manner as in the above (3), and the ratio (i) of the modified polymer to the standard polystyrene was determined from the obtained chromatogram.
  • GPC measurement was performed on the sample solution in the same manner as in (3) above, except that a column of Zorba X (silica-based gel filler), a column manufactured by Dupont, USA, was used. Obtained.
  • the modified polymer is adsorbed on the GPC column using silica gel as the filler, but the unmodified polymer is not adsorbed on the GPC column.
  • the ratio (ii) of the modified polymer can be determined. From the above ratio (i) and ratio (ii), the ratio (%) of the modified polymer in the copolymer after the modification reaction was calculated by the formula: (1 ratio (ii) Z ratio (i)) XI00 One p ⁇ ⁇ -was o
  • the measurement was performed in a constant temperature room at 23 ° C. according to JIS K6252.
  • the HAZ E value and total light transmittance of a 5 mm-thick plate sample were measured using a Nippon Denshoku Industries Co., Ltd. HAZE meter, NDH-100 1DP type.
  • the polymer solution was withdrawn and deactivated with 10 times the molar amount of water of n-butyllithium to obtain SBR-C. Thereafter, 2,6-ditert-butyl 4-methylphenol was added as a stabilizer to the polymer solution in an amount of 0.5 part by weight per 100 parts by weight of rubber, and the solvent was removed by a drum dryer, followed by drying.
  • the obtained polymer was analyzed, a styrene content of 40 weight 0/0, a vinyl bond content of the butadiene portion is 33 wt% der I got it. According to the analysis of the amount of block styrene, the presence of styrene blocks did not occur. In addition, the weight average molecular weight was 48.5 million.
  • a closed kneader (1.7 liter capacity) equipped with a temperature control device using circulating water from the outside was used. At a filling rate of 65% and a rotor speed of 66/77 rpm, 25 Siri force was put into the kneader and kneaded for 4 minutes. Next, 75 parts of the polymer and 0.15 parts of stearic acid were added, and kneading was continued for 4 minutes. The temperature of the rubber thread after discharging was 170 ° C. After cooling, the mixture was kneaded again with an open roll set at 50 ° C. to produce a polymer / silicone masterbatch. Table 1 shows the formulation.
  • a closed kneader (1.7 liter capacity) with a temperature control device using circulating water from the outside is used.
  • the beef has a filling rate of 65%, a rotor speed of 66/77 rpm, and 25 parts of silica.
  • 75 parts of the polymer and 0.15 parts of stearic acid were added and kneading was continued for 5 minutes.
  • the temperature of the rubber composition after discharging was 170 ° C.
  • the mixture was kneaded again with an open roll set at 50 ° C. to produce a master batch of polymer Z silica.
  • Table 1 shows the formulation.
  • Example 1 to 5 Using a closed kneader (with a capacity of 1.7 liters) equipped with a temperature controller using circulating water from the outside, with a filling rate of 65% and a rotor speed of 6 ⁇ 6/77 rpm, see Table 2 The respective components were put into a kneader at the same time according to the compounding recipe shown in the table, and mixed and kneaded to obtain a rubber composition. The temperature after discharge was 16 1 ° C. The rubber composition thus obtained was kneaded with sulfur and a vulcanization accelerator using an open roll set at 70 ° C., and then vulcanized at 160 ° C. for 20 minutes to produce a test piece. Table 2 shows the physical properties of the vulcanizates. It can be seen that the rubber yarn produced using the modified polymer and silica master batch of the present invention has excellent tear strength and abrasion resistance.
  • Example 2 In the same manner as in Example 1, the components were collectively charged into a kneader with the compounding recipe shown in Table 2 and kneaded to obtain a rubbery polymer composition. The temperature after discharge was 160 ° C. The rubber composition obtained in this manner was kneaded with an open roll set at 70 ° C and mixed with sulfur and a vulcanization accelerator, and then vulcanized at 160 ° C for 20 minutes to prepare a test piece.
  • Table 2 shows the physical properties of the vulcanizates.
  • Example 6 According to the same method as in Example 6, the components were collectively kneaded according to the formulation shown in Table 3. And kneaded to obtain a rubber composition.
  • the rubber composition thus obtained was kneaded with sulfur and a vulcanization accelerator using an open roll set at 70 ° C., and then vulcanized at 160 ° C. for 20 minutes to produce a test piece.
  • the rubber composition for footwear of the present invention has excellent tear strength and abrasion resistance, and is extremely excellent in adhesion to shoe materials such as nylon, leather and EVA.
  • the composition of the present invention is an extremely effective material as a sole material for various shoes utilizing these characteristics.
  • it can be processed into molded products of various shapes, and can be used for automobile parts (automobile interior materials, automobile exterior forestry), various containers such as food packaging containers, home appliances, medical equipment parts, industrial parts, toys, etc.

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Abstract

A rubber composition for footwear which comprises: (1) 100 parts by weight of a rubbery polymer; and (2) 1 to 150 parts by weight of a master batch obtained by kneading 100 parts by weight of at least one modified polymer selected among modified polymers each comprising a conjugated diene polymer, a copolymer of a conjugated diene monomer with a vinylaromatic hydrocarbon, or a hydrogenation product of either and at least one functional group bonded thereto together with 5 to 300 parts by weight of an inorganic filler. The rubber composition is excellent in tear strength and wearing resistance and further has extremely high adhesion to nylons, leathers, and EVAs which are materials for shoes. Owing to these features, the composition is an extremely effective material as a sole material for various shoes.

Description

明細書 履物用ゴム組成物 技術分野  Description Rubber composition for footwear Technical field
本発明は、 ゴム状重合体成分及び官能基含有原子団が洁合した変性重合体と無 機充填剤を予め混合したマスターバッチ成分とからなるゴム状重合体組成物であ つて、 特に引き裂き強度、 耐摩耗性、 接着性に優れる新規な履物用ゴム組成物に 関する。 背景技術  The present invention relates to a rubber-like polymer composition comprising a modified polymer in which a rubber-like polymer component and a functional group-containing atomic group are combined, and a masterbatch component in which an inorganic filler is mixed in advance. The present invention relates to a novel rubber composition for footwear having excellent abrasion resistance and adhesiveness. Background art
従来、 履物用の原料としてゴム状重合体が種々の履物用途で使用されている。 その用途に応じて要求される特性を付与するために、ゴム状重合体を主成分とし、 さらに各種の無機充填剤、 添加剤、 着色剤等を配合したゴム組成物が原料として 用いられている。 履物等の各種ゴム製品においては、 製品の外観性を向上させる ためにシリカ等の白色系充填剤が補強剤として広く使用されている。 しかし、 シ リカを補強充填剤として用いた場合、 従来のカーボンブラックと比較してゴムと の親和性が低いため、 シリカのゴム中への分散性が必ずしも良くなく、 この分散 性不良によって耐摩耗性の低下、 機械強度の低下がおこりがちである。 そこで、 カーボンブラックのような高い補強性を得るために、 ゴム組成物へのシリカ配合 にはビス一 ( 3—トリエトキシシリルプロピル) テトラスルフィ ドに代表される シラン力ップリング剤を使用してシリカの分散を改良することがおこなわれてお り、 製品コストの上昇を余儀なくされている。  Conventionally, rubber-like polymers have been used in various footwear applications as raw materials for footwear. In order to provide the properties required according to the application, a rubber composition containing a rubber-like polymer as a main component and further blending various inorganic fillers, additives, coloring agents, and the like is used as a raw material. . In various rubber products such as footwear, a white filler such as silica is widely used as a reinforcing agent to improve the appearance of the product. However, when silica is used as a reinforcing filler, the affinity for rubber is lower than that of conventional carbon black, and the dispersibility of silica in rubber is not always good. This tends to result in a decrease in mechanical properties and mechanical strength. Therefore, in order to obtain a high reinforcing property such as carbon black, silica is incorporated into a rubber composition by using a silane coupling agent represented by bis- (3-triethoxysilylpropyl) tetrasulfide. Improving variances has forced product costs to rise.
靴底材料として求められる特性して、 耐摩耗性ゃ耐ゥエツトスキッド性が良好 であること、ミツドソ一ルゃァッパーとの接着性が良好であることが挙げられる。 また、 シリカ粉体の使用は、 靴の製造工程において粉体が舞い上がり作業性が 劣るという問題があり、 また、 更に、 近年、 靴工場の作業環境改善の観点から、 靴の製造に使用する接着剤を有機溶剤系から水性接着剤へと変える動きが活発化 している。しかしながら、満足のゆく接着強度が得られていないのが現状である。 ゴム組成物を改良する方法として、 特許文献 1には、 シリカとシランカツプリ ング剤を限定しゴムに熱可塑性樹脂を混合することにより着色性と耐摩耗性が優 れる靴底に関するものが開示されているが、 水性接着剤を使用した時の接着強度 に優れたゴム組成物は得られていない。 特許文献 2にははハイシスポリブタジ ェンとスチレンレジンとシリカからなる、 軽量化、 耐摩耗性靴底材が開示されて いる。 特許文献 3には、 特定のポリシロキサン化合物を用いて耐摩耗性を改良す る履物用ゴム組成物が開示されている。 また、 特許文献 4には、 特定構造の変性 重合体とシリカの組み合わせによって、 耐摩耗性ゃ耐ゥエツトスキッド性に優れ る履物用ゴム組成物が開示されているが、 いずれも水性接着剤を使用した時の接 着強度に優れたゴム組成物は得られていない。 The characteristics required as a material for shoe soles include good abrasion resistance and good anti-skid resistance, and good adhesiveness with a mid-size wrapper. In addition, the use of silica powder has the problem that the powder rises up in the shoe manufacturing process, resulting in poor workability. In addition, in recent years, from the viewpoint of improving the working environment of shoe factories, the adhesive used in the manufacture of shoes has been used. Move to change from organic solvent-based to water-based adhesive are doing. However, at present, satisfactory adhesive strength has not been obtained. As a method for improving a rubber composition, Patent Document 1 discloses a shoe sole having excellent coloring and abrasion resistance by limiting silica and a silane coupling agent and mixing a rubber with a thermoplastic resin. However, a rubber composition having excellent adhesive strength when using an aqueous adhesive has not been obtained. Patent Document 2 discloses a lightweight, wear-resistant shoe sole material made of high-cis polybutadiene, styrene resin, and silica. Patent Document 3 discloses a rubber composition for footwear in which a specific polysiloxane compound is used to improve abrasion resistance. Patent Document 4 discloses a rubber composition for footwear having excellent abrasion resistance and anti-skid resistance by combining a modified polymer having a specific structure with silica. A rubber composition having excellent adhesive strength when used has not been obtained.
特許文献 5及び特許文献 6には、 変性重合体と補強性充填剤からなるマスター バッチを用いたゴム組成物が開示されているが、 履物用ゴム組成物として重要な 特性である接着強度の記載が全くない。  Patent Documents 5 and 6 disclose a rubber composition using a masterbatch comprising a modified polymer and a reinforcing filler, but the adhesive strength, which is an important property as a rubber composition for footwear, is described. There is no.
[特許文献 1] 特開昭 62- 1 37002号公報  [Patent Document 1] JP-A-62-137002
[特許文献 2] 特開 2000- 236 905号公報  [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-236905
[特許文献 3] 特開 2002— 1 9 140 1号公報  [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-191401
[特許文献 4] 特開 2002— 2849 3 1号公報  [Patent Document 4] Japanese Patent Application Laid-Open No. 2002-2849 31
[特許文献 5] 特開平 8— 23 1 766号公報  [Patent Document 5] Japanese Patent Application Laid-Open No. 8-23 1766
[特許文献 6] 特開 2000— 1 36 26 9号公報 発明の開示  [Patent Document 6] Japanese Patent Application Laid-Open No. 2000-136269 discloses the invention
本発明は、 ゴム状重合体と無機充填剤から得られるゴム組成物において、 官能 基含有原子団が結合している変性重合体と無機充填剤のマスターバツチを作製し、 該マスターバツチとゴム状重合体を含むゴム組成物とすることで、引き裂き強度、 耐摩耗性、 接着性に優れ、 また靴工場の作業環境を改善できる履物用ゴム組成物 を提供することにある。  The present invention provides a rubber composition obtained from a rubbery polymer and an inorganic filler, wherein a masterbatch of a modified polymer having a functional group-containing atomic group bonded thereto and an inorganic filler is produced, and the masterbatch and the rubbery polymer are prepared. An object of the present invention is to provide a rubber composition for footwear which has excellent tear strength, abrasion resistance and adhesiveness and can improve the working environment of a shoe factory by using a rubber composition containing
本発明者らは、 共役ジェン系重合体又はビニル芳香族炭化水素と共役ジェン系 単量体からなる共重合体、 或いはこれらの水添物と無機充填剤とのゴム組成物の 特性改良について鋭意検討した結果、 ゴム状重合体と無機充填剤を含むゴム組成 物を製造する際に、 特定の官能基を付与した変性重合体と無機充填剤を予め混練 したマスターバッチを使用することで、 引き裂き強度、 耐摩耗性、 接着性に優れ た履物用ゴム組成物が得られることを見出し、 本発明を完成するに至った。 The present inventors have proposed that a conjugated gen-based polymer or a vinyl aromatic hydrocarbon and a conjugated gen-based As a result of intensive studies on the improvement of the properties of a rubber composition comprising a monomer copolymer or a hydrogenated product thereof and an inorganic filler, a rubber composition containing a rubbery polymer and an inorganic filler was produced. By using a masterbatch in which a modified polymer having a specific functional group and an inorganic filler are kneaded in advance, a rubber composition for footwear with excellent tear strength, abrasion resistance and adhesion can be obtained. Heading, the present invention has been completed.
すなわち、 本発明は下記の通りである。  That is, the present invention is as follows.
1 . 成分 （1 ) ゴム状重合体： 1 0 0重量部；及び成分 （2 ) 共役ジェン系重 合体又は共役ジェン系単量体とビニル芳香族炭化水素からなる共重合体又はそれ らの水添物に官能基含有原子団が少なくとも 1個結合している変性重合体から選 ばれる少なくとも 1種の変性重合体 1 0 0重量部に無機充填剤 5 ~ 3 0 0重量部 を混練して得られるマスターバッチ： 1〜1 5 0重量部を含む履物用ゴム組成物。  1. Component (1) rubbery polymer: 100 parts by weight; and component (2) a conjugated-gen-based polymer or a copolymer of a conjugated-gen-based monomer and a vinyl aromatic hydrocarbon, or water thereof. At least one modified polymer selected from modified polymers having at least one functional group-containing atomic group bonded to the additive is mixed with 100 parts by weight of inorganic filler and 5 to 300 parts by weight of an inorganic filler. Masterbatch: Rubber composition for footwear comprising 1 to 150 parts by weight.
2 . 成分 （2 ) が無機充填剤 5〜 3 0 0重量部の全量を予め混練機に投入して 混練し、 次いで変性重合体を加えて混練して得られるマスターバツチである前項 1に記載の履物用ゴム組成物。  2. The masterbatch according to the above item 1, wherein the component (2) is a masterbatch obtained by previously charging a kneader by charging a total amount of 5 to 300 parts by weight of an inorganic filler into a kneader, and then adding and kneading a modified polymer. Rubber composition for footwear.
3 . 成分 （2 ) が無機充填剤 5〜 3 0 0重量部を 2回以上分割して混練機に投 入して順次混練して得られるマスターバッチである前項 1に記載の履物用ゴム組 成物。  3. The rubber set for footwear according to the above item 1, wherein the component (2) is a master batch obtained by dividing 5 to 300 parts by weight of the inorganic filler into two or more portions and putting the mixture into a kneading machine and kneading sequentially. Adult.
4 . 成分 （2 ) が無機充填剤の 2 0〜8 0重量％を予め混練機に投入して混練 し、 次いで変性重合体を加え、 更に当該無機充填剤の残量を加えて混練したマス ターバツチである前項 1に記載の履物用ゴム組成物。  4. The component (2) is charged with 20 to 80% by weight of the inorganic filler in a kneader in advance and kneaded, then the modified polymer is added, and the remaining amount of the inorganic filler is added to the kneaded mass. 2. The rubber composition for footwear according to the above item 1, which is a turbach.
5 . 成分 （3 ) として、 更に無機充填剤を 0 . 1〜 1 5 0重量部含む前項 1に 記載の履物用ゴム組成物。  5. The rubber composition for footwear according to the above item 1, further comprising 0.1 to 150 parts by weight of an inorganic filler as the component (3).
6 . 変性重合体の官能基含有原子団が、 水酸基、 エポキシ基、 アミノ基、 イミ ノ基、 シラノール基、 アルコキシシラン基から選ばれる官能基を少なくとも 1個 有する原子団である前項 1に記載の履物用ゴム組成物。  6. The functional group according to item 1 above, wherein the functional group-containing atomic group of the modified polymer is an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, an imino group, a silanol group, and an alkoxysilane group. Rubber composition for footwear.
7 . 変性重合体が、 下記式 （1 ) 〜 （1 4 ) から選ばれる原子団が少なくとも 1個結合している変性重合体である前項 1に記載の履物用ゴム組成物。 ェ o CO 00 σι CO r7. The rubber composition for footwear according to item 1, wherein the modified polymer is a modified polymer in which at least one atomic group selected from the following formulas (1) to (14) is bonded. O CO 00 σι CO r
CO to o CO to o
H C  H C
1 1 1 1 1 H o O ― z Z z ζ z z o o = O Ji 73 ji  1 1 1 1 1 H O O ― z Z z ζ z z o o = O Ji 73 ji
73 刀 7) 73 sword 7)
C H C H
刀 1 1 1  Sword 1 1 1
70 Ji  70 Ji
J} o 1 刀 1  J} o 1 sword 1
73 ω o  73 ω o
1 1 ェ 1 1 1 1
O o ω 〇O o ω 〇
N刀 N sword
刀 刀 丄 〇 ― N ェ Katana sword丄〇 - N E
73  73
71 Z  71 Z
Z Ji  Z Ji
71  71
7J  7J
Ji  Ji
( So刀 O刀— I "  (So sword O sword— I "
O C IO C I
O H o刀 O H o sword
o  o
C _ O刀 I C _ O sword I
Cェ Cェ _ C ェ C ェ _
o cェ刀  o c sword
R  R
O (上記式 （1) ~ (14) において、 Nは窒素原子、 S iは珪素原子、 Oは酸 素原子、 Cは炭素原子、 Hは水素原子を表し、 R1, R 2は各々独立に水素原子又 は炭素数 1〜 24の炭化水素基を表し、且つ、該炭化水素基は、所望により、各々 独立に、 水酸基、 エポキシ基、 アミノ基、 炭素数 1〜24の炭化水素基を有する イミノ基、 シラノール基及び炭素数 1〜 24のアルコキシシラン基からなる群よ り選ばれる少なく とも 1種の官能基を有してもよく、 各 R 3は各々独立に炭素数 1〜48の 2価の炭化水素基を表し、 且つ、 所望により、 各々独立に、 水酸基、 エポキシ基、 アミノ基、 炭素数 1〜24の炭化水素基を有するイミノ基、 シラノ ール基及び炭素数 1〜24のアルコキシシラン基からなる群より選ばれる少なく とも 1種の官能基を有してもよく、 各 R4は各々独立に水素原子又は炭素数 1〜 24の炭化水素基を表す。） O (In the above formulas (1) to (14), N is a nitrogen atom, Si is a silicon atom, O is an oxygen atom, C is a carbon atom, H is a hydrogen atom, and R 1 and R 2 are each independently Represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and each of the hydrocarbon groups independently has a hydroxyl group, an epoxy group, an amino group, or a hydrocarbon group having 1 to 24 carbon atoms, if desired. It may have at least one functional group selected from the group consisting of an imino group, a silanol group and an alkoxysilane group having 1 to 24 carbon atoms, and each R 3 is independently a group having 1 to 48 carbon atoms. A hydroxyl group, an epoxy group, an amino group, an imino group having a hydrocarbon group having 1 to 24 carbon atoms, a silanol group, and a Each R 4 may have at least one functional group selected from the group consisting of alkoxysilane groups. Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.)
8. 成分 （2) 、 当該変性重合体と無機充填剤の混練の際に、 更に当該変性 重合体に結合している官能基と反応性を有する化合物 （4) を当該変性重合体 1 00重量部に対して 0. 01〜20重量部添加して得られたマスターバッチであ る前項 1に記載の履物用ゴム組成物。  8. When the component (2) is kneaded with the modified polymer and the inorganic filler, the compound (4) having a reactivity with a functional group bonded to the modified polymer is further added to the modified polymer by 100 wt. 2. The rubber composition for footwear according to item 1, which is a masterbatch obtained by adding 0.01 to 20 parts by weight per part by weight.
9. 成分 （2) 力 当該変性重合体と無機充填剤の混練物に、 更に当該変性重 合体に結合している官能基と反応性を有する化合物 （4) を当該変性重合体 1 0 0重量部に対して 0. 01〜20重量部混練して得られたマスターバッチである 前項 1に記載の履物用ゴム組成物。  9. Component (2) Force The compound (4) having a reactivity with the functional group bonded to the modified polymer is added to the kneaded product of the modified polymer and the inorganic filler at 100 wt. The rubber composition for footwear according to the above item 1, which is a master batch obtained by kneading 0.01 to 20 parts by weight per part by weight.
1 0. 成分 （2) に使用する変性重合体が、 当該変性重合体に結合している官 能基と反応性を有する化合物 （4) を当該変性重合体に結合している官能基 1当 量あたり 0. 3〜1 0モルを用いて反応させた変性重合体である前項 1に記載の 履物用ゴム組成物。  10. The modified polymer used for the component (2) may be a compound (4) having a reactivity with a functional group bound to the modified polymer. 2. The rubber composition for footwear according to the item 1, which is a modified polymer reacted by using 0.3 to 10 mol per amount.
1 1. 化合物 （4) が力ルポキシル基、 酸無水物基、 イソシァネート基、 ェポ キシ基、 シラノール基、 アルコキシシラン基から選ばれる官能基を有する化合物 である前項 8または 9に記載の履物用ゴム組成物。  1 1. The compound for footwear according to the above item 8 or 9, wherein the compound (4) is a compound having a functional group selected from a carboxylic acid group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. Rubber composition.
1 2. 成分 （1) ゴム状重合体： 100重量部；及び成分 （2) 共役ジェン系 重合体又は共役ジェン系単量体とビニル芳香族炭化水素からなる共重合体又はそ れらの水添物に官能基含有原子団が少なくとも 1個結合している変性重合体から 選ばれる少なくとも 1種の変性重合体 1 0 0重量部に無機充填剤 5〜 3 0 0重量 部を混練して得られるマスターバッチ： 1〜1 5 0重量部を混練する工程を含む 履物用ゴム組成物の製造方法。 1 2. Component (1) rubbery polymer: 100 parts by weight; and component (2) a conjugated polymer or a copolymer comprising a conjugated monomer and a vinyl aromatic hydrocarbon, or a copolymer thereof. At least one modified polymer selected from modified polymers in which at least one functional group-containing atomic group is bonded to the hydrogenated product is added with 5 to 300 parts by weight of an inorganic filler in 100 parts by weight. Masterbatch obtained by kneading: A method for producing a rubber composition for footwear, including a step of kneading 1 to 150 parts by weight.
1 3 . 成分 （2 ) が無機充填剤 5〜3 0 0重量部の全量を混練機に投入して混 練し、 次いで変性重合体を加えて混練して得られるマスターバッチである前項 1 2に記載の履物用ゴム組成物の製造方法。  13. The master batch in which the component (2) is a masterbatch obtained by charging the kneader with the entire amount of 5 to 300 parts by weight of the inorganic filler and kneading the mixture, and then adding and kneading the modified polymer. 3. The method for producing a rubber composition for footwear according to item 1.
1 4 . 成分 （ 2 ) が無機充填剤 5〜 3 0 0重量部を 2回以上分割して混練機に 投入して順次混練して得られるマスターバッチである前項 1 2に記載の履物用ゴ ム組成物の製造方法。  14. The shoe for footwear according to the above item 12, which is a master batch obtained by dividing the component (2) by 5 to 300 parts by weight of the inorganic filler two or more times and putting into a kneading machine to be kneaded sequentially. A method for producing a composition.
1 5 . 無機充填剤 5〜 3 0 0重量部の全量を混練機に投入して混練し、 次いで 変性重合体を加えて混練する前項 1に記載のマスターバツチの製造方法。  15. The method for producing a master batch according to the above item 1, wherein the whole amount of 5 to 300 parts by weight of the inorganic filler is put into a kneader and kneaded, and then a modified polymer is added and kneaded.
1 6 . 無機充填剤の 2 0〜 8 0重量％を予め混練機に投入して混練し、 次いで 変性重合体を加え混練し、 更に当該無機充填剤の残量を加えて混練する前項 1に 記載のマスターパッチの製造方法。  16. 20 to 80% by weight of the inorganic filler is put into a kneader in advance and kneaded, then the modified polymer is added and kneaded, and the remaining amount of the inorganic filler is added and kneaded. A method for producing the master patch described above.
特定の官能基含有原子団が結合している変性重合体と無機充填剤のマスターバ ツチを用いて製造した本発明の履物用ゴム組成物は、 引き裂き強度、 耐摩耗性、 水性接着を用いた時の接着性に優れ、 また、 靴工場の作業環境を改善できるゴム 組成物である。 発明を実施するための最良の形態  The rubber composition for footwear of the present invention manufactured using a modified polymer having a specific functional group-containing atomic group bonded thereto and a master batch of an inorganic filler has a tear strength, abrasion resistance, and water-based adhesion. It is a rubber composition that has excellent adhesiveness and can improve the working environment of a shoe factory. BEST MODE FOR CARRYING OUT THE INVENTION
本発明について、 以下具体的説明する。  The present invention will be specifically described below.
本発明の履物用ゴム組成物を構成する成分 （1 ) であるゴム状重合体の種類は 特に限定されないが、 共役ジェン系重合体またはその水添物、 共役ジェン系単量 体とビニル芳香族炭化水素からなるランダム共重合体またはその水添物、 共役ジ ェン系単量体とビュル芳香族炭化水素からなるプロック共重合体またはその水添 物、 非ジェン系重合体、 天然ゴム等があげられる。 具体的には、 ブタジエンゴム 又はその水素添加物、 ィソプレンゴム又はその水素添加物、 スチレン-ブタジェ ンゴム又はその水素添加物、 スチレン一ブタジエンブロック共重合体又はその水 素添加物、 スチレン- イソプレンプロック共重合体又はその水素添加物等のスチ レン系エラス トマ一、 アタリロュ トリル— ブタジェンゴム又はその水素添加物等 であり、 また、 非ジェン系重合体としては、 エチレン- プロピレンゴム、 ェチレ ン- プロピレン- ジェンゴム、 エチレン- ブテン - ジェンゴム、 エチレン- ブテ ンゴム、 ェチェン- へキセンゴム、 エチレン - 才クテンゴム等のォレフィン系ェ ラス トマー、 プチルゴム、 臭素化ブチルゴム、 アク リルゴム、 フッ素ゴム、 シリ コーンゴム、 塩素化ポリエチレンゴム、 ェピクロルヒ ドリンゴム、 α、 j3 _ 不飽 和ュトリル - ァク リル酸エステル- 共役ジェン共重合ゴム、 ウレタンゴム等など があげられる。 これらのゴム状重合体は、 官能基を付与した変性ゴムであっても 良い。 上記ゴム状重合体を単独で、 或いは、 2種類以上のゴム状重合体を混合し た混合物として使用することがでる。 The type of the rubbery polymer which is the component (1) constituting the rubber composition for footwear of the present invention is not particularly limited, but may be a conjugated polymer or a hydrogenated product thereof, a conjugated monomer and a vinyl aromatic. Random copolymers of hydrocarbons or hydrogenated products thereof, block copolymers of conjugated diene monomers and butyl aromatic hydrocarbons or hydrogenated products thereof, non-gen-based polymers, natural rubber, etc. can give. Specifically, butadiene rubber or its hydrogenated product, isoprene rubber or its hydrogenated product, styrene-butadiene Styrene-based elastomer such as styrene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof, styrene-isoprene block copolymer or hydrogenated product thereof, atarilor tri-butadiene rubber or hydrogenated product thereof And non-gen-based polymers such as ethylene-propylene rubber, ethylene-propylene-gen rubber, ethylene-butene-gen rubber, ethylene-butene rubber, ethen-hexene rubber, and ethylene-butene rubber. Olefin elastomer, butyl rubber, brominated butyl rubber, acryl rubber, fluoro rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, j3_unsaturated nitrile-acrylic acid ester-conjugated gen copolymer rubber, Urethane rubber, etc. And the like. These rubbery polymers may be modified rubbers having a functional group. The rubbery polymer can be used alone or as a mixture of two or more rubbery polymers.
本発明の履物用ゴム組成物を構成する成分 （2 ) は、 共役ジェン系重合体又は 共役ジェン系単量体とビュル芳香族炭化水素からなる共重合体又はそれらの水添 物に官能基含有原子団が少なく とも 1個結合している変性重合体から選ばれる少 なくとも 1種の変性重合体と無機充填剤を予め混練してマスターバツチ化したゴ ム組成物である。  The component (2) constituting the rubber composition for footwear of the present invention contains a functional group in a conjugated gen-based polymer or a copolymer composed of a conjugated gen-based monomer and butyl aromatic hydrocarbon or a hydrogenated product thereof. A rubber composition obtained by kneading at least one modified polymer selected from modified polymers having at least one atomic group and an inorganic filler in advance and forming a master batch.
本発明の成分（ 2 )において用いられる変性共役ジェン系重合体又は共役ジェン 系単量体とビュル芳香族炭化水素からなる変性共重合体は、 少なくとも 1種類の 共役ジェン系単量体及び少なく とも 1種類のビニル芳香族芳香族炭化水素とを有 機リチウム触媒の存在下で溶液重合させることにより製造することができる。 本 発明の変性重合体の製造方法は、 本発明の構造を有する重合体を得ることができ れば、 如何なる製造方法も採用することができる。  The modified conjugated gen-based polymer or modified copolymer comprising a conjugated gen-based monomer and a butyl aromatic hydrocarbon used in the component (2) of the present invention comprises at least one conjugated gen-based monomer and at least one conjugated-gen monomer. It can be produced by solution polymerization of one kind of vinyl aromatic aromatic hydrocarbon in the presence of an organic lithium catalyst. As for the method for producing the modified polymer of the present invention, any production method can be adopted as long as a polymer having the structure of the present invention can be obtained.
本発明における共役ジェン系単量体とは一対の共役二重結合を有するジォレフ ィンであり、 例えば 1， 3 - ブタジエン、 2 - メチル- 1， 3 - ブタジエン (ィ ソプレン）、 2 , 3 - ジメチル— 1 , 3— ブタジエン、 1 , 3— ペンタジェン、 1 , 3 -へキサジェンなどが挙げられるが、 特に一般的なものとしては 1 , 3 - ブタ ジェン、 イソプレンが挙げられる。 これらは重合体の製造において一種のみなら ず二種以上を使用してもよい。 The conjugated diene monomer in the present invention is a diolefin having a pair of conjugated double bonds, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3- Dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like can be mentioned, and particularly common ones are 1,3-butadiene and isoprene. These are the only ones in the production of polymers Alternatively, two or more kinds may be used.
また、 ビュル芳香族炭化水素としては、 スチレン、 0 - メチルスチレン、 - メチルスチレン、 - t e r t - ブチノレスチレン、 1， 3— ジメチルスチレン、 a - メチルスチレン、 ビニノレナフタレン、 ビニルァントラセンなどが挙げられる が、 特に一般的なものとしてはスチレン、 ひ- メチルスチレンが挙げられる。 こ れらは重合体の製造において一種のみならず二種以上を使用してもよい。  In addition, examples of butyl aromatic hydrocarbons include styrene, 0-methylstyrene, -methylstyrene, -tert-butynolestyrene, 1,3-dimethylstyrene, a-methylstyrene, vinylinalephthalene, and vinylanthracene. Among them, styrene and methyl styrene are particularly common. These may be used alone or in combination of two or more in the production of the polymer.
変性重合体の製造に用いられる溶媒としては、 ブタン、 ペンタン、 へキサン、 ィソペンタン、 ヘプタン、 オクタン、 ィソオクタン等の脂肪族炭化水素、 シクロ ペンタン、 メチノレシク口ペンタン、 シク口へキサン、 メチノレシク口へキサン、 ェ チルシクロへキサン等の脂環式炭化水素、 或いはベンゼン、 トルエン、 ェチルベ ンゼン、 キシレン等の芳香族炭化水素などの炭化水素系溶媒が使用できる。 これ らは一種のみならず二種以上を混合して使用してもよい。  Solvents used in the production of the modified polymer include butane, pentane, hexane, isopentane, heptane, octane, isooctane, and other aliphatic hydrocarbons, cyclopentane, methinoresic pentane, cyclohexane, methinoresic hexane, Hydrocarbon solvents such as alicyclic hydrocarbons such as ethylcyclohexane or aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or in combination of two or more.
また、 変性重合体の製造に用いられる有機リチウム化合物は、 分子中に 1個以 上のリチウム原子を結合した化合物であり、 例えばェチルリチウム、 n - プロピ ルリチウム、 イソプロピルリチウム、 n - ブチルリチウム、 s e c - ブチルリチ ゥム、 t e r t - プチルリチウム、 へキサメチレンジリチウム、 ブタジェニノレジ リチウム、 イソプレニルジリチウムなどが挙げられる。 さらに、 米国特許第 5 , 7 0 8， 0 9 2号明細書、 英国特許第 2， 2 4 1 , 2 3 9号明細書、 米国特許第 5 , 5 2 7 , 7 5 3号明細書等に開示されているアミ ドリチウムなどの有機アル 力リ金属化合物も使用することができる。 これらは一種のみならず二種以上を混 合して使用してもよい。 又、 有機リチウム化合物は、 重合体の製造において重合 途中で 1回以上分割添加してもよい。  The organic lithium compound used in the production of the modified polymer is a compound in which one or more lithium atoms are bonded in a molecule, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec- Butyllithium, tert-butyllithium, hexamethylenedilithium, butageninoresitium lithium, isoprenyldilithium and the like. Further, U.S. Pat. No. 5,708,092, British Patent No. 2,241,239, U.S. Pat. No. 5,527,753, etc. Organic metal compounds such as amide lithium disclosed in U.S. Pat. These may be used alone or in combination of two or more. Further, the organolithium compound may be dividedly added one or more times during the polymerization in the production of the polymer.
本発明において、 重合体を製造している時の重合速度の調整、 重合体中の共役 ジェン部分のミク口構造の変更、 共役ジェン系単量体とビニル芳香族炭化水素と の反応性比の調整などの目的で極性化合物ゃランダム化剤を使用することができ る。 極性化合物やランダム化剤としては、 エーテル類、 アミン類、 チォエーテル 類、 ホスホルアミ ド、 アルキルベンゼンスルホン酸のカリウム塩又はナトリウム 塩、 カリゥムまたはナトリゥムのアルコキシドなどが挙げられる。 エーテル類の例と してはジメチルエーテル、 ジェチルエーテル、 ジフエニルェ ーテノレ、 テトラヒ ドロフラン、 ジエチレングリ コーノレジメチノレエーテノレ、 ジェチ レンダリコールジブチルエーテル等が挙げられる。 ァミン類としては第三級アミ ン、 トリメチルァミン、 トリエチルァミン、 テ トラメチルエチレンジァミン、 そ の他環状第三級ァミン等が挙げられる。ホスフィン及びホスホルアミ ドとしては、 トリフエニルホスフィン、 へキサメチルホスホルァミ ドなどが挙げられる。 In the present invention, adjusting the polymerization rate during the production of the polymer, changing the microstructure of the conjugated gen moiety in the polymer, and adjusting the reactivity ratio between the conjugated gen-based monomer and the vinyl aromatic hydrocarbon. A polar compound / randomizing agent can be used for adjustment or the like. Examples of the polar compound and the randomizing agent include ethers, amines, thioethers, phosphoramides, potassium or sodium salts of alkylbenzenesulfonic acids, and alkoxides of potassium or sodium. Examples of the ethers include dimethyl ether, getyl ether, diphenyl ether phenol, tetrahydrofuran, diethylene glycol dimethyl methino ole ether, and jeti lendarichol dibutyl ether. Examples of the amines include tertiary amines, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines. Examples of phosphines and phosphoramides include triphenylphosphine, hexamethylphosphoramide and the like.
重合体を製造する際の重合温度は、 好ましくは- 1 0~1 50°C、 より好まし くは 30〜1 20°Cである。 重合に要する時間は条件によって異なるが、 好まし くは 48時間以内であり、 特に好適には 0. 5〜1 0時間である。 又、 重合系の 雰囲気は窒素ガスなどの不活性ガス雰囲気にすることが好ましい。 重合系の圧力 は、 上記の重合温度範囲でモノマー及び溶媒を液相に維持するのに充分な圧力の 範囲にすればよく、 特に限定されるものではないが、 通常 0. 2〜2MP aであ り、 好ましくは 0. 3〜1. 5MP aである。 反応温度は、 0〜1 50°Cの範囲 が好ましく、 より好ましくは 20〜 1 20°C、 更に好ましくは 50~ 1 00°Cの 範囲である。 更に、 重合系内は触媒及びリ ビングポリマーを不活性化させるよう な不純物、 例えば水、 酸素、 炭酸ガスなどが混入しないようにすることが好まし レ、。  The polymerization temperature in producing the polymer is preferably −10 to 150 ° C., and more preferably 30 to 120 ° C. The time required for the polymerization varies depending on the conditions, but is preferably within 48 hours, particularly preferably 0.5 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The pressure of the polymerization system may be in a range of a pressure sufficient to maintain the monomer and the solvent in a liquid phase within the above-mentioned polymerization temperature range, and is not particularly limited, but is usually 0.2 to 2 MPa. Yes, preferably 0.3 to 1.5 MPa. The reaction temperature is preferably in the range of 0 to 150 ° C, more preferably 20 to 120 ° C, and still more preferably 50 to 100 ° C. Further, it is preferable that impurities such as water, oxygen, and carbon dioxide gas which inactivate the catalyst and the living polymer are not mixed in the polymerization system.
本発明の成分 （2) で使用する共役ジェン系重合体又はその水添物の変性重合 体は、 共役ジェン系単量体単独重合体またはビニル芳香族炭化水素含有量が 5 w t %未満の共役ジェン系重合体の変性重合体である。 共役ジェン系重合体又はそ の水添物の構造は直鎖状であっても分岐状であっても、 また、 これらの任意の混 合物であっても良い。 また、 共役ジェン系単量体とビニル芳香族炭化水素からな る共重合体又はその水添物は、 ランダム共重合体であってもプロック共重合体で あっても良い。 また、 変性共重合体又はその水添物の構造は、 直鎖状であっても 分岐状であっても、 これらの任意の混合物であっても良い。  The modified polymer of the conjugated gen-based polymer or its hydrogenated product used in the component (2) of the present invention is a conjugated gen-based monomer homopolymer or a conjugated polymer having a vinyl aromatic hydrocarbon content of less than 5 wt%. It is a modified polymer of a gen-based polymer. The structure of the conjugated gen-based polymer or its hydrogenated product may be linear or branched, or may be an arbitrary mixture thereof. Further, the copolymer comprising a conjugated diene monomer and a vinyl aromatic hydrocarbon or a hydrogenated product thereof may be a random copolymer or a block copolymer. The structure of the modified copolymer or the hydrogenated product thereof may be linear, branched, or an arbitrary mixture thereof.
本発明の成分 （2) で使用する共役ジェン系単量体とビニル芳香族炭化水素か らなるランダム共重合体又はその水添物のビニル芳香族炭化水素含有量は通常 5 〜 9 5 w t °/oの範囲であり、 好ましくは 1 0〜 90 w t %、 更に好ましくは 1 5 〜8 5 w t %の範囲である。 またランダム共重合体又はその水添物の重合体鎖に は、 ビエル芳香族炭化水素含有量の異なるランダム共重合体ブロックが 2個以上 存在しても、 更には共役ジェン重合体ブロック又はその水添物が 1個以上存在し ても良い。 The random copolymer comprising the conjugated diene monomer and the vinyl aromatic hydrocarbon used in the component (2) of the present invention or the hydrogenated product thereof usually has a vinyl aromatic hydrocarbon content of 5 to 95 wt °. / o, preferably from 10 to 90 wt%, more preferably 15 885 wt%. In addition, even if two or more random copolymer blocks having different Bier aromatic hydrocarbon contents are present in the polymer chain of the random copolymer or its hydrogenated product, the conjugated diene polymer block or its water One or more additives may be present.
共役ジェン系重合体の変性重合体ゃランダム共重合体の変性重合体は、 共役ジ ェン系重合体ゃランダム共重合体のリビング末端に後述する変性剤を付加反応す ることにより得られる。  A modified polymer of a conjugated gen-based polymer / a modified copolymer of a random copolymer can be obtained by subjecting a living terminal of a conjugated gen-based polymer / random copolymer to a modification agent described later by an addition reaction.
本発明の成分 （2) で使用する共役ジェン系単量体とビニル芳香族炭化水素か らなるプロック共重合体又はその水添物のビニル芳香族炭化水素含有量は、 通常 5〜 9 5 w t %の範囲であり、 より好ましくは 1 0〜 9 0 w t °/0、 更に好ましく は 1 5〜8 5 w t %の範囲である。 ブロック共重合体又はその水添物のビュル芳 香族炭化水素含有量が 6 0 w t %以上、 好ましくは 6 5 w t %以上の場合は樹脂 的な特性を有し、 6 0 w t %未満、 好ましくは 5 5 w t %以下の場合は弹性的な 特性を有する。 The block copolymer comprising a conjugated diene monomer and a vinyl aromatic hydrocarbon used in the component (2) of the present invention or a hydrogenated product thereof generally has a vinyl aromatic hydrocarbon content of 5 to 95 wt. %, More preferably from 10 to 90 wt% / 0 , even more preferably from 15 to 85 wt%. If the block copolymer or its hydrogenated product has a Bull aromatic hydrocarbon content of at least 60 wt%, preferably at least 65 wt%, it has resinous properties and is less than 60 wt%, preferably Has sexual properties when it is less than 55 wt%.
ブロック共重合体の製造方法としては、例えば特公昭 3 6- 1 9 2 8 6号公報、 特公昭 4 3- 1 7 9 7 9号公報、 特公昭 4 6- 3 24 1 5号公報、 特公昭 4 9 - As a method for producing the block copolymer, for example, Japanese Patent Publication No. 36-192686, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32415, Kimiaki 4 9-
3 6 9 5 7号公報、特公昭 48- 2 4 2 3号公報、特公昭 4 8- 4 1 0 6号公報、 特公昭 5 6- 28 9 2 5号公報、 特公昭 5 1- 4 9 5 6 7号公報、 特開昭 5 9 -JP-B-36-957, JP-B-48-242, JP-B-48-410, JP-B-56-28-925, JP-B-51-49 No. 567, JP-A-59-
1 6 6 5 1 8号公報、 特開昭 6 0- 1 8 6 5 7 7号公報などに記載された方法が 挙げられる。 Examples of the method include the methods described in Japanese Patent Application Laid-Open No. 1666518 and Japanese Patent Application Laid-Open No. 60-185677.
これらの方法で得られるプロック共重合体のリビング末端に後述する変性剤を 付加反応することにより本発明で使用するプロック共重合体の変性重合体が得ら れ、 例えば下記一般式で表される構造を有する。  A modified polymer of the block copolymer used in the present invention can be obtained by adding and reacting a modifying agent described below to the living terminal of the block copolymer obtained by these methods, and is represented by the following general formula, for example. Having a structure.
(A- B) n- X、 A- (B- A) n- X、  (A- B) n- X, A- (B- A) n- X,
B - (A- B) n - X、 X- (A- B) n、  B-(A- B) n-X, X- (A- B) n,
X- (A- B) n- X、 X- A- (B- A) n - X、  X- (A- B) n- X, X- A- (B- A) n-X,
X- B- (A- B) n- X、 [ (B - A) n]m- X、  X- B- (A- B) n- X, [(B-A) n] m- X,
[ (A- B) n]m- X、 [ (B- A) n- B]m- X、 [ (A- B ) n- A] ra - X [(A- B) n] m- X, [(B- A) n- B] m- X, [(A- B) n- A] ra-X
(上式において、 Aはビニル芳香族炭化水素を主体とする重合体プロックであり、 Bは共役ジェン系単量体を主体とする重合体プロックである。 Aブロックと ブ 口ックとの境界は必ずしも明瞭に区別される必要はない。又、 nは 1以上の整数、 好ましくは 1〜5の整数である。 mは 2以上の整数、 好ましくは 2〜1 1の整数 である。 Xは、 後述する官能基を有する原子団が結合している変性剤の残基を示 す。 Xを後述するメタレーション反応で付加させる場合は、 Aブロック及び/又 は Bブロックの側鎖に結合している）  (In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbon, and B is a polymer block mainly composed of conjugated diene monomer. Boundary between A block and block Need not be clearly distinguished, and n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X is Indicates the residue of the modifier to which an atomic group having a functional group described below is bonded When X is added by a metallation reaction described below, it is bonded to the side chain of the A block and / or B block. ing)
尚、 上記の一般式で示した構造において、 ビニル芳香族炭化水素を主体とする 重合体プロック Aはビュル芳香族炭化水素を好ましくは 5 0 w t %以上、 より好 ましくは 7 O w t %以上含有するビュル芳香族炭化水素と共役ジェン系単量体と の共重合体プロック又はビニル芳香族炭化水素の単独重合体プロックであり、 ビ ニル芳香族炭化水素は均一に分布していても、 又テーパー状に分布していてもよ い。 共役ジェン系単量体を主体とする重合体プロック Bは共役ジェン系単量体を 好ましくは 5 0 w t。/。を超える量で、 より好ましくは 6 0 w t %以上含有する共 役ジェン系単量体とビニル芳香族炭化水素との共重合体プロック又は共役ジェン 系単量体の単独重合体プロックである。  In the structure represented by the above general formula, the polymer block A mainly composed of vinyl aromatic hydrocarbon preferably contains 50% by weight or more, more preferably 70% by weight or more of butyl aromatic hydrocarbon. A copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene monomer or a homopolymer block of a vinyl aromatic hydrocarbon, wherein the vinyl aromatic hydrocarbon is uniformly distributed, It may be distributed in a tapered shape. The polymer block B mainly containing a conjugated diene monomer is preferably 50 wt. /. It is a copolymer block of a co-gen monomer and a vinyl aromatic hydrocarbon containing more than 60 wt% or more, and more preferably a homopolymer block of a conjugated j-mon monomer.
また、 該変性ブロック共重合体中には、 ビニル芳香族炭化水素が均一に分布し ている部分及び/又はテーパー状に分布している部分がそれぞれ複数個共存して いてもよい。 本発明で使用する変性ブロック共重合体は、 上記一般式で表される 変性プロック共重合体の任意の混合物でもよい。  In the modified block copolymer, a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions where vinyl aromatic hydrocarbons are distributed in a tapered shape may coexist. The modified block copolymer used in the present invention may be any mixture of the modified block copolymer represented by the above general formula.
変性プロック共重合体に組み込まれているビニル芳香族炭化水素重合体プロッ クの割合 （ビニル芳香族炭化水素のブロック率という） は、 耐摩耗性を重視する 場合 5◦ w t %未満、 好ましくは 5〜 4 5 w t %、 更に好ましくは 1 0〜4 0 w t %にすることが、 また成形品の剛性保持の点から 5 0 w t %以上、 好ましくは 5 0〜 9 7 w t °/0、 更に好ましくは 6 0〜 9 5 w t %、 とりわけ好ましくは 7 0 〜9 2 w t °/oに調整することが推奨される。 The proportion of the vinyl aromatic hydrocarbon polymer block incorporated in the modified block copolymer (referred to as the vinyl aromatic hydrocarbon block rate) is less than 5 ° wt% when wear resistance is important, and preferably less than 5%. To 45 wt%, more preferably 10 to 40 wt%, and more than 50 wt%, preferably 50 to 97 wt ° / 0 , more preferably from the viewpoint of maintaining the rigidity of the molded article. Is recommended to be adjusted to 60 to 95 wt%, particularly preferably 70 to 92 wt ° / o.
プロック共重合体に組み込まれているビニル芳香族炭化水素のプロック率の測 定は、 四酸化ォスミゥムを触媒としてターシャリーブチルハイドロパーォキサイ ドによりブロック共重合体を酸化分解する方法 （I . M. KO LTHOF F, e t a 1. , J . P o 1 y m. S c i . 1， 429 (1 946) に記載の方法） によ り得たビニル芳香族炭化水素重合体ブロック成分 （但し平均重合度が約 10以下 のビュル芳香族炭化水素重合体成分は除かれている） を用いて、 次の式から求め ることができる。 Measurement of block rate of vinyl aromatic hydrocarbon incorporated in block copolymer. The method was determined by oxidizing and decomposing a block copolymer with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IMKOLTHOF F, eta 1., J.Po1ym.Sci. 1, 429 (1 946)) The vinyl aromatic hydrocarbon polymer block component obtained by the above method (however, the BU aromatic polymer component having an average degree of polymerization of about 10 or less is excluded) ) Can be obtained from the following equation.
ビニル芳香族炭化水素のプロック率 (w t %)  Block ratio of vinyl aromatic hydrocarbon (wt%)
= (ブロック共重合体中のビニル芳香族炭化水素重合体プロックの重量） /プロック共重合体中の全ビニル芳香族炭化水素の重量） X 100 本発明において、 変性共役ジェン系重合体又は共役ジェン系単量体とビニル芳 香族炭化水素からなる変性共重合体中の共役ジェン部分のミクロ構造 （シス、 ト ランス、 ビニルの比率） は、 後述する極性化合物等の使用により任意に変えるこ とができる。 ビュル結合含有量は特に限定されないが、 共役ジェン系単量体とし て 1， 3 -ブタジエンを使用した場合には、ビニル結合量は好ましくは 5〜90%、 より好ましくは 1 0〜80%、 共役ジェン系単量体としてィソプレンを使用した 場合又は 1， 3-ブタジエンとイソプレンを併用した場合には、 1, 2-ビニル結 合と 3, 4 -ビュル結合の合計であるビュル結合量は好ましくは 3~80%、 'よ り好ましくは 5〜 70%である。ここで、 ビニル結合含有量とは，重合体中に 1， 2_結合、 3, 4—結合及び 1， 4—結合の結合様式で組み込まれている共役ジ ェン系単量体のうち， 1， 2一結合及び 3 , 4一結合で組み込まれているものの 割合である。 変性重合体中のビニル結合は重合体鎖中に均一に分布していても、 テーパー状に分布していても、 或いはビュル結合の異なる重合体プロックが 2個 以上存在しても良い。 ビュル結合含有量は後述する極性化合物等の使用により任 意に変えることができる。  = (Weight of vinyl aromatic hydrocarbon polymer block in block copolymer) / weight of total vinyl aromatic hydrocarbon in block copolymer) X 100 In the present invention, the modified conjugated polymer or conjugated gen The microstructure (ratio of cis, trans, and vinyl) of the conjugated gen moiety in the modified copolymer composed of a vinyl monomer and a vinyl aromatic hydrocarbon can be arbitrarily changed by using a polar compound described below. Can be. The content of the Bull bond is not particularly limited, but when 1,3-butadiene is used as the conjugated diene monomer, the vinyl bond content is preferably 5 to 90%, more preferably 10 to 80%, When isoprene is used as the conjugated diene monomer or when 1,3-butadiene and isoprene are used in combination, the number of butyl bonds, which is the sum of 1,2-vinyl bonds and 3,4-butyl bonds, is preferable. Is 3 to 80%, and more preferably 5 to 70%. Here, the vinyl bond content refers to the conjugated diene monomer incorporated in the polymer in a 1,2_ bond, 3,4-linkage, and 1,4-linkage bond mode. This is the ratio of those incorporated in 1,2 single bonds and 3,4 single bonds. The vinyl bonds in the modified polymer may be uniformly distributed in the polymer chain, may be tapered, or may have two or more polymer blocks having different Bull bonds. The Bull bond content can be arbitrarily changed by using a polar compound described below.
但し、 変性ブロック共重合体の水添物を使用する場合、 そのミクロ構造は共 役ジェン系単量体として 1， 3-ブタジエンを使用した場合には、 ビニル結合量 は好ましくは 1 0〜 80 %、 更に好ましくは 25〜 75 °/0であり、 共役ジェン系 単量体としてィソプレンを使用した場合又は 1 , 3-ブタジエンとイソプレンを 併用した場合には、 1, 2-ビニル結合と 3， 4-ビニル結合の合計であるビニル 結合量は好ましくは 5〜 70 °/0であることが推奨される。 変性重合体中の共役ジ ェン系単量体に基づくビニル結合含有量は、 核磁気共鳴装置 （NMR) を用いて 知ることができる。 ' However, when a hydrogenated product of a modified block copolymer is used, its microstructure is preferably from 10 to 80 when 1,3-butadiene is used as a syngeneic monomer. %, More preferably 25 to 75 ° / 0 , when isoprene is used as the conjugated diene monomer or when 1,3-butadiene and isoprene are used. When used in combination, it is recommended that the total amount of vinyl bonds, which is the sum of 1,2-vinyl bonds and 3,4-vinyl bonds, be 5 to 70 ° / 0 . The vinyl bond content based on the conjugated diene monomer in the modified polymer can be known by using a nuclear magnetic resonance apparatus (NMR). '
共役ジェン系重合体や共役ジェン系単量体とビニル芳香族炭化水素からなる共 重合体の製造において、 共役ジェン系単量体としてイソプレンと 1， 3- ブタジ ェンを併用する場合、 イソプレンと 1， 3- ブタジエンの重量比は好ましくは 9 5/5〜 5/95、 より好ましくは 90ノ 1 0〜： 10/90、 更に好ましくは 8 5Zl 5〜1 5/8 5である。 特に、 低温特性に優れたゴム組成物を得る場合に は、 イソプレンと 1， 3- ブタジエンの重量比は好ましくは 49/5 1〜 5/ 9 5、 より好ましくは 45/55〜10Z90、 更に好ましくは 40/60〜1 5 /8 5であることが推奨される。 ィソプレンと 1 , 3- ブタジエンを併用すると 高温での成形加工においても機械的特性の良好なゴム組成物が得られる。  In the production of conjugated gen-based polymers or copolymers of conjugated gen-based monomers and vinyl aromatic hydrocarbons, when isoprene and 1,3-butadiene are used together as conjugated gen-based monomers, The weight ratio of 1,3-butadiene is preferably 95/5 to 5/95, more preferably 90 to 10/90, and even more preferably 85 to 105/85. In particular, when a rubber composition having excellent low-temperature properties is obtained, the weight ratio of isoprene to 1,3-butadiene is preferably 49/5 1 to 5/95, more preferably 45/55 to 10Z90, and still more preferably. Is recommended to be between 40/60 and 15/85. When isoprene and 1,3-butadiene are used in combination, a rubber composition having good mechanical properties can be obtained even at high temperatures.
次に、 本発明の成分 （2) で使用する変性重合体について説明する。 変性重合 体は、 有機リチウム化合物を重合触媒として得た重合体のリビング末端に官能基 含有変性剤を反応させて、 官能基含有原子団を付加することで製造することがで きる。 該官能基含有原子団は重合体の少なく とも 1つの重合体鎖末端に結合して いる。  Next, the modified polymer used in the component (2) of the present invention will be described. The modified polymer can be produced by reacting a functional group-containing modifying agent with a living terminal of a polymer obtained using an organolithium compound as a polymerization catalyst and adding a functional group-containing atomic group. The functional group-containing atomic group is bonded to at least one polymer chain terminal of the polymer.
変性重合体に結合している官能基含有原子団の官能基の例として、 水酸基、 力 ルボニル基、 チォカルポニル基、 酸ハロゲン化物基、 酸無水物基、 力ルポキシル 基、 チォカルボキシル酸基、 アルデヒ ド基、 チオアルデヒ ド基、 カルボン酸エス テル基、 アミ ド基、 スルホン酸基、 スルホン酸エステル基、 リン酸基、 リン酸ェ ステル基、 アミノ基、 イミノ基、 シァノ基、 ピリジル基、 キノリン基、 エポキシ 基、チォエポキシ基、スルフィ ド基、ィソシァネート基、ィソチオシァネート基、 ハロゲン化ケィ素基、 シラノール基、 アルコキシシラン基、 ハロゲン化スズ基、 アルコキシスズ基、 フエニルスズ基等からなる群より選ばれる少なくとも 1種の 官能基が挙げられる。 上記の官能基のうち、 水酸基、 エポキシ基、 アミノ基、 ィ ミノ基、 シラノール基、 アルコキシシラン基が特に好ましい。 水酸基、 エポキシ基、 アミノ基、 イミノ基、 シラノール基、 アルコキシシラン 基からなる群から選ばれる少なく とも 1種の官能基を有する原子団の好ましい例 として、 下記式 （1) 〜 （1 4) からなる群より選ばれる式で表される少なくと も 1種のものが挙げられる。 Examples of functional groups of the functional group-containing atomic group bonded to the modified polymer include a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carbonyl group, a thiocarboxylic acid group, and an aldehyde. Group, thioaldehyde group, carboxylic ester group, amide group, sulfonic acid group, sulfonic ester group, phosphoric acid group, phosphoric ester group, amino group, imino group, cyano group, pyridyl group, quinoline group, Selected from the group consisting of an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilane group, a tin halide group, an alkoxytin group, and a phenyltin group. At least one functional group. Of the above functional groups, a hydroxyl group, an epoxy group, an amino group, an amino group, a silanol group, and an alkoxysilane group are particularly preferred. Preferred examples of the atomic group having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, an imino group, a silanol group, and an alkoxysilane group include those represented by the following formulas (1) to (14). At least one kind represented by a formula selected from the group consisting of:
Figure imgf000016_0001
O o
Figure imgf000016_0001
O o
^  ^
Figure imgf000016_0002
Figure imgf000016_0002
上記式 （1 ) 〜 （1 4 ) において、 Nは窒素原子、 S iは珪素原子、 Oは酸 素原子、 Cは炭素原子、 Hは水素原子を表し、 R 1 , R 2は各々独立に水素原子又 は炭素数 1〜2 4の炭化水素基を表し、且つ、該炭化水素基は、所望により、各々 独立に、 水酸基、 エポキシ基、 アミノ基、 炭素数 1〜2 4の炭化水素基を有する イミノ基、 シラノール基及ぴ炭素数 1〜2 4のアルコキシシラン基からなる群よ り選ばれる少なく とも 1種の官能基を有してもよく、 各 R 3は各々独立に炭素数 1〜4 8の 2価の炭化水素基を表し、 且つ、 所望により、 各々独立に、 水酸基、 エポキシ基、 アミノ基、 炭素数 1〜2 4の炭化水素基を有するイミノ基、 シラノ ール基及び炭素数 1〜2 4のアルコキシシラン基からなる群より選ばれる少なく とも 1種の官能基を有してもよく、 各 R 4は各々独立に水素原子又は炭素数 1〜In the above formulas (1) to (14), N is a nitrogen atom, Si is a silicon atom, O is an oxygen atom, C is a carbon atom, H is a hydrogen atom, and R 1 and R 2 are each independently Represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and each of the hydrocarbon groups may be independently a hydroxyl group, an epoxy group, an amino group, a hydrocarbon group having 1 to 24 carbon atoms, if desired. May have at least one functional group selected from the group consisting of an imino group, a silanol group and an alkoxysilane group having 1 to 24 carbon atoms, and each R 3 independently has 1 carbon atom ~ 48 divalent hydrocarbon groups, and, if desired, each independently represents a hydroxyl group, an epoxy group, an amino group, an imino group having a hydrocarbon group having 1 to 24 carbon atoms, a silanol group, and It may have at least one functional group selected from the group consisting of alkoxysilane groups having 1 to 24 carbon atoms, Each R 4 is independently a hydrogen atom or carbon number 1 to
2 4の炭化水素基を表す。 Represents 24 hydrocarbon groups.
本発明において、 変性重合体に結合している上記の官能基含有原子団を形成す るために用いることができる変性剤としては、 上記の官能基を有する公知の化合 物及び/又は形成し得る公知の化合物を用いることができる。 例えば特公平 4一 In the present invention, as the modifying agent that can be used to form the functional group-containing atomic group bonded to the modified polymer, a known compound having the above functional group and / or a known compound having the above functional group can be formed. Known compounds can be used. For example, Tokuhei 41
3 9 4 9 5号公報 （米国特許第 5， 1 1 5， 0 3 5号に対応） に記載された末端 変性処理剤を用いることができる、 具体的には、 下記のものが挙げられる。 上記式 （1 ) 〜 （6 ) の官能基を有する変性剤の例としては、 テトラグリシジ ルメタキシレンジァミン、 テトラグリシジルー 1 , 3 _ビスアミノメチルシク口 へキサン、 テ トラグリシジルー p—フエ-レンジァミン、 テ トラグリシジルジァ ミノジフエニノレメタン、ジグリシジノレァニリン、ジグリシジノレオノレソ トノレイジン、 N— ( 1 , 3—ジブチルプチリデン） 一 3— （トリエトキシシリノレ） 一 1—プロ パンァミン、 4ージ （/3— トリメ トキシシリルェチル） アミノスチレン、 4ージThe terminal modifying agent described in Japanese Patent No. 39495/95 (corresponding to US Pat. No. 5,115,035) can be used, and specific examples include the following. Examples of the modifying agents having the functional groups represented by the above formulas (1) to (6) include tetraglycidyl metaxylene diamine, tetraglycidyl 1,3-bisaminomethylcyclohexane, and tetraglycidyl p-phenylene diamine. , Tetraglycidyldiaminodipheninolemethane, Diglycidinoleaniline, Diglycidinolenolesotonoleidine, N- (1,3-Dibutylbutylidene) 1-3- (Triethoxysilinole) 1-1-Propanamine , 4 di (/ 3—trimethoxysilyl ethyl) aminostyrene, 4 di
( ー トリエトキシシリルェチル） アミノスチレン、 4 _ジ ( γ— トリメ トキシ シリルプロピル) 了ミノスチレン、 4—ジ ( γ— トリエトキシシリルプロピル) アミノスチレンが挙げられる。 (-Triethoxysilylethyl) aminostyrene, 4-di ( γ -trimethoxysilylpropyl) amino styrene, and 4-di ( γ -triethoxysilylpropyl) aminostyrene.
上記式 （7 ) の官能基を有する変性剤の例としては、 ε—力プロラタ トン、 δExamples of the modifier having a functional group represented by the above formula (7) include ε -force prolatatone, δ
—バレロラタ トン、 プチ口ラク トン、 γ一力プロラタ トン、 γ—バレロラタ トン などの環状ラタ トンが挙げられる。 上記式 （8 ) の官能基を有する変性剤の例としては、 4ーメ トキシベンゾフエ ノン、 4ーェトキシベンゾフエノン、 4， 4， 一ビス (メ トキシ) ベンゾフエノ ン、 4 , 4， -ビス (ェトキシ) ベンゾフエノン、 γ—グリシドキシェチルトリ メ トキシシラン、 ーグリシドキシプロビルトリメ トキシシランが挙げられる。 上記式 （9 ) 及び （1 0 ) の官能基を有する変性剤の例としては、 γ—グリシ ドキシプチルトリメ トキシシラン、 γ—ダリシドキシプロピルトリエトキシシラ ン、 γ—グリシドキシプロピルトリプロポキシシラン、 y—グリシドキシプロピ ルトリブトキシシランが挙げられる。 —Ratatones such as valerolatatones, petit mouth lactones, γ-pro-prolatatatons, and γ-valerolatatones. Examples of the modifying agent having the functional group of the above formula (8) include 4-methoxybenzophenone, 4-ethoxybenzophenone, 4,4,1-bis (methoxy) benzophenone, 4,4, -bis (Ethoxy) benzophenone, γ-glycidoxyshethyltrimethoxysilane, and -glycidoxypropyltrimethoxysilane. Examples of the modifying agents having the functional groups of the above formulas (9) and (10) include γ-glycidoxybutyltrimethoxysilane, γ-daricidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxy. Silane and y-glycidoxypropyl tributoxy silane.
上記式 （1 1 ) の官能基を有する変性剤の例としては、 1， 3—ジメチルー 2 一イミダゾリジノン、 1， 3—ジェチル一 2 _イミダゾリジノンが挙げられる。 上記式 （1 2 ) の官能基を有する変性剤の例としては、 N , N， 一ジメチルプ 口ピレンゥレア、 N—メチルピロリ ドンなどが挙げられる。  Examples of the modifying agent having a functional group represented by the above formula (11) include 1,3-dimethyl-21-imidazolidinone and 1,3-getyl-12-imidazolidinone. Examples of the modifying agent having a functional group represented by the above formula (12) include N, N, 1-dimethylpyrene perylene, N-methylpyrrolidone, and the like.
また、 上記式 （1 3 ) 及び （1 4 ) の官能基を有する原子団を有する変性重合 体は、 それぞれ、 上記式 （1 1 ) 及び （1 2 ) の官能基含有原子団を有する非水 添変性重合体を水添することによって得られる。  Further, the modified polymer having an atomic group having a functional group represented by the above formula (13) or (14) is a non-aqueous polymer having an atomic group having a functional group represented by the above formula (11) or (12), respectively. It is obtained by hydrogenating the addition-modified polymer.
本発明の成分 （2 ) で使用する変性重合体の水添物は、 重合体を変性してから 水添することによつても製造できるし、 重合体を水添した後、 変性することによ つても製造できる。 たとえば、 重合体を変性してから水添する場合、 有機リチウ ム化合物を重合触媒として用いて得られた重合体のリビング末端に、 上記の変性 剤と反応させることにより変性重合体を得、 得られた変性重合体を水添すること により、 水添物の変性重合体が得られる。  The hydrogenated product of the modified polymer used in the component (2) of the present invention can be produced by modifying the polymer and then hydrogenating it. Alternatively, the hydrogenated polymer is modified after hydrogenation. Can also be manufactured. For example, when a polymer is modified and then hydrogenated, a modified polymer is obtained by reacting the living terminal of the polymer obtained using an organic lithium compound as a polymerization catalyst with the above-mentioned modifying agent to obtain a modified polymer. By hydrogenating the obtained modified polymer, a hydrogenated modified polymer is obtained.
また、 本発明の成分 （2 ) で使用する変性重合体を得る他の方法として、 重合 体に有機リチウム化合物等の有機アル力リ金属化合物を反応 (メタレーシヨン反 応） させ、 有機アルカリ金属化合物が付加した重合体を得、 これに上記の変性剤 を付加反応させる方法が挙げられる。 この場合は、 重合体の水添物を得た後にメ タレーシヨン反応させ、 上記の変性剤を反応させて水添物の変性重合体を得るこ ともできる。  As another method for obtaining the modified polymer used in the component (2) of the present invention, an organic alkali metal compound such as an organolithium compound is reacted with the polymer (metallation reaction) to obtain an organic alkali metal compound. There is a method in which an added polymer is obtained and the above-mentioned modifier is subjected to an addition reaction. In this case, a hydrogenated product of the polymer may be obtained and then subjected to a metalation reaction, and the above-mentioned modifier may be reacted to obtain a modified polymer of the hydrogenated product.
なお、 変性剤の種類により、 変性剤を反応させた段階で水酸基やアミノ基等は 有機金属塩となっていることもあるが、 その場合には水やアルコールなどの活性 水素を有する化合物で処理することにより、 水酸基ゃァミノ基等にすることがで きる。 Depending on the type of denaturing agent, the hydroxyl group, amino group, etc. may be It may be an organic metal salt, but in such a case, it can be converted to a hydroxyl group or a amino group by treating with a compound having active hydrogen such as water or alcohol.
本発明において、 変性反応をおこなう際の反応圧力は特に限定されるものでは ないが、 通常 0. 2〜2MP aであり、 好ましくは 0. 3〜lMP aである。 反 応温度は、 0〜 1 50°Cの範囲が好ましく、 より好ましくは 20〜 1 20°C、 更 に好ましくは 50〜 100°Cの範囲である。 変性反応に要する時間は、 一般に調 整する際の反応温度に左右されるが 1秒から 1 0時間の範囲であり、 好ましくは 1秒〜 3時間の範囲である。  In the present invention, the reaction pressure at the time of performing the denaturation reaction is not particularly limited, but is usually 0.2 to 2 MPa, preferably 0.3 to 1 MPa. The reaction temperature is preferably in the range of 0 to 150 ° C, more preferably 20 to 120 ° C, and even more preferably 50 to 100 ° C. The time required for the denaturation reaction generally depends on the reaction temperature during the adjustment, but is in the range of 1 second to 10 hours, preferably in the range of 1 second to 3 hours.
本発明においては、 重合体に変性剤を反応させた後に変性されていない重合体 が変性重合体に混在していてもよい。 変性重合体に混在する未変性の重合体の量 は、 変性重合体の重量に対して好ましくは 70重量。 /0以下、 より好ましくは 60 重量％以下、 更に好ましくは 50重量％以下である。 In the present invention, a polymer that has not been modified after reacting a modifying agent with the polymer may be mixed with the modified polymer. The amount of the unmodified polymer mixed in the modified polymer is preferably 70% by weight based on the weight of the modified polymer. / 0 or less, more preferably 60% by weight or less, further preferably 50% by weight or less.
本発明において、 変性重合体の水添物は、 上記で得られた変性重合体を水素添 加することにより得られる。 水添触媒としては、 特に制限されず、 従来から公知 である （1) N i、 P t、 P d、 Ru等の金属をカーボン、 シリカ、 アルミナ、 ケイソゥ土等に担持させた担持型不均一系水添触媒、 （2) N i、 C o、 F e、 C r等の有機酸塩又はァセチルァセトン塩などの遷移金属塩と有機アルミニゥム等 の還元剤とを用いる、 いわゆるチーグラー型水添触媒、 （3) T i、 Ru、 R h、 Z r等の有機金属化合物等のいわゆる有機金属錯体等の均一系水添触媒が用いら れる。  In the present invention, a hydrogenated product of the modified polymer is obtained by hydrogenating the modified polymer obtained above. The hydrogenation catalyst is not particularly limited, and is conventionally known. (1) Non-uniform supported type in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, and the like. (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe and Cr or a transition metal salt such as acetyl aceton salt and a reducing agent such as organic aluminum. (3) A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh and Zr is used.
具体的な水添触媒としては、 特公昭 42- 8 704号公報、 特公昭 43- 6 6 36号公報、 特公昭 6 3- 484 1号公報、 特公平 1- 3 79 70号公報、 特公 平 1- 5385 1号公報、 特公平 2- 904 1号公報に記載された水添触媒を使 用することができる。 好ましい水添触媒としてはチタノセン化合物および Zまた は還元性有機金属化合物との混合物があげられる。 チタノセン化合物としては、 特開平 8- 1092 1 9号公報に記載された化合物が使用できるが、 具体例とし ては、 ビスシクロペンタジェ二/レチタンジクロライ ド、 モノペンタメチノレシク口 ペンタジェニルチタントリクロライ ド等の （置換） シクロペンタジェ-ル骨格、 インデニル骨格あるいはフルォレニル骨格を有する配位子を少なくとも 1つ以上 もつ化合物があげられる。 また、 還元性有機金属化合物としては、 有機リチウム 等の有機アルカリ金属化合物、 有機マグネシウム化合物、 有機アルミニウム化合 物、 有機ホウ素化合物あるいは有機亜鉛化合物等があげられる。 Specific examples of the hydrogenation catalyst include JP-B-42-8704, JP-B-43-636, JP-B-63-4841, JP-B-1-37970, and JP-B The hydrogenation catalysts described in Japanese Patent Application Laid-Open Nos. 1-53851 and 2-9041 can be used. Preferred hydrogenation catalysts include mixtures with titanocene compounds and Z or reducing organometallic compounds. As the titanocene compound, compounds described in JP-A-8-10992 can be used. Specific examples thereof include biscyclopentadiene / retitanium dichloride and monopentamethinoresic compound. Compounds having at least one ligand having a (substituted) cyclopentagel skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as pentagenenyl titanium trichloride, may be mentioned. Examples of the reducing organic metal compound include organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds, and organic zinc compounds.
水添反応は好ましくは 0〜200°C、 より好ましくは 30〜 1 50 °Cの温度範 囲で実施される。 水添反応に使用される水素の圧力は、 好ましくは 0. 1〜1 5 MP a、 より好ましくは 0. 2〜： L 0MP a、 更に好ましくは◦. 3〜5MP a が推奨される。 また、 水添反応時間は好ましくは 3分〜 10時間、 より好ましく は 1 0分〜 5時間である。 水添反応は、 バッチプロセス、 連続プロセス、 或いは それらの組み合わせのいずれでも用いることができる。  The hydrogenation reaction is preferably carried out in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to: L0 MPa, and still more preferably ◦3 to 5 MPa. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction can be used in a batch process, a continuous process, or a combination thereof.
本発明に使用される変性重合体の水添物において、 共役ジェン系単量体単位に 基づく不飽和二重結合のトータル水素添加率は目的に合わせて任意に選択でき、 特に限定されない。熱安定性及び耐候性の良好な変性重合体の水添物を得る場合、 変性重合体中の共役ジェン系単量体単位に基づく不飽和二重結合の 70。/。以上、 好ましくは 80%以上、 更に好ましくは 90%以上が水添されていていることが 推奨される。 また、 一部のみが水添されていても良い。 一部のみを水添する場合 には、 水添率が 10%以上 70%未満、 或いは 1 5%以上 6 5%未満、 所望によ つては 20%以上 60%未満にすることが好ましい。 更に、 水素添加前の共役ジ ェン系単量体に基づくビュル結合の水素添加率は、 好ましくは 8 5 %以上、 より 好ましくは 90%以上、 更に好ましくは 9 5%以上であることが、 熱安定性に優 れたゴム組成物を得る上で推奨される。 ここで、 ビニル結合の水素添加率とは、 変性重合体中に組み込まれている水素添加前の共役ジェン系単量体に基づくビ二 ル結合のうち水素添加されたビニル結合の割合をいう。 なお、 変性ランダム共重 合体や変性プロック共重合体中のビニル芳香族炭化水素に基づく芳香族二重結合 の水添率については特に制限はないが、 好ましくは 50%以下、 より好ましくは 30%以下、 更に好ましくは 20%以下が推奨される。 水添率は、 核磁気共鳴装 置 （NMR) により知ることができる。 次に、 本発明において、 マスターバッチの調整で使用する変性重合体に結合し ている官能基と反応性を有する化合物 （4 ) を反応させた二次変性重合体を用い ることもできる。 二次変性重合体とは、 化合物（4 )である二次変性剤を本発明の 変性重合体と反応させることによって得られるものであって、 該二次変性剤は該 変性重合体の官能基と反応性を有する官能基を有する化合物である。 In the hydrogenated product of the modified polymer used in the present invention, the total hydrogenation rate of the unsaturated double bond based on the conjugated diene monomer unit can be arbitrarily selected according to the purpose, and is not particularly limited. In order to obtain a hydrogenated product of a modified polymer having good thermal stability and weather resistance, an unsaturated double bond based on a conjugated diene monomer unit in the modified polymer is 70. /. As mentioned above, it is recommended that 80% or more, more preferably 90% or more be hydrogenated. Also, only a part may be hydrogenated. When only a part is hydrogenated, the hydrogenation ratio is preferably 10% or more and less than 70%, or 15% or more and less than 65%, and if desired, 20% or more and less than 60%. Further, the hydrogenation rate of the Bull bond based on the conjugated diene monomer before hydrogenation is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. It is recommended for obtaining a rubber composition having excellent thermal stability. Here, the hydrogenation rate of vinyl bonds refers to the ratio of hydrogenated vinyl bonds to vinyl bonds based on the conjugated gen-based monomer before hydrogenation incorporated in the modified polymer. The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the modified random copolymer or modified block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30%. Or less, more preferably 20% or less is recommended. The hydrogenation rate can be determined by a nuclear magnetic resonance apparatus (NMR). Next, in the present invention, a secondary modified polymer obtained by reacting a compound (4) having reactivity with a functional group bonded to the modified polymer used in the preparation of the masterbatch can also be used. The secondary modified polymer is obtained by reacting a secondary modifier, which is the compound (4), with the modified polymer of the present invention, and the secondary modified agent has a functional group of the modified polymer. A compound having a functional group reactive with
化合物（4 )である二次変性剤の官能基の好ましい例として、 カルボキシル基、 酸無水物基、 イソシァネート基、 エポキシ基、 シラノール基及びアルコキシシラ ン基から選ばれる少なくとも 1種が挙げられる。 上記の官能基を少なくとも 2個 以上有している二次変性剤が特に好ましい。 伹し、 官能基が酸無水物基である場 合は、 酸無水物基を 1個のみ有する二次変性剤も特に好ましい。 変性重合体に二 次変性剤を反応させる場合の二次変性剤の量は、 変性重合体に結合されている官 能基 1当量あたり、 通常 0 . 3〜 1 0モル、 好ましくは 0 . 4〜5モル、 更に好 ましくは 0 . 5〜 4モルの範囲である。  Preferred examples of the functional group of the secondary modifier as the compound (4) include at least one selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. Particularly preferred are secondary modifiers having at least two of the above functional groups. However, when the functional group is an acid anhydride group, a secondary modifier having only one acid anhydride group is also particularly preferred. When reacting the modified polymer with the secondary modifier, the amount of the secondary modifier is usually 0.3 to 10 mol, preferably 0.4, per equivalent of the functional group bonded to the modified polymer. -5 mol, more preferably 0.5-4 mol.
変性重合体に二次変性剤を反応させる方法は、 特に制限されるものではないが 公知の方法が利用できる。 例えば、 後述する溶融混練方法や各成分を溶媒等に溶 解又は分散混合して反応させる方法などが挙げられる。 各成分を溶媒等に溶解又 は分散混合して反応させる方法において、 溶媒としては各成分を溶解又は分散す るものであれば特に限定はなく、 脂肪族炭化水素、 脂環式炭化水素、 芳香族炭化 水素などの炭化水素溶媒の他、 含ハロゲン系溶媒、 エステル系溶媒、 エーテル系 溶媒などが使用できる。 かかる方法において変性重合体に二次変性剤を反応させ る温度は、 通常一 1 0〜 1 5 0 °C、 好ましくは 3 0 ~ 1 2 0 °Cである。 反応に要 する時間は一般に調整する際の反応温度に左右されるが、通常 3時間以内であり、 好ましくは数秒〜 1時間である。 特に好ましい方法は、 製造した変性重合体の溶 液中に二次変性剤を添加して反応させることにより二次変性重合体を得る方法で ある。  The method of reacting the modified polymer with the secondary modifier is not particularly limited, but a known method can be used. For example, a melt kneading method described later, a method in which each component is dissolved or dispersed and mixed in a solvent or the like, and the reaction is performed are exemplified. In the method of reacting each component by dissolving or dispersing in a solvent or the like, the solvent is not particularly limited as long as it dissolves or disperses each component. Aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic In addition to hydrocarbon solvents such as group hydrocarbons, halogen-containing solvents, ester solvents, ether solvents and the like can be used. In such a method, the temperature at which the modified polymer is reacted with the secondary modifier is usually 110 to 150 ° C, preferably 30 to 120 ° C. The time required for the reaction generally depends on the reaction temperature at the time of adjustment, but is usually within 3 hours, and preferably several seconds to 1 hour. A particularly preferred method is a method of obtaining a secondary modified polymer by adding a secondary modifier to a solution of the produced modified polymer and reacting.
次に二次変性剤の具体例について説明する。 カルボキシル基を有する二次変性 剤の例としては、マレイン酸、 シユウ酸、 コハク酸、 アジピン酸、ァゼライン酸、 セバシン酸、 ドデカンジカルボン酸、 力ルバリル酸、 シクロへキサンジカルボン 酸、 シクロペンタンジカルボン酸等の脂肪族カルボン酸；テレフタル酸、 イソフ タル酸、 オルトフタル酸、 ナフタレンジカルボン酸、 ビフエニルジカルボン酸、 トリメシン酸、 トリメリット酸、 ピロメリ ット酸等の芳香族カルボン酸が挙げら れる。 Next, specific examples of the secondary modifier will be described. Examples of the secondary modifier having a carboxyl group include maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, levalilic acid, and cyclohexanedicarboxylic acid. Acids, aliphatic carboxylic acids such as cyclopentanedicarboxylic acid; aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid and pyromellitic acid; No.
酸無水物基を有する二次変性剤の例としては、 無水マレイン酸、 無水ィタコン 酸、 無水ピロメリッ ト酸、 シス一 4—シクロへキサン一 1， 2—ジカルボン酸無 水物、 1， 2 , 4 , 5—ベンゼンテトラカルボン酸二無水物、 5— （2 , 5—ジ 才キシテトラヒ ドロ一 3—フラ二ノレ） 一 3ーメチルー 3—シク口へキセン一 1， 2—ジカルボン酸無水物が挙げられる。  Examples of the secondary modifier having an acid anhydride group include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-1,4-cyclohexane-1,1,2-dicarboxylic anhydride, 1,2, 4,5-benzenetetracarboxylic dianhydride, 5- (2,5-dihydroxytetratetra-3-furaninole) -1,3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Can be
ィソシアナ一ト基を有する二次変性剤の例としては、 トルイレンジイソシアナ ート、 ジフヱニルメタンジィソシアナ一ト、 多官能芳香族ィソシアナ一ト (即ち イソシアナ一ト基が 3個以上芳香族環に結合した化合物） 等が挙げられる。  Examples of the secondary modifier having an isocyanate group include tolylene diisocyanate, diphenylmethane diisocyanate, and a polyfunctional aromatic isocyanate (that is, when three or more isocyanate groups are aromatic). Compound bonded to an aromatic ring).
エポキシ基を有する二次変性剤の例としてはテトラダリジジル— 1， 3—ビス アミノメチルシクロへキサン、 テトラグリシジルー m—キシレンジァミン、 ジグ リシジルァニリン、 エチレングリ コールジグリシジル、 プロピレンダリコールジ グリシジル、 テレフタル酸ジグリシジルエステルァクリレート等が挙げられる。 シラノール基を有する二次変性剤の例としては、 変性重合体を得るために使用 される変性剤として記載した上記のアルコキシシラン化合物の加水分解物等が挙 げられる。  Examples of the secondary modifier having an epoxy group include tetradaridyl-1,3-bisaminomethylcyclohexane, tetraglycidyl m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene dalicol diglycidyl, terephthal. Acid diglycidyl ester acrylate and the like. Examples of the secondary modifier having a silanol group include a hydrolyzate of the above-mentioned alkoxysilane compound described as a modifier used for obtaining a modified polymer.
アルコキシシラン基を有する二次変性剤の例としては、 ビス一 （3—トリエト キシシリルプロピル) ーテ トラスルファン、 ビス一 ( 3— トリエトキシシリルプ 口ピル） 一ジスルファン、 ェトキシシロキサンオリゴマーが挙げられる。  Examples of the secondary modifier having an alkoxysilane group include bis- (3-triethoxysilylpropyl) -tetrasulfan, bis- (3-triethoxysilylpropyl) pill, di-sulfane, and ethoxysiloxane oligomer. No.
また、 反応性を有する官能性オリゴマーも二次変性剤として使用することもで きる。 官能性オリゴマーの官能基は、 変性重合体に結合している官能基と反応性 を有する官能基であれば、 特に限定はない。 官能性オリゴマーの好ましい例とし て、 水酸基、 アミノ基、 力ルポキシル基、 酸無水物基、 イソシァネート基、 ェポ キシ基、 シラノール基、 アルコキシシラン基からなる群より選ばれる少なく とも 一種の官能基を有する官能性オリゴマーが挙げられる。 これらの官能性オリゴマ 一の数平均分子量は、 通常 3 0 0以上で 3 , 0 0 0 0未満、 好ましくは 5 0 0以 上で 1 5， 0 0 0未満、 更に好ましくは 1 , 0 0 0以上で 2 0， 0 0 0未満であ る。 官能性オリゴマーの具体例としては、 上記官能基を少なくとも 1個有するブ タジェンオリゴマーまたはその水添物、 上記官能基を少なくとも 1個有するィソ プレンオリゴマーまたはその水添物、 上記官能基を少なくとも 1個有するェチレ ンオリ ゴマー、 上記官能基を少なくとも 1個有するプロピレンオリゴマー、 ェチ レンォキサイドオリゴマー、 プロピレンォキサイドオリゴマー、 エチレンォキサ ィドープロピレンォキサイド共重合オリゴマー、 スチレン一無水マレイン酸共重 合体オリゴマー、 エチレン—酢酸ビエル共重合オリゴマーのケン化物等が挙げら れる。 In addition, a reactive functional oligomer can also be used as the secondary modifier. The functional group of the functional oligomer is not particularly limited as long as it has a reactivity with the functional group bonded to the modified polymer. Preferred examples of the functional oligomer include at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a hydroxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. Functional oligomers. These functional oligomers The number average molecular weight of one is usually at least 300 and less than 3,000, preferably at least 50,000 and less than 15,500, more preferably at least 1,000 and more than 20,000. It is less than 00. Specific examples of the functional oligomer include a butadiene oligomer having at least one functional group or a hydrogenated product thereof, an isoprene oligomer having at least one functional group or a hydrogenated product thereof, and at least one of the above functional groups. Ethylene oligomer having one, propylene oligomer having at least one of the above functional groups, ethylene oxide oligomer, propylene oxide oligomer, ethylene oxide propylene oxide copolymerization oligomer, styrene-maleic anhydride copolymer Examples include a coalesced oligomer and a saponified product of an ethylene-vinyl acetate copolymer oligomer.
本発明において特に好ましい二次変性剤の例として、 力ルポキシル基を 2個以 上有するカルボン酸又はその酸無水物、 或いは酸無水物基、 イソシァネート基、 エポキシ基、 シラノール基、 アルコキシシラン基を 2個以上有す変性剤であり、 具体例として、 無水マレイン酸、 無水ピロメ リ ッ ト酸、 1， 2 , 4， 5—べンゼ ンテトラカルボン酸二無水物、 トルイレンジイソシアナート、 テトラグリジジル 一 1 , 3—ビスアミノメチルシク口へキサン、 ビス一 ( 3— ト .リエトキシシリル プロピル） ーテ トラスノレファン、 スチレン一無水マレイン酸共重合体オリゴマー 等が挙げられる。  Particularly preferred examples of the secondary modifier in the present invention include a carboxylic acid having two or more carboxylic acid groups or an acid anhydride thereof, or an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, or an alkoxysilane group. Modifiers, such as maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, tetraglycidyl Examples thereof include 1,3-bisaminomethylcyclohexane, bis- (3-to.riethoxysilylpropyl) -tetranoslephane, and a styrene-monomaleic anhydride copolymer oligomer.
また、 成分 （2 ) のマスターバッチを調整する際に、 変性重合体と無機充填剤 の他に上記の化合物 ( 4 ) である二次変性剤を添加することができる。 二次変性 剤の量は、 当該変性重合体 1 0 0重量部に対して 0 . 0 1〜2 0重量部、 好まし くは 0 . 0 2〜1 0重量部、 更に好ましくは 0 . 0 5〜 7重量部の範囲である。 本発明の成分 （2 ) で使用する変性重合体又は二次変性重合体の重量平均分子 量は、 ゴム組成物の機械的強度及び耐摩耗性の点から 3万以上、 加工性の点から 1 2 0万以下であることが好ましく、 より好ましくは 5万〜 1 0 0万、 更に好ま しくは 1 0〜8 0万の範囲である。 変性重合体の重量平均分子量は、 ゲルパーミ ユエーションクロマトグラフィー ( G P C ) による測定を行い、 クロマトグラム のピークの分子量を、 市販の標準ポリスチレンの測定から求めた検量線 （標準ポ リスチレンのピーク分子量を使用して作成） を使用して求めることができる。 上記のようにして得られた変性重合体の溶液は、 必要に応じて触媒残渣を除去 し、 変性重合体を溶液から分離することができる。 溶媒の分離の方法としては、 例えば重合後又は水添後の溶液にァセトンまたはアルコール等の重合体に対する 貧溶媒となる極性溶媒を加えて重合体を沈澱させて回収する方法、 変性重合体の 溶液を撹拌下熱湯中に投入し、 スチームストリッビングにより溶媒を除去して回 収する方法、 または直接重合体溶液を加熱して溶媒を留去する方法等を挙げるこ とができる。 尚、 本発明で使用する変性重合体又はその水添物には、 各種フエノ ール系安定剤、 リン系安定剤、 ィォゥ系安定剤、 アミン系安定剤等の安定剤を添 加することができる。 When preparing the masterbatch of the component (2), a secondary modifier, which is the compound (4), can be added in addition to the modified polymer and the inorganic filler. The amount of the secondary modifier is 0.01 to 20 parts by weight, preferably 0.02 to 10 parts by weight, more preferably 0.02 to 100 parts by weight based on 100 parts by weight of the modified polymer. It is in the range of 5 to 7 parts by weight. The weight average molecular weight of the modified polymer or the secondary modified polymer used in the component (2) of the present invention is 30,000 or more from the viewpoint of the mechanical strength and abrasion resistance of the rubber composition, and 1 or more from the viewpoint of processability. It is preferably 200,000 or less, more preferably 50,000 to 100,000, and still more preferably 10 to 800,000. The weight-average molecular weight of the modified polymer was measured by gel permeation chromatography (GPC), and the molecular weight of the peak in the chromatogram was determined from a calibration curve (standard (Created using the peak molecular weight of polystyrene). From the solution of the modified polymer obtained as described above, the catalyst residue can be removed as necessary, and the modified polymer can be separated from the solution. As a method for separating the solvent, for example, a method of adding a polar solvent which is a poor solvent for the polymer such as acetone or alcohol to the solution after polymerization or hydrogenation to precipitate and recover the polymer, a solution of the modified polymer, Into the boiling water with stirring and removing the solvent by steam stripping to recover the solvent, or directly heating the polymer solution to distill off the solvent. The modified polymer or its hydrogenated product used in the present invention may contain various phenol-based stabilizers, phosphorus-based stabilizers, zeo-based stabilizers, and amine-based stabilizers. it can.
本発明において、 成分 （2 ) のマスターバッチの原料として用いられる無機充 填剤又は成分（3 ) の無機充填剤は、公知の補強性充填剤、例えば、天然シリ力、 湿式法又は乾式法で製造した合成シリカ、 カオリン、 マイ力、 タルク、 クレイ、 モンモリロナイト、 ゼォライト、 天然ケィ酸塩、 ケィ酸カルシウム、 ケィ酸アル ミニゥム等の合成ケィ酸塩、 水酸化マグネシウム、 水酸化アルミニウム、 水酸化 カルシウム、 水酸化バリウム等の金属水酸化物、 アルミナ、 酸化チタン、 酸化マ グネシゥム、 酸化亜鉛等の金属酸化物、 軽質炭酸カルシウム、 重質炭酸カルシゥ ム、 種々の表面処理炭酸カルシウム、 炭酸マグネシウムなどの金属炭酸化物、 硫 酸バリウム、 硫酸マグネシウム、 硫酸カルシウム等の金属硫酸化物、 アルミユウ ム、 ブロンズ等の金属粉、 カーボンブラック等の少なくとも 1種の成分である。 好ましい無機充填剤として、 シリカ系無機充填剤、 金属酸化物、 金属水酸化物、 力一ボンが挙げられる。 上記の無機充填剤を単独で使用しても良いし、 2種類以 上を組み合わせて使用することもできる。  In the present invention, the inorganic filler used as a raw material of the master batch of the component (2) or the inorganic filler of the component (3) may be a known reinforcing filler, for example, a natural silicic acid, a wet method or a dry method. Manufactured synthetic silica, kaolin, My power, talc, clay, montmorillonite, zeolite, natural silicate, calcium silicate, aluminum silicate, etc., synthetic silicate, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, Metal hydroxides such as barium hydroxide, metal oxides such as alumina, titanium oxide, magnesium oxide and zinc oxide, light calcium carbonate, heavy calcium carbonate, various surface-treated calcium carbonates, and metal carbonates such as magnesium carbonate Metal sulfates such as chlorides, barium sulfate, magnesium sulfate, calcium sulfate, aluminum Arm, metal powder such as bronze, it is at least one component such as carbon black. Preferred inorganic fillers include silica-based inorganic fillers, metal oxides, metal hydroxides, and carbon. The above-mentioned inorganic fillers may be used alone or in combination of two or more.
シリカ系無機充填剤とは化学式 S i O 2を構成単位の主成分とする固体粒子の ことをいい、 例えばシリカ、 クレイ、 タルク、 マイ力、 珪藻土、 ウォラストナイ ト、 モンモリロナイト、 ゼォライト、 ガラス繊維等の無機繊維状物質などを用い ることができる。 また表面を疎水化したシリカ系無機充填剤や、 シリカ系無機充 填剤とシリカ系以外の無機充填剤の混合物も使用できる。 本発明においてはシリ 力が好ましい。 シリカとしては乾式法ホワイトカーボン、 湿式法ホワイトカーボ ン、 合成ケィ酸塩系ホワイトカーボン、 コロイダルシリカと呼ばれているもの等 が使用できる。 これらは粒径が 0. 0 1〜1 50 /zmのものが好ましい。 また本 発明の組成物において、 シリカが組成物中に分散し、 シリカの添加効果を十分に 発揮するためには、 平均分散粒子径 0. 0 5〜1 μιηが好ましく、 より好ましく は 0. 05〜0. 5 imである。 Silica-based inorganic filler refers to solid particles whose main component is the chemical formula SiO 2, for example, silica, clay, talc, Mai force, diatomaceous earth, wollastonite, montmorillonite, zeolite, glass fiber, etc. An inorganic fibrous substance or the like can be used. In addition, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica-based inorganic filler can also be used. In the present invention, Force is preferred. Silicas such as dry-process white carbon, wet-process white carbon, synthetic silicate-based white carbon, and colloidal silica can be used. These preferably have a particle size of 0.01 to 150 / zm. In the composition of the present invention, in order to disperse silica in the composition and sufficiently exert the effect of adding silica, the average dispersed particle diameter is preferably 0.05 to 1 μιη, more preferably 0.05. ~ 0.5 im.
次に金属酸化物とは、 ィ匕学式 MxOy (Mは金属原子、 x、 yは各々 1〜6の 整数） を構成単位の主成分とする固体粒子のことをいい、 例えばアルミナ、 酸化 チタン、 酸化マグネシウム、 酸化亜鉛等を用いることができる。 また金属酸化物 と金属酸化物以外の無機充填剤の混合物も使用できる。 また本発明で用いる金属 水酸化物は、 水酸化アルミニウム、 水酸化マグネシウム、 水酸化ジルコニウム、 水和珪酸アルミニウム、 水和珪酸マグネシウム、 塩基性炭酸マグネシウム、 ハイ ドロタルサイト、 水酸化カルシウム、 水酸化バリウム、 酸化錫の水和物、 硼砂等 の無機金属化合物の水和物等、 水和系無機充填材であり、 中でも水酸化マグネシ ゥム、 水酸化アルミニウムが好ましい。  Next, a metal oxide is a solid particle mainly composed of a structural unit represented by the formula MxOy (M is a metal atom, x and y are each an integer of 1 to 6), such as alumina and titanium oxide. , Magnesium oxide, zinc oxide and the like can be used. Also, a mixture of a metal oxide and an inorganic filler other than the metal oxide can be used. The metal hydroxide used in the present invention is aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, aluminum silicate hydrate, magnesium silicate hydrate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide. Hydrate of tin oxide, hydrate of inorganic metal compounds such as borax, etc., are hydrated inorganic fillers, among which magnesium hydroxide and aluminum hydroxide are preferable.
カーボンブラックとしては、 FT、 SRF、 FEF、 HAF、 I SAF、 S A F等の各クラスのカーボンブラックが使用でき、 窒素吸着比表面積が 5 Omg/ g以上、 DB P吸油量が 80m l/l O O gのカーポンプラックが好ましい。 本発明において、 成分 （2) のマスターバッチの調整に使用する無機充填剤の 量は、 変性重合体 1 00重量部に対して 5〜300重量部、 好ましくは 5〜20 0重量部、 更に好ましくは 1 0〜1 50重量部の範囲である。 無機充填剤の量が 300重量部を超えると、 無機充填剤の分散性が劣りマスターバッチの加工性が 悪くなる。 また、 5重量部未満では本発明の効果である接着性が劣る。  As carbon black, carbon black of each class such as FT, SRF, FEF, HAF, ISAF and SAF can be used.Nitrogen adsorption specific surface area is more than 5 Omg / g, DBP oil absorption is 80 ml / l OO g Are preferred. In the present invention, the amount of the inorganic filler used for preparing the master batch of the component (2) is 5 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 100 parts by weight of the modified polymer. Ranges from 10 to 150 parts by weight. If the amount of the inorganic filler exceeds 300 parts by weight, the dispersibility of the inorganic filler is inferior, and the workability of the master batch becomes poor. On the other hand, when the amount is less than 5 parts by weight, the adhesiveness as an effect of the present invention is inferior.
また、 本発明において成分 （3) の無機充填剤の配合量は、 成分 （1) のゴム 状重合体 100重量部に対し 0. 1〜 1 50量部、好ましくは 5〜 100重量部、 更に好ましくは 5〜 50量部である。 無機充填剤の配合量が 1 50重量部を超え ると無機充填剤の分散性が劣り、 加工性及び機械強度が劣るため好ましくない。 本発明の履物用ゴム組成物の製造にシリカ系無機充填剤を用いた場合、 シラン カップリング剤を使用することができる。 シランカップリング剤は、 ゴム状重合 体と無機充填剤の相互作用を緊密にするためのものであり、 ゴム状重合体と無機 充填剤とにそれぞれ親和性あるいは結合性の基を有しているものである。 具体的 には、 ビス- [ 3 - (トリエトキシシリル） - プロピル] ― テ トラスルフィ ド、 ビス— [ 3 - (トリエトキシシリル） - プロピル] - ジスルフィ ド、 ビス— [ 2 - (トリエトキシシリル） - ェチル] - テ トラスルフィ ド、 3 - メルカプトプロ ピル- トリメ トキシシラン、 ビニルトリメ トキシシラン、 ビュルトリエトキシシ ラン等があげられる。 In the present invention, the compounding amount of the inorganic filler of the component (3) is 0.1 to 150 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the rubbery polymer of the component (1). Preferably it is 5 to 50 parts by weight. If the amount of the inorganic filler exceeds 150 parts by weight, the dispersibility of the inorganic filler is poor, and the processability and the mechanical strength are poor. When a silica-based inorganic filler is used in the production of the rubber composition for footwear of the present invention, Coupling agents can be used. The silane coupling agent is for tightening the interaction between the rubber-like polymer and the inorganic filler, and has an affinity or binding group for the rubber-like polymer and the inorganic filler, respectively. Things. Specifically, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- (triethoxysilyl) -Ethyl]-tetrasulfide, 3-mercaptopropyl-trimethoxysilane, vinyltrimethoxysilane, butyltriethoxysilane and the like.
好ましいシランカツプリング剤は、 アルコキシシランを有すると同時に硫黄が 2個以上連結したポリスルフィ ド結合を有するものであり、 その例としてはビス - [ 3— (トリエトキシシリル） -プロピル] - テ トラスルフィ ド、 ビス- [ 3 - (トリエトキシシリル) - プロピル] - ジスルフィドなどがあげられる。 シラ ンカツプリング剤の配合量は、 補強性充填剤に対して、 0 . 1〜 3 0重量％、 好 ましくは 0 . 5〜2 0重量％、 更に好ましくは 1〜 1 5重量％である。  Preferred silane coupling agents are those that have an alkoxysilane and a polysulfide bond in which two or more sulfur atoms are linked, such as bis- [3- (triethoxysilyl) -propyl] -tetrasulfide. And bis- [3- (triethoxysilyl) -propyl] -disulfide. The amount of the silane coupling agent is from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight, based on the reinforcing filler.
本発明の成分 （2 ) のマスターバッチにおいて、 無機充填剤と親和性が高い官 能基が結合している変性重合体を使用することで、 無機充填剤の表面に存在する 官能基と変性重合体との間で、 化学的な結合や水素結合等の物理的な相互作用が 効果的に発現され、 引き裂き強度、 耐摩耗性、 接着性に優れた履物用ゴム組成物 を得ることができる。  In the master batch of the component (2) of the present invention, by using a modified polymer in which a functional group having a high affinity is bonded to the inorganic filler, the functional group present on the surface of the inorganic filler and the modified polymer can be used. A physical interaction such as a chemical bond or a hydrogen bond is effectively developed with the union, and a rubber composition for footwear excellent in tear strength, abrasion resistance and adhesiveness can be obtained.
本発明の成分 （2 ) であるマスターバッチの製造方法は、 特に制限されるもの ではなく公知の方法が利用できる。 例えば、 バンバリ- ミキサ-、 単軸スクリュ 一押出機、 2軸スクリュ-押出機、 コニ - ダ、 多軸スクリュー押出機、 ロール等 の一般的な混合機を用いた混練方法、 各成分を溶解、 混合した後、 溶剤を加熱除 去する方法等が用いられる。 好ましい方法はバンバリ一ミキサー、 コエーダーで 各成分を混練する方法である。  The method for producing the masterbatch which is the component (2) of the present invention is not particularly limited, and a known method can be used. For example, a kneading method using a general mixer such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, a roll, etc. After mixing, a method of removing the solvent by heating or the like is used. A preferred method is to knead each component with a Banbury mixer and a coadar.
マスターバッチを製造するにあたり、 変性重合体及び無機充填剤の添加順序に は制限が無く、 全成分を一度に混練機に入れて混合する方法、 各成分を 2回以上 分割して混合機に入れて順次混練する方法、変性重合体を混練機に入れて混練し、 その後無機充填剤を加えて混練する方法、 無機充填剤を混練機に入れて混練し、 その後変性重合体を加えて混練する方法、 無機充填剤を連続的に混練機に入れて 混練する方法等が採用できる。 There is no restriction on the order of addition of the modified polymer and inorganic filler in the production of the masterbatch.A method in which all the components are put into a kneader at a time and mixed, and each component is divided twice or more and put in a mixer Kneading sequentially, kneading the modified polymer into a kneading machine, After that, a method of adding and kneading an inorganic filler, a method of putting an inorganic filler in a kneader and kneading, a method of adding and kneading a modified polymer, and a method of continuously putting the inorganic filler in a kneader and kneading, etc. Can be adopted.
マスターバツチを製造する際の混練温度は、 変性重合体の劣化や変性重合体と 無機充填剤の相互作用を促進し無機充填剤の分散性の良いマスターバッチを得る 為に、 一般に 8 0〜3 0 0 °Cが好ましく、 より好ましくは 1 3 0〜2 5 0 °C、 更 に好ましくは 1 5 0 ~ 2 2 0 °Cの範囲である。 また、 混練時間は、 無機充填剤の 分散性、 マスターバッチの生産性、 変性重合体の劣化等の点から、 一般に 0 . 2 ~ 6 0分が好ましく、 より好ましくは 0 . 5〜3 0分、 更に好ましくは 1〜2 0 分の範囲である。  The kneading temperature at the time of manufacturing the master batch is generally from 80 to 30 in order to promote the deterioration of the modified polymer and the interaction between the modified polymer and the inorganic filler and to obtain a master batch with good dispersibility of the inorganic filler. The temperature is preferably 0 ° C, more preferably from 130 to 250 ° C, and still more preferably from 150 to 220 ° C. The kneading time is generally preferably from 0.2 to 60 minutes, more preferably from 0.5 to 30 minutes, from the viewpoint of the dispersibility of the inorganic filler, the productivity of the masterbatch, and the deterioration of the modified polymer. It is more preferably in the range of 1 to 20 minutes.
特に好ましい方法は、 無機充填剤の全量を予め混練機に入れて混練し、 次いで 変性重合体を加えて混練して製造する方法、 無機充填剤を 2回以上分割して混練 機に投入して変性重合体と無機充填剤を混練して製造する方法である。  A particularly preferred method is a method in which the entire amount of the inorganic filler is previously kneaded in a kneader and kneaded, and then the modified polymer is added and kneaded, and the inorganic filler is divided into two or more portions and put into the kneader. This is a method in which a modified polymer and an inorganic filler are kneaded and produced.
無機充填剤を 2回以上分割して混練機に入れる方法としては、 マスターバッチ を製造する工程の煩雑さを考盧すると、 無機充填剤を 2〜1 0回に分割して添加 することが好ましく、 特に 2〜 5回に分割して添加する方法が好ましい。 具体的 には、 無機充填剤の 2 0〜 8 0重量。/。、 好ましくは 3 0〜8 0重量％、 更に好ま しくは 4 0〜 8 0重量％を予め混練機に投入し、 混練時間を 1秒〜 6 0分、 好ま しくは 0 . 5分〜 3 0分、 更に好ましくは 1分〜 2 0分の範囲で混練した後、 変 性重合体を入れて混練時間を 1秒〜 6 0分、 好ましくは 2 0秒〜 3 0分、 更に好 ましくは 1分〜 2 0分の範囲で混練し、 次いで残りの無機充填剤を加えて、 混練 時間を 1秒〜 6 0分、 好ましくは 0 . 5分〜 3 0分、 更に好ましくは 1分〜 2 0 分の範囲で混練して製造する方法である。 もう一つの好ましい方法として、 無機 充填剤の全量を予め混練機に投入し、 混練時間を 1秒〜 6 0分、 好ましくは 0 . 5分〜 3 0分、 更に好ましくは 1分〜 2 0分の範囲で混練した後、 変性重合体を 入れて混練時間を 1秒〜 6 0分、 好ましくは 0 . 5分〜 3 0分、 更に好ましくは 1分〜 2 0分の範囲で混練して製造する方法がある。  As a method of dividing the inorganic filler into the kneader twice or more, it is preferable to add the inorganic filler in 2 to 10 times, considering the complexity of the process of manufacturing the master batch. In particular, a method of adding in 2 to 5 portions is preferable. Specifically, 20 to 80 weight of the inorganic filler. /. Preferably, 30 to 80% by weight, more preferably 40 to 80% by weight, is previously charged into the kneader, and the kneading time is 1 second to 60 minutes, preferably 0.5 minute to 30 minutes. Minutes, more preferably from 1 minute to 20 minutes, and then a kneading time of 1 second to 60 minutes, preferably 20 seconds to 30 minutes, more preferably Kneading is carried out for 1 minute to 20 minutes, and then the remaining inorganic filler is added, and the kneading time is 1 second to 60 minutes, preferably 0.5 minute to 30 minutes, more preferably 1 minute to 2 minutes. This is a method of producing by kneading in the range of 0 minutes. As another preferred method, the entire amount of the inorganic filler is previously charged into a kneader, and the kneading time is 1 second to 60 minutes, preferably 0.5 minute to 30 minutes, more preferably 1 minute to 20 minutes. And then kneading the modified polymer for a kneading time of 1 second to 60 minutes, preferably 0.5 minute to 30 minutes, more preferably 1 minute to 20 minutes. There is a way to do that.
特に好ましい形態のマスターバッチを調整する為に最も重要なことは、 無機充 填剤 5〜300重量部の少なくとも 20重量。/。以上を予め混練機に入れ、 温度を 50〜 300 °C、 好ましくは 70〜 250 °C、 更に好ましくは 100〜 200 °C の範囲で混練し、 その後残りの成分を入れて混練することでマスターバッチを調 整することである。 The most important factor in preparing a particularly preferred form of masterbatch is Filler 5 to 300 parts by weight at least 20 parts by weight. /. The above is put in a kneader in advance, and the temperature is kneaded in the range of 50 to 300 ° C, preferably 70 to 250 ° C, more preferably 100 to 200 ° C, and then the remaining components are mixed and kneaded. Adjusting the batch.
本発明の履物用ゴム組成物は、ゴム状重合体（成分 1)及びマスターバッチ（成 分 2)、 又はゴム状重合体 （成分 1) 及びマスターバッチ （成分 2) 及び無機充填 剤（成分 3) を含むゴム組成物である。 マスターバッチの量は、 ゴム状重合体（成 分 1) 100重量部に対して 1〜 150重量部、 好ましくは 5〜100重量部、 更に好ましくは 10〜70重量部の範囲である。  The rubber composition for footwear of the present invention comprises a rubbery polymer (component 1) and a masterbatch (component 2), or a rubbery polymer (component 1) and a masterbatch (component 2) and an inorganic filler (component 3). ). The amount of the masterbatch is in the range of 1 to 150 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 70 parts by weight, per 100 parts by weight of the rubbery polymer (component 1).
本発明の履物用ゴム組成物の製造方法は、 特に制限されるものではなく、 公知 の方法が利用できる。 例えば、 バンバリ- ミキサ- 、 単軸スク リュー押出機、 2 軸スクリュ-押出機、 コニ- ダ、 多軸スクリユー押出機等の一般的な混和機を用 V、た混練方法等が用いられる。  The method for producing the rubber composition for footwear of the present invention is not particularly limited, and a known method can be used. For example, a kneading method using a general kneader such as a Banbury mixer, a single screw extruder, a two-screw extruder, a coneder, a multi-screw extruder, or the like is used.
また本発明の履物用ゴム組成物を製造するにあたり、 各成分の添加順序には制 限が無く、 成分 （1)、 成分 （2)、 成分 （3) を一度に混練機に入れて混練する 方法、 任意の成分を予備混合した後、 残りの成分を添加する等の方法が採用でき る。 混練温度は、 ゴム状重合体や変性重合体の熱劣化の点から、 50〜300°C が好ましく、 より好ましくは 70〜 250 °C、 更に好ましくは 100〜 200 °C である。 また、 混練時間は、 無機充填剤の分散性やゴム組成物の生産性、 変性重 合体やゴム状重合体の劣化等の点から、 一般に 0. 2〜60分が好ましく、 より 好ましくは 0. 5〜30分、 更に好ましくは 1〜20分の範囲である。  In the production of the rubber composition for footwear of the present invention, there is no restriction on the order of addition of each component, and the components (1), (2) and (3) are put into a kneader at a time and kneaded. A method can be adopted in which any components are premixed and then the remaining components are added. The kneading temperature is preferably from 50 to 300 ° C, more preferably from 70 to 250 ° C, further preferably from 100 to 200 ° C, from the viewpoint of thermal deterioration of the rubbery polymer or the modified polymer. The kneading time is generally preferably from 0.2 to 60 minutes, more preferably from 0.2 to 60 minutes, in view of the dispersibility of the inorganic filler, the productivity of the rubber composition, the deterioration of the modified polymer and the rubbery polymer, and the like. The range is 5 to 30 minutes, more preferably 1 to 20 minutes.
本発明の履物用ゴム組成物は、 変性重合体と無機充填剤を上記に示した特定の 製造方法で混練して得られる無機フィラーの分散性に優れるマスターバッチを用 いることに特徴がある。 従来から行われているゴム状重合体又は変性重合体と無 機充填剤とを混練して得られる履物用ゴム組成物と比較して、 無機充填剤の分散 性が向上したことによつて耐摩耗性と接着性に優れる履物用ゴム組成物を得るこ とができる。 ゴム組成物中の無機充填剤の分散性は、 透過型電子顕微鏡や走査型 プロ一プ顕微鏡装置等を用いることによつて確認することができる。 本発明において、 その他必要に応じて任意の添加剤を配合することができる。 添加剤の種類は、 ゴム状重合体の配合に一般的に用いられるものであれば特に制 限はない。 亜鉛華、 ステアリン酸、 加硫助剤、 老化防止剤、 加工助剤、 ベへニン 酸、 ステアリン酸亜鉛、 ステアリン酸カルシウム、 ステアリン酸マグネシウム、 エチレンビスステアロアミ ド等の滑剤、 離型剤、 パラフィン系プロセスオイル、 ナフテン系プロセスオイル、 芳香族系プロセスオイル、 パラフィン、 有機ポリシ ロキサン、 ミネラルオイル等の軟化剤 '可塑剤、 ヒンダードフエノール系酸化防 止剤、 リン系熱安定剤等の酸化防止剤、 ヒンダードアミン系光安定剤、 ベンゾト リアゾール系紫外線吸収剤、 難燃剤、 帯電防止剤、 有機繊維、 ガラス繊維、 炭素 繊維、金属ウイスカ一等の補強剤、着色剤、その他添加剤或いはこれらの混合物、The rubber composition for footwear of the present invention is characterized by using a masterbatch excellent in dispersibility of an inorganic filler obtained by kneading a modified polymer and an inorganic filler by the above-mentioned specific production method. Compared with the conventional rubber composition for footwear obtained by kneading a rubber-like polymer or a modified polymer with an inorganic filler, the dispersibility of the inorganic filler is improved, thereby improving the resistance. A rubber composition for footwear having excellent abrasion and adhesion can be obtained. The dispersibility of the inorganic filler in the rubber composition can be confirmed by using a transmission electron microscope, a scanning prop microscope, or the like. In the present invention, other optional additives can be blended as required. The type of additive is not particularly limited as long as it is generally used for compounding a rubber-like polymer. Zinc white, stearic acid, vulcanization aid, anti-aging agent, processing aid, lubricant such as behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bis-stearamide, mold release agent, paraffin Anti-oxidants such as plasticizers, hindered phenol-based antioxidants, and phosphorus-based heat stabilizers, such as plasticizers, naphthenic process oils, aromatic process oils, paraffins, organic polysiloxanes, and mineral oils , Hindered amine-based light stabilizers, benzotriazole-based ultraviolet absorbers, flame retardants, antistatic agents, organic fibers, glass fibers, carbon fibers, reinforcing agents such as metal whiskers, coloring agents, other additives or mixtures thereof,
「ゴム.プラスチック配合薬品」 （ラバーダイジェスト社編） などに記載されたも のが挙げられる。 実施例 Examples include those described in “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest). Example
本発明を実施例に基づいて説明するが、 本発明はこれらの例によって何ら限定 されるものではない。  The present invention will be described based on examples, but the present invention is not limited to these examples.
[スチレン ·ブタジェンゴムの分析方法]  [Styrene / butadiene rubber analysis method]
(1) 結合スチレン量  (1) Amount of bound styrene
紫外分光光度計 (日本分光社製 V- 5 20 UV) で、 標準ポリスチレンの U V吸収強度と比較して求めた。  It was determined by comparing the UV absorption intensity of standard polystyrene with an ultraviolet spectrophotometer (V-520 UV manufactured by JASCO Corporation).
(2) ブタジエン中の 1， 2ビニル結合量  (2) 1,2-vinyl bond content in butadiene
赤外分光光度計 （日本分光社製 V- 5 20 UV) で測定しハンプトン法で 求めた。  It was measured with an infrared spectrophotometer (V-520 UV manufactured by JASCO Corporation) and determined by the Hampton method.
(3) 分子量  (3) Molecular weight
GPC (装置：島津製作所社製 LC 10、 カラム ：島津製作所社製 S h i mp a c GPC 805 +GPC 804+GP C 804 + GPC 803)で測定した。 溶媒にはテトラヒ ドロフランを用い、 測定条件は、 温度 35°Cで行った。 分子量 は、 クロマトグラムのピークの分子量を、 市販の標準ポリスチレンの測定から求 めた検量線 （標準ポリスチレンのピーク分子量を使用して作成） を使用して求め た重量平均分子量である。 GPC (apparatus: LC10 manufactured by Shimadzu Corporation, column: Shimpac GPC805 + GPC804 + GPC804 + GPC803 manufactured by Shimadzu Corporation) was used. Tetrahydrofuran was used as a solvent, and the measurement was performed at a temperature of 35 ° C. The molecular weight is obtained by measuring the molecular weight of the peak in the chromatogram from the measurement of commercially available standard polystyrene. It is the weight average molecular weight obtained using the calibration curve (created using the peak molecular weight of standard polystyrene).
(4) 未変性重合体の割合  (4) Unmodified polymer ratio
テトラヒロドロフラン 20m lに変性重合体 10 m gと重量平均分子量 800 0の低分子量内部標準ポリスチレン l Omgを溶解して試料溶液とした。 試料溶 液について、 上記 (3) と同様の方法で G P C測定を行い、 得られたクロマトグ ラムから標準ポリスチレンに対する変性重合体の比 （ i ) を求めた。 また、 上記 試料溶液について、 米国デュポン社製のカラムである Z o r b a X (シリカ系ゲ ル充填剤）のカラムを用いた以外、上記（3) と同様の方法で G P C測定を行い、 クロマトグラムを得た。 変性した重合体はシリカ系ゲルを充填剤とした G PC力 ラムに吸着するが、 未変性の重合体は該 G P Cカラムには吸着しないので、 得ら れたクロマトグラムからは、 標準ポリスチレンに対する未変性重合体の比 （ii) を求めることができる。 上記の比 （ i ) 及び比 （ii) から、 変性反応後の共重合 体中の変性重合体の割合 （％) を式： （1一比 （ii) Z比 （ i )) X I 00によつ p†^-した o  A sample solution was prepared by dissolving 10 mg of the modified polymer and lOmg of low-molecular-weight internal standard polystyrene having a weight average molecular weight of 8000 in 20 ml of tetrahydrofuran. GPC measurement was performed on the sample solution in the same manner as in the above (3), and the ratio (i) of the modified polymer to the standard polystyrene was determined from the obtained chromatogram. GPC measurement was performed on the sample solution in the same manner as in (3) above, except that a column of Zorba X (silica-based gel filler), a column manufactured by Dupont, USA, was used. Obtained. The modified polymer is adsorbed on the GPC column using silica gel as the filler, but the unmodified polymer is not adsorbed on the GPC column. The ratio (ii) of the modified polymer can be determined. From the above ratio (i) and ratio (ii), the ratio (%) of the modified polymer in the copolymer after the modification reaction was calculated by the formula: (1 ratio (ii) Z ratio (i)) XI00 One p † ^ -was o
[ゴム状重合体組成物の物性測定] [Measurement of physical properties of rubber-like polymer composition]
(1) 引張試験  (1) Tensile test
J I S K6 25 1に準拠し、 23 °C恒温室で測定した。  It was measured in a 23 ° C constant temperature room according to JIS K6251.
(2) 引き裂き試験  (2) Tear test
J I S K625 2に準拠し、 2 3 °C恒温室で測定した。  The measurement was performed in a constant temperature room at 23 ° C. according to JIS K6252.
(3) 硬度の測定  (3) Hardness measurement
高分子計器 （株） 製 ASKER硬度計 型式 Cを使用して、 23°C恒温室で 測定した。  Using an ASKER hardness tester Model C manufactured by Kobunshi Keiki Co., Ltd., it was measured in a constant temperature room at 23 ° C.
(4) 透明性  (4) Transparency
日本電色工業 （株） 製 HAZEメーター、 NDH— 100 1 D P型を使用し、 厚さ 5 mmの板サンプルの HAZ E値と全光線透過率を測定した。  The HAZ E value and total light transmittance of a 5 mm-thick plate sample were measured using a Nippon Denshoku Industries Co., Ltd. HAZE meter, NDH-100 1DP type.
(5) 耐摩耗性指数 アクロン型試験機で、 サンプルの摩耗減量を測定し、 下記式で求められる指数を 耐摩耗性の指標として求めた。 (5) Wear resistance index The abrasion loss of the sample was measured using an Akron-type testing machine, and the index determined by the following equation was determined as an index of wear resistance.
指数 = 〔（サンプルの摩耗減量） Z (標準サンプルの摩耗減量）〕 X I 00 Exponent = [(Wear loss of sample) Z (Wear loss of standard sample)] X I 00
(6) 接着性試験  (6) Adhesion test
水性プライマー （AQUACE PR-503) 及び水性接着剤 （AQUACE W- 06) を用いて、 ゴム組成物と被着体 （レザー、 ナイロン、 EVA) を接着させた後の剥離強度を 測定した。  Using a water-based primer (AQUACE PR-503) and a water-based adhesive (AQUACE W-06), the peel strength after bonding the rubber composition to an adherend (leather, nylon, EVA) was measured.
[ジェン系重合体の調製] [Preparation of gen-based polymer]
(S B R— Aの製造）  (Manufacture of SBR—A)
窒素置換した攪拌機付き 10 Lオートクレープに精製したシクロへキサン 5. Cyclohexane purified to 10 L autoclave with a stirrer replaced with nitrogen 5.
5 k gとスチレンモノマー 0. 4 O k g及び 1， 3—ブタジエン◦. 45 k gを 入れ、 攪拌しながら温度を 60°Cまで昇温してテトラヒ ドロフラン 32 gと n— プチルリチウム 0. 83 g (1 5 °/0シクロへキサン溶液） を添加して重合反応を 開始した。 重合の途中から最高温度の 9 2°Cになるまでの 5分間 1， 3—ブタジ ェン 0. 1 5 k gを重合系中に連続して添加した。 重合の最高温度から 1分後 に、 重合開始剤として使用した n—プチルリチウムに対して、 0. 38モルのテ トラグリシジルー 1 , 3—ビスアミノメチルシク口へキサンを添加して反応させ て SBR— Aを得た。 その後、 重合体溶液に安定剤として 2， 6—ジー t e r t ブチルー 4一メチルフエノールをゴム 1 0◦重量部当たり 0. 5重量部添加し、 ドラムドライヤーで脱溶媒、 乾燥して仕上げた。 得られたポリマーを分析したと ころ，スチレン含有量は 40重量％、ブタジエン部のビュル結合含量は 33重量0 /0 であった。 プロックスチレン量の分析値よりスチレンのプロックは存在していな かった。 また、 重量平均分子量は 49. 3万、 変性率は 7 1%であった。 5 kg and 0.4 kg of styrene monomer and 45 kg of 1,3-butadiene were added, and the temperature was raised to 60 ° C with stirring, and 32 g of tetrahydrofuran and 0.83 g of n-butyllithium ( (15 ° / 0 cyclohexane solution) was added to initiate the polymerization reaction. During the polymerization, 0.15-kg of 1,3-butadiene was continuously added to the polymerization system for 5 minutes until the temperature reached a maximum of 92 ° C. One minute after the maximum temperature of the polymerization, 0.38 mol of tetraglycidyl 1,3-bisaminomethylcyclohexane was added to n-butyllithium used as the polymerization initiator to cause a reaction. — Got A. Thereafter, 0.5 parts by weight of 2,6-di-tert-butyl-4-methylphenol as a stabilizer was added to the polymer solution per 10 parts by weight of the rubber, and the solvent was removed by a drum dryer and dried to finish. The resulting polymer was analyzed with rollers, a styrene content of 40 wt%, Bulle bond content of the butadiene portion was 33 weight 0/0. From the analysis of the amount of styrene block, there was no styrene block. In addition, the weight average molecular weight was 499.30, and the modification rate was 71%.
(S BR— Bの製造）  (Manufacture of SBR-B)
窒素置換した攪拌機付き 10 Lオートクレープに精製したシクロへキサン 5. 5 k gとスチレンモノマー 0. 40 k g及び 1, 3—ブタジエン 0. 45 k gを 入れ、 攪拌しながら温度を 60°Cまで昇温してテトラヒ ドロフラン 32 gと n— ブチルリチウム 0. 83 g (1 5%シクロへキサン溶液） を添加して重合反応を 開始した。 重合の途中から最高温度の 92°Cになるまでの 5分間 1， 3—ブタジ ェン 0. 1 5 k gを重合系中に連続して添加した。 重合の最高温度から 1分後 に、 重合開始剤として使用した n—プチルリチウムに対して、 1モルの 1， 3 _ ジメチルー 2—イミダゾリジノンを添加して反応させて S BR— Bを得た。 その 後、 重合体溶液に安定剤として 2， 6—ジー t e r tプチルー 4ーメチルフエノ ールをゴム 1 00重量部当たり 0. 5重量部添加し、ドラムドライヤーで脱溶媒、 乾燥して仕上げた。 得られたポリマーを分析したところ， スチレン含有量は 40 重量0 /0、 ブタジエン部のビュル結合含量は 3 3重量％であった。 ブロックスチレ ン量の分析値よりスチレンのブロックは存在していなかった。 また、 重量平均分 子量は 49. 1万、 変性率は 80 %であつた。 5.5 kg of purified cyclohexane, 0.40 kg of styrene monomer and 0.45 kg of 1,3-butadiene were placed in a 10 L autoclave equipped with a stirrer purged with nitrogen, and the temperature was raised to 60 ° C with stirring. And 32 g of tetrahydrofuran and n— 0.83 g (15% cyclohexane solution) of butyllithium was added to initiate the polymerization reaction. During the polymerization, 0.1-kg of 1,3-butadiene was continuously added to the polymerization system for 5 minutes until the maximum temperature reached 92 ° C. One minute after the maximum temperature of polymerization, 1 mol of 1,3-dimethyl-2-imidazolidinone was added to n-butyllithium used as a polymerization initiator and reacted to obtain SBR-B. Was. Thereafter, 0.5 parts by weight of 2,6-ditert-butyl-4-methylphenol as a stabilizer was added to the polymer solution per 100 parts by weight of the rubber, and the solvent was removed by a drum drier and dried to finish. The obtained polymer was analyzed, a styrene content of 40 weight 0/0, Bulle bond content of the butadiene portion was 3 3 wt%. From the analysis of the block styrene content, no styrene block was present. In addition, the weight average molecular weight was 49.1 million, and the denaturation rate was 80%.
(S B R— Cの製造）  (Manufacture of SBR-C)
上記で得られた S B R— B： 1 80 gに 2次変性剤である無水マレイン酸を O. 1 gブレンドし、 温度制御装置を付属した密閉混練機 （内容量 0. 3リ ッ トル） を使用し、 混練温度 1 00 °C、 混練時間 3分の条件で混練することで二次変性重 合体を得た。  180 g of the SBR-B obtained above was blended with 1 g of maleic anhydride as a secondary modifier, and the mixture was mixed in a closed kneader (0.3 liter capacity) equipped with a temperature controller. The resulting mixture was kneaded at a kneading temperature of 100 ° C. and a kneading time of 3 minutes to obtain a secondary modified polymer.
(S B R— Dの製造）  (Manufacture of SBR-D)
窒素置換した攪拌機付き 1 0 Lオートクレープに精製したシク口へキサン 5. 5 k gとスチレンモノマー 0. 40 k g及び 1， 3—ブタジエン 0. 45 k gを 入れ、 攪拌しながら温度を 60°Cまで昇温してテトラヒ ドロフラン 32 gと n— プチルリチウム 0. 8 3 g (1 5%シクロへキサン溶液） を添加して重合反応を 開始した。 重合の途中から最高温度の 89°Cになるまでの 5分間 1， 3—プタジ ェン 0. 1 5 k gを重合系中に連続して添加した。 最高温度が 89 °Cになり 3 分後に重合体溶液を抜き出し n—ブチルリチウムの 10倍モルの水で失活して S BR— Cを得た。 その後、 重合体溶液に安定剤として 2， 6—ジー t e r tプチ ルー 4一メチルフエノールをゴム 100重量部当たり 0. 5重量部添加し、 ドラ ムドライヤーで脱溶媒、乾燥して仕上げた。得られたポリマーを分析したところ， スチレン含有量は 40重量0 /0、 ブタジエン部のビニル結合含量は 33重量％であ つた。 プロックスチレン量の分析値よりスチレンのブロックは存在してレ、なかつ た。 また、 重量平均分子量は 48. 5万であった。 Into a 10 L autoclave equipped with a nitrogen-substituted stirrer, 5.5 kg of purified hexane and 0.40 kg of styrene monomer and 0.45 kg of 1,3-butadiene were added, and the temperature was raised to 60 ° C with stirring. After the temperature was raised, 32 g of tetrahydrofuran and 0.83 g of n-butyllithium (15% cyclohexane solution) were added to initiate the polymerization reaction. During the polymerization, 0.1 kg of 1,3-butadiene was continuously added to the polymerization system for 5 minutes until the maximum temperature reached 89 ° C. After the maximum temperature reached 89 ° C and 3 minutes later, the polymer solution was withdrawn and deactivated with 10 times the molar amount of water of n-butyllithium to obtain SBR-C. Thereafter, 2,6-ditert-butyl 4-methylphenol was added as a stabilizer to the polymer solution in an amount of 0.5 part by weight per 100 parts by weight of rubber, and the solvent was removed by a drum dryer, followed by drying. The obtained polymer was analyzed, a styrene content of 40 weight 0/0, a vinyl bond content of the butadiene portion is 33 wt% der I got it. According to the analysis of the amount of block styrene, the presence of styrene blocks did not occur. In addition, the weight average molecular weight was 48.5 million.
[マスターバッチの作製] [Preparation of master batch]
(MB— 1)  (MB— 1)
外部より循環水による温度制御装置を付属した密閉混練機 （內容量 1. 7リッ トル） を使用し、 充填率 65%、 ローター回転数 66/77 r pmの条件で、 最 初に 25部のシリ力を混練機に投入し 4分間混練した。 次いで重合体 75部及び ステアリン酸 0. 1 5部を投入して 4分間混練を続けた。 排出後のゴム糸且成物の 温度は 170°Cであった。 冷却後、 50°Cに設定したオープンロールにて再度混 練して重合体/シリ力のマスターバッチを作製した。 表 1に配合処方を す。  A closed kneader (1.7 liter capacity) equipped with a temperature control device using circulating water from the outside was used. At a filling rate of 65% and a rotor speed of 66/77 rpm, 25 Siri force was put into the kneader and kneaded for 4 minutes. Next, 75 parts of the polymer and 0.15 parts of stearic acid were added, and kneading was continued for 4 minutes. The temperature of the rubber thread after discharging was 170 ° C. After cooling, the mixture was kneaded again with an open roll set at 50 ° C. to produce a polymer / silicone masterbatch. Table 1 shows the formulation.
(MB— 2、 3、 4、 6)  (MB—2, 3, 4, 6)
外部より循環水による温度制御装置を付属した密閉混練機 （内容量 1. 7リツ トル） を使用し、 充填率 65%、 ローター回転数 66/77 r pmの条件で、 最 初に 12. 5部のシリ力を混練機に投入し 4分間混練した。 次いで重合体 75部 及びステアリン酸 0. 15部を投入し 3分間混練した後、 更にシリカ 12. 5部 を投入し 3分間混練を続けた。 排出後のゴム組成物の温度は 1 70°Cで つた。 冷却後、 50°Cに設定したオープンロールにて再度混練して重合体/シ 17力のマ スターバッチを作製した。 表 1に配合処方を示す。  Using a closed kneader (1.7 liter capacity) equipped with a temperature control device using circulating water from the outside, with a filling rate of 65% and a rotor rotation speed of 66/77 rpm, the initial 12.5 Parts were put into a kneader and kneaded for 4 minutes. Next, 75 parts of the polymer and 0.15 parts of stearic acid were charged and kneaded for 3 minutes. Then, 12.5 parts of silica was further charged and kneading was continued for 3 minutes. The temperature of the rubber composition after discharging was 170 ° C. After cooling, the mixture was kneaded again with an open roll set at 50 ° C. to prepare a master batch of 17 polymer / polymer. Table 1 shows the formulation.
(MB - 5)  (MB-5)
外部より循環水による温度制御装置を付属した密閉混練機 （内容量 1. 7リツ トル） を使用し、 充填率 65%、 ローター回転数 66/77 r pmの条ィ牛で、 シ リカ 25部及び重合体 75部及びステアリン酸 0. 1 5部を投入して 5分間混練 を続けた。 排出後のゴム組成物の温度は 1 70°Cであった。 冷却後、 50°Cに設 定したオープンロールにて再度混練して重合体 Zシリカのマスターバッチを作製 した。 表 1に配合処方を示す。  A closed kneader (1.7 liter capacity) with a temperature control device using circulating water from the outside is used. The beef has a filling rate of 65%, a rotor speed of 66/77 rpm, and 25 parts of silica. And 75 parts of the polymer and 0.15 parts of stearic acid were added and kneading was continued for 5 minutes. The temperature of the rubber composition after discharging was 170 ° C. After cooling, the mixture was kneaded again with an open roll set at 50 ° C. to produce a master batch of polymer Z silica. Table 1 shows the formulation.
[実施例 1〜 5 ] 外部より循環水による温度制御装置を付属した密閉混練機 （内容量 1 . 7リツ トル） を使用し、 充填率 6 5 %、 ローター回転数 6 <6 / 7 7 r p mの条件で、 表 2に示す配合処方で各成分を一括して混練機に投入し混,練することでゴム組成物 を得た。排出後の温度は 1 6 1 °Cであった。こうして得られたゴム組成物を 7 0 °C に設定したオープンロールにて硫黄、 加硫促進剤を入れ混練した後、 1 6 0 °Cで 2 0分間加硫して試験片を作製した。 表 2に加硫物の物性を示す。 本発明の変性 重合体とシリカのマスターバッチを用いて作製したゴム糸且成物は、 引き裂き強度 と耐摩耗性に優れることがわかる。 [Examples 1 to 5] Using a closed kneader (with a capacity of 1.7 liters) equipped with a temperature controller using circulating water from the outside, with a filling rate of 65% and a rotor speed of 6 <6/77 rpm, see Table 2 The respective components were put into a kneader at the same time according to the compounding recipe shown in the table, and mixed and kneaded to obtain a rubber composition. The temperature after discharge was 16 1 ° C. The rubber composition thus obtained was kneaded with sulfur and a vulcanization accelerator using an open roll set at 70 ° C., and then vulcanized at 160 ° C. for 20 minutes to produce a test piece. Table 2 shows the physical properties of the vulcanizates. It can be seen that the rubber yarn produced using the modified polymer and silica master batch of the present invention has excellent tear strength and abrasion resistance.
[比較例 1〜 2 ] [Comparative Examples 1-2]
実施例 1と同様の方法により、 表 2に示す配合処方で各成分を一括して混練機 に投入し混練することでゴム状重合体組成物を得た。 排出後の温度は 1 6 0 °Cで あった。 こうして得られたゴム組成物を 7 0 °Cに設定したオープンロールにて硫 黄、 加硫促進剤を入れ混練した後、 1 6 0 °Cで 2 0分間加硫して試験片を作製し た。 表 2に加硫物の物性を示す。  In the same manner as in Example 1, the components were collectively charged into a kneader with the compounding recipe shown in Table 2 and kneaded to obtain a rubbery polymer composition. The temperature after discharge was 160 ° C. The rubber composition obtained in this manner was kneaded with an open roll set at 70 ° C and mixed with sulfur and a vulcanization accelerator, and then vulcanized at 160 ° C for 20 minutes to prepare a test piece. Was. Table 2 shows the physical properties of the vulcanizates.
[実施例 6〜 1 2 ] [Examples 6 to 12]
外部より循環水による温度制御装置を付属した密閉混練機 （内容量 1 . 7リツ トル） を使用し、 充填率 6 5 %、 ローター回転数 6 6 / 7 7 r p mの条件で、 表 3に示す配合処方で各成分を一括して混練機に投入し混練することでゴム組成物 を得た。排出後の温度は 1 6 0 °Cであった。こうして得られたゴム組成物を 7 0 °C に設定したオープンロールにて硫黄、 加硫促進剤を入れ混練した後、 1 6 0 °Cで 2 0分間加硫して試験片を作製した。 表 3に加硫物の接着強度を示す。 本発明の 変性重合体とシリカのマスターバッチを用いて作製したゴム組成物は、 接着性に 優れることがわかる。  Using a closed kneader (1.7 liter capacity) with a temperature control device using circulating water from the outside, as shown in Table 3 under the conditions of a filling rate of 65% and a rotor rotation speed of 66/77 rpm The rubber composition was obtained by putting all the components together in a compounding recipe into a kneader and kneading them. The temperature after discharge was 160 ° C. The rubber composition thus obtained was kneaded with sulfur and a vulcanization accelerator using an open roll set at 70 ° C., and then vulcanized at 160 ° C. for 20 minutes to produce a test piece. Table 3 shows the adhesive strength of the vulcanizates. It can be seen that the rubber composition produced using the masterbatch of the modified polymer and silica of the present invention has excellent adhesiveness.
[比較例 3〜 4 ] [Comparative Examples 3-4]
実施例 6と同様の方法により、 表 3に示す配合処方で各成分を一括して混練機 に投入し混練することでゴム組成物を得た。 こうして得られたゴム組成物を 7 0 °Cに設定したオープンロールにて硫黄、加硫促進剤を入れ混練した後、 1 6 0 °C で 2 0分間加硫して試験片を作製した。 According to the same method as in Example 6, the components were collectively kneaded according to the formulation shown in Table 3. And kneaded to obtain a rubber composition. The rubber composition thus obtained was kneaded with sulfur and a vulcanization accelerator using an open roll set at 70 ° C., and then vulcanized at 160 ° C. for 20 minutes to produce a test piece.
表 1 table 1
Figure imgf000036_0001
Figure imgf000036_0001
*1:トクャマ社製 商品名： Tokusil UR-T * 1: Trade name: Tokusil UR-T
表 2 Table 2
Figure imgf000037_0001
Figure imgf000037_0001
* 1：ハィシスポリブタジエン（1 . 4シス結合量 95重量％)  * 1: Hycis polybutadiene (1.4 cis bond amount 95% by weight)
* 2 :ポリイソプレンゴム  * 2: Polyisoprene rubber
* 3 :トクャマ社製 商品名： Tokusil UR-T  * 3: Product name: Tokusil UR-T
* 4： Degussa社製 シランカツプリング剤 Si69  * 4: Degussa silane coupling agent Si69
物質名：ビス- [3- (トリエトキシシリル)-プロピル]-テトラスルフイド Substance name: Bis- [3- (triethoxysilyl) -propyl] -tetrasulfide
表 3 Table 3
Figure imgf000038_0001
Figure imgf000038_0001
* 1：ハイシスポリブタジエン（1.4シス結合量 95重量％) * 1: High cis polybutadiene (1.4 cis bond amount 95% by weight)
* 2:ポリイソプレンゴム * 2: Polyisoprene rubber
* 3：口一ディア社製 商品名： ZeosiM 75 * 3: Mouth-Dia product name: ZeosiM 75
本発明を詳細にまた特定の実施態様を参照して説明したが、'本発明の精神と範 囲を逸脱することなく様々な変更や修正を加えるこ'とができることは当業者にと つて明らかである。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that 'various changes and modifications may be made without departing from the spirit and scope of the invention. It is.
本出願は、 2003年 10月 29 0出願の日本特許出願（特願 2003— 369255) に基づ くものであり、 その内容はここに参照として取り込まれる。 産業上の利用可能性  This application is based on a Japanese patent application filed on Oct. 2003 (Japanese Patent Application No. 2003-369255), the contents of which are incorporated herein by reference. Industrial applicability
本発明の履物用ゴム組成物は、 優れた引き裂き強度と耐摩耗性を有し、 更に靴 の材料であるナイロン、 レザー、 E V Aとの接着性に極めて優れる。 本発明の組 成物は、 これらの特徴を生かして各種シューズのソール材として極めて有効な材 料である。 また、 各種形状の成型品に加工でき、 自動車部品 （自動車内装材料、 自動車外装林料）、 食品包装容器などの各種容器、 家電用品、 医療機器部品、 工業 部品、 玩具等に用いることができる。  INDUSTRIAL APPLICABILITY The rubber composition for footwear of the present invention has excellent tear strength and abrasion resistance, and is extremely excellent in adhesion to shoe materials such as nylon, leather and EVA. The composition of the present invention is an extremely effective material as a sole material for various shoes utilizing these characteristics. In addition, it can be processed into molded products of various shapes, and can be used for automobile parts (automobile interior materials, automobile exterior forestry), various containers such as food packaging containers, home appliances, medical equipment parts, industrial parts, toys, etc.

Claims

請求の範囲 The scope of the claims
1 . 成分 （ 1 ) ゴム状重合体： 1 0 0重量部；及び 1. Component (1) Rubbery polymer: 100 parts by weight; and
成分 （2 ) 共役ジェン系重合体又は共役ジェン系単量体とビュル芳香族炭化水 素からなる共重合体又はそれらの水添物に官能基含有原子団が少なくとも 1個結 合している変性重合体から選ばれる少なくとも 1種の変性重合体 1 0 0重量部に 無機充填剤 5〜3 0 0重量部を混練して得られるマスターバッチ： 1〜1 5 0重 を含む履物用ゴム組成物。  Component (2) Modification in which at least one functional group-containing atomic group is bonded to a conjugated polymer or a copolymer composed of a conjugated aromatic monomer and butyl aromatic hydrocarbon or a hydrogenated product thereof. Masterbatch obtained by kneading 5 to 300 parts by weight of an inorganic filler into 100 parts by weight of at least one modified polymer selected from polymers: 1 to 150 parts by weight Rubber composition for footwear .
2 . 成分 （2 ) が無機充填剤 5〜3 0◦重量部の全量を予め混練機に投入して 混練し、 次いで変性重合体を加えて混練して得られるマスターバッチである請求 項 1に記載の履物用ゴム組成物。 2. The masterbatch according to claim 1, wherein the component (2) is a masterbatch obtained by previously charging 5 to 30 parts by weight of the inorganic filler into a kneader, kneading the mixture, and then adding and kneading a modified polymer. The rubber composition for footwear according to the above.
3 . 成分 （ 2 ) が無機充填剤 5〜 3 0 0重量部を 2回以上分割して混練機に投 入して順次混練して得られるマスターバッチである請求項 1に記載の履物用ゴム 組成物。 3. The rubber for footwear according to claim 1, wherein the component (2) is a masterbatch obtained by dividing 5 to 300 parts by weight of an inorganic filler into two or more portions, putting the resulting mixture into a kneader, and kneading the masterbatch sequentially. Composition.
4 . 成分 （2 ) が無機充填剤の 2 0〜 8 0重量％を予め混練機に投」 し、 次いで変性重合体を加え混練し、 更に当該無機充填剤の残量を加えて混練し たマスター ツチである請求項 1に記載の履物用ゴム組成物。 4. 20 to 80% by weight of the component (2) of the inorganic filler was previously poured into a kneader, then the modified polymer was added and kneaded, and the remaining amount of the inorganic filler was added and kneaded. 2. The rubber composition for footwear according to claim 1, which is a master stick.
5 . 成分 （ 3 ) として、 更に無機充填剤を 0 . 1〜 1 5 0重量部含む請求項 1 に記載の履物用ゴム組成物。 5. The rubber composition for footwear according to claim 1, further comprising 0.1 to 150 parts by weight of an inorganic filler as the component (3).
6 . 変性重合体の官能基含有原子団が、 水酸基、 エポキシ基、 アミノ基、 イミ ノ基、 シラノール基、 アルコキシシラン基から選ばれる官能基を少なくとも 1個 有する原子団である請求項 1に記載の履物用ゴム組成物。 6. The modified polymer according to claim 1, wherein the functional group-containing atomic group has at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, an imino group, a silanol group, and an alkoxysilane group. Rubber composition for footwear.
. 変性重合体が、 下記式 （1) 〜 （14) から選ばれる原子団が少なくとも 個結合している変性重合体である請求項 1に記載の履物用ゴム組成物。 The rubber composition for footwear according to claim 1, wherein the modified polymer is a modified polymer in which at least one atomic group selected from the following formulas (1) to (14) is bonded.
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(上記式 （1) 〜 （14) において、 Nは窒素原子、 S iは珪素原子、 Oは酸 素原子、 Cは炭素原子、 Hは水素原子を表し、 R1, R 2は各々独立に水素原子又 は炭素数 1~24の炭化水素基を表し、且つ、該炭化水素基は、所望により、各々 独立に、 水酸基、 エポキシ基、 アミノ基、 炭素数 1〜 24の炭化水素基を有する イミノ基、 シラノール基及び炭素数 1〜 24のアルコキシシラン基からなる群よ り選ばれる少なくとも 1種の官能基を有してもよく、 各 R 3は各々独立に炭素数 1〜48の 2価の炭化水素基を表し、 且つ、 所望により、 各々独立に、 水酸基、 エポキシ基、 アミノ基、 炭素数 1〜24の炭化水素基を有するイミノ基、 シラノ ール基及び炭素数 1〜 24のアルコキシシラン基からなる群より選ばれる少なく とも 1種の官能基を有してもよく、 各 R4は各々独立に水素原子又は炭素数 1〜 24の炭化水素基を表す。） (In the above formulas (1) to (14), N is a nitrogen atom, Si is a silicon atom, O is an oxygen atom, C is a carbon atom, H is a hydrogen atom, and R 1 and R 2 are each independently Represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and each of the hydrocarbon groups independently has a hydroxyl group, an epoxy group, an amino group, or a hydrocarbon group having 1 to 24 carbon atoms, if desired. It may have at least one functional group selected from the group consisting of an imino group, a silanol group and an alkoxysilane group having 1 to 24 carbon atoms, and each R 3 is independently a divalent group having 1 to 48 carbon atoms. And, if desired, each independently represents a hydroxyl group, an epoxy group, an amino group, an imino group having a hydrocarbon group having 1 to 24 carbon atoms, a silanol group, and an alkoxy group having 1 to 24 carbon atoms. at least selected from the group consisting of silane groups may have one functional group, each R 4 Each independently represent a hydrogen atom or a hydrocarbon group of carbon number 1-24.)
8. 成分 （2) 1 当該変性重合体と無機充填剤の混練の際に、 更に当該変性 重合体に結合している官能基と反応性を有する化合物 （4) を当該変性重合体 1 00重量部に対して 0. 0 1〜20重量部添加して得られたマスターバッチであ る請求項 1に記載の履物用ゴム組成物。 8. Component (2) 1 At the time of kneading the modified polymer and the inorganic filler, a compound (4) having a reactivity with a functional group bonded to the modified polymer is further added to the modified polymer in an amount of 100 wt. The rubber composition for footwear according to claim 1, which is a masterbatch obtained by adding 0.01 to 20 parts by weight per part by weight.
9. 成分 （2) 力 S、 当該変性重合体と無機充填剤の混練物に、 更に当該変性重 合体に結合している官能基と反応性を有する化合物 （4) を当該変性重合体 1 0 0重量部に対して 0. 01〜20重量部混練して得られたマスターバッチである 請求項 1に記載の履物用ゴム組成物。 9. Component (2) Force S, the kneaded product of the modified polymer and the inorganic filler, and the compound (4) reactive with the functional group bonded to the modified polymer are added to the modified polymer. The rubber composition for footwear according to claim 1, which is a master batch obtained by kneading 0.01 to 20 parts by weight with respect to 0 parts by weight.
10. 成分 （2) に使用する変性重合体が、 当該変性重合体に結合している官 能基と反応性を有する化合物 （4) を当該変性重合体に結合している官能基 1当 量あたり 0. 3〜1 0モルを用いて反応させた変性重合体である請求項 1に記載 の履物用ゴム組成物。 10. The modified polymer used as the component (2) has a compound (4) having a reactivity with a functional group bonded to the modified polymer, and a functional group binding to the modified polymer (1 equivalent). The rubber composition for footwear according to claim 1, which is a modified polymer reacted by using 0.3 to 10 moles per unit.
1 1. 化合物 （4) がカルボキシル基、 酸無水物基、 イソシァネート基、 ヱポ キシ基、 シラノール基、 アルコキシシラン基から選ばれる官能基を有する化合物 である請求項 8または 9に記載の履物用ゴム組成物。 1 1. Compound (4) has a carboxyl group, an acid anhydride group, an isocyanate group, The rubber composition for footwear according to claim 8 or 9, which is a compound having a functional group selected from a xy group, a silanol group, and an alkoxysilane group.
1 2 . 成分 （ 1 ) ゴム状重合体： 1 0 0重量部；及び 12. Component (1) Rubbery polymer: 100 parts by weight; and
成分 （2 ) 共役ジェン系重合体又は共役ジェン系単量体とビニル芳香族炭化水 素からなる共重合体又はそれらの水添物に官能基含有原子団が少なくとも 1個結 合している変性重合体から選ばれる少なくとも 1種の変性重合体 1 0 0重量部に 無機充填剤 5〜 3 0 0重量部を混練して得られるマスターバッチ： 1〜1 5 0重 を混練する工程を含む履物用ゴム組成物の製造方法。  Component (2) Modification in which at least one functional group-containing atomic group is bonded to a conjugated polymer or a copolymer of a conjugated monomer and a vinyl aromatic hydrocarbon or a hydrogenated product thereof. Masterbatch obtained by kneading 5 to 300 parts by weight of an inorganic filler into 100 parts by weight of at least one modified polymer selected from polymers: Footwear including a step of kneading 1 to 150 parts by weight Of producing a rubber composition for rubber.
1 3 . 成分 （ 2 ) が無機充填剤 5〜 3 0 0重量部の全量を混練機に投入して混 練し、 次いで変性重合体を加えて混練して得られるマスターバッチである請求項 1 2に記載の履物用ゴム組成物の製造方法。 13. The component (2) is a masterbatch obtained by charging and kneading the entire amount of 5 to 300 parts by weight of the inorganic filler into a kneader, and then kneading by adding a modified polymer. 3. The method for producing the rubber composition for footwear according to 2.
1 4 . 成分 （ 2 ) が無機充填剤 5〜 3 0 0重量部を 2回以上分割して混練機に 投入して順次混練して得られるマスターバッチである請求項 1 2に記載の履物用 ゴム組成物の製造方法。 14. The footwear according to claim 12, wherein the component (2) is a masterbatch obtained by dividing 5 to 300 parts by weight of the inorganic filler into two or more portions and putting the mixture into a kneading machine to sequentially knead the components. A method for producing a rubber composition.
1 5 . 無機充填剤 5〜 3 0 0重量部の全量を混練機に投入して混練し、 次いで 変性重合体を加えて混練する請求項 1に記載のマスターバツチの製造方法。 15. The method for producing a master batch according to claim 1, wherein the entire amount of 5 to 300 parts by weight of the inorganic filler is put into a kneader and kneaded, and then a modified polymer is added and kneaded.
1 6 . 無機充填剤の 2 0〜 8 0重量％を予め混練機に投入して混練し、 次いで 変性重合体を加え混練し、 更に当該無機充填剤の残量を加えて混練する請求項 1 に記載のマスターバツチの製造方法。 16. 20 to 80% by weight of the inorganic filler is previously charged into a kneader and kneaded, then the modified polymer is added and kneaded, and the remaining amount of the inorganic filler is added and kneaded. 3. The method for producing a master batch described in 1. above.
PCT/JP2004/016465 2003-10-29 2004-10-29 Rubber composition for footwear WO2005040267A1 (en)

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