Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
• • 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
  • D06M15/263—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
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

• the present invention relates to a water- and oil-repellent treatment for fabrics, and to fabrics.
• a water- and oil-repellent treatment for fabrics contains a polyolefin resin, a polyolefin composite acrylic resin having an acrylic polymer, and an aqueous medium (see, for example, Patent Document 1).
• the problem that this invention aims to solve is to provide a water- and oil-repellent treatment for fabrics that does not contain fluorine compounds, which are of concern for their environmental impact, and that can exhibit excellent water- and oil-repellency.
• the present invention relates to a water- and oil-repellent treatment agent for fabrics, which contains a chlorinated polyolefin composite acrylic resin (A) having a chlorinated polyolefin resin (a1) and an acrylic polymer (a2), an aqueous medium (B), and a modified silicone oil (C), characterized in that the modified silicone oil (C) contains an amino-modified silicone oil (c1) and a polyether-modified silicone oil (c2).
• the water- and oil-repellent treatment agent for fabrics of the present invention can impart excellent water- and oil-repellent properties to the substrate, and can therefore be suitably used as a water- and oil-repellent treatment agent for fabrics made of fibers such as cotton, silk, wool, hemp, polyethylene, nylon, polyester, polyurethane, and rayon.
• the chlorinated polyolefin resin (a1) is a chlorinated polyolefin resin
• examples of the polyolefin resin include polypropylene, high density polyethylene, ultra-high molecular weight polyethylene, linear low density polyethylene, low density polyethylene, very low density polyethylene, ultra-low density polyethylene, polymethylpentene, ethylene-propylene copolymer, propylene-1-butene random copolymer, propylene-ethylene-1-butene random copolymer, copolymer of propylene and ⁇ -olefin having 5 to 12 carbon atoms, propylene-non-conjugated diene copolymer, ethylene-non-conjugated diene copolymer, ethylene-propylene-non-conjugated diene copolymer, polybutene, ethylene-vinyl acetate copolymer, ethylene-vinyltrimethoxysilane copolymer, ethylene-methyl
• the chlorinated polyolefin resin (a1) may be used alone or in combination of two or more types, but preferably contains a chlorinated polypropylene resin.
• the acid value of the acrylic polymer (a2) may be 1 to 15 mgKOH/g, or 3 to 12 mgKOH/g.
• (meth)acrylate refers to either or both of methacrylate and acrylate
• (meth)acrylic acid refers to either or both of methacrylic acid and acrylic acid
• (anhydride)maleic acid refers to either or both of maleic anhydride and maleic acid.
• the mass ratio (a1/a2) of the chlorinated polyolefin resin (a1) to the acrylic polymer (a2) is preferably 5/95 to 40/60, and more preferably 5/95 to 30/70, since this improves the balance of water repellency and oil repellency.
• the underwater polymerization method or the emulsion polymerization method is preferred since the chlorinated polyolefin composite acrylic resin (A) can be easily obtained.
• An example of a method for obtaining the chlorinated polyolefin composite acrylic resin (A) by emulsion polymerization is a method in which the monomer raw material for the acrylic polymer (a2) is radically polymerized in an aqueous medium in the presence of the chlorinated polyolefin resin (a1), an emulsifier, and a polymerization initiator at a temperature of 50 to 100°C.
• the emulsifier examples include anionic emulsifiers such as sulfate esters of higher alcohols and their salts, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, sulfate half ester salts of polyoxyethylene alkyl ethers, alkyl diphenyl ether disulfonates, and dialkyl succinate sulfonates; nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene diphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, and acetylene diols; cationic emulsifiers such as alkyl ammonium salts; and amphoteric emulsifiers such as alkyl (amide) betaines and alkyl dimethyl amine
• polymerization initiator examples include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and azobiscyanovaleric acid; organic peroxides such as tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, and tert-butyl hydroperoxide; and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.
• These polymerization initiators can be used alone or in combination of two or more kinds. It is also preferable to use these polymerization initiators in an amount of 0.1 to 10% by mass based on the total amount of the monomers that are the raw materials for the polymer.
• the dispersion stability of the chlorinated polyolefin composite acrylic resin (A) is further improved, it is preferable to adjust the pH with a basic compound and/or an acidic compound.
• the basic compound include organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-aminoethanol, and 2-dimethylaminoethanol; inorganic basic compounds such as ammonia (water), sodium hydroxide, and potassium hydroxide; and quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, and trimethylbenzylammonium hydroxide.
• These basic compounds can be used alone or in combination of two or more.
• the acidic compounds include, for example, carboxylic acid compounds such as formic acid, acetic acid, propionic acid, and lactic acid; monoesters and diesters of phosphoric acid such as monomethyl phosphate and dimethyl phosphate; organic sulfonic acid compounds such as methanesulfonic acid, benzenesulfonic acid, and dodecylbenzenesulfonic acid; and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
• carboxylic acid compounds are preferred. These acidic compounds can be used alone or in combination of two or more kinds.
• the aqueous medium (B) may be water, an organic solvent miscible with water, or a mixture thereof.
• organic solvents miscible with water include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; alkyl ethers of polyalkylene glycols; and lactams such as N-methyl-2-pyrrolidone.
• water alone may be used, or a mixture of water and an organic solvent miscible with water may be used, or an organic solvent miscible with water alone may be used. From the standpoint of safety and environmental impact, water alone or a mixture of water and an organic solvent miscible with water is preferred, and it is particularly preferred to use water alone.
• aqueous medium (B) that is the same as that used when producing the chlorinated polyolefin composite acrylic resin (A) by the underwater polymerization method and emulsion polymerization method.
• the water- and oil-repellent treatment agent for fabrics of the present invention contains the chlorinated polyolefin composite acrylic resin (A) and the aqueous medium (B), and is preferably prepared by diluting with water an aqueous dispersion in which the chlorinated polyolefin composite acrylic resin (A) is dispersed in the aqueous medium (B), the aqueous dispersion being obtained by an emulsion polymerization method or the like.
• the amount of organic solvents in the water/oil repellent treatment agent for fabrics of the present invention can be reduced.
• the modified silicone oil (C) includes amino-modified silicone oil (c1) and polyether-modified silicone oil (c2).
• the amino-modified silicone oil (c1) is a silicone having an amino group, but a silicone oil having an aminopropyl group or an iminopropyl group is preferred, and a silicone oil having an iminopropyl group is more preferred.
• the functional group equivalent weight of the amino-modified silicone oil (c1) is preferably 1,000 to 7,000.
• the polyether-modified silicone oil (c2) is a silicone having a polyether structure, and the HLB of the polyether-modified silicone oil (c2) is preferably 5 to 13.
• the mass ratio (c1/c2) of the amino modified silicone oil (c1) to the polyether modified silicone oil (c2) is preferably 10/90 to 90/10, and more preferably 20/80 to 80/20.
• the content of the amino-modified silicone oil (c1) is preferably 0.5 to 25% by mass, and more preferably 2 to 20% by mass, relative to 100% by mass of the acrylic polymer (A), because this improves the balance between water repellency and oil repellency.
• the content of the polyether-modified silicone oil (c2) is preferably 0.5 to 25% by mass, and more preferably 2 to 20% by mass, relative to 100% by mass of the acrylic polymer (A), because this improves the balance between water repellency and oil repellency.
• the water- and oil-repellent treatment agent for fabrics of the present invention can also contain silicone oils other than the modified silicone oil (C).
• the amount of chlorinated polyolefin composite acrylic resin (A) in the water/oil repellent treatment agent for fabrics of the present invention is preferably less than 10% by mass, more preferably less than 3% by mass, and is preferably 0.05% or more, more preferably 0.1% or more.
• the aqueous medium (B) in the water/oil repellent treatment agent for fabrics of the present invention is preferably 90% by mass or more, more preferably 97% by mass or more, and is preferably less than 99.95% by mass, more preferably less than 99.9%.
• the water/oil repellent treatment agent for fabrics of the present invention can be used in combination with additives such as water repellents, oil repellents, dispersants, curing catalysts, lubricants, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light resistance stabilizers, fluorescent whitening agents, foaming agents, pH adjusters, leveling agents, gelling inhibitors, dispersion stabilizers, antioxidants, radical scavengers, heat resistance agents, inorganic fillers, organic fillers, plasticizers, reinforcing agents, catalysts, antibacterial agents, mildew inhibitors, rust inhibitors, thermoplastic resins, thermosetting resins, pigments, dyes, conductivity agents, antistatic agents, moisture permeability enhancers, oil repellents, hollow foams, compounds containing crystal water, flame retardants, water absorbents, moisture absorbents, deodorizers, foam stabilizers, defoamers, antifungal agents, preservatives, anti-alg
• the water- and oil-repellent treatment agent for fabrics of the present invention preferably contains a nonionic dispersant such as polyoxyalkylene alkyl ether, since this makes it possible to make the dispersion state of each component more uniform.
• a nonionic dispersant such as polyoxyalkylene alkyl ether
• the content of the nonionic dispersant in the water- and oil-repellent treatment agent for fabrics is preferably 0.1 to 10 mass %, and more preferably 0.2 to 5 mass %, per 100 mass parts of the chlorinated polyolefin composite acrylic resin (A), because this makes the dispersion state of each component more uniform.
• Fabrics that can be treated with the water- and oil-repellent treatment agent for fabrics of the present invention include, for example, fabrics made of chemical fibers such as nylon, polyester, polyurethane, polypropylene, and rayon, and fabrics made of a blend of two or more of the above chemical fibers.
• Hitenol LA-12 were dissolved in 120 parts by mass of ion-exchanged water to prepare an emulsifier aqueous solution, to which was added a mixture of 34 parts by mass of chlorinated polyolefin resin (a1-1) (Nippon Paper Industries Co., Ltd.
• aqueous dispersion (1) of chlorinated polyolefin composite acrylic resin was obtained.
• the property values of this aqueous dispersion were 40% by mass of nonvolatile content, pH 7.4, and viscosity 9 mPa ⁇ s.
• Example 1 Production and evaluation of water- and oil-repellent treatment agent for fabric (1)
• a dispersant Noigen XL-41
• Noigen XL-41 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
• polyoxyalkylene branched decyl ether 3 parts by mass of amino-modified silicone oil
• DOWSIL SF-8417 manufactured by Dow Toray Industries, Inc.
• polyether-modified silicone oil (“DOWSIL SF-8410” manufactured by Dow Toray Industries, Inc.) were added, and then the non-volatile content was adjusted to 0.6% by mass with ion-exchanged water to obtain a water/oil repellent treatment agent (1) for fabric.
• Example 2 Production and evaluation of water- and oil-repellent treatment agent for fabric (2)
• a water- and oil-repellent treatment agent for fabrics (2) having a non-volatile content of 0.6% by mass was obtained in the same manner as in Example 1, except that the amino-modified silicone oil used in Example 1 was changed from 3 parts by mass to 2 parts by mass, and the polyether-modified silicone oil was changed from 1 part by mass to 2 parts by mass.
• Example 3 Production and evaluation of water- and oil-repellent treatment agent for fabric (3)
• a water- and oil-repellent treatment agent for fabrics (3) having a non-volatile content of 0.6% by mass was obtained in the same manner as in Example 1, except that the amino-modified silicone oil used in Example 1 was changed from 3 parts by mass to 1 part by mass, and the polyether-modified silicone oil was changed from 1 part by mass to 3 parts by mass.
• Example 4 Production and evaluation of water- and oil-repellent treatment agent for fabric (4)
• a water- and oil-repellent treatment agent for fabrics (4) having a nonvolatile content of 0.6% by mass was obtained in the same manner as in Example 1, except that the water dispersion (1) of the chlorinated polyolefin-composite acrylic resin used in Example 1 was changed to the water dispersion (2) of the chlorinated polyolefin-composite acrylic resin.
• Example 5 Production and evaluation of water- and oil-repellent treatment agent for fabric (5)
• a water- and oil-repellent treatment agent for fabrics (5) having a nonvolatile content of 0.6% by mass was obtained in the same manner as in Example 1, except that the aqueous dispersion (1) of chlorinated polyolefin-composite acrylic resin used in Example 1 was changed to the aqueous dispersion (2) of chlorinated polyolefin-composite acrylic resin, the amount of amino-modified silicone oil was changed from 3 parts by mass to 1 part by mass, and the amount of polyether-modified silicone oil was changed from 1 part by mass to 3 parts by mass.
• the water/oil repellent treatment agent for fabric obtained above was applied to a base fabric (high density nylon fabric) by a dip nip method using a mangle coater at a basis weight of 15.6 g/ m2 wet, and then dried at 130°C for 5 minutes and then at 160°C for 5 minutes to obtain a test fabric.
• water- and oil-repellent treatment agents for fabrics of the present invention in Examples 1 to 5 can impart water- and oil-repellency.
• Comparative Example 1 is an example in which chlorinated polyolefin resin, an essential raw material of the present invention, was not used, and it was confirmed that the oil repellency was insufficient.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Textile Engineering (AREA)
• Combustion & Propulsion (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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Citations (5)

• 2024
  • 2024-10-24 WO PCT/JP2024/037855 patent/WO2025134527A1/ja active Pending
  • 2024-10-24 JP JP2025522181A patent/JP7790636B2/ja active Active

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