Classifications

• • 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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