WO2024237206A1 - 被覆繊維及びそれを用いた成形体 - Google Patents

被覆繊維及びそれを用いた成形体 Download PDF

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WO2024237206A1
WO2024237206A1 PCT/JP2024/017455 JP2024017455W WO2024237206A1 WO 2024237206 A1 WO2024237206 A1 WO 2024237206A1 JP 2024017455 W JP2024017455 W JP 2024017455W WO 2024237206 A1 WO2024237206 A1 WO 2024237206A1
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conjugated diene
rubber
diene rubber
mass
molecular weight
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French (fr)
Japanese (ja)
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亮平 渡邉
祥史 麻生
稔 岡本
彩花 藤井
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to EP24807158.1A priority Critical patent/EP4711518A1/en
Priority to KR1020257036658A priority patent/KR20260010383A/ko
Priority to JP2025520564A priority patent/JPWO2024237206A1/ja
Priority to CN202480031087.0A priority patent/CN121195097A/zh
Publication of WO2024237206A1 publication Critical patent/WO2024237206A1/ja
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/062—Load-responsive characteristics stiff, shape retention
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial

Definitions

  • the present invention relates to a coated fiber that has excellent adhesion to rubber, and a molded article made using the same.
  • Patent Document 3 describes a reinforcing fiber having an adhesive component containing a conjugated diene rubber and an oil on at least a part of the surface of the fiber, and the vapor pressure of the oil at 20° C. is 10 Pa or less.
  • Patent Document 4 describes a surface-modified fiber having a fiber and a surface-modified layer covering at least a portion of the surface of the fiber, the solid surface zeta potential of the surface of the surface-modified layer being within a specific range.
  • Patent Document 5 further describes a reinforcing fiber having a fiber, a surface-modified layer covering at least a portion of the surface of the fiber, and an adhesive layer containing a conjugated diene rubber covering at least a portion of the surface-modified layer, the surface-modified layer having one or more functional groups selected from primary to tertiary amino groups and imino groups, and containing a polyamine compound having a weight average molecular weight (Mw) of 300 or more.
  • Mw weight average molecular weight
  • the objective of the present invention is to provide a coated fiber using an adhesive composition that does not contain resorcinol or formaldehyde, which has excellent adhesion to rubber, excellent convergence, and excellent strength after friction, and which can be produced while suppressing contamination of the production equipment, and a molded article using the same.
  • the inventors conducted extensive research to solve the above problems, and discovered that even when a relatively low molecular weight conjugated diene rubber is used as the adhesive composition, by adjusting the molecular weight distribution curve of the coating by GPC analysis to have a peak in a specific range and by providing a specific ratio between the two areas in the specific ranges by GPC analysis, it is possible to obtain a coated fiber that has excellent adhesion to rubber and convergence without using resorcin and formaldehyde, as well as excellent strength after friction, and that also suppresses contamination of the manufacturing equipment, and thus completed the present invention.
  • the present invention provides a coated fiber using an adhesive composition that does not contain resorcinol or formaldehyde, which has excellent adhesion and convergence with rubber, as well as excellent strength after friction, and can be produced while suppressing contamination of the production equipment, and a molded article using the same.
  • FIG. 1 is a schematic diagram showing a metal friction tester for coated fibers.
  • FIG. 2 is a reference diagram of a molecular weight distribution curve having a maximum point near a molecular weight of 7,000.
  • FIG. 3 is a reference diagram of a molecular weight distribution curve having a maximum point near a molecular weight of 10,000.
  • the coated fiber of the present invention is a coated fiber obtained by coating a fiber with a coating material containing one or more selected from the group consisting of an adhesive composition containing a conjugated diene rubber and a reaction product of the adhesive composition, and is characterized in that the molecular weight distribution curve of the coating material obtained by GPC analysis satisfies both of the following conditions (1) and (2). Note that the molecular weight distribution curve obtained by GPC analysis in the present invention is one analyzed by the method described in the Examples.
  • the molecular weight distribution curve of the coating by GPC analysis has at least one peak in the molecular weight range of 2,600 to 19,000.
  • a peak means a maximum point in the molecular weight distribution curve.
  • a maximum point is observed near a molecular weight of about 7,000, which means the peak.
  • a maximum point is observed near 10,000, which also means the peak.
  • the peak is derived from a component containing a conjugated diene rubber.
  • the adhesion to rubber particularly to a low polarity rubber such as EPDM (ethylene propylene diene rubber)
  • Having a peak means that a component in a specific molecular weight range is present in greater amounts than other components, and adhesiveness can be expressed together with components having molecular weights in the vicinity of the peak.
  • the range to have at least one peak it is possible to suppress process contamination during the production of the coated fiber because the coating does not contain a compound having an excessively large molecular weight.
  • the molecular weight range in which the one peak exists is preferably 2,600 to 15,000, more preferably 4,500 to 14,000, even more preferably 6,000 to 13,000, even more preferably 7,000 to 12,000, and particularly preferably 8,000 to 11,000.
  • the molecular weight distribution curve of the coating by GPC analysis has an area ratio [(A)/(B)] of 0.5 to 9.0, where (A) is the area under the curve in the range of 2,600 to 19,000 molecular weight, and (B) is the area under the curve in the range of 19,000 to 540,000 molecular weight.
  • the area ratio is within the above range, the balance between the relatively low molecular weight compounds and the relatively high molecular weight compounds in the coating is good, and it is possible to suppress process contamination while improving adhesion to rubber. Furthermore, it is possible to improve the convergence of the coated fiber and the strength after friction.
  • the area ratio [(A)/(B)] is preferably 1.0 to 8.8, more preferably 1.4 to 8.7, and even more preferably 1.8 to 8.5.
  • the areas (A) and (B) are derived from a component containing a conjugated diene rubber.
  • the area ratio [(A)/(B)] is preferably 1.0 to 5.0, more preferably 1.5 to 3.5, and even more preferably 2.0 to 3.5.
  • the above area ratio can be achieved, for example, by using a low molecular weight conjugated diene rubber and crosslinking the low molecular weight conjugated diene rubbers with each other using a crosslinking agent described later.
  • the adhesive composition used in the present invention contains a conjugated diene rubber.
  • the adhesive composition contains a modified conjugated diene rubber.
  • the fiber is covered with a coating containing one or more selected from the group consisting of an adhesive composition containing a relatively low molecular weight conjugated diene rubber (preferably a modified conjugated diene rubber) and a reactant of the adhesive composition (i.e., a reactant obtained by reacting the conjugated diene rubber (preferably a modified conjugated diene rubber) with itself), and the reactant is obtained by adjusting it so as not to react excessively, so that it has an excellent effect of having excellent adhesion while not contaminating the manufacturing process.
  • a reactant of the adhesive composition i.e., a reactant obtained by reacting the conjugated diene rubber (preferably a modified conjugated diene rubber) with itself
  • the coated fiber of the present invention is also excellent in convergence and strength after friction.
  • the "coated fiber” is any fiber in which at least a portion of the surface is coated with the coating.
  • the fiber may have a coating present on at least a portion of the surface, for example, as a film or layer, or the fiber may have a coating contained in its raw material and the coating present on part of the surface of the fiber itself.
  • the conjugated diene rubber used in the present invention contains at least a monomer unit derived from a conjugated diene in the molecule (hereinafter also referred to as a "conjugated diene unit").
  • the conjugated diene rubber contains 50 mol % or more of a monomer unit derived from a conjugated diene in the total monomer units in the conjugated diene rubber.
  • conjugated diene monomer examples include butadiene, 2-methyl-1,3-butadiene (hereinafter also referred to as "isoprene"), 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene, acrylonitrile, and farnesene.
  • conjugated dienes may be used alone or in combination of two or more.
  • the conjugated diene rubber preferably has a monomer unit derived from one or more selected from the group consisting of butadiene, isoprene, chloroprene, acrylonitrile, and farnesene, and more preferably has a monomer unit derived from one or more selected from butadiene and isoprene.
  • the conjugated diene rubber used in the present invention may contain units derived from other monomers than the conjugated diene monomers, so long as the units do not impair adhesion.
  • other monomers include copolymerizable ethylenically unsaturated monomers and aromatic vinyl compounds.
  • the ethylenically unsaturated monomer include olefins such as ethylene, 1-butene, and isobutylene.
  • aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene.
  • the conjugated diene rubber contains a monomer unit derived from a monomer other than a conjugated diene monomer, the content thereof is preferably 30 mol % or less, more preferably 10 mol % or less, and further preferably 5 mol % or less.
  • the conjugated diene rubber used in the present invention may be unmodified, but preferably has a functional group in a part thereof, more preferably has a hydrogen-bonding functional group, and more preferably is a modified conjugated diene rubber containing a conjugated diene unit in at least a part of the polymer chain and having a hydrogen-bonding functional group in a side chain or at an end of the polymer chain.
  • the unmodified conjugated diene rubber and the modified conjugated diene rubber may be used in combination. In the case of modified conjugated diene rubber, the interaction with the adherend rubber and fiber leads to more effective adhesion between them.
  • the modified conjugated diene rubber and the adherend rubber are vulcanized to form a covalent bond, a strong cohesive force is generated, which further improves the adhesion. Furthermore, when hydrophilic fibers are used as the fibers, it is believed that the hydrogen-bonding functional groups contained in the modified conjugated diene rubber form hydrogen bonds with the hydrophilic fibers, thereby improving adhesion.
  • hydrogen bond refers to a bonding interaction formed between a hydrogen atom (donor) that is bonded to an atom with high electronegativity (O, N, S, etc.) and is electrically positively polarized, and an electronegative atom (acceptor) that has a lone pair of electrons.
  • a "hydrogen-bonding functional group” is a functional group that can function as a donor and an acceptor in the hydrogen bond. Specific examples include hydroxyl groups, ether groups, mercapto groups, carboxy groups, carbonyl groups, aldehyde groups, amino groups, imino groups, imidazole groups, urethane groups, amide groups, urea groups, isocyanate groups, nitrile groups, silanol groups, and derivatives thereof.
  • An example of a derivative of an aldehyde group is an acetalized product thereof.
  • An example of a derivative of a carboxy group is a salt thereof, an esterified product thereof, an amidated product thereof, and an acid anhydride thereof.
  • An example of a derivative of a silanol group is an esterified product thereof.
  • an example of a carboxy group is a group derived from a monocarboxylic acid or a group derived from a dicarboxylic acid.
  • At least one selected from a hydroxy group, an aldehyde group, an acetalized product of an aldehyde group, a carboxy group, a salt of a carboxy group, an esterified product of a carboxy group, an acid anhydride of a carboxy group, a carbonyl group, a silanol group, an esterified product of a silanol group, an amino group, an imidazole group, and a mercapto group is preferred.
  • one or more selected from hydroxyl group, carboxyl group, carbonyl group, salt of carboxyl group, esterified product of carboxyl group, and acid anhydride of carboxyl group are preferred, one or more selected from carboxyl group, esterified product of carboxyl group, and acid anhydride of carboxyl group are more preferred, and esterified product of maleic anhydride and functional groups derived from maleic anhydride are even more preferred.
  • the number of hydrogen-bonding functional groups in the modified conjugated diene rubber is preferably 2 or more, and more preferably 3 or more, on average, per molecule, from the viewpoint of obtaining a coated fiber with excellent rubber adhesion. Furthermore, the number of hydrogen-bonding functional groups is preferably 80 or less, more preferably 40 or less, even more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less, on average, per molecule, from the viewpoint of controlling the viscosity of the modified conjugated diene rubber within an appropriate range and improving handleability.
  • the average number of hydrogen-bonding functional groups per molecule of the modified conjugated diene rubber is calculated from the equivalent weight (g/eq) of the hydrogen-bonding functional groups of the modified conjugated diene rubber and the number average molecular weight Mn in terms of styrene, based on the following formula:
  • the equivalent weight of the hydrogen-bonding functional groups of the modified conjugated diene rubber means the mass of the conjugated diene bonded to each hydrogen-bonding functional group and the mass of other monomers other than the conjugated diene that are included as necessary.
  • Average number of hydrogen-bonding functional groups per molecule [(number average molecular weight (Mn))/(molecular weight of styrene unit) ⁇ (average molecular weight of conjugated diene and other monomer units other than conjugated diene contained as necessary)]/(equivalent weight of hydrogen-bonding functional group)
  • the method for calculating the equivalent weight of the hydrogen-bonding functional group can be appropriately selected depending on the type of the hydrogen-bonding functional group.
  • Methods for obtaining modified conjugated diene rubber include, for example, a method for obtaining the rubber by adding a modifying compound to a polymerized product of a conjugated diene monomer (hereinafter, also referred to as "production method (1)”), a method for obtaining the rubber by oxidizing a conjugated diene polymer (hereinafter, also referred to as "production method (2)”), a method for obtaining the rubber by copolymerizing a conjugated diene monomer with a radically polymerizable compound having a hydrogen-bonding functional group (hereinafter, also referred to as "production method (3)”), and a method for adding a modifying compound capable of reacting with the polymerization active terminal to a polymerized product of an unmodified conjugated diene monomer having a polymerization active terminal before adding a polymerization terminator (hereinafter, also referred to as "production method (4)").
  • production method (1) a method for obtaining the rubber by adding a modifying
  • the production method (1) is a method in which a modifying compound is added to a polymer of a conjugated diene monomer, that is, an unmodified conjugated diene rubber (hereinafter also referred to as "unmodified conjugated diene rubber").
  • the unmodified conjugated diene rubber can be obtained by polymerizing a conjugated diene and, if necessary, a monomer other than the conjugated diene, for example, by emulsion polymerization or solution polymerization. Of the above methods, the solution polymerization method is preferred as the method for producing the unmodified conjugated diene rubber.
  • a known method or a method similar to a known method can be applied.
  • a predetermined amount of a monomer containing a conjugated diene is polymerized in a solvent using a Ziegler catalyst, a metallocene catalyst, or an anionically polymerizable active metal or active metal compound, if necessary in the presence of a polar compound.
  • the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, toluene, and xylene.
  • aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane
  • alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane
  • aromatic hydrocarbons such as benzene, toluene, and xylene.
  • active metals capable of anion polymerization include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanoid rare earth metals such as lanthanum and neodymium.
  • alkali metals and alkaline earth metals are preferred, and alkali metals are more preferred.
  • an organic alkali metal compound is preferred.
  • the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; polyfunctional organic lithium compounds such as dilithiomethane, dilithionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene, and the like.
  • organic lithium compounds are preferred, and organic monolithium compounds are more preferred.
  • the amount of the organic alkali metal compound used can be appropriately set depending on the melt viscosity, molecular weight, etc. of the target unmodified conjugated diene rubber and modified conjugated diene rubber, but it is usually used in an amount of 0.01 to 3 parts by mass based on 100 parts by mass of all monomers including conjugated diene.
  • the above-mentioned organic alkali metal compounds can also be reacted with secondary amines such as dibutylamine, dihexylamine, dibenzylamine, etc. to form organic alkali metal amides.
  • polar compounds are usually used to adjust the microstructure of the conjugated diene moiety without deactivating the reaction.
  • polar compounds include ether compounds such as dibutyl ether, tetrahydrofuran, ethylene glycol diethyl ether, and 2,2-di(2-tetrahydrofuryl)propane; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides; and phosphine compounds.
  • the polar compound is usually used in an amount of 0.01 to 1,000 moles per mole of the organic alkali metal compound.
  • the temperature of the solution polymerization is usually ⁇ 80 to +150° C., preferably 0 to 100° C., and more preferably 10 to 90° C.
  • the polymerization may be carried out in either a batch or continuous manner.
  • the polymerization reaction can be terminated by adding a polymerization terminator.
  • the polymerization terminator include alcohols such as methanol and isopropanol.
  • the resulting polymerization reaction liquid is poured into a poor solvent such as methanol to precipitate the polymerized product, or the polymerization reaction liquid is washed with water, separated, and then dried to isolate the unmodified conjugated diene rubber.
  • the emulsion polymerization method may be a known method or a method similar to a known method, for example, a monomer containing a predetermined amount of conjugated diene is emulsified and dispersed in the presence of an emulsifier, and emulsion-polymerized by a radical polymerization initiator.
  • the emulsifier include salts of long-chain fatty acids having 10 or more carbon atoms, rosin acid salts, etc.
  • the long-chain fatty acid salts include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid.
  • the dispersion solvent water is usually used, and it may contain a water-soluble organic solvent such as methanol or ethanol within a range that does not impair the stability during polymerization.
  • a water-soluble organic solvent such as methanol or ethanol
  • the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, and hydrogen peroxide.
  • a chain transfer agent may be used.
  • chain transfer agent examples include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, terpinolene, ⁇ -terpinene, and ⁇ -methylstyrene dimer.
  • the temperature of the emulsion polymerization can be set appropriately depending on the type of radical polymerization initiator used, but is usually 0 to 100°C, and preferably 0 to 60°C.
  • the polymerization method may be either continuous polymerization or batch polymerization.
  • the polymerization reaction can be stopped by adding a polymerization terminator.
  • polymerization terminators include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine, and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.
  • an antioxidant may be added as necessary.
  • unreacted monomers are removed from the obtained latex as necessary, and then the polymerized product is coagulated using a salt such as sodium chloride, calcium chloride, or potassium chloride as a coagulant, and an acid such as nitric acid or sulfuric acid is added as necessary to adjust the pH of the coagulation system to a predetermined value, after which the dispersion solvent is separated and the polymerized product is recovered.
  • the polymerized product is washed with water, dehydrated, and dried to obtain an unmodified conjugated diene rubber. Note that, during coagulation, the latex and an extender oil that has been previously made into an emulsified dispersion may be mixed as necessary, and the product may be recovered as an oil-extended unmodified conjugated diene rubber.
  • the modified compound used in the manufacturing method (1) is not particularly limited, but from the viewpoint of improving the adhesiveness of the coated fiber, it is preferable to use a compound having a hydrogen-bonding functional group.
  • the hydrogen-bonding functional group include the same as those described above. Among them, from the viewpoint of the strength of the hydrogen bonding force, an amino group, an imidazole group, a urea group, a hydroxy group, a mercapto group, a silanol group, an aldehyde group, a carboxy group, and a derivative thereof are preferable. As a derivative of a carboxy group, a salt thereof, an ester thereof, an amidation thereof, or an acid anhydride thereof is preferable.
  • These modified compounds having a hydrogen-bonding functional group may be used alone or in combination of two or more kinds.
  • the modified compounds include, for example, unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid; unsaturated carboxylic anhydrides such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and itaconic anhydride; unsaturated carboxylic esters such as maleic acid esters, fumaric acid esters, citraconic acid esters, and itaconic acid esters; unsaturated carboxylic amides such as maleic acid amides, fumaric acid amides, citraconic acid amides, and itaconic acid amides; unsaturated carboxylic imides such as maleic acid imides, fumaric acid imides, citraconic acid imides, and itaconic acid imides; vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, mercaptomethyl methyl dienes, Examples of silane compounds include mercaptomethyltri
  • the amount of the modified compound used is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, and even more preferably 1 to 30 parts by mass, per 100 parts by mass of the unmodified conjugated diene rubber.
  • the reaction temperature is usually preferably 0 to 200°C, more preferably 50 to 200°C.
  • the amount of the modified compound added to the modified conjugated diene rubber is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 1.5 to 20 parts by mass, per 100 parts by mass of the unmodified conjugated diene rubber.
  • the amount of the modified compound added to the modified conjugated diene rubber can be calculated based on the acid value of the modified compound, or can be determined using various analytical instruments such as infrared spectroscopy and nuclear magnetic resonance spectroscopy. Note that since it is difficult to uniformly measure the amount of the modified compound added using a specific measurement method, it is necessary to select an appropriate analysis method depending on the type of modified compound used.
  • the method of adding the modifying compound to the unmodified conjugated diene rubber is not particularly limited, and examples thereof include a method of adding a liquid unmodified conjugated diene rubber, one or more modifying compounds selected from unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, silane compounds, etc., and further adding a radical generator as necessary, and heating the mixture in the presence or absence of an organic solvent.
  • a radical generator used, and commercially available organic peroxides, azo compounds, hydrogen peroxide, etc. can be used.
  • the organic solvent used in the above method generally includes hydrocarbon solvents and halogenated hydrocarbon solvents, and among these, hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene are preferred.
  • the above-mentioned modifying compound may be grafted onto an unmodified conjugated diene rubber to introduce a hydrogen-bonding functional group, and then a modifying compound capable of reacting with the functional group may be added to introduce another hydrogen-bonding functional group into the polymer.
  • a modifying compound capable of reacting with the functional group may be added to introduce another hydrogen-bonding functional group into the polymer.
  • maleic anhydride may be grafted onto an unmodified conjugated diene rubber obtained by living anionic polymerization, and then the rubber may be reacted with a compound having a hydroxyl group, such as 2-hydroxyethyl methacrylate or methanol, or with a compound such as water.
  • an antioxidant may be added from the viewpoint of suppressing side reactions, etc.
  • the antioxidant a commercially available one can be used, and examples thereof include butylated hydroxytoluene (BHT), N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (Nocrac 6C), etc.
  • the amount of the antioxidant added is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the unmodified conjugated diene rubber.
  • the amount of the antioxidant added is within the above range, side reactions can be suppressed, and the modified conjugated diene rubber can be obtained in good yield.
  • the production method (2) includes a method of obtaining an oxidized conjugated diene rubber having a functional group or bond containing oxygen generated by an oxidation reaction in the molecule by oxidizing an unmodified conjugated diene rubber as a raw material.
  • the functional group or bond include a hydroxy group, an aldehyde group, a carbonyl group, a carboxy group, an ether bond, etc.
  • the unmodified conjugated diene rubber can be obtained by the same method as the production method (1).
  • Examples of the method for oxidizing the raw material conjugated diene rubber include a method of heat treating the raw material conjugated diene rubber at a temperature equal to or higher than the oxidation temperature (hereinafter also referred to as “production method (2-1)”), a method of irradiating the raw material conjugated diene rubber with light having an absorption wavelength to activate the raw material conjugated diene rubber and reacting it with oxygen (hereinafter also referred to as "production method (2-2)”), etc.
  • the method of heat treating the raw material conjugated diene rubber at a temperature equal to or higher than the oxidation temperature is preferred.
  • the stage at which the oxidation reaction of the conjugated diene rubber is carried out is not particularly limited, and may be carried out before mixing the conjugated diene rubber with oil, after mixing the conjugated diene rubber with oil, or after adhering the conjugated diene rubber and oil in a mixed state to the fibers.
  • the production method (2-1) is a method in which an unmodified conjugated diene rubber as a raw material is heat-treated at a temperature equal to or higher than the oxidation temperature in an atmosphere containing oxygen, preferably in an air atmosphere.
  • the heat treatment temperature is not particularly limited as long as it is a temperature at which the raw material conjugated diene rubber is oxidized, but from the viewpoint of increasing the reaction rate of the oxidation and improving productivity, the temperature is preferably 150° C. or higher, more preferably 170° C. or higher, and even more preferably 190° C. or higher.
  • the temperature is preferably 240° C. or lower, and more preferably 220° C. or lower, from the viewpoint of preventing deterioration of the fiber.
  • the heat treatment time is not particularly limited as long as the raw material conjugated diene rubber is not deteriorated, but is preferably 30 minutes or less, more preferably 20 minutes or less. From the viewpoint of sufficiently oxidizing the unmodified conjugated diene rubber, the heat treatment time is preferably 1 second or more, more preferably 10 seconds or more, and even more preferably 30 seconds or more.
  • the temperature required for the oxidation reaction can be lowered by adding a thermal radical generator to the raw material conjugated diene rubber.
  • thermal radical generator examples include peroxides, azo compounds, redox initiators, etc. Among them, peroxides are preferred from the viewpoint that the thermal radical generator bonds with the conjugated diene rubber and a structure containing oxygen is added to the conjugated diene rubber.
  • peroxides examples include t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctanoate, t-butyl peroxyneodecanoate, t-butyl peroxyisobutyrate, lauroyl peroxide, t-amyl peroxypivalate, t-butyl peroxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, and ammonium persulfate.
  • azo compound examples include azobisisobutyronitrile (AIBN), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-butanenitrile), 4,4'-azobis(4-pentanoic acid), 1,1'-azobis(cyclohexanecarbonitrile), 2-(t-butylazo)-2-cyanopropane, and 2,2'-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]propane.
  • AIBN azobisisobutyronitrile
  • 2,2'-azobis(isobutyronitrile) 2,2'-azobis(2-butanenitrile)
  • 1,1'-azobis(cyclohexanecarbonitrile) 2-(t-butylazo)-2-cyanopropane
  • thermal radical generators may be used alone or in combination of two or more.
  • a redox initiator may also be used as the thermal radical generator.
  • the redox initiator include a combination of persulfate, acidic sodium sulfite, and ferrous sulfate, a combination of t-butyl hydroperoxide, acidic sodium sulfite, and ferrous sulfate, and a combination of p-menthane hydroperoxide, ferrous sulfate, sodium ethylenediaminetetraacetate, and sodium formaldehyde sulfoxylate.
  • the production method (2-2) is a method in which the raw material unmodified conjugated diene rubber is activated by being irradiated with light having an absorption wavelength thereof, and reacted with oxygen.
  • the production method (2-2) is carried out in an atmosphere containing oxygen, preferably in an air atmosphere.
  • the wavelength of the light used is not particularly limited as long as it is absorbed by the raw material conjugated diene rubber to cause a radical reaction, but ultraviolet light that is strongly absorbed by the raw material conjugated diene rubber is preferred.
  • a photoradical generator to the raw material conjugated diene rubber, the amount of light irradiation required for the oxidation reaction can be reduced.
  • the photoradical generators include, for example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4,4'-dimethoxybenzophenone, benzoin propyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydro
  • the photoradical generator include bis-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamin
  • the production method (3) includes a method in which a conjugated diene monomer and a radically polymerizable compound having a hydrogen-bonding functional group are randomly copolymerized, block copolymerized, or graft copolymerized by a known method.
  • the radical polymerizable compound having hydrogen-bonding functional group used in the manufacturing method (3) is not particularly limited as long as it is a compound having both hydrogen-bonding functional group and reactive multiple bond in the molecule.
  • Specific examples thereof include aldehyde having reactive multiple bond, acetalized product of the aldehyde; monocarboxylic acid having reactive multiple bond, salt of the monocarboxylic acid, esterified product of the monocarboxylic acid, acid anhydride of the monocarboxylic acid; dicarboxylic acid having reactive multiple bond, salt of the dicarboxylic acid, esterified product of the dicarboxylic acid, acid anhydride of the dicarboxylic acid; and amine compound having reactive multiple bond.
  • aldehydes having a reactive carbon-carbon double bond examples include acrolein, methacrolein, crotonaldehyde, 3-butenal, 2-methyl-2-butenal, 2-methyl-3-butenal, 2,2-dimethyl-3-butenal, 3-methyl-2-butenal, 3-methyl-3-butenal, 2-pentenal, 2-methyl-2-pentenal, 3-pentenal, 3-methyl-2 ...butenal, 3-methyl-2-butenal, 3-methyl-2-butenal, 3-methyl-2-butenal, 3-methyl-2-butenal, 3-methyl-2-butenal, 3-methyl-2-butenal, 3-methyl-2-butenal, 3-methyl-butenal, 3-methyl-butenal, 3-methyl-butenal, 3-methyl-butenal, 3-methyl-butenal, 3-methyl-butenal, 3-methyl-butenal, 3-methyl-butenal, 3-methyl-tenal, 3-methyl- Tyl-4-pentenal, 4-pentenal, 4-methyl-4-penten
  • examples of acetalized products of aldehydes having a reactive carbon-carbon double bond include acetalized products of the aldehydes, specifically 3-(1,3-dioxalan-2-yl)-3-methyl-1-propene, which is an acetalized product of 2-methyl-3-butenal, and 3-(1,3-dioxalan-2-yl)-2-methyl-1-propene, which is an acetalized product of 3-methyl-3-butenal.
  • aldehydes having multiple bonds and acetalized products of the aldehydes examples of aldehydes having a reactive carbon-carbon triple bond and acetalized products thereof include aldehydes having a carbon-carbon triple bond such as propioaldehyde, 2-butyn-1-al, and 2-pentyn-1-al, and acetalized products of the aldehydes.
  • aldehydes having a reactive carbon-carbon double bond are preferred, such as acrolein, methacrolein, crotonaldehyde, 3-butenal, 2-methyl-2-butenal, 2-methyl-3-butenal, 2,2-dimethyl-3-butenal, 3-methyl-2-butenal, 3-methyl-3-butenal, 2- At least one selected from pentenal, 2-methyl-2-pentenal, 3-pentenal, 3-methyl-4-pentenal, 4-pentenal, 4-methyl-4-pentenal, 2-hexenal, 3-hexenal, 4-hexenal, 5-hexenal, 7-octenal, 2-ethylcrotonaldehyde, 3-(dimethylamino)acrolein, and 2,4-pentadienal is preferred.
  • Examples of the monocarboxylic acid having a multiple bond, the salt of the monocarboxylic acid, the ester of the monocarboxylic acid, and the acid anhydride of the monocarboxylic acid include (meth)acrylic acid, the sodium salt of (meth)acrylic acid, the potassium salt of (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, vinyl (meth)acrylate, 2-(trifluoromethyl)-2-propanediol ...
  • (fluoromethyl)acrylic acid methyl 2-trifluoromethylacrylate, ethyl 2-trifluoromethylacrylate, propyl 2-trifluoromethylacrylate, 2-butyl 2-trifluoromethylacrylate, 2-hydroxyethyl 2-trifluoromethylacrylate, vinyl 2-trifluoromethylacrylate, methyl cinnamate, vinyl cinnamate, methyl crotonate, vinyl crotonate, methyl 3-methyl-3-butenoate, vinyl 3-methyl-3-butenoate, vinyl 3-methyl-3-butenoate, methyl 4-pentenoate, vinyl 4-pentenoate, methyl 2-methyl-4-pentenoate, vinyl 2-methyl-4-pentenoate, methyl 5-hexenoate, vinyl 5-hexenoate, methyl 3,3-dimethyl-4-pentenoate, 3,3 -dimethyl-4-pentenoic acid vinyl, methyl 7-octenoic acid, vinyl 7-octenoic acid, methyl trans-3
  • the dicarboxylic acids having multiple bonds, the salts of the dicarboxylic acids, the esterified products of the dicarboxylic acids, and the acid anhydrides of the dicarboxylic acids include, for example, dicarboxylic acids having reactive carbon-carbon double bonds, the salts of the dicarboxylic acids, the esterified products of the dicarboxylic acids, and the acid anhydrides of the dicarboxylic acids, such as maleic acid, sodium maleate, potassium maleate, methyl maleate, dimethyl maleate, maleic anhydride, itaconic acid, methyl itaconate, dimethyl itaconate, itaconic anhydride, himic acid, methyl himic acid, dimethyl himic acid, and himic anhydride.
  • dicarboxylic acids having reactive carbon-carbon double bonds such as maleic acid, sodium maleate, potassium maleate, methyl maleate, dimethyl maleate, maleic anhydride, itaconic acid, methyl itaconate, dimethyl ita
  • the salt of the monocarboxylic acid, the ester of the monocarboxylic acid, the monocarboxylic anhydride, the dicarboxylic acid having a multiple bond, the salt of the dicarboxylic acid, the ester of the dicarboxylic acid, and the anhydride of the dicarboxylic acid a compound having a reactive carbon-carbon double bond is preferred, and among them, one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, vinyl (meth)acrylate, (meth)acrylic anhydride, 2-(trifluoromethyl)acrylic anhydride, cinnamic anhydride, crotonic anhydride, methyl maleate, dimethyl maleate, maleic anhydride, methyl itaconate, dimethyl itaconate, and itaconic anhydride are more preferred because of their good reactivity during copolymer
  • examples of amine compounds having a reactive carbon-carbon double bond include allylamine, 3-butenylamine, 4-pentenylamine, 5-hexenylamine, 6-heptenylamine, 7-octenylamine, oleylamine, 2-methylallylamine, 4-aminostyrene, 4-vinylbenzylamine, 2-allylglycine, S-allylcysteine, ⁇ -allylalanine, 2-allylaniline, geranylamine, vigabatrin, 4-vinylaniline, and 4-vinyloxyaniline.
  • one or more selected from allylamine, 3-butenylamine, and 4-pentenylamine are preferred because of their good reactivity during copolymerization.
  • the production method (4) is a method in which a modifying compound capable of reacting with the polymerization active terminal is added to a polymerized product of an unmodified conjugated diene monomer having a polymerization active terminal (unmodified conjugated diene rubber) before adding a polymerization terminator.
  • the unmodified conjugated diene rubber having a polymerization active terminal can be obtained by polymerizing a conjugated diene monomer and, if necessary, other monomers other than the conjugated diene, for example, by emulsion polymerization or solution polymerization, as in the production method (1).
  • Examples of the modifying compound that can be used in the production method (4) include modifying agents such as dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylene diisocyanate, carbon dioxide, ethylene oxide, succinic anhydride, 4,4'-bis(diethylamino)benzophenone, N-vinylpyrrolidone, N-methylpyrrolidone, 4-dimethylaminobenzylideneaniline, and dimethylimidazolidinone, or other modifying agents described in JP2011-132298A.
  • modifying agents such as dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetragly
  • the amount of the modifying compound used is preferably 0.01 to 100 molar equivalents relative to the organic alkali metal compound, for example, when the polymerization is carried out using an organic alkali metal compound.
  • the reaction temperature is usually ⁇ 80 to +150° C., preferably 0 to 100° C., and more preferably 10 to 90° C.
  • the modifying compound may be added before the addition of the polymerization terminator to introduce a hydrogen-bonding functional group into the unmodified conjugated diene rubber, and then a modifying compound capable of reacting with the functional group may be added to introduce another hydrogen-bonding functional group into the polymer.
  • the modified conjugated diene rubber may contain units derived from other monomers than the conjugated diene monomer and the radical polymerizable compound having a hydrogen-bonding functional group, so long as the units do not impair adhesion.
  • examples of other monomers include copolymerizable ethylenically unsaturated monomers and aromatic vinyl compounds, and the specific compounds and contents are the same as those described above.
  • the weight average molecular weight (Mw) of the conjugated diene rubber is not particularly limited, but it is preferable to include at least a low molecular weight conjugated diene rubber in the following range.
  • the weight average molecular weight of the low molecular weight conjugated diene rubber is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, even more preferably 4,000 or more, even more preferably 5,000 or more, and may be 7,000 or more from the viewpoint of improving adhesiveness, and is preferably 26,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, even more preferably 12,000 or less, and even more preferably 10,000 or less from the viewpoint of handleability.
  • the weight average molecular weight is preferably 1,000 to 26,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 15,000, even more preferably 4,000 to 12,000, even more preferably 5,000 to 10,000, and even more preferably 7,000 to 10,000.
  • a preferred embodiment of the coating in the coated fiber of the present invention is one that contains two or more different conjugated diene rubbers.
  • “different types of conjugated diene rubbers” means that at least one of the physical properties or characteristics, such as the type of monomer unit contained, the presence or absence of functional groups (presence or absence of modification), the type and number of functional groups, weight average molecular weight, number average molecular weight, etc., is different.
  • the number average molecular weight (Mn) of the conjugated diene rubber is not particularly limited, but from the viewpoint of improving adhesion, it is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 2,500 or more, even more preferably 3,000 or more, and even more preferably 3,500 or more, and from the viewpoint of handleability, it is preferably 20,000 or less, more preferably 18,000 or less, and even more preferably 15,000 or less. More specifically, the number average molecular weight is preferably 1,000 to 20,000, more preferably 2,000 to 18,000, even more preferably 2,500 to 15,000, even more preferably 3,000 to 15,000, and even more preferably 3,500 to 15,000.
  • the Mw and Mn of the conjugated diene rubber are the weight average molecular weight and number average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC), and specifically, can be determined by the method described in the examples.
  • the weight average molecular weight and number average molecular weight of the conjugated diene rubber can be adjusted to desired values by adjusting the type and amount of the solvent in the production method.
  • the molecular weight distribution (Mw/Mn) of the conjugated diene rubber is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, even more preferably 1.0 to 2.0, even more preferably 1.0 to 1.5, and particularly preferably 1.0 to 1.3.
  • Mw/Mn refers to the ratio of the weight average molecular weight (Mw)/number average molecular weight (Mn) calculated in terms of standard polystyrene, determined by GPC measurement.
  • the conjugated diene rubber is preferably in a liquid state.
  • liquid indicates that the melt viscosity of the conjugated diene rubber measured at 38 ° C. is 4,000 Pa ⁇ s or less.
  • the melt viscosity is preferably 0.1 Pa ⁇ s or more, more preferably 0.5 Pa ⁇ s or more, and even more preferably 1.0 Pa ⁇ s or more, and from the viewpoint of handleability, it is preferably 2,000 Pa ⁇ s or less, more preferably 1,500 Pa ⁇ s or less, and even more preferably 1,000 Pa ⁇ s or less.
  • the melt viscosity measured at 38 ° C. is preferably 0.1 to 4,000 Pa ⁇ s, more preferably 0.1 to 2,000 Pa ⁇ s, more preferably 0.5 to 1,500 Pa ⁇ s, and even more preferably 1.0 to 1,000 Pa ⁇ s.
  • the melt viscosity of the conjugated diene rubber means a viscosity measured at 38° C. using a Brookfield viscometer (B-type viscometer), and specifically, it can be determined by the method described in the examples.
  • the glass transition temperature (Tg) of conjugated diene rubber may vary depending on the vinyl content of the conjugated diene units, the type of conjugated diene, the content of units derived from monomers other than the conjugated diene, etc., but is preferably -100 to +10°C, more preferably -100 to 0°C, and even more preferably -100 to -5°C. If the Tg is within the above range, high viscosity can be suppressed and handling becomes easy. Tg can be determined by the method described in the examples.
  • the vinyl content of the conjugated diene rubber is preferably 80 mol% or less, more preferably 50 mol% or less, and even more preferably 30 mol% or less.
  • the lower limit of the vinyl content may be 0 mol%, and the vinyl content may be 0 mol%.
  • the "vinyl content” means the total mol % of conjugated diene units bonded via 1,2-bonds or 3,4-bonds (conjugated diene units bonded via a bond other than 1,4-bonds) out of a total of 100 mol % of conjugated diene units contained in a conjugated diene rubber.
  • the vinyl content can be calculated from the integral ratio of a signal derived from conjugated diene units bonded via 1,2-bonds or 3,4-bonds to a signal derived from conjugated diene units bonded via 1,4-bonds using 1H-NMR.
  • the content of the conjugated diene rubber in the water-based adhesive described below is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 25% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less. More specifically, the content of the conjugated diene rubber in the water-based adhesive described below is preferably 0.1 to 25% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, and even more preferably 1 to 5% by mass. When the content of the conjugated diene rubber in the water-based adhesive is within the above range, it is possible to prevent the viscosity of the water-based adhesive from becoming extremely high while obtaining sufficient adhesive strength.
  • the adhesive composition contains a crosslinking agent.
  • a crosslinking agent even when a low molecular weight conjugated diene rubber is used, the low molecular weight conjugated diene rubbers can be bonded together via a covalent bond, and the conjugated diene rubber and the fiber can be bonded via a covalent bond.
  • a crosslinking agent even when the temperature becomes high during vulcanization, the above-mentioned conjugated diene rubber is less likely to be absorbed by the rubber to be adhered (adherend), so that sufficient adhesive strength can be exhibited.
  • a crosslinking agent in the present invention excellent adhesiveness to an adherend made of a highly polar rubber can be exhibited.
  • a crosslinking agent in the present invention the convergence of the coated fiber can be improved, and the strength after friction can also be improved.
  • crosslinking agent used in the present invention is a compound capable of forming a covalent bond with both the conjugated diene rubber and the fiber, and examples thereof include epoxy resins, isocyanate resins, oxazoline group-containing resins, carbodiimide group-containing resins, amino resins, and polyester resins.
  • epoxy resins isocyanate resins
  • oxazoline group-containing resins oxazoline group-containing resins
  • carbodiimide group-containing resins amino resins
  • polyester resins one or more selected from the group consisting of epoxy resins and isocyanate resins are preferred, and it is more preferred to use epoxy resins and isocyanate resins in combination.
  • the content of the crosslinking agent is preferably 0.01% by mass or more in the water-based adhesive described later, more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, in order to suppress the absorption of the conjugated diene rubber into the rubber to be adhered and to improve the adhesive strength. More specifically, the content of the crosslinking agent is preferably 0.01 to 15% by mass in the water-based adhesive described later, more preferably 0.5 to 10% by mass, and even more preferably 0.8 to 5% by mass.
  • the crosslinking agent in the water-based adhesive If the content of the crosslinking agent in the water-based adhesive is equal to or greater than the lower limit, the crosslinking agent reacts with the conjugated diene rubber to suppress the absorption of the conjugated diene rubber into the elastomer. In addition, the convergence of the coated fiber can be improved, and the strength after friction can also be improved. On the other hand, if the content of the crosslinking agent in the water-based adhesive is equal to or less than the upper limit, the adhesive strength of the adhesive composition can be prevented from becoming excessively high.
  • the content of the crosslinking agent per 100 parts by mass of the conjugated diene rubber is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 45 parts by mass or more, and preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less, from the viewpoint of improving adhesion to the rubber. More specifically, in the water-based adhesive described below, the content of the crosslinking agent per 100 parts by mass of the conjugated diene rubber is preferably 10 to 100 parts by mass, more preferably 30 to 90 parts by mass, and even more preferably 45 to 80 parts by mass.
  • the adhesive composition further contains an oil having a vapor pressure of 10 Pa or less at 20 ° C.
  • the oil does not volatilize for a long period of time even after the adhesive composition is applied to the surface of the fiber, so that the adhesive composition is less likely to cause coating unevenness, and therefore the adhesiveness of the adhesive composition can be improved and contamination of the manufacturing equipment during production can be suppressed.
  • the conjugated diene rubber is used in combination with an oil having a vapor pressure of 10 Pa or less at 20 ° C., the convergence of the coated fiber is also improved. From these viewpoints, the vapor pressure of the oil at 20 ° C.
  • the vapor pressure of oil at 20° C. refers to a value calculated from an optimum curve obtained by applying the Antoine equation to a measured value measured by a gas flow method.
  • the oil having a vapor pressure of 10 Pa or less at 20° C. that can be used in the present invention is not particularly limited as long as it is compatible with the conjugated diene rubber, and examples of the oil include natural oils and synthetic oils.
  • examples of the natural oil include mineral oils and vegetable oils.
  • mineral oils include paraffinic mineral oils, aromatic mineral oils, and naphthenic mineral oils obtained by conventional refining methods such as solvent refining and hydrogenation refining, as well as wax produced by the Fischer-Tropsch process (gas-to-liquid wax) and mineral oils produced by isomerizing wax.
  • paraffinic mineral oils include the "Diana Process Oil” series manufactured by Idemitsu Kosan Co., Ltd. and the “Super Oil” series manufactured by JX Nippon Oil & Energy Corporation.
  • vegetable oils include linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, camellia oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, cottonseed oil, coconut oil, palm kernel oil, and rice bran oil.
  • Examples of synthetic oils include hydrocarbon synthetic oils, ester synthetic oils, and ether synthetic oils.
  • Examples of hydrocarbon synthetic oils include ⁇ -olefin oligomers such as polybutene, polyisobutylene, 1-octene oligomers, 1-decene oligomers, and ethylene-propylene copolymers, or hydrogenated products thereof, alkylbenzenes, and alkylnaphthalenes.
  • Examples of ester synthetic oils include triglycerin fatty acid esters, diglycerin fatty acid esters, monoglycerin fatty acid esters, monoalcohol fatty acid esters, and polyhydric alcohol fatty acid esters.
  • ether synthetic oils include polyoxyalkylene glycols and polyphenyl ethers.
  • commercially available synthetic oils include the "Linearene” series manufactured by Idemitsu Kosan Co., Ltd., and "FGC32", “FGC46”, and “FGC68” manufactured by ANDEROL.
  • triglycerol fatty acid esters, phthalic acid esters, and adipic acid esters are preferred, and 2-ethylhexanoic acid triglyceride and adipic acid esters are more preferred.
  • the oil may be one selected from the above natural oils and synthetic oils, or a mixture of two or more natural oils, two or more synthetic oils, or one or more natural oils and one or more synthetic oils.
  • mineral oils are preferred, and one or more oils selected from paraffinic mineral oils and naphthenic mineral oils are more preferred.
  • the flash point of the oil used in the present invention is preferably 70°C or higher from the viewpoint of safety. From this viewpoint, the flash point of the oil is more preferably 100°C or higher, even more preferably 130°C or higher, and even more preferably 140°C or higher. There is no particular upper limit to the flash point of the oil, but it is preferably 320°C or lower.
  • the oil content in the water-based adhesive described below is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 25% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. More specifically, the oil content in the water-based adhesive described below is preferably 0.1 to 25% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, and even more preferably 2 to 10% by mass.
  • the content of oil per 100 parts by mass of conjugated diene rubber is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and even more preferably 70 parts by mass or more, and is preferably 300 parts by mass or less, more preferably 280 parts by mass or less, and even more preferably 250 parts by mass or less, from the viewpoint of improving adhesion to the rubber and improving the convergence of the coated fiber. More specifically, in the water-based adhesive described below, the content of oil per 100 parts by mass of conjugated diene rubber is preferably 50 to 300 parts by mass, more preferably 60 to 280 parts by mass, and even more preferably 70 to 250 parts by mass.
  • a surfactant may be used to prepare an emulsion containing the conjugated diene rubber.
  • the surfactant used in the present invention is not particularly limited, and examples thereof include cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants. Among these, nonionic surfactants are preferred from the viewpoint of compatibility between the adhesive composition and the rubber.
  • nonionic surfactants include polyoxyalkylene type nonionic surfactants such as higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, styrenated phenol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol aliphatic ester alkylene oxide adducts, higher alkylamine alkylene oxide adducts, and fatty acid amide alkylene oxide adducts, as well as polyhydric alcohol type nonionic surfactants such as alkylglycoxides and sucrose fatty acid esters. These nonionic surfactants may be used alone or, if necessary, in combination of two or more. Commercially available nonionic surfactants include "Adetol TN100", “Adetol PC-6", “Adetol PC-8", “Adetol PC-10", and “Adetol SO-80" manufactured by ADEKA CORPORATION.
  • cationic surfactants examples include alkyl ammonium acetate salts, alkyl dimethyl benzyl ammonium salts, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl pyridinium salts, oxyalkylene alkyl amines, polyoxyalkylene alkyl amines, etc. These cationic surfactants may be used alone or, if necessary, in combination of two or more kinds.
  • anionic surfactant examples include carboxylates such as fatty acid soaps, higher alcohol sulfates, higher alkyl polyalkylene glycol ether sulfates, sulfates of styrenated phenol alkylene oxide adducts, sulfates of alkylphenol alkylene oxide adducts, sulfated oils, sulfated fatty acid esters, sulfated fatty acids, sulfated olefins, and other sulfate esters, alkylbenzene sulfonates, alkylnaphthalene sulfonates, naphthalene sulfonates, formalin condensates such as naphthalene sulfonic acid, ⁇ -olefin sulfonates, paraffin sulfonates, sulfonates such as sulfosuccinic acid diesters, and higher alcohol phosphates.
  • zwitterionic surfactants examples include alkyl carboxybetaines.
  • the HLB (Hydrophilic-Lipophilic Balance) value of the nonionic surfactant is preferably 6 to 17.
  • the HLB value is within the above range, a coated fiber having good compatibility with conjugated diene rubber and oil and good adhesion to rubber can be obtained.
  • the adhesive composition is attached to the fiber as an emulsion.
  • the lower limit of the HLB value is more preferably 8 or more, and even more preferably 10 or more.
  • the upper limit of the HLB value is more preferably 16 or less, and even more preferably 14 or less.
  • the HLB value is an index showing the balance between hydrophilicity and lipophilicity, and is expressed as a value from 0 to 20.
  • the HLB value can be calculated by the following formula (I) based on the Griffin method.
  • HLB value 20 x sum of formula weights of hydrophilic parts / molecular weight (I)
  • the nonionic surfactant can be identified by detecting and measuring the molecular weight and constitutional units using mass spectrometry, and by detecting and measuring the structure using 1 H and 13 C-NMR, and the structure can be identified based on these, so that the HLB value can be calculated using the identified information using formula (I).
  • a method for separating the nonionic surfactant from the adhesive composition for example, a method of fractionating and isolating the surfactant by reverse phase liquid chromatography can be mentioned.
  • the content of the surfactant in the emulsion is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of the conjugated diene rubber.
  • the method for producing the emulsion there is no particular limitation on the method for producing the emulsion, and it is preferable to prepare the emulsion by a mechanical method or a chemical method, and then dilute it to a desired concentration for use.
  • mechanical methods include methods using a homogenizer, a homomixer, a disperser mixer, a colloid mill, a pipeline mixer, a high-pressure homogenizer, an ultrasonic emulsifier, etc., which can be used alone or in combination.
  • Examples of chemical methods include inversion emulsification, D-phase emulsification, HLB temperature emulsification, gel emulsification, and liquid crystal emulsification, among which the inversion emulsification is preferred from the viewpoint of easily obtaining an emulsion having a fine particle size.
  • alkaline substances such as sodium hydroxide, potassium hydroxide, and amines can be added as necessary to adjust the pH.
  • the amount of the alkaline substance per 100 parts by mass of the conjugated diene rubber in the emulsion is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, from the viewpoint of improving the stability of the emulsion.
  • the adhesive composition preferably has a viscosity measured at 50°C of 500 Pa ⁇ s or less.
  • the adhesive composition can be efficiently attached to the fibers, and the adhesive composition is less likely to adhere to the manufacturing equipment, so that contamination of the manufacturing equipment can be suppressed.
  • the adhesive composition preferably has a viscosity measured at 50°C of 250 Pa ⁇ s or less, more preferably 100 Pa ⁇ s or less, and even more preferably 80 Pa ⁇ s or less.
  • the viscosity may be preferably 0.01 Pa ⁇ s or more, more preferably 0.03 Pa ⁇ s or more, and even more preferably 0.05 Pa ⁇ s or more. More specifically, the adhesive composition preferably has a viscosity measured at 50°C of 0.01 to 250 Pa ⁇ s, more preferably 0.03 to 100 Pa ⁇ s, and even more preferably 0.05 to 80 Pa ⁇ s.
  • the viscosity of the adhesive composition at 50° C. means a viscosity measured using a Brookfield viscometer (B-type viscometer) at 50° C. The rotor and the rotation speed during the measurement are appropriately set so as to be close to the full scale.
  • the adhesive composition of the present invention may contain other components other than the conjugated diene rubber, oil, crosslinking agent, surfactant, and alkaline substance, within the range that does not impair the adhesion to rubber.
  • the other components include water, other polymers, acids, antioxidants, curing agents, dispersants, pigments, dyes, adhesion aids, carbon black, and the like.
  • the content thereof is preferably 10,000 parts by mass or less, more preferably 1,000 parts by mass or less, even more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 25 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the conjugated diene rubber.
  • the coating in the present invention is formed, for example, by attaching an aqueous adhesive containing an emulsion containing the conjugated diene rubber, a crosslinking agent, water, and other components as necessary to a fiber, and then drying and heat treating the aqueous adhesive to form a coating containing the adhesive composition and/or a reaction product of the adhesive composition on the surface of the fiber.
  • the method for producing the water-based adhesive is not particularly limited, and the water-based adhesive can be produced by mixing each component. Specifically, the water-based adhesive can be obtained by mixing the emulsion containing the conjugated diene rubber, the crosslinking agent, water, and other components as necessary, by a known method.
  • the water-based adhesive may be a one-component system or a two-component system, but a one-component system is preferable.
  • a one-component system not only saves space in production equipment, but also reduces the environmental impact by shortening the processing steps.
  • the adhesive composition used in the present invention can obtain a coated fiber having excellent adhesion to rubber even if it does not contain formaldehyde or a resin made from formaldehyde, which is harmful to the human body.
  • the adhesive composition contains a resin made from formaldehyde
  • examples of the resin include resorcinol/formaldehyde resin, phenol/formaldehyde resin, melamine/formaldehyde resin, and derivatives thereof.
  • the adhesive composition contains the formaldehyde component (formaldehyde and a resin made from formaldehyde), the content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, particularly more preferably 1 part by mass or less, and particularly preferably substantially none, relative to 100 parts by mass of the conjugated diene rubber.
  • the content of the formaldehyde component can be measured by extracting the adhesive composition from the coated fiber with a solvent such as toluene, and then using HPLC or the like.
  • fibers used for the coated fiber of the present invention hydrophilic fibers are preferred from the viewpoint of affinity with the adhesive composition.
  • the term "fiber” includes not only short fibers and long fibers, but also nonwoven fabrics, woven fabrics, knitted fabrics, felts, sponges, and other forms.
  • hydrophilic synthetic fibers include synthetic fibers made of a thermoplastic resin having hydrophilic functional groups such as hydroxyl groups, carboxyl groups, sulfonic acid groups, and amino groups, and/or hydrophilic bonds such as amide bonds.
  • thermoplastic resins include polyvinyl alcohol-based resins, polyamide-based resins (aliphatic polyamides such as polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, and polyamide 9C (a polyamide composed of nonanediamine and cyclohexanedicarboxylic acid); semi-aromatic polyamides synthesized from aromatic dicarboxylic acids and aliphatic diamines, such as polyamide 9T (a polyamide composed of nonanediamine and terephthalic acid); wholly aromatic polyamides synthesized from aromatic dicarboxylic acids and aromatic diamines, such as polyparaphenylene terephthalamide), and polyacrylamide-based resins).
  • hydrophilic synthetic fibers may be used alone or in combination of two or more. These hydrophilic synthetic fibers may be further subjected to a hydrophilization treatment to be described later in order to further enhance the hydrophilicity.
  • hydrophilic natural fibers include natural cellulose fibers such as wood pulp, e.g., kraft pulp, and non-wood pulp, e.g., cotton pulp and straw pulp.
  • Hydrophilic regenerated fibers include regenerated cellulosic fibers such as rayon, lyocell, cupra, and polynosic. These natural fibers and regenerated fibers may be used alone or in combination of two or more. These hydrophilic natural fibers and regenerated fibers may be further subjected to a hydrophilization treatment described later in order to further enhance the hydrophilicity.
  • Hydrophilic fibers only need to have hydrophilic surfaces, and may be, for example, hydrophobic fibers whose surfaces have been treated to make them hydrophilic, or core-sheath composite fibers in which the core is made of a hydrophobic resin and the sheath is made of a hydrophilic resin.
  • hydrophilic resins that make up the sheath see the descriptions of hydrophilic synthetic fibers.
  • hydrophobic fibers made of hydrophobic resins include polyolefin fibers such as polyethylene and polypropylene, polyester fibers such as polyethylene terephthalate, and wholly aromatic polyester fibers, and among these, polyester fibers are preferred.
  • the hydrophilization treatment is not particularly limited as long as it is a treatment that chemically or physically imparts hydrophilic functional groups to the fiber surface.
  • it can be performed by modifying the hydrophobic fiber made of the hydrophobic resin with a compound or a derivative thereof that contains a hydrophilic functional group such as an isocyanate group, an epoxy group, a hydroxyl group, an amino group, an ether group, an aldehyde group, a carbonyl group, a carboxyl group, or a urethane group, or by modifying the surface by electron beam irradiation.
  • hydrophilic fibers used in the present invention from the viewpoint of being used as covering fibers, synthetic fibers and regenerated fibers are preferred, and among them, one or more types selected from the group consisting of polyamide-based fibers, polyvinyl alcohol-based fibers, polyester-based fibers, and regenerated cellulose-based fibers are preferred.
  • hydrophilic fibers particularly when the conjugated diene rubber contained in the adhesive composition is a modified conjugated diene rubber, a strong affinity effect with the hydrophilic fibers is exhibited and the adhesive composition and the hydrophilic fibers are firmly bound to each other, thereby making it possible to improve the adhesive strength to the rubber.
  • a polyvinyl alcohol-based fiber having a single fiber fineness of about 0.1 to 30 dtex that is commercially available from Kuraray Co., Ltd. under the product name "Vinylon" can be suitably used.
  • the fibers may be used alone or in combination of two or more kinds.
  • the fibers used in the coated fiber of the present invention may be monofilament or multifilament, with multifilament being preferred.
  • the single yarn fineness is preferably 30 to 20,000 dtex, more preferably 100 to 10,000 dtex, and even more preferably 300 to 5,000 dtex.
  • the single yarn fineness is preferably 0.1 to 30.0 dtex, more preferably 0.5 to 15.0 dtex, and even more preferably 1.0 to 10.0 dtex, and the total fineness is preferably 50 to 10,000 dtex, more preferably 100 to 6,000 dtex, and even more preferably 250 to 4,500 dtex.
  • the method for producing the coated fiber of the present invention is not particularly limited, but the coated fiber of the present invention is preferably obtained by adhering an aqueous adhesive containing the conjugated diene rubber to the fiber and then heating it. More specifically, the coated fiber of the present invention is more preferably obtained by a method including a step of adhering to a fiber an aqueous adhesive which is a mixture of an emulsion of the conjugated diene rubber, the oil, and the surfactant, a crosslinking agent, water, and other components as necessary, and a step of adhering the aqueous adhesive to the fiber, followed by drying and heating.
  • an aqueous adhesive which is a mixture of an emulsion of the conjugated diene rubber, the oil, and the surfactant, a crosslinking agent, water, and other components as necessary
  • a coated fiber by a method in which the aqueous adhesive is applied to the fiber and then heated, because the adhesive composition formed by drying the aqueous adhesive on the fiber surface further reacts with heat to generate a reaction product, and a coating containing the reaction product covers the fiber.
  • the reaction product is preferably one in which conjugated diene rubbers are bonded together via a crosslinking agent, and/or one in which the conjugated diene rubber and the fiber are bonded together via a crosslinking agent, and more specifically, the reaction product is preferably one in which conjugated diene rubbers are bonded together via a crosslinking agent, and/or one in which the conjugated diene rubber and the crosslinking agent are bonded together, and by bonding these reaction products to the fiber, the adhesive composition is more firmly fixed to the fiber surface, and the adhesion to the rubber is improved.
  • the reaction product when the reaction product includes one in which the conjugated diene rubbers are bonded together via a crosslinking agent, the reaction product contains a crosslinked body of an appropriate molecular weight, and the process contamination resistance is improved while maintaining adhesion. Furthermore, when the reaction product contains the conjugated diene rubber and the fiber bonded via a crosslinking agent (more specifically, when the reaction product contains the conjugated diene rubber and a crosslinking agent bonded together and the adhesive composition is more firmly fixed to the fiber surface), adhesion to rubber in particular is improved.
  • method (I) comprises forming a coating containing one or more selected from the group consisting of the adhesive composition and reaction products of the adhesive composition on the surface of the fiber.
  • the method (I) is preferably a method including the following step I-1, but it is not limited to water-based adhesives, and other solvent-based (organic solvent-based) adhesives can also be used.
  • Step I-1 A step of attaching a water-based adhesive to the surface of the fiber
  • the method for applying the aqueous adhesive to the fibers is not particularly limited, and examples thereof include a method in which the aqueous adhesive is applied as is, and a method in which a solvent is added to the aqueous adhesive as necessary.
  • the method for applying the water-based adhesive is preferably one or more methods selected from immersion, roll coater, oiling roller, oiling guide, nozzle (spray) application, brush application, and the like.
  • the coated fiber of the present invention can be obtained by applying the aqueous adhesive to the fiber and then allowing it to settle at room temperature of about 20° C. for about 3 to 10 days, but in some cases, the following step I-2 may be carried out.
  • Step I-2 A step of heat treating the fiber to which the aqueous adhesive obtained in step I-1 is attached.
  • the heat treatment in step I-2 is preferably carried out at a treatment temperature of 100 to 200° C. for a treatment time of 0.1 seconds to 2 minutes. Since the conjugated diene rubber contained in the adhesive composition has reactive multiple bonds, the heat treatment in the presence of oxygen is preferably at 200° C. or less, and more preferably at 175° C. or less.
  • the heat treatment temperature is within the above range, the conjugated diene rubber does not react excessively, and a coated fiber that satisfies the above conditions (1) and (2) can be obtained, and as a result, a coated fiber having excellent adhesion to rubber can be obtained.
  • the heat treatment time is preferably 90 seconds or less, more preferably 60 seconds or less, and even more preferably 45 seconds or less, and may be 0.1 seconds or more, 0.2 seconds or more, or 0.5 seconds or more.
  • the amount of the coating attached is preferably 0.01 to 10.0 parts by mass, more preferably 0.1 to 5.0 parts by mass, and even more preferably 1.0 to 3.0 parts by mass, per 100 parts by mass of the fiber used as the raw material, from the viewpoint of improving the adhesion between the coated fiber and the rubber.
  • the coated fiber of the present invention comprises the fiber and a coating containing the adhesive composition and/or its reaction product.
  • the coating in the coated fiber of the present invention may contain other components in addition to the adhesive composition and/or its reaction product. Examples of other components include crosslinkers, acids, bases, inorganic salts, organic salts, pigments, dyes, antioxidants, polymerization initiators, plasticizers, etc.
  • the total content of the fiber and the adhesive composition and/or its reaction product in the coated fiber is preferably 80 mass % or more, more preferably 90 mass % or more, and even more preferably 95 mass % or more, from the viewpoints of improving adhesion to rubber and reinforcing strength.
  • the content of the coating in the coated fiber of the present invention is preferably 0.1 to 20.0 parts by mass, more preferably 0.3 to 15.0 parts by mass, and even more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the fiber.
  • the content of the coating in the coated fiber can be determined by the method described in the Examples. From the viewpoint of more easily achieving the effects of the present invention, the total content of the adhesive composition and/or its reaction product in the coating is preferably 1 to 100% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 60% by mass. From the same viewpoint, the content of the conjugated diene rubber in the coating is preferably 1 to 90% by mass, more preferably 5 to 75% by mass, and even more preferably 10 to 50% by mass. The content of the conjugated diene rubber in the coating can be determined by the method described in the Examples.
  • the coated fiber is preferably a raw fiber having a single filament fineness of 0.1 to 30 dtex, and more preferably a multifilament.
  • the raw fiber may have a single filament fineness of less than 0.1 dtex, but is preferably 0.1 dtex or more because of the difficulty of industrial production. If the raw fiber has a single filament fineness of 30 dtex or less, the surface area of the fiber when made into a coated fiber is increased, improving adhesion to rubber.
  • the coated fiber of the present invention is preferably a multifilament, and has a single filament fineness of preferably 0.3 dtex or more, more preferably 0.5 dtex or more, and even more preferably 1 dtex or more, and preferably 20 dtex or less, more preferably 15 dtex or less, and even more preferably 10 dtex or less. More specifically, the covered fiber of the present invention preferably has a single filament fineness of the raw fiber of 0.3 to 20 dtex, more preferably 0.5 to 15 dtex, and even more preferably 1 to 10 dtex.
  • the rubber adhesion of the coated fiber of the present invention is preferably 15.0 N/25.4 mm or more, more preferably 20.0 N/25.4 mm or more, even more preferably 25.0 N/25.4 mm or more, even more preferably 30.0 N/25.4 mm or more, and usually 200 N/25.4 mm or less. More specifically, the rubber adhesion of the coated fiber of the present invention is preferably 15.0 to 200 N/25.4 mm, more preferably 20.0 to 200 N/25.4 mm, even more preferably 25.0 to 200 N/25.4 mm, even more preferably 30.0 to 200 N/25.4 mm.
  • the rubber adhesion of the coated fiber is equal to or greater than the lower limit, woven fabrics, knitted fabrics, and molded articles having excellent reinforcing strength can be obtained.
  • the rubber adhesion of the coated fiber can be measured by the method described in the Examples.
  • the coated fiber of the present invention can be used in any shape, but is preferably used in the form of a fiber cord, woven fabric, knitted fabric, etc., which contains at least a portion of the coated fiber, and is more preferably used as a woven fabric or knitted fabric which contains at least a portion of the coated fiber.
  • a fiber cord woven fabric, knitted fabric, etc.
  • it can be used as a knitted fabric to be bonded to rubber.
  • It can also be used as a coated fiber to be embedded in resin, cement, etc.
  • the molded article of the present invention is not particularly limited as long as it uses the coated fiber.
  • a molded article using the coated fiber and a rubber component (hereinafter also referred to as a "rubber molded article") is particularly preferred, since the coated fiber has excellent adhesion to rubber.
  • the coated fiber used in the rubber molded article is preferably used as a woven or knitted fabric at least partially containing the coated fiber, and more preferably used as a laminate in which a reinforcing layer made of a woven or knitted fabric at least partially containing the coated fiber and a rubber layer are laminated.
  • the rubber molded article can be used as a component of rubber products such as tires, e.g., automobile tires, belts, e.g., conveyor belts, timing belts, hoses, and vibration-proof rubber. Among these, it is more preferable to use the rubber molded article as a tire, a belt, or a hose.
  • the present invention can be used for various members, such as belts, carcass plies, breakers, bead tapes, etc., which are made of composite materials of coated fibers and rubber components.
  • the hose can be used for the purpose of transporting various fluids in various applications, and is suitable, for example, as a hose for transporting fluids in automobiles.
  • the hose it is preferable to use the hose as a hose for liquid fuels in automobiles, a brake oil hose, and a hose for refrigerants in automobiles, and it is more preferable to use the hose as a brake oil hose in automobiles.
  • the rubber molded article is preferably molded using the coated fiber and a rubber composition obtained by compounding a rubber component with compounding agents normally used in the rubber industry.
  • the rubber component is not particularly limited, and examples thereof include NR (natural rubber), IR (polyisoprene rubber), BR (polybutadiene rubber), SBR (styrene-butadiene rubber), NBR (nitrile rubber), EPM (ethylene-propylene copolymer rubber), EPDM (ethylene-propylene-non-conjugated diene copolymer rubber), IIR (butyl rubber), halogenated butyl rubber, and CR (chloroprene rubber).
  • NR IR
  • BR IR
  • SBR IR
  • EPDM CR
  • CR CR
  • EPDM CR
  • These rubber components may be used alone or in combination of two or more.
  • natural rubber alone or in combination of natural rubber and SBR.
  • the mass ratio of natural rubber to SBR is preferably in the range of 50/50 to 90/10, from the viewpoint of suppressing deterioration of physical properties due to reversion of rubber.
  • the natural rubber includes, for example, natural rubber commonly used in the tire industry, such as TSR (Technically Specified Rubber) such as SMR (TSR made in Malaysia), SIR (TSR made in Indonesia), and STR (TSR made in Thailand), and RSS (Ribbed Smoked Sheet), as well as modified natural rubber such as high-purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, hydrogenated natural rubber, and grafted natural rubber.
  • TSR Technicalnically Specified Rubber
  • SMR SIR
  • STR Tintered Smoked Sheet
  • modified natural rubber such as high-purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, hydrogenated natural rubber, and grafted natural rubber.
  • the SBR may be any of those commonly used in tires, but specifically, the styrene content is preferably 0.1 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 15 to 35% by mass.
  • the vinyl content is preferably 0.1 to 60% by mass, and even more preferably 0.1 to 55% by mass.
  • the weight average molecular weight (Mw) of the SBR is preferably 100,000 to 2,500,000, more preferably 150,000 to 2,000,000, and even more preferably 200,000 to 1,500,000. Within the above range, both processability and mechanical strength can be achieved.
  • the weight average molecular weight of the SBR is the weight average molecular weight calculated in terms of polystyrene and determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the SBR may be modified SBR having a functional group introduced therein, as long as the effect of the present invention is not impaired. Examples of the functional group include an amino group, an alkoxysilyl group, a hydroxy group, an epoxy group, and a carboxy group.
  • the rubber composition may further contain a filler in addition to the rubber component.
  • a filler examples include inorganic fillers such as carbon black, silica, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fiber, fibrous filler, and glass balloons; and organic fillers such as resin particles, wood powder, fibrous filler, and cork powder.
  • inorganic fillers such as carbon black, silica, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, titanium oxide, glass fiber, fibrous filler, and glass balloons
  • organic fillers such as resin particles, wood powder, fibrous filler, and cork powder.
  • the carbon black examples include furnace black, channel black, thermal black, acetylene black, and ketjen black. Among these carbon blacks, furnace black is preferred from the viewpoint of improving the crosslinking rate and mechanical strength.
  • the average particle size of the carbon black is preferably 5 to 100 nm, more preferably 5 to 80 nm, and even more preferably 5 to 70 nm.
  • the average particle size of the carbon black can be determined by measuring the diameter of the particles using a transmission electron microscope and calculating the average value.
  • silica examples include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc. Among these silicas, wet silica is preferred.
  • the average particle size of the silica is preferably from 0.5 to 200 nm, more preferably from 5 to 150 nm, and even more preferably from 10 to 100 nm. The average particle size of the silica can be determined by measuring the diameter of the particles using a transmission electron microscope and calculating the average value.
  • the amount of the filler per 100 parts by mass of the rubber component is preferably 20 to 150 parts by mass, more preferably 25 to 130 parts by mass, and further preferably 25 to 110 parts by mass.
  • the content thereof is preferably 20 to 120 parts by mass, more preferably 20 to 90 parts by mass, and further preferably 20 to 80 parts by mass, based on 100 parts by mass of the rubber component.
  • the rubber composition may further contain a crosslinking agent to crosslink the rubber component.
  • a crosslinking agent examples include sulfur, sulfur compounds, oxygen, organic peroxides, phenolic resins, amino resins, quinones and quinone dioxime derivatives, halogen compounds, aldehyde compounds, alcohol compounds, epoxy compounds, metal halides and organometallic halides, and silane compounds.
  • These crosslinking agents may be used alone or in combination of two or more.
  • the content of the crosslinking agent is usually 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.8 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • the rubber composition may further contain a vulcanization accelerator, for example, when sulfur or a sulfur compound is contained as a crosslinking agent for crosslinking (vulcanizing) the rubber component.
  • a vulcanization accelerator for example, when sulfur or a sulfur compound is contained as a crosslinking agent for crosslinking (vulcanizing) the rubber component.
  • the vulcanization accelerator include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamic acid compounds, aldehyde-amine compounds, aldehyde-ammonia compounds, imidazoline compounds, and xanthate compounds. These vulcanization accelerators may be used alone or in combination of two or more.
  • the content of the vulcanization accelerator is usually 0.1 to 15 parts by mass, and preferably 0.1 to 10 parts by mass, per 100 parts by mass of the rubber component.
  • the rubber composition may further contain a vulcanization aid.
  • the vulcanization aid include fatty acids such as stearic acid, metal oxides such as zinc oxide, and fatty acid metal salts such as zinc stearate. These vulcanization aids may be used alone or in combination of two or more.
  • the content of the vulcanization aid is usually 0.1 to 15 parts by mass, and preferably 1 to 10 parts by mass, per 100 parts by mass of the rubber component.
  • the rubber composition contains silica as a filler
  • the rubber composition further contains a silane coupling agent, such as a sulfide compound, a mercapto compound, a vinyl compound, an amino compound, a glycidoxy compound, a nitro compound, or a chloro compound.
  • silane coupling agents may be used alone or in combination of two or more.
  • the silane coupling agent is preferably contained in an amount of 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, based on 100 parts by mass of silica. When the content of the silane coupling agent is within the above range, dispersibility, coupling effect, and reinforcing property are improved.
  • the rubber composition may contain, as needed, a resin component as a softener, such as silicone oil, aromatic oil, TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solvates), RAE (Residual Aromatic Extracts), process oil such as paraffin oil or naphthenic oil, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, C9 resin, rosin resin, coumarone-indene resin, or phenolic resin, for the purpose of improving processability, fluidity, etc., within a range that does not impair the effects of the present invention.
  • a resin component such as a softener, such as silicone oil, aromatic oil, TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solvates), RAE (Residual Aromatic Extracts), process oil such as paraffin oil or naphthenic oil, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, C9 resin, rosin resin,
  • the rubber composition may contain additives such as antiaging agents, waxes, antioxidants, lubricants, light stabilizers, scorch inhibitors, processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, matting agents, antiblocking agents, UV absorbers, release agents, foaming agents, antibacterial agents, antifungal agents, and fragrances, as necessary, to improve weather resistance, heat resistance, oxidation resistance, and the like, within a range that does not impair the effects of the present invention.
  • antioxidants include hindered phenol compounds, phosphorus compounds, lactone compounds, and hydroxyl compounds.
  • antiaging agents include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds, and phosphorus compounds. These additives may be used alone or in combination of two or more.
  • the coated fiber is embedded in the unvulcanized rubber composition, and the rubber composition is vulcanized to obtain a molded article in which the fiber and rubber component are bonded via the adhesive composition and/or its reaction product.
  • the brake oil hose for automobiles may, for example, have an inner rubber layer and an outer rubber layer, with one or two reinforcing layers made of the coated fiber between the inner and outer rubber layers.
  • the rubber components constituting the inner rubber layer and the outer rubber layer include those mentioned above. Among them, examples of the rubber components constituting the inner rubber layer include EPDM, SBR, etc., and examples of the rubber components constituting the outer rubber layer include EPDM, CR, etc.
  • the reinforcing layer can be formed by braiding a coated fiber. In the method for producing the brake oil hose, a reinforcing layer (first reinforcing layer) made by braiding the coated fiber is formed on the outer surface of the inner rubber layer.
  • an intermediate rubber layer may be further formed on the outer surface of the first reinforcing layer, and a reinforcing layer (second reinforcing layer) made by braiding the coated fiber may be formed on the outer surface of the intermediate rubber layer. Then, the outer rubber layer is formed on the outer surface of the reinforcing layer (first reinforcing layer or second reinforcing layer), and the hose is vulcanized to produce the brake oil hose.
  • the vulcanization temperature can be appropriately selected depending on the type of constituent materials of each layer of the brake oil hose, but it is preferable that the vulcanization temperature be 200°C or lower from the viewpoint of suppressing deterioration of the rubber and the covering fiber and improving the adhesive strength between the rubber and the covering fiber.
  • Production Example 1 Production of modified conjugated diene rubber (A-1) A thoroughly dried 5L autoclave was purged with nitrogen, and 1260g of hexane and 132g of n-butyllithium (17% by mass hexane solution) were charged. The temperature was raised to 50°C, and then 1260g of butadiene was successively added under stirring conditions while controlling the polymerization temperature to 50°C, and polymerization was carried out for 1 hour. Methanol was then added to terminate the polymerization reaction, and a polymer solution was obtained. Water was added to the obtained polymer solution and stirred, and the polymer solution was washed with water.
  • A-1 A thoroughly dried 5L autoclave was purged with nitrogen, and 1260g of hexane and 132g of n-butyllithium (17% by mass hexane solution) were charged. The temperature was raised to 50°C, and then 1260g of butadiene was successively added under stirring conditions while controlling the polymerization temperature to
  • Production Example 2 Production of modified conjugated diene rubber (A-2) A thoroughly dried 5L autoclave was purged with nitrogen, and 1260g of hexane and 90.0g of n-butyllithium (17% by mass hexane solution) were charged. The temperature was raised to 50°C, and then 1260g of butadiene was successively added under stirring conditions while controlling the polymerization temperature to 50°C, and polymerization was carried out for 1 hour. Methanol was then added to terminate the polymerization reaction, and a polymer solution was obtained. Water was added to the obtained polymer solution and stirred, and the polymer solution was washed with water. After stopping the stirring and confirming that the polymer solution phase and the water phase were separated, the water was separated.
  • A-2 modified conjugated diene rubber
  • the polymer solution after washing was vacuum dried at 70°C for 24 hours to obtain an unmodified liquid polybutadiene (A'-2).
  • 500 g of the unmodified liquid polybutadiene (A'-2) was charged into a 1 L autoclave that had been purged with nitrogen, and 25 g of maleic anhydride and 0.5 g of N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (trade name "Nocrac 6C", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) were added and reacted at 170°C for 24 hours to obtain maleic anhydride modified liquid polybutadiene.
  • Production Example 3 Production of modified conjugated diene rubber (A-3) A thoroughly dried 5L autoclave was purged with nitrogen, and 1260g of hexane and 28.0g of n-butyllithium (17% by mass hexane solution) were charged. The temperature was raised to 50°C, and then 1260g of butadiene was successively added under stirring conditions while controlling the polymerization temperature to 50°C, and polymerization was carried out for 1 hour. Methanol was then added to terminate the polymerization reaction, and a polymer solution was obtained. Water was added to the obtained polymer solution and stirred, and the polymer solution was washed with water. After stopping the stirring and confirming that the polymer solution phase and the water phase were separated, the water was separated.
  • A-3 A thoroughly dried 5L autoclave was purged with nitrogen, and 1260g of hexane and 28.0g of n-butyllithium (17% by mass hexane solution) were charged. The temperature was raised to 50°C,
  • the polymer solution after washing was vacuum dried at 70°C for 24 hours to obtain an unmodified liquid polybutadiene (A'-3).
  • 500 g of the unmodified liquid polybutadiene (A'-3) was charged into a 1 L autoclave that had been purged with nitrogen, and 25 g of maleic anhydride and 0.5 g of N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (trade name "Nocrac 6C", manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) were added and reacted at 170°C for 24 hours to obtain maleic anhydride modified liquid polybutadiene.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw/Mn molecular weight distribution
  • melt viscosity of the conjugated diene rubber at 38° C. was measured by a Brookfield viscometer (manufactured by BROOKFIELD ENGINEERING LABS. INC.).
  • the average number of hydrogen-bonding functional groups per molecule of the modified conjugated diene rubber was calculated from the equivalent weight (g/eq) of the hydrogen-bonding functional groups of the modified conjugated diene rubber and the number average molecular weight Mn in terms of styrene by the following formula.
  • Average number of hydrogen-bonding functional groups per molecule [(number average molecular weight (Mn))/(molecular weight of styrene unit) ⁇ (average molecular weight of conjugated diene and other monomer units other than conjugated diene contained as necessary)]/(equivalent weight of hydrogen-bonding functional group)
  • Mn number average molecular weight
  • styrene unit molecular weight of conjugated diene and other monomer units other than conjugated diene contained as necessary
  • the method for calculating the equivalent weight of the hydrogen-bonding functional group was appropriately selected depending on the type of the hydrogen-bonding functional group.
  • the average number of hydrogen-bonding functional groups per molecule of the monomethyl maleate-modified conjugated diene rubber was calculated by determining the acid value of the monomethyl maleate-modified conjugated diene rubber and calculating the equivalent weight (g/eq) of the hydrogen-bonding functional groups from the acid value.
  • the sample after the modification reaction was washed four times with methanol (5 mL per 1 g of sample) to remove impurities such as antioxidants, and then the sample was dried under reduced pressure for 12 hours at 80° C.
  • Acid value (mgKOH/g) (AB) x F x 5.611/S
  • the mass of the hydrogen-bonding functional group contained in 1 g of the monomethyl maleate-modified conjugated diene rubber was calculated according to the following formula, and the mass other than the functional group (polymer main chain mass) contained in 1 g of the monomethyl maleate-modified conjugated diene rubber was calculated. Then, the equivalent weight (g/eq) of the hydrogen-bonding functional group was calculated according to the following formula.
  • EHTG 2-ethylhexanoic acid triglyceride
  • HLB value 12.4,
  • Preparation Example 2 Preparation of emulsion (E-2) of modified conjugated diene rubber (A-2) An emulsion (E-2) of a mixture of modified conjugated diene rubber (A-2) and oil was obtained in the same manner as in Preparation Example 1, except that the type of modified conjugated diene rubber used was A-2.
  • Preparation Example 3 Preparation of emulsion (E-3) of modified conjugated diene rubber (A-3) An emulsion (E-3) of a mixture of modified conjugated diene rubber (A-3) and oil was obtained in the same manner as in Preparation Example 1, except that the type of modified conjugated diene rubber used was A-3.
  • Preparation Example 4 Preparation of emulsion (E-4) of modified conjugated diene rubber (A-2) An emulsion (E-4) of a mixture of modified conjugated diene rubber (A-2) and oil was obtained in the same manner as in Preparation Example 2, except that the surfactant used was two types of nonionic surfactants (product names "Adekator TN-40" and "Adekator LB-53B", ADEKA Corporation).
  • Preparation Example 5 Preparation of emulsion (E-5) by mixing two kinds of modified conjugated diene rubbers (A-2, A-3) An emulsion (E-5) of a mixture of two kinds of modified conjugated diene rubbers (A-2, A-3) and oil was obtained in the same manner as in Preparation Example 1, except that the types of modified conjugated diene rubbers used were two kinds, A-2 and A-3, and 12.5 g of A-2 and 37.5 g of A-3 were used.
  • Preparation Example 6 Preparation of emulsion (E-6) of two kinds of modified conjugated diene rubbers (A-2, A-3) mixed together An emulsion (E-6) of a mixture of two kinds of modified conjugated diene rubbers (A-2, A-3) and oil was obtained in the same manner as in Preparation Example 5, except that the amounts of the two kinds of modified conjugated diene rubbers A-2 and A-3 used were 37.5 g for A-2 and 12.5 g for A-3.
  • Preparation Example 7 Preparation of emulsion (E-7) of unmodified conjugated diene rubber (L-1) An emulsion (E-7) of a mixture of unmodified conjugated diene rubber (L-1) and oil was obtained in the same manner as in Preparation Example 1, except that unmodified conjugated diene rubber L-1 was used instead of the modified conjugated diene rubber.
  • Example 1 The emulsion (E-1) prepared by the above method was mixed with an isocyanate compound (product name "SU268-A”, manufactured by Meisei Chemical Industry Co., Ltd.), an epoxy resin (product name “Denacol EX-512", manufactured by Nagase ChemteX Corporation) and water so as to have the composition shown in Table 2, to prepare a water-based adhesive (AD-1). Next, polyvinyl alcohol (PVA) fibers (product name "Kuralon 1239", total fineness 1330 dtex, single filament fineness 6.65 dtex, Kuraray Co., Ltd.) were immersed in the obtained aqueous adhesive, and the liquid was squeezed out with a roller.
  • PVA polyvinyl alcohol
  • the obtained fiber was then dried at 115°C for 30 seconds, and further heat-treated at 150°C for 30 seconds, and then wound up to produce a PVA fiber coated with a coating containing one or more selected from the group consisting of adhesive compositions and/or reactants of adhesive compositions.
  • Examples 2 to 7 and Comparative Examples 1 to 3> A PVA fiber coated with a coating material was prepared in the same manner as in Example 1, except that the composition of the water-based adhesive was changed according to the description in Table 2.
  • the coated fiber to which the adhesive composition was applied was sampled at a length of 100 m, and its mass was measured.
  • the fineness (unit: dtex) of the coated fiber to which the adhesive composition was applied was calculated by (mass (unit: g) of 100 m length of fiber) ⁇ 100.
  • THF tetrahydrofuran
  • the extract was concentrated with an evaporator, vacuum dried at 40°C for 16 hours, and then dissolved in THF again to adjust the concentration to 0.1 w/v%.
  • GPC analysis was performed under the following conditions.
  • the molecular weight distribution curve obtained from the RI detector was obtained by using polymethyl methacrylate (PMMA) as a calibration curve standard and the analysis software attached to the analyzer.
  • the obtained detection data was cut out and analyzed in the range of detection times of 8.1 to 10.6 minutes.
  • ⁇ GPC analysis conditions Measurement equipment: OMNISEC RESOLVE, OMNISEC REVEAL (Malvern) Sample concentration: 0.1 w/v% Mobile phase solvent: THF Injection volume: 100 ⁇ L Flow rate: 1.0mL/min Measurement temperature: 40°C Filter filtration: 0.45 ⁇ m filter column: KF806L (Shodex) Detector: RI detector included with the device. Calibration material: PMMA Analysis software: OMNISEC software
  • Peak analysis In the molecular weight distribution curve obtained by GPC analysis, it was judged whether or not there was a peak in the molecular weight range of 2,600 to 19,000, and if there was a peak, the molecular weight was calculated.
  • EPDM rubber 100 parts by mass Filler (carbon black): 60 parts by mass Softener (paraffin-based process oil): 20 parts by mass Crosslinking agent (sulfur powder): 1.5 parts by mass Vulcanization aid (zinc oxide type 2, stearic acid): 6 parts by mass Vulcanization accelerator (thiazole-based, thiuram-based): 1.5 parts by mass
  • the coated fibers (multifilament with a total fineness of 1330 dtex and a single yarn fineness of 6.65 dtex) produced in Examples 1 to 7 and Comparative Examples 1 to 3 were cut to a length of 120 cm, and then the upper end of the coated fiber was tied to a hook attached to a wall surface and fixed. A weight of 1 kg was tied to the lower end of the fixed coated fiber so that the weight did not contact the ground, and the fiber was suspended in mid-air. The fiber was cut at a position 100 cm from the upper knot of the fiber tied to the wall surface, and the length of the disturbed convergence of the coated fiber was measured from the lower end after cutting. The results are shown in Table 3. In this evaluation, a shorter disturbance length indicates better convergence.
  • the present invention can provide a coated fiber having excellent adhesion to rubber. Furthermore, the present invention can provide a coated fiber having excellent convergence and strength after friction, which can be produced while suppressing contamination of the production equipment, and a molded article using the same. All Examples showed practically effective values for adhesion and residual fiber strength. The convergence, which affects processability, also showed satisfactory values, with Examples 2, 3, and 7 in particular showing excellent convergence.
  • Examples 1 to 4 and 7 which used only low molecular weight conjugated diene rubber as the material, showed smaller and better results than Examples 5 and 6, which contained two types of conjugated diene rubber with different molecular weights, and this was probably due to the influence of high molecular weight conjugated diene rubber, which is presumed to have a more complicated crosslinking structure.
  • Example 4 is an example in which the amount of coating attached was large, but the process contamination was small and showed good results. The adhesion was comparable to other Examples.

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  • Chemical & Material Sciences (AREA)
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PCT/JP2024/017455 2023-05-12 2024-05-10 被覆繊維及びそれを用いた成形体 Ceased WO2024237206A1 (ja)

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Publication number Priority date Publication date Assignee Title
JPS544976A (en) 1977-06-13 1979-01-16 Mitsuboshi Belting Ltd Bonding of fibers for reinforcing rubbers
JPS582370A (ja) 1981-06-30 1983-01-07 Sumitomo Naugatuck Co Ltd ゴムと繊維の接着剤
JPS60209071A (ja) * 1984-03-26 1985-10-21 株式会社クラレ 繊維処理剤
JP2011132298A (ja) 2009-12-22 2011-07-07 Sumitomo Rubber Ind Ltd 変性共重合体、それを用いたゴム組成物および空気入りタイヤ
WO2020175404A1 (ja) 2019-02-27 2020-09-03 株式会社クラレ 補強繊維及びその製造方法、並びにそれを用いた成形体
WO2021106559A1 (ja) 2019-11-27 2021-06-03 株式会社クラレ 表面改質繊維、補強繊維、及びそれを用いた成形体
WO2022045344A1 (ja) * 2020-08-31 2022-03-03 株式会社クラレ エマルション組成物及びその製造方法
WO2022044460A1 (ja) 2020-08-25 2022-03-03 株式会社クラレ 補強繊維、及びそれを用いた成形体
JP2022040774A (ja) * 2020-08-31 2022-03-11 株式会社クラレ 成形体及びその製造方法
WO2023085413A1 (ja) * 2021-11-15 2023-05-19 株式会社クラレ 水系接着剤、それを用いた補強繊維、及び補強繊維を用いたエラストマー製品

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS544976A (en) 1977-06-13 1979-01-16 Mitsuboshi Belting Ltd Bonding of fibers for reinforcing rubbers
JPS582370A (ja) 1981-06-30 1983-01-07 Sumitomo Naugatuck Co Ltd ゴムと繊維の接着剤
JPS60209071A (ja) * 1984-03-26 1985-10-21 株式会社クラレ 繊維処理剤
JP2011132298A (ja) 2009-12-22 2011-07-07 Sumitomo Rubber Ind Ltd 変性共重合体、それを用いたゴム組成物および空気入りタイヤ
WO2020175404A1 (ja) 2019-02-27 2020-09-03 株式会社クラレ 補強繊維及びその製造方法、並びにそれを用いた成形体
WO2021106559A1 (ja) 2019-11-27 2021-06-03 株式会社クラレ 表面改質繊維、補強繊維、及びそれを用いた成形体
WO2022044460A1 (ja) 2020-08-25 2022-03-03 株式会社クラレ 補強繊維、及びそれを用いた成形体
WO2022045344A1 (ja) * 2020-08-31 2022-03-03 株式会社クラレ エマルション組成物及びその製造方法
JP2022040774A (ja) * 2020-08-31 2022-03-11 株式会社クラレ 成形体及びその製造方法
WO2023085413A1 (ja) * 2021-11-15 2023-05-19 株式会社クラレ 水系接着剤、それを用いた補強繊維、及び補強繊維を用いたエラストマー製品

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Title
See also references of EP4711518A1

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