WO2018003572A1 - Adhesive for organic fiber and method for treating organic fiber - Google Patents

Adhesive for organic fiber and method for treating organic fiber Download PDF

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Publication number
WO2018003572A1
WO2018003572A1 PCT/JP2017/022530 JP2017022530W WO2018003572A1 WO 2018003572 A1 WO2018003572 A1 WO 2018003572A1 JP 2017022530 W JP2017022530 W JP 2017022530W WO 2018003572 A1 WO2018003572 A1 WO 2018003572A1
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WO
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Prior art keywords
component
fiber
adhesive
organic
organic fiber
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PCT/JP2017/022530
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French (fr)
Japanese (ja)
Inventor
細見　哲也
將人 伏木
豊浩 永野
Original Assignee
ナガセケムテックス株式会社
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Application filed by ナガセケムテックス株式会社 filed Critical ナガセケムテックス株式会社
Priority to KR1020187024169A priority Critical patent/KR20190040127A/en
Priority to CN201780032255.8A priority patent/CN109196161A/en
Priority to JP2018525068A priority patent/JPWO2018003572A1/en
Publication of WO2018003572A1 publication Critical patent/WO2018003572A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J197/00—Adhesives based on lignin-containing materials
    • C09J197/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J121/00—Adhesives based on unspecified rubbers
    • C09J121/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09J127/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J197/00—Adhesives based on lignin-containing materials
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives 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
    • 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
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • 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
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • 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
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters 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
    • 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
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone 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
    • D06M15/19—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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde 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
    • D06M15/19—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

Definitions

  • the present invention relates to an adhesive for organic fibers and a method for treating organic fibers.
  • Organic rubber such as polyester fiber is used as a reinforcing material for rubber used for tires, various hoses, and various belts such as timing belts, conveyor belts, and V-belts.
  • an RFL (resorcin / formalin / latex) adhesive containing resorcin, formalin and rubber latex is heat-cured to bond the tire cord, which is an organic fiber, to the tire rubber. It is known to ensure adhesion. Specifically, the RFL adhesive is attached to the organic fiber and heat-cured as this treatment. Before the treatment with the RFL adhesive, the organic fiber is subjected to the same treatment with an epoxy resin. It is also known that the adhesive force is further improved.
  • RFL resorcin / formalin / latex
  • RF resin is inferior in storage stability and therefore has a short usable period and usable period.
  • RF resin is inferior in storage stability and therefore has a short usable period and usable period.
  • the conventional adhesive can improve the blending work environment because it does not contain an RF resin, but it still has a problem of poor storage stability because it contains an epoxy compound as an alternative material.
  • the present invention provides an adhesive for organic fibers that can reduce the amount of formalin used, and exhibits excellent adhesion between organic fibers and rubber and excellent storage stability. Let it be an issue.
  • the first of the present invention is at least one component (A1) selected from the group consisting of polyphenols, chlorophenol resins and lignin resins, and a water-soluble polymer other than the component (A1) or other than the component (A1). It is related with the adhesive for organic fibers characterized by including the at least 1 sort (s) of component (B1) selected from the water-dispersible polymer of this, and substantially not containing the precondensate of resorcin and formalin.
  • the second of the present invention is a mixture (A2) of at least one component selected from the group consisting of polyphenols, chlorophenol resins, and lignin resins, a melamine derivative or hexamethylenetetramine, and other than the component (A2). Or at least one component (B2) selected from water-dispersible polymers other than the component (A2), and substantially free of an initial condensate of resorcin and formalin.
  • the present invention relates to an adhesive for organic fibers.
  • the component (B1) or (B2) contains (b1) ionomer resin, (b2) rubber latex, (b3) acrylic resin, (b4) olefin resin, and (b5) chloride. It is preferably at least one component selected from the group consisting of vinyl resins and (b6) vinyl acetate resins.
  • the organic fiber adhesive preferably contains a blocked isocyanate compound (C).
  • the organic fiber is preferably at least one selected from the group consisting of nylon fiber, rayon fiber, polyester fiber and aramid fiber.
  • the third aspect of the present invention relates to a method for treating organic fibers, including a step of treating organic fibers with the adhesive for organic fibers.
  • 4th of this invention is related with the processing method of an organic fiber including the process of (1) and (2) below.
  • the organic fiber is preferably at least one selected from the group consisting of nylon fiber, rayon fiber, polyester fiber and aramid fiber.
  • 5th of this invention is related with the organic fiber processed by the processing method of the said organic fiber.
  • the sixth aspect of the present invention relates to a tire, a hose or a belt using the organic fiber.
  • the present invention provides an organic fiber adhesive that can reduce the amount of formalin used, exhibits excellent adhesion between organic fibers and rubber, and exhibits excellent storage stability.
  • the first of the adhesives for organic fibers of the present invention is at least one component (A1) selected from the group consisting of polyphenols, chlorophenol resins and lignin resins, and a water-soluble polymer other than the component (A1) or It contains at least one component (B1) selected from water-dispersible polymers other than the component (A1), and does not substantially contain an initial condensate of resorcin and formalin.
  • A1 selected from the group consisting of polyphenols, chlorophenol resins and lignin resins
  • B1 selected from water-dispersible polymers other than the component (A1)
  • the component (A1) is at least one component selected from the group consisting of polyphenols, chlorophenol resins, and lignin resins.
  • Polyphenols broadly include those having a structure having two or more hydroxyl groups on the benzene ring, for example, mononuclear polyhydric phenol compounds such as resorcin, catechol, pyrogallol, phloroglucinol, gallic acid, and chlorogenic acid; Mention may be made of polynuclear polyphenol compounds such as ellagic acid, tannic acid and tannin derivatives.
  • the chlorophenol resin is a compound obtained by co-condensing a chlorophenol monomer and resorcin with formaldehyde.
  • the lignin resin is selected from the group consisting of a lignin derivative obtained by decomposing biomass; a modified product of a lignin derivative; a polymer obtained by polymerizing a lignin derivative or a lignin derivative-modified product; One or more selected from the group consisting of a phenol skeleton, a 2-methoxyphenol skeleton and a 2,6-dimethoxyphenol skeleton.
  • Component (B1) is at least one component selected from water-soluble polymers other than component (A1) or water-dispersible polymers other than component (A1).
  • the component (B1) is not particularly limited as long as it is a water-soluble or water-dispersible polymer. Specifically, for example, (b1) ionomer resin, (b2) rubber latex, (b3) acrylic resin, (B4) Olefin resins, (b5) vinyl chloride resins, (b6) vinyl acetate resins, and the like.
  • the ionomer resin is a copolymer of a monoolefin such as ethylene or propylene and an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, and part of the polymer chain formed by the copolymer.
  • the carboxyl group is a salt formed of a monovalent or divalent metal ion, and the polymer chain is chemically partially cross-linked through the metal ion.
  • Typical metals include Ca, Zn, Mg, Na and the like.
  • the ionomer resin is preferably used as an aqueous dispersion, and the pH of the aqueous dispersion of (b1) ionomer resin is preferably in the range of 7.5 to 13, preferably in the range of 8 to 10. It is more preferable that This is because when (b1) the ionomer resin is partially crosslinked within the range of 7.5 or more and 13 or less, a uniform adhesive layer having high cohesive force can be formed. (B1) When the pH of the aqueous dispersion of ionomer resin is less than 7.5, the state of the aqueous dispersion becomes unstable and gelation tends to occur.
  • (b1) pendant carboxyl groups between the polymer chains of the ionomer resin are not neutralized, and partial chemical crosslinking is eliminated. (B1) When the pH of the aqueous dispersion of the ionomer resin exceeds 13, the viscosity of the aqueous dispersion tends to fluctuate, making it difficult to control the adhesive quality.
  • the weight average molecular weight of the ionomer resin is not particularly limited, but is preferably 10,000 or more and 100,000 or less. If it is less than 10,000, the cohesive strength of the resin may decrease and the adhesive force may decrease, and if it exceeds 100,000, the resulting fiber may become too hard and fatigue resistance may decrease. It is.
  • a weight average molecular weight means the weight average molecular weight of styrene conversion measured by gel permeation chromatography (GPC).
  • (B1) As the ionomer resin, for example, Chemipearl S300 (manufactured by Mitsui Chemicals), Chemipearl S200 (manufactured by Mitsui Chemicals) or the like can be used. These various (b1) ionomer resins can be used alone or in combination of two or more.
  • Rubber latex refers to an emulsion in which a polymer produced by polymerizing natural rubber or a diene monomer is dispersed in water.
  • examples of the rubber latex include natural rubber latex, styrene / butadiene copolymer latex, and styrene / butadiene / vinylpyridine copolymer latex.
  • styrene / butadiene / vinylpyridine copolymer latex is preferable because high adhesive strength can be obtained with respect to natural rubber and styrene butadiene rubber.
  • These various (b2) rubber latexes can be used alone or in combination of two or more.
  • the acrylic resin is a resin obtained by polymerizing a polymerization component containing at least one acrylic monomer.
  • the acrylic monomer include methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isopropyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate or the like can be used.
  • These various (b3) acrylic resins can be used alone or in combination of two or more.
  • the olefin resin is a resin obtained by polymerizing a polymerization component containing at least one olefin monomer.
  • olefin monomer ethylene, propylene, isoprene, butadiene, isobutylene, or the like can be used.
  • ethylene, propylene, isoprene, butadiene, isobutylene, or the like can be used.
  • These various (b4) olefin resins can be used alone or in combination of two or more.
  • the vinyl chloride resin is a resin obtained by polymerizing a polymerization component containing at least one vinyl chloride monomer.
  • vinyl chloride monomers examples include vinyl chloride and vinylidene chloride. These various (b5) vinyl chloride resins can be used alone or in combination of two or more.
  • the vinyl acetate resin is a resin obtained by polymerizing a polymerization component containing at least one vinyl acetate monomer.
  • the vinyl acetate monomer for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate and the like can be used.
  • vinyl acetate resins can be used alone or in combination of two or more.
  • the second of the adhesives for organic fibers of the present invention is a mixture (A2) of at least one component selected from the group consisting of polyphenols, chlorophenol resins and lignin resins, and a melamine derivative or hexamethylenetetramine, and It contains at least one component (B2) selected from water-soluble polymers other than the component (A2) or water-dispersible polymers other than the component (A2), and substantially contains an initial condensate of resorcin and formalin. There is nothing.
  • Component (A2) is a mixture of at least one component selected from the group consisting of polyphenols, chlorophenol resins, and lignin resins, and a melamine derivative or hexamethylenetetramine.
  • a melamine derivative is a compound having a triazine skeleton in the molecule. Any of the polyphenols, the chlorophenol resin, and the lignin resin can be the same as the component (A1).
  • chlorophenol resins and lignin resins
  • resorcin is particularly preferable because it can coexist with a melamine derivative or hexamethylenetetramine so that the curing reaction of the adhesive for organic fibers proceeds and adhesion can be improved.
  • Component (B2) is at least one component selected from water-soluble polymers other than component (A2) or water-dispersible polymers other than component (A2).
  • the component (B2) can be the same as the component (B1), and is not particularly limited as long as it is a water-soluble or water-dispersible polymer.
  • (b1) ionomer resin, (b2) rubber latex, (b3) acrylic resin, (b4) olefin resin, (b5) vinyl chloride resin and (b6) vinyl acetate resin Can be mentioned.
  • Both the first and second organic fiber adhesives of the present invention are substantially free of an initial condensate of resorcin and formalin.
  • the initial condensate of resorcin and formalin is obtained by reacting resorcin and formaldehyde in water in the presence of an acidic catalyst such as hydrochloric acid or sulfuric acid, an alkali metal hydroxide such as sodium hydroxide, or ammonia. It is obtained.
  • an acidic catalyst such as hydrochloric acid or sulfuric acid, an alkali metal hydroxide such as sodium hydroxide, or ammonia. It is obtained.
  • it is not limited to the case where it does not contain at all substantially, but the presence of the unavoidable initial condensate of resorcin and formalin is permitted.
  • an adhesive for organic fibers it is 1% by weight or less.
  • both of the first and second adhesives for organic fibers of the present invention contain a blocked isocyanate compound (C).
  • the blocked isocyanate compound (C) is a compound that is generated by a reaction between an isocyanate compound and a blocking agent, and is temporarily inactivated by a group derived from the blocking agent. When heated at a predetermined temperature, the group derived from the blocking agent Dissociates to form isocyanate groups.
  • isocyanate compound those having two or more isocyanate groups in the molecule can be used.
  • diisocyanates having two isocyanate groups include hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, tolylene diisocyanate, trimethylhexamethylene diisocyanate, metaphenylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, Diphenylpropane diisocyanate, biphenyl diisocyanate, and their isomers, alkyl-substituted products, halides, hydrogenated products to the benzene ring, and the like can be used.
  • triisocyanates having 3 isocyanate groups tetraisocyanates having 4 isocyanate groups
  • polymethylene polyphenyl polyisocyanate, and the like can also be used.
  • isocyanate compounds can be used alone or in combination of two or more.
  • tolylene diisocyanate metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene Polyphenyl polyisocyanate is preferred.
  • Blocking agents include lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propiolactam; phenols such as phenol, cresol, resorcinol, xylenol; methanol, ethanol, n-propyl alcohol, isopropyl Alcohols such as alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol; formamidoxime, acetoaldoxime, Acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexa Oxime such N'okishimu; dimethyl malonate, diethyl malonate, ethyl ace
  • the content of the blocked isocyanate compound (C) is preferably 5 parts by weight or more and 30 parts by weight or less, preferably 10 parts by weight or more with respect to 100 parts by weight of the component (B1) or (B2) in the organic fiber adhesive of the present invention. 20 parts by weight or less is more preferable.
  • gum can be improved. If the amount is less than 5 parts by weight, a sufficient effect of improving adhesiveness cannot be obtained, and if it exceeds 30 parts by weight, the fiber may become too hard or fatigue resistance may be lowered.
  • Content of a block isocyanate compound (C) can be suitably adjusted according to the kind of rubber
  • the solid content concentration of the organic fiber adhesive is preferably 5% by weight to 30% by weight, and more preferably 10% by weight to 25% by weight. This is because higher adhesion to rubber can be obtained. If the amount is less than 5% by weight, the amount of the adhesive for organic fibers attached to the organic fiber is small, and sufficient adhesive strength may not be obtained. If the amount exceeds 30% by weight, the resulting fiber becomes hard and bent. This is because the fatigue strength and the like may be lowered.
  • the adhesive for organic fibers of the present invention is preferably aqueous, that is, contains water or a solvent containing water as a main component.
  • Water or a solvent mainly composed of water dissolves or disperses the component (A1) and the component (B1), or the component (A2) and the component (B2), and uniformly attaches these components to the organic fiber. Functions as a solvent.
  • the organic fiber adhesive according to the present invention may contain the following optional components as necessary within the range not hindering the object and effect of the present invention.
  • a vulcanization regulator for example, zinc white, antioxidant, antifoaming agent, wetting agent and the like can be mentioned.
  • the adhesive for organic fibers according to the present invention can be used for treating various organic fibers.
  • the various organic fibers include fibers usually used as reinforcing materials for tires, various hoses, and belts such as timing belts, conveyor belts, and V belts.
  • the fiber include nylon fiber; rayon fiber; vinylon fiber; polyester fiber such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); aramid fiber; and polyurethane fiber.
  • organic fibers since the mechanical strength can be particularly improved by the treatment with the adhesive for organic fibers of the present invention, at least selected from the group consisting of nylon fibers, rayon fibers, polyester fibers, and aramid fibers. One type is preferably used.
  • the organic fiber according to the present invention may be in the form of filament yarn, cord, woven fabric, woven fabric or the like.
  • nylon fiber for example, two 940 decitex multifilaments are twisted 47 times / 10 cm in total, and then two lower twisted cords are combined to apply the same number of upper twists in the opposite direction to the lower twist. Multiplying can be used.
  • rayon fiber for example, two 1840 dtex multifilaments are twisted 47 times / 10 cm each, and then two lower twisted cords are combined and the same number of upper twists in the opposite direction to the lower twist. Multiplying can be used.
  • polyester fibers include melt spinning of polyethylene terephthalate having a yarn viscosity of 0.95, stretching two 1,500 denier multifilaments, respectively, and twisting them 40 times / 10 cm, and then twisting them. A combination of two cords with the same number of upper twists in the opposite direction to the lower twist may be used.
  • aramid fiber for example, after applying a twist of 35 times / 10 cm in combination of two aromatic polyamide multifilaments (Kevlar manufactured by DuPont) having a display fineness of 1,500 denier and 1,000 filaments, A combination of the two lower twist cords and applying the same number of upper twists in the opposite direction to the lower twist may be used.
  • the processing method of the organic fiber of this invention includes the process processed with the adhesive agent for organic fibers of this invention.
  • Treating organic fibers with an adhesive for organic fibers includes a treatment performed for adhering various components contained in the adhesive for organic fibers to the organic fibers and a subsequent heat treatment.
  • an adhesion method for example, an arbitrary method such as application using a roller, spraying from a nozzle, immersion in a bath solution (adhesive for organic fibers) can be used.
  • a heating method for example, the organic fiber to which the organic fiber adhesive is attached is dried at 100 ° C. or higher and 250 ° C. or lower for 1 minute or longer and 5 minutes or shorter, and further at 150 ° C. or higher and 250 ° C.
  • the heat treatment conditions after the drying treatment are preferably 180 ° C. or higher and 240 ° C. or lower and 1 minute or longer and 2 minutes or shorter.
  • the temperature is too low, the adhesive strength to rubber may be insufficient, and if it is too high, the organic fibers may be deteriorated and cause a decrease in strength.
  • the amount of the organic fiber adhesive of the present invention attached to the organic fiber is 0.1% by weight or more based on the solid content in order to prevent the resulting fiber from becoming too hard while obtaining sufficient adhesive strength. It is preferably 10% by weight or less, and more preferably 1% by weight or more and 7% by weight or less.
  • the unit [wt%] of the adhesion amount is the weight of the solid content obtained by setting the organic fiber weight to 100.
  • a squeezing by a pressure roller In order to adjust the amount of adhesion to the organic fiber, regardless of whether the organic fiber is treated with the adhesive for organic fiber of the present invention, and the first treatment agent and the second treatment agent described later, a squeezing by a pressure roller, a scraper It is also possible to further employ means such as scratching by air, blowing by air blowing, suction, hitting by a beater, and the like.
  • organic fiber processing agents other than the adhesive agent for organic fibers of this invention, before processing with the adhesive agent for organic fibers of this invention.
  • organic fiber processing method include organic fiber processing methods including the following steps (1) and (2). (1) The process of processing organic fiber with the 1st processing agent containing an epoxy compound or a halohydrin compound (2) The organic fiber processed with the 1st processing agent is processed with the 2nd processing agent containing the adhesive agent for organic fibers of this invention.
  • Treating the organic fiber with the first treating agent containing an epoxy compound or a halohydrin compound includes a treatment performed for attaching various components contained in the first treating agent to the organic fiber and a subsequent heat treatment.
  • an attachment method for example, any method such as application using a roller, spraying from a nozzle, immersion in a bath liquid (first treatment agent) can be used.
  • a heating method for example, after drying the organic fiber to which the first treatment agent is attached at 100 ° C. or more and 250 ° C. or less for 1 minute or more and 5 minutes or less, 150 ° C. or more and 250 ° C. or less and 1 minute or more and 5 minutes or less And a method of performing a heat treatment.
  • the heat treatment conditions after the drying treatment are preferably 180 ° C. or higher and 240 ° C. or lower and 2 minutes or longer and 3 minutes or shorter.
  • the temperature is too low, the adhesive strength to rubber may be insufficient, and if it is too high, the organic fibers may be deteriorated and cause a decrease in strength.
  • the epoxy compound is a compound having two or more epoxy groups in the molecule.
  • the epoxy compound is a compound having two or more epoxy groups in the molecule.
  • ethylene glycol glycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether are preferable because of their high water solubility.
  • the first treating agent contains a halohydrin compound or an epoxy compound, but may contain only one of the halohydrin compound or the epoxy compound, or may contain both the halohydrin compound and the epoxy compound.
  • a halohydrin compound refers to a compound having a constituent part bonded to carbon in which a halogen and a hydroxy group are intermingled.
  • halohydrin compound examples include a compound (halohydrin ether compound) obtained by reacting a polyhydric alcohol compound and epihalohydrin under acidic conditions.
  • the polyhydric alcohol refers to an alcohol having two or more hydroxyl groups in the molecule, and is not particularly limited.
  • glycols such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; erythritol, xylitol, sorbitol
  • sugar alcohols such as multirole
  • hydroxycarboxylic acids such as dimethylolbutanoic acid, tartaric acid, and glyceric acid
  • glycerin diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, and pentaerythritol.
  • epihalohydrins examples include epichlorohydrin and epibromohydrin.
  • the reaction between the polyhydric alcohol compound and the epihalohydrin is, for example, by adding an epihalohydrin to the polyhydric alcohol in the presence of a Lewis acid catalyst such as boron trifluoride diethyl ether complex, tin tetrachloride, aluminum chloride, and the like at 50 ° C. or higher. It can be performed in a temperature range of 150 ° C. or lower.
  • a Lewis acid catalyst such as boron trifluoride diethyl ether complex, tin tetrachloride, aluminum chloride, and the like at 50 ° C. or higher. It can be performed in a temperature range of 150 ° C. or lower.
  • sugar alcohols such as sorbitol and a reaction product of polyglycerin and epihalohydrins are preferable because they are multifunctional and highly water-soluble.
  • the concentration of the halohydrin compound or epoxy compound in the first treatment agent is preferably 0.5% by weight or more and 10% by weight or less, more preferably 0.7% by weight or more and 5% by weight or less, as the total concentration of the halohydrin compound and the epoxy compound. preferable. This is because higher adhesion to rubber can be obtained. On the other hand, if it is less than 0.5% by weight, the adhesive strength may be lowered, and if it exceeds 10% by weight, the amount of adhesion to the fiber increases and the fiber may become too hard, which is not preferable.
  • the total solid content concentration of the first treatment agent is preferably 1% by weight or more and 20% by weight or less, and more preferably 2% by weight or more and 10% by weight or less. This is because higher adhesion to rubber can be obtained. If the amount is less than 1% by weight, the amount of adhesion may be insufficient, and sufficient adhesive strength may not be obtained. If the amount exceeds 20% by weight, the amount of the first treatment agent component attached to the organic fiber becomes too large. This is because the fibers may become too hard, or gels may be generated in the fibers and the processing apparatus.
  • resins copolymerizable with epoxy compounds or halohydrin compounds curing agents, organic thickeners, antioxidants, light stabilizers, adhesion improvers, reinforcing agents, softeners , Colorants, leveling agents, flame retardants, antistatic agents and the like.
  • Examples of the resin copolymerizable with the halohydrin compound or epoxy compound include polyvinyl alcohol (PVA), aqueous acrylic resin, aqueous polyurethane resin, and the like.
  • PVA polyvinyl alcohol
  • acrylic resin aqueous acrylic resin
  • polyurethane resin aqueous polyurethane resin
  • curing agent examples include blocked isocyanate compound-modified polyamines, polyamide resins, polymercaptan resins, polysulfide resins, carbodiimides, and the like.
  • the organic fiber adhesive of the present invention is used as the second treating agent, it can be carried out by the same means and conditions as those of the organic fiber treatment method including the step of treating with the organic fiber adhesive of the present invention.
  • the heat treatment condition is preferably 180 ° C. or higher and 240 ° C. or lower and 1 minute or longer and 2 minutes or shorter.
  • the amount of adhesion of the second treatment agent to the organic fiber is 0.1% by weight or more and 10% by weight or less based on the solid content in order to prevent the resulting fiber from becoming too hard while obtaining sufficient adhesive strength. Is preferably 0.5 wt% or more and 5 wt% or less.
  • optional components in the second treating agent include a vulcanization regulator, zinc white, an antioxidant, an antifoaming agent, and a wetting agent.
  • the organic fiber processed by the organic fiber processing method of the present invention can be used for a tire, a hose, a belt, or the like.
  • part or % means “part by weight” or “% by weight”, respectively, unless otherwise specified.
  • Evaluation of adhesive strength in Examples and Comparative Examples was performed by the method shown in Evaluation 1 of adhesive strength or Evaluation 2 of adhesive strength below.
  • Example 1 Among the components (B2), as the rubber latex (b2), 43 g of Nippon 2518FS (manufactured by Nippon Zeon Co., Ltd., vinylpyridine / styrene / butadiene terpolymer aqueous emulsion, total solid concentration: 40.5%) and NIPPOL LX-112 ( 18.5 g of a styrene / butadiene copolymer 41% aqueous emulsion (40.5% total solid concentration, manufactured by Nippon Zeon Co., Ltd.) is diluted with 209 g of water, and resorcinol 3. 4 g and 0.9 g of hexamethylenetetramine were added to prepare a treating agent.
  • Nippon 2518FS manufactured by Nippon Zeon Co., Ltd., vinylpyridine / styrene / butadiene terpolymer aqueous emulsion, total solid concentration: 40.
  • Nylon cords which are nylon fibers (two 940 decitex multifilaments, are combined to prepare a lower twisted cord 47 times / 10 cm as organic fibers. Further, two lower twisted cords are combined and After being immersed in the treatment agent, the upper twist was 47 times / 10 cm in the opposite direction), dried at 150 ° C. for 130 seconds, and subsequently heat treated at 240 ° C. for 70 seconds. About the obtained organic fiber after a process, the adhesive force was measured by the evaluation method shown in Evaluation 1 of adhesive strength. The results are shown in Table 1.
  • Example 2 4.8 g of sorbitol polyglycidyl ether is added to 265 g of water with stirring, and 30.3 g of ⁇ -caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid content concentration 54%) is added thereto as the blocked isocyanate compound (C).
  • One treatment agent was prepared.
  • component (B1) (b2) rubber latex, Nippon 2518FS (manufactured by Nippon Zeon Co., Ltd., vinylpyridine / styrene / butadiene terpolymer aqueous emulsion, total solid concentration 40.5%) 43 g and Nippon LX-112 ( 18.5 g of styrene-butadiene copolymer (41% water emulsion, total solid concentration: 40.5%) manufactured by Nippon Zeon Co., Ltd. was diluted with 209 g of water, and chlorophenol resin was used as component (A1) in this diluted solution. (Denabond (condensate of chlorophenol, formaldehyde and resorcin), Nagase ChemteX Corporation, total solid content concentration 20%) 21.4 g was added to prepare a second treatment agent.
  • Nippon 2518FS manufactured by Nippon Zeon Co., Ltd., vinylpyridine / styrene
  • polyester cord polyethylene terephthalate having a yarn viscosity of 0.95 is melt-spun, and two stretched 1,500 denier multifilaments are combined and twisted 40 times / 10 cm to form a twisted cord.
  • the two twisted cords were prepared, and the same number of upper twists were applied in the opposite direction to the lower twist), and after dipping in the first treatment agent, they were dried at 150 ° C. for 130 seconds, Subsequently, heat treatment was performed at 240 ° C. for 130 seconds. Next, after being immersed in the second treatment agent, it was dried at 150 ° C. for 130 seconds, and subsequently heat-treated at 240 ° C. for 70 seconds.
  • the adhesive force was measured by the evaluation method shown in Evaluation 1 of adhesive strength. The results are shown in Table 2.
  • Example 3 209 g of water in the second treatment agent is added to 226 g, and 21.4 g of chlorophenol resin (denabond (condensate of chlorophenol, formaldehyde and resorcin), manufactured by Nagase ChemteX Corporation, total solid content concentration 20%) is lignin resin (
  • chlorophenol resin denabond (condensate of chlorophenol, formaldehyde and resorcin), manufactured by Nagase ChemteX Corporation, total solid content concentration 20%
  • lignin resin The organic fiber was treated in the same manner as in Example 2 except that the amount was changed to 4.3 g (sodium lignin sulfonate).
  • the adhesive force was measured by the evaluation method shown in Evaluation 1 of adhesive strength. The results are shown in Table 2.
  • Example 4 209 g of water in the second treating agent was added to 226 g, 21.4 g of chlorophenol resin (denabond (condensate of chlorophenol, formaldehyde and resorcin), manufactured by Nagase ChemteX Corporation, total solid content concentration 20%) 2.
  • the organic fiber was treated in the same manner as in Example 2 except that the amount was changed to 4 g and 0.9 g of hexamethylenetetramine.
  • the adhesive force was measured by the evaluation method shown in Evaluation 1 of adhesive strength. The results are shown in Table 2.
  • the treatment of the organic fibers was performed in the same manner as in Example 2, and the adhesion strength of the obtained organic fibers after the treatment was measured by the evaluation method shown in Evaluation 1 of adhesion strength. The results are shown in Table 2.
  • Example 5 4.8 g of sorbitol polyglycidyl ether is added to 352 g of water while stirring, and 26.7 g of an ⁇ -caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid content concentration 54%) is added thereto as the blocked isocyanate compound (C).
  • One treatment agent was prepared.
  • component (B1) 69.7 g of Chemipearl S300 (Mitsui Chemical Co., Ltd., total solid content 35%) as (b1) ionomer resin was diluted with 86 g of water, and component (A1) was diluted into this diluted solution.
  • component (A1) 2.5 g of tannic acid was added as polyphenols, and 2.7 g of 37% formaldehyde aqueous solution and blocked isocyanate compound (C) as an ⁇ -caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid concentration 54%) ) 3.7g was added to prepare a second treating agent.
  • Example 6 Except that 86 g of water in the second treating agent was changed to 76 g and 2.5 g of tannic acid was changed to 12.4 g of chlorophenol resin (Denabond (manufactured by Nagase ChemteX Corporation, total solid content 20%)) 12.4 g.
  • the organic fiber was treated in the same manner as in No. 5. About the obtained organic fiber after a process, the adhesive force was measured by the evaluation method shown in Evaluation 2 of adhesive strength. The results are shown in Table 3.
  • Example 7 The same procedure as in Example 5 was performed except that 2.5 g of tannic acid in the second treatment agent was changed to 2.0 g of resorcin and 0.5 g of hexamethylenetetramine. About the obtained organic fiber after a process, the adhesive force was measured by the evaluation method shown in Evaluation 2 of adhesive strength. The results are shown in Table 3.
  • the treating agent prepared without using the initial condensate of resorcin and formalin in Example 1 is superior to the treating agent containing the initial condensate of resorcin and formalin in Comparative Example 1. Showed good adhesion.
  • the treatment agents prepared without using the initial condensate of resorcin and formalin in Examples 2 to 4 are all the initial condensate of resorcin and formalin in Comparative Example 2.
  • the treatment agent containing the RFL solution to be used excellent adhesion was exhibited.
  • the treatment agent does not contain an RFL solution, the amount of formalin used can be reduced, and the working environment can be improved.
  • component (A1) or component (A2) is used, storage stability is improved. Also excellent.

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Abstract

The purpose of the invention is to provide an adhesive for organic fibers that is capable of reducing the amount of formalin used and that exhibits excellent storage stability and excellent adhesiveness between organic fibers and rubber. Disclosed is an adhesive for organic fibers that is characterized by: including at least one type of component (A1) selected from the group consisting of polyphenols, chlorophenol resin, and lignin resin, and at least one type of component (B1) selected from water-soluble polymers other than said component (A1) or water-dispersible polymers other than said component (A1); and substantially not including an initial condensate of resorcin and formalin.

Description

有機繊維用接着剤及び有機繊維の処理方法Organic fiber adhesive and organic fiber processing method
　本発明は、有機繊維用接着剤及び有機繊維の処理方法に関する。 The present invention relates to an adhesive for organic fibers and a method for treating organic fibers.
　タイヤ、各種のホース類、並びにタイミングベルト、コンベアベルト及びＶベルト等の各種ベルト類などに用いられるゴムには、補強材としてポリエステル繊維等の有機繊維が使用される。従来、有機繊維であるタイヤコードと、タイヤ用ゴムとの接着のために、レゾルシン、ホルマリン及びゴムラテックスを含むＲＦＬ（レゾルシン・ホルマリン・ラテックス）接着剤を熱硬化する処理を行い、その接着剤の接着力を確保することが知られている。この処理としては具体的には、有機繊維にＲＦＬ接着剤を付着して熱硬化する処理を行うところ、ＲＦＬ接着剤で処理する前に、有機繊維にエポキシ樹脂で同様の処理を施しておくことにより、接着力がさらに向上することも知られている。 Organic rubber such as polyester fiber is used as a reinforcing material for rubber used for tires, various hoses, and various belts such as timing belts, conveyor belts, and V-belts. Conventionally, an RFL (resorcin / formalin / latex) adhesive containing resorcin, formalin and rubber latex is heat-cured to bond the tire cord, which is an organic fiber, to the tire rubber. It is known to ensure adhesion. Specifically, the RFL adhesive is attached to the organic fiber and heat-cured as this treatment. Before the treatment with the RFL adhesive, the organic fiber is subjected to the same treatment with an epoxy resin. It is also known that the adhesive force is further improved.
　しかしながら、ＲＦＬ接着剤の製造に用いるホルマリンは、レゾルシンを架橋させるための重要な原材料ではあるものの、発がん性の疑いがあるため、近年、環境、特に作業環境を考慮して、使用時の大気中への放出の抑制及び使用量の削減が求められている。さらに、ＲＦＬ（レゾルシン・ホルマリン・ラテックス）は、ＲＦ（レゾルシン・ホルマリン）樹脂及びゴムラテックスを混合熟成することにより得られるところ、ＲＦ樹脂は保存安定性に劣るため使用可能期間が短く、使用可能期間を経過した場合は廃棄せざるを得ないという課題もある。 However, although formalin used in the production of RFL adhesive is an important raw material for crosslinking resorcin, it is suspected to be carcinogenic. Therefore, in recent years, considering the environment, particularly the working environment, There is a need to reduce the amount released and the amount used. Furthermore, RFL (resorcin / formalin / latex) is obtained by mixing and aging RF (resorcin / formalin) resin and rubber latex. RF resin is inferior in storage stability and therefore has a short usable period and usable period. There is also a problem that when it has passed, it must be discarded.
　先行文献１では、レゾルシンおよびホルマリンを含まない、特定の組成の有機繊維コード用接着剤組成物として、（ブロックド）イソシアネート化合物および／またはアミン系硬化剤と、エポキシ化合物と、ゴムラテックスとを含む有機繊維コード用接着剤組成物を提案している。 In the prior art document 1, as the adhesive composition for organic fiber cords having a specific composition not containing resorcin and formalin, (blocked) isocyanate compound and / or amine-based curing agent, epoxy compound, and rubber latex are included. An adhesive composition for organic fiber cords is proposed.
国際公開第２０１０／１２５９９２号International Publication No. 2010/125992
　しかしながら、従来の接着剤では、ＲＦ樹脂を含まないため配合作業環境を良好にすることができる一方で、代替材料としてエポキシ化合物を含むため保存安定性は悪いといった問題が残っていた。このような事情のもと、本発明は、ホルマリンの使用量の削減が可能で、有機繊維とゴムとの優れた接着性及び優れた保存安定性を示す有機繊維用接着剤を提供することを課題とする。 However, the conventional adhesive can improve the blending work environment because it does not contain an RF resin, but it still has a problem of poor storage stability because it contains an epoxy compound as an alternative material. Under such circumstances, the present invention provides an adhesive for organic fibers that can reduce the amount of formalin used, and exhibits excellent adhesion between organic fibers and rubber and excellent storage stability. Let it be an issue.
　本発明の第一は、ポリフェノール類、クロルフェノール樹脂及びリグニン樹脂からなる群より選択される少なくとも１種の成分（Ａ１）、及び前記成分（Ａ１）以外の水溶性ポリマー又は前記成分（Ａ１）以外の水分散性ポリマーから選択される少なくとも１種の成分（Ｂ１）を含み、レゾルシンとホルマリンとの初期縮合物を実質的に含まないことを特徴とする有機繊維用接着剤に関する。 The first of the present invention is at least one component (A1) selected from the group consisting of polyphenols, chlorophenol resins and lignin resins, and a water-soluble polymer other than the component (A1) or other than the component (A1). It is related with the adhesive for organic fibers characterized by including the at least 1 sort (s) of component (B1) selected from the water-dispersible polymer of this, and substantially not containing the precondensate of resorcin and formalin.
　本発明の第二は、ポリフェノール類、クロルフェノール樹脂及びリグニン樹脂からなる群より選択される少なくとも１種の成分と、メラミン誘導体又はヘキサメチレンテトラミンとの混合物（Ａ２）、及び前記成分（Ａ２）以外の水溶性ポリマー又は前記成分（Ａ２）以外の水分散性ポリマーから選択される少なくとも１種の成分（Ｂ２）を含み、レゾルシンとホルマリンとの初期縮合物を実質的に含まないことを特徴とする有機繊維用接着剤に関する。 The second of the present invention is a mixture (A2) of at least one component selected from the group consisting of polyphenols, chlorophenol resins, and lignin resins, a melamine derivative or hexamethylenetetramine, and other than the component (A2). Or at least one component (B2) selected from water-dispersible polymers other than the component (A2), and substantially free of an initial condensate of resorcin and formalin. The present invention relates to an adhesive for organic fibers.
　前記有機繊維用接着剤は、前記成分（Ｂ１）又は（Ｂ２）が、それぞれ（ｂ１）アイオノマー樹脂、（ｂ２）ゴムラテックス、（ｂ３）アクリル系樹脂、（ｂ４）オレフィン系樹脂、（ｂ５）塩化ビニル系樹脂及び（ｂ６）酢酸ビニル系樹脂からなる群より選択される少なくとも１種の成分であることが好ましい。 In the organic fiber adhesive, the component (B1) or (B2) contains (b1) ionomer resin, (b2) rubber latex, (b3) acrylic resin, (b4) olefin resin, and (b5) chloride. It is preferably at least one component selected from the group consisting of vinyl resins and (b6) vinyl acetate resins.
　前記有機繊維用接着剤は、ブロックイソシアネート化合物（Ｃ）を含むことが好ましい。 The organic fiber adhesive preferably contains a blocked isocyanate compound (C).
　前記有機繊維用接着剤について、前記有機繊維がナイロン繊維、レーヨン繊維、ポリエステル繊維及びアラミド繊維からなる群より選択される少なくとも１種であることが好ましい。 Regarding the organic fiber adhesive, the organic fiber is preferably at least one selected from the group consisting of nylon fiber, rayon fiber, polyester fiber and aramid fiber.
　本発明の第三は、有機繊維を前記有機繊維用接着剤で処理する工程を含む、有機繊維の処理方法に関する。 The third aspect of the present invention relates to a method for treating organic fibers, including a step of treating organic fibers with the adhesive for organic fibers.
　本発明の第四は、以下（１）及び（２）の工程を含む、有機繊維の処理方法に関する。
　（１）エポキシ化合物又はハロヒドリン化合物を含む第１処理剤で有機繊維を処理する工程
　（２）第１処理剤で処理した有機繊維を前記有機繊維用接着剤を含む第２処理剤で処理する工程 4th of this invention is related with the processing method of an organic fiber including the process of (1) and (2) below.
(1) The process of processing organic fiber with the 1st processing agent containing an epoxy compound or a halohydrin compound (2) The process of processing the organic fiber processed with the 1st processing agent with the 2nd processing agent containing the adhesive agent for said organic fibers
　前記有機繊維の処理方法について、前記有機繊維がナイロン繊維、レーヨン繊維、ポリエステル繊維及びアラミド繊維からなる群より選択される少なくとも１種であることが好ましい。 Regarding the method for treating the organic fiber, the organic fiber is preferably at least one selected from the group consisting of nylon fiber, rayon fiber, polyester fiber and aramid fiber.
　本発明の第五は、前記有機繊維の処理方法により処理された有機繊維に関する。 5th of this invention is related with the organic fiber processed by the processing method of the said organic fiber.
　本発明の第六は、前記有機繊維を用いたタイヤ、ホース又はベルトに関する。 The sixth aspect of the present invention relates to a tire, a hose or a belt using the organic fiber.
　本発明は、ホルマリンの使用量の削減が可能で、有機繊維とゴムとの優れた接着性及び優れた保存安定性を示す有機繊維用接着剤を提供する。 The present invention provides an organic fiber adhesive that can reduce the amount of formalin used, exhibits excellent adhesion between organic fibers and rubber, and exhibits excellent storage stability.
　以下、本発明の好ましい実施の形態の一例を具体的に説明する。本発明の有機繊維用接着剤の第一は、ポリフェノール類、クロルフェノール樹脂及びリグニン樹脂からなる群より選択される少なくとも１種の成分（Ａ１）、及び前記成分（Ａ１）以外の水溶性ポリマー又は前記成分（Ａ１）以外の水分散性ポリマーから選択される少なくとも１種の成分（Ｂ１）を含み、レゾルシンとホルマリンとの初期縮合物を実質的に含まないものである。 Hereinafter, an example of a preferred embodiment of the present invention will be specifically described. The first of the adhesives for organic fibers of the present invention is at least one component (A1) selected from the group consisting of polyphenols, chlorophenol resins and lignin resins, and a water-soluble polymer other than the component (A1) or It contains at least one component (B1) selected from water-dispersible polymers other than the component (A1), and does not substantially contain an initial condensate of resorcin and formalin.
　［成分（Ａ１）］
　成分（Ａ１）は、ポリフェノール類、クロルフェノール樹脂及びリグニン樹脂からなる群より選択される少なくとも１種の成分である。ポリフェノール類は、ベンゼン環上に２個以上のヒドロキシル基を有する構造を備えるものを広く含み、例えば、レゾルシン、カテコール、ピロガロール、フロログルシノール、没食子酸、クロロゲン酸などの単核多価フェノール化合物；エラグ酸、タンニン酸及びタンニン誘導体などの多核の多価フェノール化合物を挙げることができる。クロルフェノール樹脂は、クロルフェノールモノマーおよびレゾルシンをホルムアルデヒドと共縮合した化合物である。さらに、リグニン樹脂は、バイオマスを分解して得られるリグニン誘導体；リグニン誘導体の変性物；リグニン誘導体又はリグニン誘導体変性物を重合したもの；及びリグニン誘導体を重合した後に変性したものからなる群より選択される一種以上を含むものであり、フェノール骨格、２－メトキシフェノール骨格及び２，６－ジメトキシフェノール骨格からなる群より選択される一種以上を含む。 [Component (A1)]
The component (A1) is at least one component selected from the group consisting of polyphenols, chlorophenol resins, and lignin resins. Polyphenols broadly include those having a structure having two or more hydroxyl groups on the benzene ring, for example, mononuclear polyhydric phenol compounds such as resorcin, catechol, pyrogallol, phloroglucinol, gallic acid, and chlorogenic acid; Mention may be made of polynuclear polyphenol compounds such as ellagic acid, tannic acid and tannin derivatives. The chlorophenol resin is a compound obtained by co-condensing a chlorophenol monomer and resorcin with formaldehyde. Further, the lignin resin is selected from the group consisting of a lignin derivative obtained by decomposing biomass; a modified product of a lignin derivative; a polymer obtained by polymerizing a lignin derivative or a lignin derivative-modified product; One or more selected from the group consisting of a phenol skeleton, a 2-methoxyphenol skeleton and a 2,6-dimethoxyphenol skeleton.
　［成分（Ｂ１）］
　成分（Ｂ１）は、成分（Ａ１）以外の水溶性ポリマー又は成分（Ａ１）以外の水分散性ポリマーから選択される少なくとも１種の成分である。成分（Ｂ１）としては、水溶性又は水分散性のポリマーであれば、特に限定されないが、具体的には、例えば、（ｂ１）アイオノマー樹脂、（ｂ２）ゴムラテックス、（ｂ３）アクリル系樹脂、（ｂ４）オレフィン系樹脂、（ｂ５）塩化ビニル系樹脂及び（ｂ６）酢酸ビニル系樹脂などが挙げられる。 [Component (B1)]
Component (B1) is at least one component selected from water-soluble polymers other than component (A1) or water-dispersible polymers other than component (A1). The component (B1) is not particularly limited as long as it is a water-soluble or water-dispersible polymer. Specifically, for example, (b1) ionomer resin, (b2) rubber latex, (b3) acrylic resin, (B4) Olefin resins, (b5) vinyl chloride resins, (b6) vinyl acetate resins, and the like.
　（（ｂ１）アイオノマー樹脂）
　（ｂ１）アイオノマー樹脂は、エチレン、プロピレン等のモノオレフィンと、アクリル酸、メタクリル酸等の不飽和モノカルボン酸との共重合体であり、その共重合体が形成する高分子鎖間の一部のカルボキシル基が、１価又は２価の金属イオンで塩を形成しているもので、該高分子鎖は該金属イオンを介して化学的に部分架橋されている。代表的な金属としてはＣａ、Ｚｎ、Ｍｇ、Ｎａ等が挙げられる。 ((B1) ionomer resin)
(B1) The ionomer resin is a copolymer of a monoolefin such as ethylene or propylene and an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, and part of the polymer chain formed by the copolymer. In which the carboxyl group is a salt formed of a monovalent or divalent metal ion, and the polymer chain is chemically partially cross-linked through the metal ion. Typical metals include Ca, Zn, Mg, Na and the like.
　（ｂ１）アイオノマー樹脂は、水分散液として使用することが好ましく、（ｂ１）アイオノマー樹脂の水分散液のｐＨは、７．５以上１３以下の範囲であることが好ましく、８以上１０以下の範囲であることがより好ましい。７．５以上１３以下の範囲であることにより、（ｂ１）アイオノマー樹脂の部分的な架橋が維持され、凝集力の高い均一な接着剤層を形成することができるためである。（ｂ１）アイオノマー樹脂の水分散液のｐＨが７．５未満であると、その水分散液の状態が不安定になりゲル化しやすくなる。また、（ｂ１）アイオノマー樹脂の高分子鎖間のペンダントカルボキシル基が中和されなくなり、部分的な化学架橋がなくなる。（ｂ１）アイオノマー樹脂の水分散液のｐＨが１３を超えると、その水分散液の粘度が変動しやすくなり、接着性の品質管理が難しくなる。 (B1) The ionomer resin is preferably used as an aqueous dispersion, and the pH of the aqueous dispersion of (b1) ionomer resin is preferably in the range of 7.5 to 13, preferably in the range of 8 to 10. It is more preferable that This is because when (b1) the ionomer resin is partially crosslinked within the range of 7.5 or more and 13 or less, a uniform adhesive layer having high cohesive force can be formed. (B1) When the pH of the aqueous dispersion of ionomer resin is less than 7.5, the state of the aqueous dispersion becomes unstable and gelation tends to occur. Further, (b1) pendant carboxyl groups between the polymer chains of the ionomer resin are not neutralized, and partial chemical crosslinking is eliminated. (B1) When the pH of the aqueous dispersion of the ionomer resin exceeds 13, the viscosity of the aqueous dispersion tends to fluctuate, making it difficult to control the adhesive quality.
　（ｂ１）アイオノマー樹脂の重量平均分子量は、特に限定されないが、１０，０００以上１００，０００以下であることが好ましい。１０，０００未満であると、樹脂の凝集力が低下して接着力が低下することがあり、１００，０００を超えると、得られる繊維が硬くなり過ぎ、耐疲労性が低下することがあるためである。本発明において、重量平均分子量とは、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定されたスチレン換算の重量平均分子量をいう。 (B1) The weight average molecular weight of the ionomer resin is not particularly limited, but is preferably 10,000 or more and 100,000 or less. If it is less than 10,000, the cohesive strength of the resin may decrease and the adhesive force may decrease, and if it exceeds 100,000, the resulting fiber may become too hard and fatigue resistance may decrease. It is. In this invention, a weight average molecular weight means the weight average molecular weight of styrene conversion measured by gel permeation chromatography (GPC).
　（ｂ１）アイオノマー樹脂としては、例えば、ケミパールＳ３００（三井化学株式会社製）、ケミパールＳ２００（三井化学株式会社製）等を用いることができる。これら各種（ｂ１）アイオノマー樹脂は、１種単独で又は２種以上併用することができる。 (B1) As the ionomer resin, for example, Chemipearl S300 (manufactured by Mitsui Chemicals), Chemipearl S200 (manufactured by Mitsui Chemicals) or the like can be used. These various (b1) ionomer resins can be used alone or in combination of two or more.
　（（ｂ２）ゴムラテックス）
　（ｂ２）ゴムラテックスは、天然ゴムまたはジエン系モノマーを重合させて製造したポリマーを水分散しているエマルジョンをいう。（ｂ２）ゴムラテックスとしては、天然ゴムラテックス、スチレン・ブタジエン共重合体ラテックス、スチレン・ブタジエン・ビニルピリジン共重合体ラテックス等が挙げられる。これらの中でも、天然ゴムやスチレンブタジエンゴムに対して高い接着力が得られるため、スチレン・ブタジエン・ビニルピリジン共重合体ラテックスが好ましい。これら各種（ｂ２）ゴムラテックスは、１種単独で又は２種以上併用することができる。 ((B2) Rubber latex)
(B2) Rubber latex refers to an emulsion in which a polymer produced by polymerizing natural rubber or a diene monomer is dispersed in water. (B2) Examples of the rubber latex include natural rubber latex, styrene / butadiene copolymer latex, and styrene / butadiene / vinylpyridine copolymer latex. Among these, styrene / butadiene / vinylpyridine copolymer latex is preferable because high adhesive strength can be obtained with respect to natural rubber and styrene butadiene rubber. These various (b2) rubber latexes can be used alone or in combination of two or more.
　（（ｂ３）アクリル系樹脂）
　（ｂ３）アクリル系樹脂は、少なくとも１種のアクリル系モノマーを含む重合成分を重合して得られる樹脂である。アクリル系モノマーとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸２－エチルヘキシル等を用いることができる。これら各種（ｂ３）アクリル系樹脂は、１種単独で又は２種以上併用することができる。 ((B3) Acrylic resin)
(B3) The acrylic resin is a resin obtained by polymerizing a polymerization component containing at least one acrylic monomer. Examples of the acrylic monomer include methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isopropyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate or the like can be used. These various (b3) acrylic resins can be used alone or in combination of two or more.
　（（ｂ４）オレフィン系樹脂）
　（ｂ４）オレフィン系樹脂は、少なくとも１種のオレフィン系モノマーを含む重合成分を重合して得られる樹脂である。オレフィン系モノマーとしては、エチレン、プロピレン、イソプレン、ブタジエン、イソブチレン等を用いることができる。これら各種（ｂ４）オレフィン系樹脂は、１種単独で又は２種以上併用することができる。 ((B4) Olefin resin)
(B4) The olefin resin is a resin obtained by polymerizing a polymerization component containing at least one olefin monomer. As the olefin monomer, ethylene, propylene, isoprene, butadiene, isobutylene, or the like can be used. These various (b4) olefin resins can be used alone or in combination of two or more.
　（（ｂ５）塩化ビニル系樹脂）
　（ｂ５）塩化ビニル系樹脂は、少なくとも１種の塩化ビニル系モノマーを含む重合成分を重合して得られる樹脂である。塩化ビニル系モノマーとしては、例えば、塩化ビニル、塩化ビニリデン等を用いることができる。これら各種（ｂ５）塩化ビニル系樹脂は、１種単独で又は２種以上併用することができる。 ((B5) Vinyl chloride resin)
(B5) The vinyl chloride resin is a resin obtained by polymerizing a polymerization component containing at least one vinyl chloride monomer. Examples of vinyl chloride monomers that can be used include vinyl chloride and vinylidene chloride. These various (b5) vinyl chloride resins can be used alone or in combination of two or more.
　（（ｂ６）酢酸ビニル系樹脂）
　（ｂ６）酢酸ビニル系樹脂は、少なくとも１種の酢酸ビニル系モノマーを含む重合成分を重合して得られる樹脂である。酢酸ビニル系モノマーとしては、例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル等を用いることができる。これら各種（ｂ６）酢酸ビニル系樹脂は、１種単独で又は２種以上併用することができる。 ((B6) Vinyl acetate resin)
(B6) The vinyl acetate resin is a resin obtained by polymerizing a polymerization component containing at least one vinyl acetate monomer. As the vinyl acetate monomer, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate and the like can be used. These various (b6) vinyl acetate resins can be used alone or in combination of two or more.
　本発明の有機繊維用接着剤における成分（Ａ１）と成分（Ｂ１）の比率は、固形分量（重量）比で、成分（Ａ１）：成分（Ｂ１）＝１：１～１：１５が好ましく、１：３～１：１２がより好ましい。 The ratio of the component (A1) and the component (B1) in the adhesive for organic fibers of the present invention is preferably a solid content (weight) ratio, preferably component (A1): component (B1) = 1: 1 to 1:15, 1: 3 to 1:12 are more preferable.
　本発明の有機繊維用接着剤の第二は、ポリフェノール類、クロルフェノール樹脂及びリグニン樹脂からなる群より選択される少なくとも１種の成分と、メラミン誘導体又はヘキサメチレンテトラミンとの混合物（Ａ２）、及び前記成分（Ａ２）以外の水溶性ポリマー又は前記成分（Ａ２）以外の水分散性ポリマーから選択される少なくとも１種の成分（Ｂ２）を含み、レゾルシンとホルマリンとの初期縮合物を実質的に含まないものである。 The second of the adhesives for organic fibers of the present invention is a mixture (A2) of at least one component selected from the group consisting of polyphenols, chlorophenol resins and lignin resins, and a melamine derivative or hexamethylenetetramine, and It contains at least one component (B2) selected from water-soluble polymers other than the component (A2) or water-dispersible polymers other than the component (A2), and substantially contains an initial condensate of resorcin and formalin. There is nothing.
　［成分（Ａ２）］
　成分（Ａ２）は、ポリフェノール類、クロルフェノール樹脂及びリグニン樹脂からなる群より選択される少なくとも１種の成分と、メラミン誘導体又はヘキサメチレンテトラミンとの混合物である。メラミン誘導体は、分子内にトリアジン骨格を有する化合物である。ポリフェノール類、クロルフェノール樹脂及びリグニン樹脂のいずれも、成分（Ａ１）と同じものを用いることができる。 [Component (A2)]
Component (A2) is a mixture of at least one component selected from the group consisting of polyphenols, chlorophenol resins, and lignin resins, and a melamine derivative or hexamethylenetetramine. A melamine derivative is a compound having a triazine skeleton in the molecule. Any of the polyphenols, the chlorophenol resin, and the lignin resin can be the same as the component (A1).
　これらポリフェノール類、クロルフェノール樹脂及びリグニン樹脂の中でも、特にレゾルシンは、メラミン誘導体又はヘキサメチレンテトラミンと併存することにより、有機繊維用接着剤の硬化反応が進行し、接着性を高めることができるため好ましい。 Among these polyphenols, chlorophenol resins, and lignin resins, resorcin is particularly preferable because it can coexist with a melamine derivative or hexamethylenetetramine so that the curing reaction of the adhesive for organic fibers proceeds and adhesion can be improved. .
　［成分（Ｂ２）］
　成分（Ｂ２）は、成分（Ａ２）以外の水溶性ポリマー又は成分（Ａ２）以外の水分散性ポリマーから選択される少なくとも１種の成分である。成分（Ｂ２）としては、成分（Ｂ１）と同じものを用いることができ、水溶性又は水分散性のポリマーであれば、特に限定されない。具体的には、例えば、（ｂ１）アイオノマー樹脂、（ｂ２）ゴムラテックス、（ｂ３）アクリル系樹脂、（ｂ４）オレフィン系樹脂、（ｂ５）塩化ビニル系樹脂及び（ｂ６）酢酸ビニル系樹脂などが挙げられる。 [Component (B2)]
Component (B2) is at least one component selected from water-soluble polymers other than component (A2) or water-dispersible polymers other than component (A2). The component (B2) can be the same as the component (B1), and is not particularly limited as long as it is a water-soluble or water-dispersible polymer. Specifically, for example, (b1) ionomer resin, (b2) rubber latex, (b3) acrylic resin, (b4) olefin resin, (b5) vinyl chloride resin and (b6) vinyl acetate resin Can be mentioned.
　本発明の有機繊維用接着剤における成分（Ａ２）と成分（Ｂ２）の比率は、成分（Ａ１）と成分（Ｂ１）の場合と同様、固形分量（重量）比で、成分（Ａ２）：成分（Ｂ２）＝１：１～１：１５が好ましく、１：３～１：１２がより好ましい。 The ratio of the component (A2) and the component (B2) in the adhesive for organic fibers of the present invention is the solid content (weight) ratio as in the case of the component (A1) and the component (B1), and the component (A2): component (B2) = 1: 1 to 1:15 is preferable, and 1: 3 to 1:12 is more preferable.
　［レゾルシンとホルマリンとの初期縮合物］
　本発明の有機繊維用接着剤の第一および第二のいずれも、レゾルシンとホルマリンとの初期縮合物を実質的に含まないものである。ここで、レゾルシンとホルマリンとの初期縮合物とは、レゾルシンとホルムアルデヒドとを、塩酸や硫酸等の酸性触媒、水酸化ナトリウム等のアルカリ金属水酸化物、又はアンモニアの存在下、水中で反応させて得られるものである。また、実質的に含まないとは、全く含まない場合に限定されるものではなく、不可避的に混入するレゾルシンとホルマリンとの初期縮合物の存在を許容する。具体的には、例えば、有機繊維用接着剤において、１重量％以下である。 [Initial condensate of resorcin and formalin]
Both the first and second organic fiber adhesives of the present invention are substantially free of an initial condensate of resorcin and formalin. Here, the initial condensate of resorcin and formalin is obtained by reacting resorcin and formaldehyde in water in the presence of an acidic catalyst such as hydrochloric acid or sulfuric acid, an alkali metal hydroxide such as sodium hydroxide, or ammonia. It is obtained. Moreover, it is not limited to the case where it does not contain at all substantially, but the presence of the unavoidable initial condensate of resorcin and formalin is permitted. Specifically, for example, in an adhesive for organic fibers, it is 1% by weight or less.
　［ブロックイソシアネート化合物（Ｃ）］
　本発明の有機繊維用接着剤の第一および第二のいずれも、ブロックイソシアネート化合物（Ｃ）を含むことが好ましい。ブロックイソシアネート化合物（Ｃ）は、イソシアネート化合物とブロック剤との反応により生成し、ブロック剤由来の基により一時的に不活性化されている化合物であり、所定温度で加熱するとそのブロック剤由来の基が解離し、イソシアネート基を生成する。 [Blocked isocyanate compound (C)]
It is preferable that both of the first and second adhesives for organic fibers of the present invention contain a blocked isocyanate compound (C). The blocked isocyanate compound (C) is a compound that is generated by a reaction between an isocyanate compound and a blocking agent, and is temporarily inactivated by a group derived from the blocking agent. When heated at a predetermined temperature, the group derived from the blocking agent Dissociates to form isocyanate groups.
　イソシアネート化合物としては、分子内に２個以上のイソシアネート基を有するものを用いることができる。２個のイソシアネート基を有するジイソシアネート類としては、例えば、ヘキサメチレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、メタフェニレンジイソシアネート、ナフタレンジイソシアネート、ジフェニルエーテルジイソシアネート、ジフェニルプロパンジイソシアネート、ビフェニルジイソシアネート、及びこれらの異性体、アルキル置換体、ハロゲン化物、ベンゼン環への水素添加物等が使用できる。さらに、３個のイソシアネート基を有するトリイソシアネート類、４個のイソシアネート基を有するテトライソシアネート類、ポリメチレンポリフェニルポリイソシアネート等を使用することもできる。これらのイソシアネート化合物は、１種単独で又は２種以上併用することができる。 As the isocyanate compound, those having two or more isocyanate groups in the molecule can be used. Examples of diisocyanates having two isocyanate groups include hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, tolylene diisocyanate, trimethylhexamethylene diisocyanate, metaphenylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, Diphenylpropane diisocyanate, biphenyl diisocyanate, and their isomers, alkyl-substituted products, halides, hydrogenated products to the benzene ring, and the like can be used. Furthermore, triisocyanates having 3 isocyanate groups, tetraisocyanates having 4 isocyanate groups, polymethylene polyphenyl polyisocyanate, and the like can also be used. These isocyanate compounds can be used alone or in combination of two or more.
　これらの中でも特に、工業的に入手しやすく、得られる処理後の有機繊維用接着剤の耐熱性が良好なものとなるため、トリレンジイソシアネート、メタフェニレンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネートが好ましい。 Among these, since it is easy to obtain industrially and the heat resistance of the resulting organic fiber adhesive after treatment is good, tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene Polyphenyl polyisocyanate is preferred.
　ブロック剤としては、ε－カプロラクタム、δ－バレロラクタム、γ－ブチロラクタム、β－プロピオラクタムなどのラクタム系；フェノール、クレゾール、レゾルシノール、キシレノールなどのフェノール系；メタノール、エタノール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、イソブチルアルコール、ｔｅｒｔ－ブチルアルコール、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、ベンジルアルコールなどのアルコール系；ホルムアミドキシム、アセトアルドキシム、アセトキシム、メチルエチルケトキシム、ジアセチルモノオキシム、ベンゾフェノンオキシム、シクロヘキサノンオキシムなどのオキシム系；マロン酸ジメチル、マロン酸ジエチル、アセト酢酸エチル、アセト酢酸メチル、アセチルアセトンなどの活性メチレン系などを挙げることができる。なかでも、比較的低温で迅速にイソシアネート化合物から乖離するため、ラクタム系、フェノール系、オキシム系ブロック剤が好ましい。 Blocking agents include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam; phenols such as phenol, cresol, resorcinol, xylenol; methanol, ethanol, n-propyl alcohol, isopropyl Alcohols such as alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol; formamidoxime, acetoaldoxime, Acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexa Oxime such N'okishimu; dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and the like active methylene of acetylacetone. Of these, lactam-based, phenol-based, and oxime-based blocking agents are preferable because they rapidly deviate from the isocyanate compound at a relatively low temperature.
　ブロックイソシアネート化合物（Ｃ）の含有量は、本発明の有機繊維用接着剤における成分（Ｂ１）または（Ｂ２）１００重量部に対して、５重量部以上３０重量部以下が好ましく、１０重量部以上２０重量部以下がより好ましい。この範囲とすることにより、有機繊維とゴムとの接着性を向上することができる。５重量部未満であると、十分な接着性向上の効果が得られず、３０重量部を超えると、繊維が硬くなり過ぎたり、耐疲労性が低下することがあるため好ましくない。ブロックイソシアネート化合物（Ｃ）の含有量は、有機繊維を接着しようとするゴムの種類に応じて適宜調整することができる。 The content of the blocked isocyanate compound (C) is preferably 5 parts by weight or more and 30 parts by weight or less, preferably 10 parts by weight or more with respect to 100 parts by weight of the component (B1) or (B2) in the organic fiber adhesive of the present invention. 20 parts by weight or less is more preferable. By setting it as this range, the adhesiveness of an organic fiber and rubber | gum can be improved. If the amount is less than 5 parts by weight, a sufficient effect of improving adhesiveness cannot be obtained, and if it exceeds 30 parts by weight, the fiber may become too hard or fatigue resistance may be lowered. Content of a block isocyanate compound (C) can be suitably adjusted according to the kind of rubber | gum which is going to adhere | attach organic fiber.
　有機繊維用接着剤の固形分濃度は、５重量％以上３０重量％以下が好ましく、１０重量％以上２５重量％以下がより好ましい。ゴムに対しより高い接着力が得られるためである。５重量％未満であると、有機繊維用接着剤の有機繊維への付着量が少なく、十分な接着力が得られなくなることがあり、３０重量％を超えると、得られる繊維が硬くなり、屈曲疲労強度等が低くなることがあるためである。 The solid content concentration of the organic fiber adhesive is preferably 5% by weight to 30% by weight, and more preferably 10% by weight to 25% by weight. This is because higher adhesion to rubber can be obtained. If the amount is less than 5% by weight, the amount of the adhesive for organic fibers attached to the organic fiber is small, and sufficient adhesive strength may not be obtained. If the amount exceeds 30% by weight, the resulting fiber becomes hard and bent. This is because the fatigue strength and the like may be lowered.
　［任意成分］
　本発明の有機繊維用接着剤は、水系であること、すなわち水又は水を主成分とする溶媒を含むことが好ましい。水又は水を主成分とする溶媒は、成分（Ａ１）及び成分（Ｂ１）、又は成分（Ａ２）及び成分（Ｂ２）を溶解又は分散し、これら各成分を均一に有機繊維に付着させるための溶媒として機能する。 [Optional ingredients]
The adhesive for organic fibers of the present invention is preferably aqueous, that is, contains water or a solvent containing water as a main component. Water or a solvent mainly composed of water dissolves or disperses the component (A1) and the component (B1), or the component (A2) and the component (B2), and uniformly attaches these components to the organic fiber. Functions as a solvent.
　本発明に係る有機繊維用接着剤には、本発明の目的、効果を妨げない範囲内において、必要に応じて以下の任意成分が含まれていても良い。例えば、加硫調整剤、亜鉛華、酸化防止剤、消泡剤、及び湿潤剤などが挙げられる。 The organic fiber adhesive according to the present invention may contain the following optional components as necessary within the range not hindering the object and effect of the present invention. For example, a vulcanization regulator, zinc white, antioxidant, antifoaming agent, wetting agent and the like can be mentioned.
　［有機繊維］
　本発明に係る有機繊維用接着剤は、各種有機繊維の処理に用いることができる。各種有機繊維としては、タイヤ、各種のホース類、並びにタイミングベルト、コンベアベルト及びＶベルト等のベルト類などの補強材として通常使用される繊維が挙げられる。また、その繊維の種類としては例えば、ナイロン繊維；レーヨン繊維；ビニロン繊維；ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）等のポリエステル繊維；アラミド繊維；及びポリウレタン繊維等が挙げられる。 [Organic fiber]
The adhesive for organic fibers according to the present invention can be used for treating various organic fibers. Examples of the various organic fibers include fibers usually used as reinforcing materials for tires, various hoses, and belts such as timing belts, conveyor belts, and V belts. Examples of the fiber include nylon fiber; rayon fiber; vinylon fiber; polyester fiber such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); aramid fiber; and polyurethane fiber.
　これらの有機繊維のうち、本発明の有機繊維用接着剤の処理により、特に機械的強度を向上することができるため、ナイロン繊維、レーヨン繊維、ポリエステル繊維及びアラミド繊維からなる群から選択される少なくとも１種を用いることが好ましい。 Among these organic fibers, since the mechanical strength can be particularly improved by the treatment with the adhesive for organic fibers of the present invention, at least selected from the group consisting of nylon fibers, rayon fibers, polyester fibers, and aramid fibers. One type is preferably used.
　本発明に係る有機繊維は、フィラメント糸、コ－ド、織物、織布などの形態のいずれであってもよい。 The organic fiber according to the present invention may be in the form of filament yarn, cord, woven fabric, woven fabric or the like.
　ナイロン繊維としては、例えば、９４０デシテックスのマルチフィラメントを、それぞれ２本合わせて４７回／１０ｃｍの撚りをかけた後、この下撚コード２本を合せて下撚と反対方向に同数の上撚をかけたものが使用され得る。 As a nylon fiber, for example, two 940 decitex multifilaments are twisted 47 times / 10 cm in total, and then two lower twisted cords are combined to apply the same number of upper twists in the opposite direction to the lower twist. Multiplying can be used.
　レーヨン繊維としては、例えば、１８４０デシテックスのマルチフィラメントを、それぞれ２本合わせて４７回／１０ｃｍの撚りをかけた後、この下撚コード２本を合せて下撚と反対方向に同数の上撚をかけたものが使用され得る。 As a rayon fiber, for example, two 1840 dtex multifilaments are twisted 47 times / 10 cm each, and then two lower twisted cords are combined and the same number of upper twists in the opposite direction to the lower twist. Multiplying can be used.
　ポリエステル繊維としては、例えば、糸粘度０．９５のポリエチレンテレフタレートを溶融紡糸し、延伸した１，５００デニールのマルチフィラメントを、それぞれ２本合わせて４０回／１０ｃｍの撚りをかけた後、この下撚コード２本を合せて下撚と反対方向に同数の上撚をかけたものが使用され得る。 Examples of polyester fibers include melt spinning of polyethylene terephthalate having a yarn viscosity of 0.95, stretching two 1,500 denier multifilaments, respectively, and twisting them 40 times / 10 cm, and then twisting them. A combination of two cords with the same number of upper twists in the opposite direction to the lower twist may be used.
　アラミド繊維としては、例えば、表示繊度１，５００デニール、フィラメント数１，０００本の芳香族ポリアミドマルチフィラメント（デュポン社製ケブラー）を、それぞれ２本合わせて３５回／１０ｃｍの撚りをかけた後、この下撚コード２本を合せて下撚と反対方向に同数の上撚をかけたものが使用され得る。 As an aramid fiber, for example, after applying a twist of 35 times / 10 cm in combination of two aromatic polyamide multifilaments (Kevlar manufactured by DuPont) having a display fineness of 1,500 denier and 1,000 filaments, A combination of the two lower twist cords and applying the same number of upper twists in the opposite direction to the lower twist may be used.
　［処理方法］
　本発明の有機繊維の処理方法は、本発明の有機繊維用接着剤で処理する工程を含むものである。有機繊維用接着剤で有機繊維を処理するとは、有機繊維用接着剤に含まれる各種成分を有機繊維に付着させるために行われる処理およびその後の加熱処理を含むものである。付着方法としては、例えば、ローラーを使った塗布、ノズルからの噴霧、浴液（有機繊維用接着剤）への浸漬など任意の方法を用いることができる。加熱方法としては、例えば、有機繊維用接着剤が付着した有機繊維を１００℃以上２５０℃以下で１分以上５分以下乾燥処理した後、さらに、１５０℃以上２５０℃以下で１分以上５分以下で熱処理を行う方法が挙げられる。乾燥処理後の熱処理の条件としては、１８０℃以上２４０℃以下で１分以上２分以下であることが好ましい。特に、乾燥処理後の熱処理において、温度が低すぎると、ゴムに対する接着力が不十分となることがあり、高すぎると有機繊維が劣化し、強度低下の原因となることがあるためである。 [Processing method]
The processing method of the organic fiber of this invention includes the process processed with the adhesive agent for organic fibers of this invention. Treating organic fibers with an adhesive for organic fibers includes a treatment performed for adhering various components contained in the adhesive for organic fibers to the organic fibers and a subsequent heat treatment. As an adhesion method, for example, an arbitrary method such as application using a roller, spraying from a nozzle, immersion in a bath solution (adhesive for organic fibers) can be used. As a heating method, for example, the organic fiber to which the organic fiber adhesive is attached is dried at 100 ° C. or higher and 250 ° C. or lower for 1 minute or longer and 5 minutes or shorter, and further at 150 ° C. or higher and 250 ° C. or lower for 1 minute or longer and 5 minutes. A method of performing heat treatment is mentioned below. The heat treatment conditions after the drying treatment are preferably 180 ° C. or higher and 240 ° C. or lower and 1 minute or longer and 2 minutes or shorter. In particular, in the heat treatment after the drying treatment, if the temperature is too low, the adhesive strength to rubber may be insufficient, and if it is too high, the organic fibers may be deteriorated and cause a decrease in strength.
　本発明の有機繊維用接着剤の有機繊維への付着量は、十分な接着力を得つつも、得られる繊維が硬くなり過ぎないようにするため、固形分基準で、０．１重量％以上１０重量％以下が好ましく、１重量％以上７重量％以下がより好ましい。ここで、付着量の単位［重量％］は、有機繊維重量を１００として得られる固形分の重量である。 The amount of the organic fiber adhesive of the present invention attached to the organic fiber is 0.1% by weight or more based on the solid content in order to prevent the resulting fiber from becoming too hard while obtaining sufficient adhesive strength. It is preferably 10% by weight or less, and more preferably 1% by weight or more and 7% by weight or less. Here, the unit [wt%] of the adhesion amount is the weight of the solid content obtained by setting the organic fiber weight to 100.
　本発明の有機繊維用接着剤、並びに後述する第１処理剤及び第２処理剤のいずれによって有機繊維を処理する場合でも、有機繊維への付着量を調整するために、圧接ローラーによる絞り、スクレイパー等によるかき落とし、空気吹き付けによる吹き飛ばし、吸引、ビーターによる叩き等の手段をさらに採用してもよい。 In order to adjust the amount of adhesion to the organic fiber, regardless of whether the organic fiber is treated with the adhesive for organic fiber of the present invention, and the first treatment agent and the second treatment agent described later, a squeezing by a pressure roller, a scraper It is also possible to further employ means such as scratching by air, blowing by air blowing, suction, hitting by a beater, and the like.
　また、本発明の有機繊維用接着剤で処理する前に、有機繊維を本発明の有機繊維用接着剤以外の処理剤で処理してもよい。このような有機繊維の処理方法として、以下（１）及び（２）の工程を含む、有機繊維の処理方法が挙げられる。
　（１）エポキシ化合物又はハロヒドリン化合物を含む第１処理剤で有機繊維を処理する工程
　（２）第１処理剤で処理した有機繊維を本発明の有機繊維用接着剤を含む第２処理剤で処理する工程 Moreover, you may process organic fiber with processing agents other than the adhesive agent for organic fibers of this invention, before processing with the adhesive agent for organic fibers of this invention. Examples of the organic fiber processing method include organic fiber processing methods including the following steps (1) and (2).
(1) The process of processing organic fiber with the 1st processing agent containing an epoxy compound or a halohydrin compound (2) The organic fiber processed with the 1st processing agent is processed with the 2nd processing agent containing the adhesive agent for organic fibers of this invention. Process
　このように、有機繊維を本発明の有機繊維用接着剤を含む処理剤で処理する前に、（１）エポキシ化合物又はハロヒドリン化合物を含む第１処理剤で有機繊維を処理することにより、接着力を高めることができるため好ましい。 Thus, before processing an organic fiber with the processing agent containing the adhesive agent for organic fibers of this invention, (1) By treating an organic fiber with the 1st processing agent containing an epoxy compound or a halohydrin compound, adhesive force Can be increased, which is preferable.
　（１）エポキシ化合物又はハロヒドリン化合物を含む第１処理剤で有機繊維を処理する工程について以下詳述する。 (1) The step of treating organic fibers with a first treating agent containing an epoxy compound or a halohydrin compound will be described in detail below.
　エポキシ化合物又はハロヒドリン化合物を含む第１処理剤で有機繊維を処理するとは、第１処理剤に含まれる各種成分を有機繊維に付着させるために行われる処理およびその後の加熱処理を含むものである。付着方法としては、例えば、ローラーを使った塗布、ノズルからの噴霧、浴液（第１処理剤）への浸漬など任意の方法を用いることができる。加熱方法としては、例えば、第１処理剤が付着した有機繊維を１００℃以上２５０℃以下で１分以上５分以下乾燥処理した後、さらに、１５０℃以上２５０℃以下で１分以上５分以下で熱処理を行う方法が挙げられる。乾燥処理後の熱処理の条件としては、１８０℃以上２４０℃以下で２分以上３分以下であることが好ましい。特に、乾燥処理後の熱処理において、温度が低すぎると、ゴムに対する接着力が不十分となることがあり、高すぎると有機繊維が劣化し、強度低下の原因となることがある。 Treating the organic fiber with the first treating agent containing an epoxy compound or a halohydrin compound includes a treatment performed for attaching various components contained in the first treating agent to the organic fiber and a subsequent heat treatment. As an attachment method, for example, any method such as application using a roller, spraying from a nozzle, immersion in a bath liquid (first treatment agent) can be used. As a heating method, for example, after drying the organic fiber to which the first treatment agent is attached at 100 ° C. or more and 250 ° C. or less for 1 minute or more and 5 minutes or less, 150 ° C. or more and 250 ° C. or less and 1 minute or more and 5 minutes or less And a method of performing a heat treatment. The heat treatment conditions after the drying treatment are preferably 180 ° C. or higher and 240 ° C. or lower and 2 minutes or longer and 3 minutes or shorter. In particular, in the heat treatment after the drying treatment, if the temperature is too low, the adhesive strength to rubber may be insufficient, and if it is too high, the organic fibers may be deteriorated and cause a decrease in strength.
　第１処理剤に含まれる成分について以下詳述する。
　（エポキシ化合物）
　エポキシ化合物は、エポキシ基を分子中に２以上有する化合物である。例えば、エチレングリコールグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ビスフェノールＡジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、ノボラックグリシジルエーテル、ブロム化ビスフェノールＡジグリシジルエーテル等のグリシジルエーテル；ヘキサヒドロフタル酸グリシジルエステル、ダイマー酸グリシジルエステル等のグリシジルエステル；トリグリシジルイソシアヌレート、グリシジルヒンダントイン、テトラグリシジルジアミノジフェニルメタン、トリグリシジルパラアミノフェノール、トリグリシジルメタアミノフェノール、ジグリシジルアニリン、ジグリシジルトルイジン、テトラグリシジルメタキシレンジアミン、ジグリシジルトリブロムアニリン、テトラグリシジルビスアミノメチルシクロヘキサン等のグリシジルアミン；又は、３，４－エポキシシクロヘキシルメチルカルボキシレート、エポキシ化ポリブタジエン、エポキシ化大豆油等の脂環族あるいは脂肪族エポキサイド等、が挙げられる。これらは、１種単独で又は２種以上併用することができる。 The components contained in the first treatment agent will be described in detail below.
(Epoxy compound)
The epoxy compound is a compound having two or more epoxy groups in the molecule. For example, ethylene glycol glycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, brominated bisphenol A di Glycidyl ethers such as glycidyl ether; glycidyl esters such as glycidyl hexahydrophthalate and glycidyl dimer; triglycidyl isocyanurate, glycidylhindantoin, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol Glycidyl aniline, diglycid Glycidylamines such as toluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisaminomethylcyclohexane; or alicyclics such as 3,4-epoxycyclohexylmethylcarboxylate, epoxidized polybutadiene, epoxidized soybean oil Or an aliphatic epoxide etc. are mentioned. These can be used alone or in combination of two or more.
　これらの中でも特に、高水溶性であるため、エチレングリコールグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテルが好ましい。 Among these, ethylene glycol glycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether are preferable because of their high water solubility.
　第１処理剤には、ハロヒドリン化合物又はエポキシ化合物が含まれるところ、ハロヒドリン化合物又はエポキシ化合物のいずれか一方のみが含まれていてもよく、ハロヒドリン化合物及びエポキシ化合物の両方が含まれていてもよい。 The first treating agent contains a halohydrin compound or an epoxy compound, but may contain only one of the halohydrin compound or the epoxy compound, or may contain both the halohydrin compound and the epoxy compound.
　（ハロヒドリン化合物）
　本発明において、ハロヒドリン化合物とは、ハロゲンとヒドロキシ基がとなり合った炭素に結合した構成部分を有する化合物をいう。 (Halohydrin compounds)
In the present invention, a halohydrin compound refers to a compound having a constituent part bonded to carbon in which a halogen and a hydroxy group are intermingled.
　ハロヒドリン化合物としては、例えば、多価アルコール化合物とエピハロヒドリン類とを酸性条件下で反応させて得られる化合物（ハロヒドリンエーテル化合物）を挙げることができる。 Examples of the halohydrin compound include a compound (halohydrin ether compound) obtained by reacting a polyhydric alcohol compound and epihalohydrin under acidic conditions.
　多価アルコールとは、分子中に水酸基を２つ以上持つアルコールのことをいい、特に限定されないが、例えば、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のグリコール類；エリスリトール、キシリトール、ソルビトール、マルチロール等の糖アルコール類；ジメチロールブタン酸、酒石酸、グリセリン酸等のヒドロキシカルボン酸類；グリセリン、ジグリセリン、ポリグリセリン、トリメチロールプロパン、トリメチロールエタン、ペンタエリスリトール等を挙げることができる。 The polyhydric alcohol refers to an alcohol having two or more hydroxyl groups in the molecule, and is not particularly limited. For example, glycols such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; erythritol, xylitol, sorbitol, Examples include sugar alcohols such as multirole; hydroxycarboxylic acids such as dimethylolbutanoic acid, tartaric acid, and glyceric acid; glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, and pentaerythritol.
　また、エピハロヒドリン類としては、例えば、エピクロルヒドリン、エピブロモヒドリン等が挙げられる。 In addition, examples of epihalohydrins include epichlorohydrin and epibromohydrin.
　多価アルコール化合物とエピハロヒドリン類との反応は、例えば、三フッ化ホウ素ジエチルエーテル錯体、四塩化スズ、塩化アルミニウム等のルイス酸触媒の存在下に、多価アルコールにエピハロヒドリンを添加し、５０℃以上１５０℃以下の温度範囲にて行うことができる。 The reaction between the polyhydric alcohol compound and the epihalohydrin is, for example, by adding an epihalohydrin to the polyhydric alcohol in the presence of a Lewis acid catalyst such as boron trifluoride diethyl ether complex, tin tetrachloride, aluminum chloride, and the like at 50 ° C. or higher. It can be performed in a temperature range of 150 ° C. or lower.
　これらの中でも特に、多官能で、高水溶性であるため、ソルビトール等の糖アルコール類やポリグリセリンとエピハロヒドリン類との反応物が好ましい。 Among these, sugar alcohols such as sorbitol and a reaction product of polyglycerin and epihalohydrins are preferable because they are multifunctional and highly water-soluble.
　第１処理剤における、ハロヒドリン化合物又はエポキシ化合物の濃度は、ハロヒドリン化合物及びエポキシ化合物の合計濃度として、０．５重量％以上１０重量％以下が好ましく、０．７重量％以上５重量％以下がより好ましい。ゴムに対しより高い接着力が得られるためである。一方、０．５重量％未満であると、接着力が低下することがあり、１０重量％を超えると、繊維への付着量が多くなり、繊維が硬くなり過ぎることがあるため好ましくない。 The concentration of the halohydrin compound or epoxy compound in the first treatment agent is preferably 0.5% by weight or more and 10% by weight or less, more preferably 0.7% by weight or more and 5% by weight or less, as the total concentration of the halohydrin compound and the epoxy compound. preferable. This is because higher adhesion to rubber can be obtained. On the other hand, if it is less than 0.5% by weight, the adhesive strength may be lowered, and if it exceeds 10% by weight, the amount of adhesion to the fiber increases and the fiber may become too hard, which is not preferable.
　第１処理剤の全固形分濃度は、１重量％以上２０重量％以下が好ましく、２重量％以上１０重量％以下がより好ましい。ゴムに対しより高い接着力が得られるためである。１重量％未満であると、付着量が不足し、十分な接着力が得られなくなることがあり、２０重量％を超えると、第１処理剤の成分の有機繊維への付着量が多くなり過ぎ、繊維が硬くなり過ぎたり、繊維や処理装置にゲル物が生じることがあるためである。 The total solid content concentration of the first treatment agent is preferably 1% by weight or more and 20% by weight or less, and more preferably 2% by weight or more and 10% by weight or less. This is because higher adhesion to rubber can be obtained. If the amount is less than 1% by weight, the amount of adhesion may be insufficient, and sufficient adhesive strength may not be obtained. If the amount exceeds 20% by weight, the amount of the first treatment agent component attached to the organic fiber becomes too large. This is because the fibers may become too hard, or gels may be generated in the fibers and the processing apparatus.
　また、第１処理剤における任意成分としては、エポキシ化合物又はハロヒドリン化合物と共重合可能な樹脂、硬化剤、有機増粘剤、酸化防止剤、光安定剤、接着性向上剤、補強剤、軟化剤、着色剤、レベリング剤、難燃剤、帯電防止剤などが挙げられる。 In addition, as optional components in the first treatment agent, resins copolymerizable with epoxy compounds or halohydrin compounds, curing agents, organic thickeners, antioxidants, light stabilizers, adhesion improvers, reinforcing agents, softeners , Colorants, leveling agents, flame retardants, antistatic agents and the like.
　前記ハロヒドリン化合物若しくはエポキシ化合物と共重合可能な樹脂としては、例えば、ポリビニルアルコール（ＰＶＡ）、水性アクリル樹脂、水性ポリウレタン樹脂等が挙げられる。 Examples of the resin copolymerizable with the halohydrin compound or epoxy compound include polyvinyl alcohol (PVA), aqueous acrylic resin, aqueous polyurethane resin, and the like.
　硬化剤としては、例えば、ブロックイソシアネート化合物変性ポリアミン、ポリアミド樹脂、ポリメルカプタン樹脂、ポリスルフィド樹脂、カルボジイミド類等が挙げられる。 Examples of the curing agent include blocked isocyanate compound-modified polyamines, polyamide resins, polymercaptan resins, polysulfide resins, carbodiimides, and the like.
　（２）第１処理剤で処理した有機繊維を本発明の有機繊維用接着剤を含む第２処理剤で処理する工程について述べる。 (2) The step of treating the organic fiber treated with the first treating agent with the second treating agent containing the organic fiber adhesive of the present invention will be described.
　本発明の有機繊維用接着剤を第２処理剤として用いた場合でも、上記本発明の有機繊維用接着剤で処理する工程を含む有機繊維処理方法と同様の手段及び条件で行い得る。ただし、熱処理の条件としては、１８０℃以上２４０℃以下で１分以上２分以下であることが好ましい。 Even when the organic fiber adhesive of the present invention is used as the second treating agent, it can be carried out by the same means and conditions as those of the organic fiber treatment method including the step of treating with the organic fiber adhesive of the present invention. However, the heat treatment condition is preferably 180 ° C. or higher and 240 ° C. or lower and 1 minute or longer and 2 minutes or shorter.
　第２処理剤の有機繊維への付着量は、十分な接着力を得つつも、得られる繊維が硬くなり過ぎないようにするため、固形分基準で、０．１重量％以上１０重量％以下が好ましく、０．５重量％以上５重量％以下が好ましい。 The amount of adhesion of the second treatment agent to the organic fiber is 0.1% by weight or more and 10% by weight or less based on the solid content in order to prevent the resulting fiber from becoming too hard while obtaining sufficient adhesive strength. Is preferably 0.5 wt% or more and 5 wt% or less.
　第２処理剤における任意成分としては、加硫調整剤、亜鉛華、酸化防止剤、消泡剤、湿潤剤などが挙げられる。 Examples of optional components in the second treating agent include a vulcanization regulator, zinc white, an antioxidant, an antifoaming agent, and a wetting agent.
　［用途］
　本発明の有機繊維の処理方法により処理された有機繊維は、タイヤ、ホース又はベルト等に用いることができる。具体的には、例えば、タイヤ、ホース又はベルトの内部に備えること、より具体的には、これらの内側に積層させる等の一般的な方法により、これらタイヤ、ホース又はベルト等を補強する補強材として用いることができる。 [Usage]
The organic fiber processed by the organic fiber processing method of the present invention can be used for a tire, a hose, a belt, or the like. Specifically, for example, a reinforcing material that reinforces these tires, hoses, or belts by a general method such as providing them inside tires, hoses, or belts, and more specifically, laminating them inside them. Can be used as
　以下に実施例を掲げて本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。以下、「部」又は「％」は特記ない限り、それぞれ「重量部」又は「重量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.
　実施例及び比較例における接着力の評価は、以下の接着力の評価１又は接着力の評価２に示す方法により行った。 Evaluation of adhesive strength in Examples and Comparative Examples was performed by the method shown in Evaluation 1 of adhesive strength or Evaluation 2 of adhesive strength below.
　＜接着力の評価１＞
　実施例１乃至４及び比較例１乃至２で処理を行った有機繊維を、天然ゴムを主成分とする未加硫ゴム中に埋め込み、１５０℃で３０分間プレス加硫し、次いで有機繊維をゴムブロックから３５０ｍｍ／分の速度で引き抜いた。引き抜きに要した力は接着力として単位［Ｎ／ｃｍ］として示される。この力の数値が大きいほどゴムに対する接着性が優れている。 <Evaluation 1 of adhesive strength>
The organic fibers treated in Examples 1 to 4 and Comparative Examples 1 and 2 were embedded in an unvulcanized rubber containing natural rubber as a main component, press vulcanized at 150 ° C. for 30 minutes, and then the organic fibers were rubber. The block was pulled out at a speed of 350 mm / min. The force required for pulling out is shown as a unit [N / cm] as an adhesive force. The larger the value of this force, the better the adhesion to rubber.
　＜接着力の評価２＞
　実施例５乃至７及び比較例３で処理を行った有機繊維をそれぞれ５本ずつ用意し、その５本の有機繊維上に、エチレンプロピレン系未加硫ゴムを置き、１６０℃、３０分間プレス加硫し、次いで５本の有機繊維を２００ｍｍ／分の速度で有機繊維とゴムを剥離するのに要した力を測定した。その力は、接着力として単位［Ｎ／５本］として示される。この力の数値が大きいほどゴムに対する接着性が優れている。 <Evaluation 2 of adhesive strength>
Five organic fibers treated in each of Examples 5 to 7 and Comparative Example 3 were prepared, and ethylene propylene-based unvulcanized rubber was placed on the five organic fibers, followed by pressing at 160 ° C. for 30 minutes. Sulfur was then measured, and then the force required to peel the organic fibers and rubber from the five organic fibers at a rate of 200 mm / min was measured. The force is shown as a unit [N / 5] as an adhesive force. The larger the value of this force, the better the adhesion to rubber.
　（実施例１）
　成分（Ｂ２）のうち（ｂ２）ゴムラテックスとして、ニッポール２５１８ＦＳ（日本ゼオン株式会社製、ビニルピリジン・スチレン・ブタジエンターポリマー水乳化液、全固形分濃度４０．５％）４３ｇ及びニッポールＬＸ－１１２（日本ゼオン株式会社製、スチレン・ブタジエンコポリマー４１％水乳化液、全固形分濃度４０．５％）１８．５ｇを水２０９ｇで希釈し、この希釈液の中に成分（Ａ２）として、レゾルシン３．４ｇ及びヘキサメチレンテトラミン０．９ｇを加え、処理剤を調製した。 (Example 1)
Among the components (B2), as the rubber latex (b2), 43 g of Nippon 2518FS (manufactured by Nippon Zeon Co., Ltd., vinylpyridine / styrene / butadiene terpolymer aqueous emulsion, total solid concentration: 40.5%) and NIPPOL LX-112 ( 18.5 g of a styrene / butadiene copolymer 41% aqueous emulsion (40.5% total solid concentration, manufactured by Nippon Zeon Co., Ltd.) is diluted with 209 g of water, and resorcinol 3. 4 g and 0.9 g of hexamethylenetetramine were added to prepare a treating agent.
　有機繊維として、ナイロン繊維であるナイロンコード（９４０デシテックスのマルチフィラメントを２本合わせて下撚り４７回／１０ｃｍを行い下撚コードを作製し、さらにこの下撚コードを２本併せて、下撚と反対方向に上撚り４７回／１０ｃｍを行ったもの）を、前記処理剤中に浸漬した後、１５０℃で１３０秒間乾燥し、引き続き２４０℃で７０秒間熱処理した。得られた処理後の有機繊維について、接着力の評価１に示す評価方法により、接着力の測定を行った。結果は表１に示す。 Nylon cords, which are nylon fibers (two 940 decitex multifilaments, are combined to prepare a lower twisted cord 47 times / 10 cm as organic fibers. Further, two lower twisted cords are combined and After being immersed in the treatment agent, the upper twist was 47 times / 10 cm in the opposite direction), dried at 150 ° C. for 130 seconds, and subsequently heat treated at 240 ° C. for 70 seconds. About the obtained organic fiber after a process, the adhesive force was measured by the evaluation method shown in Evaluation 1 of adhesive strength. The results are shown in Table 1.
　（比較例１）
　（ｂ２）ゴムラテックスとして、ニッポール２５１８ＦＳ（日本ゼオン株式会社製、ビニルピリジン・スチレン・ブタジエンターポリマー水乳化液、全固形分濃度４０．５％）１７２ｇ及びニッポールＬＸ－１１２（日本ゼオン株式会社製、スチレン・ブタジエンコポリマー４１％水乳化液、全固形分濃度４０．５％）７３ｇを水７６ｇで希釈し、この希釈液の中にレゾルシン・ホルマリン初期縮合分散液２７０ｇ（レゾルシンとホルムアルデヒドのモル比は、レゾルシン：ホルムアルデヒド＝１：１．５、全固形分濃度６．５％）をゆっくりかきませながら加え、ＲＦＬ（レゾルシン・ホルマリン・ラテックス）液を調製した。得られたＲＦＬ液を水５９１ｇで希釈し、処理剤を調製した。 (Comparative Example 1)
(B2) As a rubber latex, 172 g of Nippon 2518FS (manufactured by Nippon Zeon Co., Ltd., vinylpyridine / styrene / butadiene terpolymer aqueous emulsion, total solid concentration 40.5%) and NIPPOL LX-112 (manufactured by Nippon Zeon Co., Ltd.) A styrene / butadiene copolymer 41% aqueous emulsion (total solid content concentration 40.5%) 73 g was diluted with water 76 g, and resorcin / formalin initial condensation dispersion 270 g (resorcin / formaldehyde molar ratio was Resorcin: formaldehyde = 1: 1.5, total solid concentration 6.5%) was slowly added while stirring to prepare an RFL (resorcin / formalin / latex) solution. The obtained RFL solution was diluted with 591 g of water to prepare a treatment agent.
　有機繊維の処理は実施例１と同様に行い、得られた処理後の有機繊維について、接着力の評価１に示す評価方法により、接着力の測定を行った。結果は表１に示す。 The treatment of the organic fibers was performed in the same manner as in Example 1, and the obtained organic fibers were measured for adhesive strength by the evaluation method shown in Adhesive strength evaluation 1. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（実施例２）
　ソルビトールポリグリシジルエーテル４．８ｇを水２６５ｇに攪拌しながら加え、そこへブロックイソシアネート化合物（Ｃ）として、ε－カプロラクタムブロックジフェニルメタンジイソシアネート水分散体（全固形分濃度５４％）３０．３ｇを加え、第１処理剤を調製した。 (Example 2)
4.8 g of sorbitol polyglycidyl ether is added to 265 g of water with stirring, and 30.3 g of ε-caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid content concentration 54%) is added thereto as the blocked isocyanate compound (C). One treatment agent was prepared.
　成分（Ｂ１）のうち（ｂ２）ゴムラテックスとして、ニッポール２５１８ＦＳ（日本ゼオン株式会社製、ビニルピリジン・スチレン・ブタジエンターポリマー水乳化液、全固形分濃度４０．５％）４３ｇ及びニッポールＬＸ－１１２（日本ゼオン株式会社製、スチレン・ブタジエンコポリマー４１％水乳化液、全固形分濃度４０．５％）１８．５ｇを水２０９ｇで希釈し、この希釈液の中に成分（Ａ１）として、クロルフェノール樹脂（デナボンド（クロルフェノール、ホルムアルデヒド及びレゾルシンの縮合物）、ナガセケムテックス株式会社製、全固形分濃度２０％）２１．４ｇを加え、第２処理剤を調製した。 Among the component (B1), (b2) rubber latex, Nippon 2518FS (manufactured by Nippon Zeon Co., Ltd., vinylpyridine / styrene / butadiene terpolymer aqueous emulsion, total solid concentration 40.5%) 43 g and Nippon LX-112 ( 18.5 g of styrene-butadiene copolymer (41% water emulsion, total solid concentration: 40.5%) manufactured by Nippon Zeon Co., Ltd. was diluted with 209 g of water, and chlorophenol resin was used as component (A1) in this diluted solution. (Denabond (condensate of chlorophenol, formaldehyde and resorcin), Nagase ChemteX Corporation, total solid content concentration 20%) 21.4 g was added to prepare a second treatment agent.
　有機繊維として、ポリエステル繊維であるポリエステルコード（糸粘度０．９５のポリエチレンテレフタレートを溶融紡糸し、延伸した１，５００デニールのマルチフィラメントを２本合わせて下撚り４０回／１０ｃｍを行い下撚コードを作製し、この下撚コードを２本を合わせて、下撚りと反対方向に同数の上撚りをかけたもの）を、前記第１処理剤中に浸漬した後、１５０℃で１３０秒間乾燥し、引き続き２４０℃で１３０秒間熱処理した。次いで、第２処理剤に浸漬した後、１５０℃で１３０秒間乾燥し、引き続き２４０℃で７０秒間熱処理した。得られた処理後の有機繊維について、接着力の評価１に示す評価方法により、接着力の測定を行った。結果は表２に示す。 As an organic fiber, polyester cord (polyester terephthalate having a yarn viscosity of 0.95 is melt-spun, and two stretched 1,500 denier multifilaments are combined and twisted 40 times / 10 cm to form a twisted cord. The two twisted cords were prepared, and the same number of upper twists were applied in the opposite direction to the lower twist), and after dipping in the first treatment agent, they were dried at 150 ° C. for 130 seconds, Subsequently, heat treatment was performed at 240 ° C. for 130 seconds. Next, after being immersed in the second treatment agent, it was dried at 150 ° C. for 130 seconds, and subsequently heat-treated at 240 ° C. for 70 seconds. About the obtained organic fiber after a process, the adhesive force was measured by the evaluation method shown in Evaluation 1 of adhesive strength. The results are shown in Table 2.
　（実施例３）
　第２処理剤中の水２０９ｇを２２６ｇに、クロルフェノール樹脂（デナボンド（クロルフェノール、ホルムアルデヒド及びレゾルシンの縮合物）、ナガセケムテックス株式会社製、全固形分濃度２０％）２１．４ｇをリグニン樹脂（リグニンスルホン酸ナトリウム）４．３ｇに変更した以外は、実施例２と同様に有機繊維の処理を行った。得られた処理後の有機繊維について、接着力の評価１に示す評価方法により、接着力の測定を行った。結果は表２に示す。 (Example 3)
209 g of water in the second treatment agent is added to 226 g, and 21.4 g of chlorophenol resin (denabond (condensate of chlorophenol, formaldehyde and resorcin), manufactured by Nagase ChemteX Corporation, total solid content concentration 20%) is lignin resin ( The organic fiber was treated in the same manner as in Example 2 except that the amount was changed to 4.3 g (sodium lignin sulfonate). About the obtained organic fiber after a process, the adhesive force was measured by the evaluation method shown in Evaluation 1 of adhesive strength. The results are shown in Table 2.
　（実施例４）
　第二処理剤中の水２０９ｇを２２６ｇに、クロルフェノール樹脂（デナボンド（クロルフェノール、ホルムアルデヒド及びレゾルシンの縮合物）、ナガセケムテックス株式会社製、全固形分濃度２０％）２１．４ｇをレゾルシン３．４ｇ及びヘキサメチレンテトラミン０．９ｇに変更した以外は、実施例２と同様に有機繊維の処理を行った。得られた処理後の有機繊維について、接着力の評価１に示す評価方法により、接着力の測定を行った。結果は表２に示す。 Example 4
2. 209 g of water in the second treating agent was added to 226 g, 21.4 g of chlorophenol resin (denabond (condensate of chlorophenol, formaldehyde and resorcin), manufactured by Nagase ChemteX Corporation, total solid content concentration 20%) 2. The organic fiber was treated in the same manner as in Example 2 except that the amount was changed to 4 g and 0.9 g of hexamethylenetetramine. About the obtained organic fiber after a process, the adhesive force was measured by the evaluation method shown in Evaluation 1 of adhesive strength. The results are shown in Table 2.
　（比較例２）
　ソルビトールポリグリシジルエーテル４．８ｇを水３５２ｇに攪拌しながら加え、そこへブロックイソシアネート化合物（Ｃ）として、ε－カプロラクタムブロックジフェニルメタンジイソシアネート水分散体（全固形分濃度５４％）２６．７ｇを加え、第１処理剤を調製した。 (Comparative Example 2)
4.8 g of sorbitol polyglycidyl ether is added to 352 g of water while stirring, and 26.7 g of an ε-caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid content concentration 54%) is added thereto as the blocked isocyanate compound (C). One treatment agent was prepared.
　（ｂ２）ゴムラテックスとして、ニッポール２５１８ＦＳ（日本ゼオン株式会社製、ビニルピリジン・スチレン・ブタジエンターポリマー水乳化液、全固形分濃度４０．５％）１７２ｇ及びニッポールＬＸ－１１２（日本ゼオン株式会社製、スチレン・ブタジエンコポリマー４１％水乳化液、全固形分濃度４０．５％）７３ｇを水７６ｇで希釈し、この希釈液の中にレゾルシン・ホルマリン初期縮合分散液２７０ｇ(レゾルシンとホルムアルデヒドのモル比は、１：１．５、全固形分濃度６．５％)をゆっくりかきませながら加え、ＲＦＬ液を調製した。得られたＲＦＬ液を水５９１ｇで希釈し、第２処理剤を調製した。 (B2) As a rubber latex, 172 g of Nippon 2518FS (manufactured by Nippon Zeon Co., Ltd., vinylpyridine / styrene / butadiene terpolymer aqueous emulsion, total solid concentration 40.5%) and NIPPOL LX-112 (manufactured by Nippon Zeon Co., Ltd.) A styrene / butadiene copolymer 41% aqueous emulsion (total solid concentration: 40.5%) 73 g was diluted with water 76 g, and resorcin / formalin initial condensation dispersion 270 g (molar ratio of resorcin to formaldehyde 1: 1.5, total solid concentration 6.5%) was slowly added while stirring to prepare an RFL solution. The obtained RFL solution was diluted with 591 g of water to prepare a second treatment agent.
　有機繊維の処理は実施例２と同様に行い、得られた処理後の有機繊維について、接着力の評価１に示す評価方法により、接着力の測定を行った。結果は表２に示す。 The treatment of the organic fibers was performed in the same manner as in Example 2, and the adhesion strength of the obtained organic fibers after the treatment was measured by the evaluation method shown in Evaluation 1 of adhesion strength. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　（実施例５）
　ソルビトールポリグリシジルエーテル４．８ｇを水３５２ｇに攪拌しながら加え、そこへブロックイソシアネート化合物（Ｃ）として、ε－カプロラクタムブロックジフェニルメタンジイソシアネート水分散体（全固形分濃度５４％）２６．７ｇを加え、第１処理剤を調製した。 (Example 5)
4.8 g of sorbitol polyglycidyl ether is added to 352 g of water while stirring, and 26.7 g of an ε-caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid content concentration 54%) is added thereto as the blocked isocyanate compound (C). One treatment agent was prepared.
　成分（Ｂ１）のうち（ｂ１）アイオノマー樹脂として、ケミパールＳ３００（三井化学株式会社製、全固形分濃度３５％）６９．７ｇを水８６ｇで希釈し、この希釈液の中に成分（Ａ１）のうち（ａ１）ポリフェノール類として、タンニン酸２．５ｇを加え、さらに、３７％ホルムアルデヒド水溶液２．７ｇ及びブロックイソシアネート化合物（Ｃ）として、ε－カプロラクタムブロックジフェニルメタンジイソシアネート水分散体（全固形分濃度５４％）３．７ｇを加え、第２処理剤を調製した。 Among component (B1), 69.7 g of Chemipearl S300 (Mitsui Chemical Co., Ltd., total solid content 35%) as (b1) ionomer resin was diluted with 86 g of water, and component (A1) was diluted into this diluted solution. Among them, 2.5 g of tannic acid was added as polyphenols, and 2.7 g of 37% formaldehyde aqueous solution and blocked isocyanate compound (C) as an ε-caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid concentration 54%) ) 3.7g was added to prepare a second treating agent.
　有機繊維の処理は実施例２と同様に行い、得られた処理後の有機繊維について、接着力の評価２に示す評価方法により、接着力の測定を行った。結果は表３に示す。 The treatment of organic fibers was performed in the same manner as in Example 2, and the obtained organic fibers were measured for adhesive strength by the evaluation method shown in Adhesiveness Evaluation 2. The results are shown in Table 3.
　（実施例６）
　第２処理剤中の水８６ｇを７６ｇに、タンニン酸２．５ｇをクロルフェノール樹脂（デナボンド（ナガセケムテックス株式会社製、全固形分濃度２０％））１２．４ｇに変更した以外は、実施例５と同様に有機繊維の処理を行った。得られた処理後の有機繊維について、接着力の評価２に示す評価方法により、接着力の測定を行った。結果は表３に示す。 (Example 6)
Except that 86 g of water in the second treating agent was changed to 76 g and 2.5 g of tannic acid was changed to 12.4 g of chlorophenol resin (Denabond (manufactured by Nagase ChemteX Corporation, total solid content 20%)) 12.4 g. The organic fiber was treated in the same manner as in No. 5. About the obtained organic fiber after a process, the adhesive force was measured by the evaluation method shown in Evaluation 2 of adhesive strength. The results are shown in Table 3.
　（実施例７）
　第２処理剤中のタンニン酸２．５ｇをレゾルシン２．０ｇ及びヘキサメチレンテトラミン０．５ｇに変更した以外は、実施例５と同様に行った。得られた処理後の有機繊維について、接着力の評価２に示す評価方法により、接着力の測定を行った。結果は表３に示す。 (Example 7)
The same procedure as in Example 5 was performed except that 2.5 g of tannic acid in the second treatment agent was changed to 2.0 g of resorcin and 0.5 g of hexamethylenetetramine. About the obtained organic fiber after a process, the adhesive force was measured by the evaluation method shown in Evaluation 2 of adhesive strength. The results are shown in Table 3.
　（比較例３）
　ソルビトールポリグリシジルエーテル４．８ｇを水３５２ｇに攪拌しながら加え、そこへブロックイソシアネート化合物（Ｃ）として、ε－カプロラクタムブロックジフェニルメタンジイソシアネート水分散体（全固形分濃度５４％）２６．７ｇを加え、第１処理剤を調製した。 (Comparative Example 3)
4.8 g of sorbitol polyglycidyl ether is added to 352 g of water while stirring, and 26.7 g of an ε-caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid content concentration 54%) is added thereto as the blocked isocyanate compound (C). One treatment agent was prepared.
　（ｂ１）アイオノマー樹脂として、ケミパールＳ３００（三井化学株式会社製、全固形分濃度３５％）６９．７ｇを水７４ｇで希釈し、この希釈液の中にレゾルシン・ホルマリン初期縮合分散液６７．３ｇ（レゾルシンとホルムアルデヒドのモル比は、レゾルシン：ホルムアルデヒド＝１：１．５、全固形分濃度６．５％）を加え、さらに、３７％ホルムアルデヒド水溶液４．３ｇ及びブロックイソシアネート化合物（Ｃ）として、ε－カプロラクタムブロックジフェニルメタンジイソシアネート水分散体（全固形分濃度５４％）５．９ｇを加え、第２処理剤を調製した。 (B1) As an ionomer resin, 69.7 g of Chemipearl S300 (manufactured by Mitsui Chemicals, total solid content 35%) was diluted with 74 g of water, and 67.3 g of resorcin / formalin initial condensation dispersion (in this diluted solution) The resorcinol / formaldehyde molar ratio was such that resorcin: formaldehyde = 1: 1.5, total solid concentration 6.5%), and 4.3 g of 37% formaldehyde aqueous solution and blocked isocyanate compound (C) 5.9 g of caprolactam block diphenylmethane diisocyanate aqueous dispersion (total solid concentration 54%) was added to prepare a second treating agent.
　有機繊維の処理は実施例２と同様に行い、得られた処理後の有機繊維について、接着力の評価２に示す評価方法により、接着力の測定を行った。結果は表３に示す。 The treatment of organic fibers was performed in the same manner as in Example 2, and the obtained organic fibers were measured for adhesive strength by the evaluation method shown in Adhesiveness Evaluation 2. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１に示すように、実施例１のレゾルシンとホルマリンとの初期縮合物を使用することなしに調製した処理剤が、比較例１のレゾルシンとホルマリンとの初期縮合物含む処理剤に比べ、優れた接着性を示した。また、表２に示すように、実施例２乃至４のレゾルシンとホルマリンとの初期縮合物を使用することなしに調整した処理剤は、いずれも比較例２のレゾルシンとホルマリンとの初期縮合物を使用するＲＦＬ液を含む処理剤に比べ、優れた接着性を示した。また、処理剤にはＲＦＬ液を含まないため、ホルマリンの使用量の削減が可能となり作業環境を良好にすることができ、さらに成分（Ａ１）又は成分（Ａ２）を使用するため保存安定性にも優れる。 As shown in Table 1, the treating agent prepared without using the initial condensate of resorcin and formalin in Example 1 is superior to the treating agent containing the initial condensate of resorcin and formalin in Comparative Example 1. Showed good adhesion. Further, as shown in Table 2, the treatment agents prepared without using the initial condensate of resorcin and formalin in Examples 2 to 4 are all the initial condensate of resorcin and formalin in Comparative Example 2. Compared to the treatment agent containing the RFL solution to be used, excellent adhesion was exhibited. Further, since the treatment agent does not contain an RFL solution, the amount of formalin used can be reduced, and the working environment can be improved. Furthermore, since component (A1) or component (A2) is used, storage stability is improved. Also excellent.
　さらに、表３に示すように、実施例５乃至７及び比較例３の比較により、本発明の有機繊維用接着剤によれば、レゾルシンとホルマリンとの初期縮合物を使用せずとも、レゾルシンとホルマリンとの初期縮合物を使用した場合と同等又はそれ以上に、有機繊維とゴムとの接着性を優れたものとできることが分かる。 Furthermore, as shown in Table 3, according to the comparison of Examples 5 to 7 and Comparative Example 3, according to the adhesive for organic fibers of the present invention, resorcin and the resorcin were obtained without using the initial condensate of resorcin and formalin. It can be seen that the adhesiveness between the organic fiber and the rubber can be improved to be equal to or more than when the initial condensate with formalin is used.

Claims (10)

  1. 　ポリフェノール類、クロルフェノール樹脂及びリグニン樹脂からなる群より選択される少なくとも１種の成分（Ａ１）、及び前記成分（Ａ１）以外の水溶性ポリマー又は前記成分（Ａ１）以外の水分散性ポリマーから選択される少なくとも１種の成分（Ｂ１）を含み、
    レゾルシンとホルマリンとの初期縮合物を実質的に含まないことを特徴とする有機繊維用接着剤。     Selected from at least one component (A1) selected from the group consisting of polyphenols, chlorophenol resins and lignin resins, and water-soluble polymers other than the component (A1) or water-dispersible polymers other than the component (A1) Comprising at least one component (B1)
    An adhesive for organic fibers, which is substantially free from an initial condensate of resorcin and formalin.
  2. 　ポリフェノール類、クロルフェノール樹脂及びリグニン樹脂からなる群より選択される少なくとも１種の成分と、メラミン誘導体又はヘキサメチレンテトラミンとの混合物（Ａ２）、及び前記成分（Ａ２）以外の水溶性ポリマー又は前記成分（Ａ２）以外の水分散性ポリマーから選択される少なくとも１種の成分（Ｂ２）を含み、
    レゾルシンとホルマリンとの初期縮合物を実質的に含まないことを特徴とする有機繊維用接着剤。     A mixture (A2) of at least one component selected from the group consisting of polyphenols, chlorophenol resins and lignin resins and a melamine derivative or hexamethylenetetramine, and a water-soluble polymer other than the component (A2) or the component Including at least one component (B2) selected from water-dispersible polymers other than (A2),
    An adhesive for organic fibers, which is substantially free from an initial condensate of resorcin and formalin.
  3. 　前記成分（Ｂ１）又は（Ｂ２）が、それぞれ（ｂ１）アイオノマー樹脂、（ｂ２）ゴムラテックス、（ｂ３）アクリル系樹脂、（ｂ４）オレフィン系樹脂、（ｂ５）塩化ビニル系樹脂及び（ｂ６）酢酸ビニル系樹脂からなる群より選択される少なくとも１種の成分である、請求項１又は２に記載の有機繊維用接着剤。 The component (B1) or (B2) comprises (b1) ionomer resin, (b2) rubber latex, (b3) acrylic resin, (b4) olefin resin, (b5) vinyl chloride resin and (b6) acetic acid, respectively. The adhesive for organic fibers according to claim 1 or 2, which is at least one component selected from the group consisting of vinyl resins.
  4. 　ブロックイソシアネート化合物（Ｃ）を含む、請求項１～３のいずれか１項に記載の有機繊維用接着剤。 The adhesive for organic fibers according to any one of claims 1 to 3, comprising a blocked isocyanate compound (C).
  5. 　前記有機繊維がナイロン繊維、レーヨン繊維、ポリエステル繊維及びアラミド繊維からなる群より選択される少なくとも１種である、請求項１～４のいずれか１項に記載の有機繊維用接着剤。 The organic fiber adhesive according to any one of claims 1 to 4, wherein the organic fiber is at least one selected from the group consisting of nylon fiber, rayon fiber, polyester fiber, and aramid fiber.
  6. 　有機繊維を請求項１～４のいずれか１項に記載の有機繊維用接着剤で処理する工程を含む、有機繊維の処理方法。 A method for treating organic fibers, comprising a step of treating organic fibers with the adhesive for organic fibers according to any one of claims 1 to 4.
  7. 　以下（１）及び（２）の工程を含む、有機繊維の処理方法。
    （１）エポキシ化合物又はハロヒドリン化合物を含む第１処理剤で有機繊維を処理する工程
    （２）第１処理剤で処理した有機繊維を請求項１～４のいずれか１項に記載の有機繊維用接着剤を含む第２処理剤で処理する工程     The processing method of organic fiber including the process of (1) and (2) below.
    (1) A step of treating organic fibers with a first treatment agent containing an epoxy compound or a halohydrin compound (2) An organic fiber treated with the first treatment agent for organic fibers according to any one of claims 1 to 4 The process of processing with the 2nd processing agent containing an adhesive agent
  8. 　前記有機繊維がナイロン繊維、レーヨン繊維、ポリエステル繊維及びアラミド繊維からなる群より選択される少なくとも１種である、請求項６又は７に記載の有機繊維の処理方法。 The method for treating organic fiber according to claim 6 or 7, wherein the organic fiber is at least one selected from the group consisting of nylon fiber, rayon fiber, polyester fiber and aramid fiber.
  9. 　請求項６～８のいずれか１項に記載の有機繊維の処理方法により処理された有機繊維。 Organic fiber treated by the organic fiber treatment method according to any one of claims 6 to 8.
  10. 　請求項９に記載の有機繊維を用いたタイヤ、ホース又はベルト。 A tire, a hose or a belt using the organic fiber according to claim 9.
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US20190390090A1 (en) * 2018-06-26 2019-12-26 Samsung Electronics Co., Ltd. Adhesive for pellicle, pellicle for photo mask and method for manufacturing the same
WO2020031408A1 (en) * 2018-08-07 2020-02-13 東レ・デュポン株式会社 Fiber cord for rubber reinforcement
JP2021522386A (en) * 2018-04-26 2021-08-30 ポルシェ アンデュストリ Adhesive Improvement Compositions for Textile Materials and Related Reinforced Textile Materials
WO2022137703A1 (en) * 2020-12-23 2022-06-30 株式会社ブリヂストン Adhesive composition for organic fiber, organic fiber/rubber composite, and tire
WO2022137908A1 (en) * 2020-12-23 2022-06-30 株式会社ブリヂストン Adhesive composition for organic fibers, organic fiber-rubber composite body, and tire
WO2022137861A1 (en) 2020-12-23 2022-06-30 株式会社ブリヂストン Adhesive composition, and resin material, rubber article, organic fiber-rubber composite, and tire using same
WO2023090008A1 (en) 2021-11-17 2023-05-25 株式会社ブリヂストン Adhesive composition, organic fibrous material, rubber article, organic fiber/rubber composite, and tire
WO2023090030A1 (en) 2021-11-17 2023-05-25 株式会社ブリヂストン Adhesive composition, organic fiber, organic fiber/rubber composite material, rubber article, and tire
WO2023095655A1 (en) 2021-11-25 2023-06-01 東レ株式会社 Rubber/fiber adhesion treating agent and synthetic fiber cord for rubber reinforcement using same
EP4119631A4 (en) * 2020-03-11 2023-08-23 Bridgestone Corporation Adhesive composition, rubber-organic fiber cord composite, and tire
JP7444647B2 (en) 2020-03-11 2024-03-06 株式会社ブリヂストン pneumatic tires

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Publication number Priority date Publication date Assignee Title
CN109403040A (en) * 2018-01-16 2019-03-01 烟台泰和工程材料有限公司 A kind of preparation of aramid fiber modified solution
JP2021522386A (en) * 2018-04-26 2021-08-30 ポルシェ アンデュストリ Adhesive Improvement Compositions for Textile Materials and Related Reinforced Textile Materials
JP7393346B2 (en) 2018-04-26 2023-12-06 ポルシェ アンデュストリ Adhesion improving compositions for textile materials and related reinforced textile materials
US20190390090A1 (en) * 2018-06-26 2019-12-26 Samsung Electronics Co., Ltd. Adhesive for pellicle, pellicle for photo mask and method for manufacturing the same
JP7320912B2 (en) 2018-08-07 2023-08-04 東レ・デュポン株式会社 Fiber cord for rubber reinforcement
WO2020031408A1 (en) * 2018-08-07 2020-02-13 東レ・デュポン株式会社 Fiber cord for rubber reinforcement
JPWO2020031408A1 (en) * 2018-08-07 2021-08-02 東レ・デュポン株式会社 Fiber cord for rubber reinforcement
JP7444647B2 (en) 2020-03-11 2024-03-06 株式会社ブリヂストン pneumatic tires
EP4119631A4 (en) * 2020-03-11 2023-08-23 Bridgestone Corporation Adhesive composition, rubber-organic fiber cord composite, and tire
WO2022137908A1 (en) * 2020-12-23 2022-06-30 株式会社ブリヂストン Adhesive composition for organic fibers, organic fiber-rubber composite body, and tire
WO2022137861A1 (en) 2020-12-23 2022-06-30 株式会社ブリヂストン Adhesive composition, and resin material, rubber article, organic fiber-rubber composite, and tire using same
WO2022137703A1 (en) * 2020-12-23 2022-06-30 株式会社ブリヂストン Adhesive composition for organic fiber, organic fiber/rubber composite, and tire
WO2023090030A1 (en) 2021-11-17 2023-05-25 株式会社ブリヂストン Adhesive composition, organic fiber, organic fiber/rubber composite material, rubber article, and tire
WO2023090008A1 (en) 2021-11-17 2023-05-25 株式会社ブリヂストン Adhesive composition, organic fibrous material, rubber article, organic fiber/rubber composite, and tire
WO2023095655A1 (en) 2021-11-25 2023-06-01 東レ株式会社 Rubber/fiber adhesion treating agent and synthetic fiber cord for rubber reinforcement using same

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