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
• • 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
  • C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/395—Isocyanates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
• • 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 repellent, a method for producing a water repellent fiber product, and a water repellent fiber product.
• Patent Document 1 a fluorine-based water repellent containing a fluorine element is widely used (Patent Document 1 and the like).
• Fluorine compounds such as perfluorooctanoic acid (hereinafter, referred to as “PFOA”) and perfluorooctanesulfonic acid (hereinafter, referred to as “PFOS”) contained in the fluorine-based water repellent may affect living environments, living organisms, and the like. is there. Therefore, in recent years, non-fluorine-based water repellents containing no elemental fluorine have been proposed.
• PFOA perfluorooctanoic acid
• PFOS perfluorooctanesulfonic acid
• non-fluorine-based water repellents have lower water repellency than fluorine-based water repellents, and in particular, water repellency after washing tends to be reduced. Therefore, a non-fluorinated water repellent excellent in water repellency is required.
• an object of the present invention is to provide a water repellent agent which does not contain a fluorine element and has excellent water repellency, a method for producing a water repellent fiber product using the same, and a water repellent fiber product.
• the water repellent of the present invention is characterized by containing an adduct (A) of the following components (a) and (b).
• A a vinyl polymer having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, and an imino group; and
• the method for producing a water-repellent fiber product of the present invention is characterized by including a water-repellent treatment step of treating fibers with a treatment liquid containing the water-repellent agent of the present invention.
• the water-repellent fiber product of the present invention is characterized in that the adduct (A) or the crosslinked product of the adduct (A) in the water-repellent agent of the present invention adheres to fibers.
• a water repellent agent which does not contain a fluorine element and has excellent water repellency, a method for producing a water repellent fiber product using the same, and a water repellent fiber product.
• the water repellent of the present invention may further contain, for example, a surfactant (B) and water (C).
• the water repellent of the present invention may further include, for example, an organic solvent (D), and the adduct (A) may be dissolved in the organic solvent (D).
• the component (a) is polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer, polyallylamine And at least one selected from the group consisting of polyethyleneimine.
• the ratio of the total number of hydroxyl groups, amino groups and imino groups in the component (a) to the number of isocyanate groups in the component (b) is 4/1. It may be up to 1/1.
• the water repellent of the present invention may further contain, for example, amino-modified silicone (E).
• the treatment liquid contains isocyanate (F), and the adduct (A) is crosslinked with the isocyanate (F). Good.
• the “water repellent composition” refers to a water repellent which is a composition.
• Monoisocyanate refers to an isocyanate having only one isocyanate group in one molecule.
• Polyisocyanate refers to an isocyanate having a plurality of isocyanate groups in one molecule.
• alkyl includes, for example, linear or branched alkyl.
• the alkyl group is not particularly limited, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group, pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and the like.
• alkylene includes, for example, linear alkylene (methylene or polymethylene) or branched alkylene.
• the alkylene group is not particularly limited. Examples thereof include a methylene group, a dimethylene group (ethylene group), an ethylidene group, a trimethylene group, a 1-methylethylene group (propylene group), a tetramethylene group, and a 1-methyltrimethylene group. Groups, 2-methyltrimethylene group, 1,1-dimethylethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group and the like.
• the water repellent of the present invention is characterized by containing an adduct (A) of the following components (a) and (b).
• the adduct (A) is a compound having a structure in which the following component (a) is added to an unsaturated bond of an isocyanate group (isocyanato group) in the following component (b).
• the adduct (A) is, for example, urethane.
• the “urethane” refers to a compound having a urethane bond (—NH—CO—O—).
• the adduct (A) is, for example, urea.
• the “urea” refers to a urea derivative compound having a urea bond (—NH—CO—NH—) instead of urea itself.
• Component (a) is a vinyl polymer as described above.
• Examples of the monomer include vinyl alcohol, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, and vinyl palmitate.
• the vinyl-based polymer may have, for example, a structure of a copolymer of the monomer and another monomer.
• the other monomer include ethylene, propylene, 1-butene, isobutene, 1-hexene and the like.
• the vinyl polymer is an unsaturated carboxylic acid such as acrylamide, methacrylamide, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and the like, esters, amides, anhydrides, sulfones such as vinyl sulfonic acid and the like.
• An acid monomer, dimethylaminoethyl methacrylate, vinyl imidazole, vinyl pyridine, vinyl succinimide and the like may be copolymerized.
• Component (a) is, as described above, a vinyl polymer having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, and an imino group.
• a vinyl polymer having a hydroxyl group may be used.
• the vinyl polymer having a hydroxyl group include polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer, and the like.
• the content of the vinyl alcohol structural unit is not particularly limited, but is, for example, 10 to 80 mol%, 40 to 80 mol%, or 40 to 70 mol%. It is.
• the average degree of polymerization of the ethylene-vinyl alcohol copolymer is not particularly limited, but is, for example, 100 or more, 500 or more, or 800 or more, for example, 3,000 or less, 2,500 or less, or 1,500 or less. is there.
• ethylene-vinyl alcohol copolymers include, for example, EVAL: grades E-171B, E-151B, E-105B, E-171A, E-151A, E-105A, and EVAL (trade name) manufactured by Kuraray Co., Ltd. Soarnol manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Grade AT4403, AT4406, A4412 and the like. Further, an ethylene-vinyl alcohol copolymer to which ethylene oxide has been added, which is synthesized by addition-polymerizing ethylene oxide to a vinyl group of the ethylene-vinyl alcohol copolymer, can also be used.
• the component (a) is polyvinyl alcohol
• the average degree of polymerization is not particularly limited, but is, for example, 100 to 3,000 or 150 to 2,000.
• the saponification degree of the polyvinyl alcohol is not particularly limited, it is, for example, 70% or more, 80% or more, or 90 to 100%.
• Component (a) may be, for example, a vinyl polymer having an amino group or a vinyl polymer having an imino group.
• the component (a) may be, for example, a vinyl polymer having only one of an amino group and an imino group, or a vinyl polymer having both of them.
• Examples of the vinyl polymer having at least one of the amino group and the imino group include polyallylamine and polyethyleneimine. The molecular weight of the polyallylamine and polyethyleneimine is not particularly limited, but is, for example, 300 to 100,000.
• Component (a) is, for example, as described above, polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer, polyallylamine, and polyethyleneimine. At least one selected from the group consisting of:
• Component (b) is an isocyanate having an aliphatic group having 8 or more carbon atoms, as described above.
• Component (b) may be a monoisocyanate or a polyisocyanate, for example, a monoisocyanate.
• the aliphatic group include an alkyl group, an alkenyl group, and an alkynyl group, and an alkyl group is preferable.
• the aliphatic group may be branched, but is preferably linear.
• the aliphatic group has 8 or more carbon atoms, and the upper limit is not particularly limited, but is, for example, 30 or less, or 20 or less.
• Examples of the component (b) include monoalkyl isocyanates such as octyl isocyanate, dodecyl isocyanate (lauryl isocyanate), and octadecyl isocyanate (stearyl isocyanate), and particularly preferably octadecyl isocyanate (stearyl isocyanate).
• monoalkyl isocyanates such as octyl isocyanate, dodecyl isocyanate (lauryl isocyanate), and octadecyl isocyanate (stearyl isocyanate), and particularly preferably octadecyl isocyanate (stearyl isocyanate).
• octadecyl isocyanate for example, a mixture containing a monoalkyl isocyanate having 12 carbon atoms, 14 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, and 20 carbon
• the content of each component in the mixture is preferably 1 to 10% by mass of an isocyanate having 16 carbon atoms in the alkyl group, 0.5 to 4% by mass of an isocyanate having 17 carbon atoms in the alkyl group, It is a mixture of an alkyl group having 18 carbon atoms in the group in an amount of 80 to 98% by mass.
• the mixture may be, for example, a mixture of 8 to 9% by mass of an isocyanate having 16 carbon atoms in an alkyl group, 3 to 4% by mass of an isocyanate having 17 carbon atoms in an alkyl group, and 18% by mass of an isocyanate having 18 carbon atoms in an alkyl group.
• component (b) may be used alone or in combination of two or more.
• the ratio of the total number of hydroxyl groups, amino groups, and imino groups in the component (a) to the number of isocyanate groups in the component (b) is not particularly limited. As described above, the ratio may be 4/1 to 1/1, for example, 4/3 to 1/1 or 2/1 to 1/1.
• the method for producing the adduct (A) is not particularly limited, and may be, for example, the same as or similar to a general addition reaction of a hydroxyl group-containing polymer or an imino group-containing polymer with an isocyanate. Specifically, the method for producing the adduct (A) can be performed, for example, as follows.
• component (a) may or may not be dehydrated as required.
• the dehydration is not particularly limited.
• the component (a) in the form of particles is dispersed in a nonpolar solvent such as toluene, and azeotropic dehydration is performed.
• a nonpolar solvent such as toluene
• azeotropic dehydration is performed.
• a method of removing water by a dryer or the like can be used.
• azeotropic dehydration is preferred from the viewpoint of efficiency and the like.
• azeotropic dehydration for example, a method of separating and removing water in the middle of a reflux device while performing reflux may be used.
• the solvent used is not particularly limited as long as it is a solvent azeotropic with water, but toluene and xylene are preferred from the viewpoint of solubility with the water repellent of the present invention.
• the water content in the component (a) after the water removal step is not particularly limited, but is preferably 150 ppm or less.
• a catalyst used for a general urethane-forming reaction with isocyanate can be used for component (a), if necessary.
• a reaction catalyst a highly water-soluble weakly acidic alkali metal salt, an organic One or two or more tin salts (for example, dibutyltin dilaurate), zinc salts, zirconium complexes, bismuth salts, tertiary amines and their salts (for example, trade names DBU, DBN, and UCASTA102 manufactured by San Apro Corporation) are added.
• a water-soluble solvent such as dimethyl sulfoxide or a water-insoluble solvent such as toluene may be added.
• the component (b) isocyanate
• the catalyst is added, for example, before the reaction, but may be added during the reaction, or may be added in plural times.
• the reaction temperature and the reaction time are not particularly limited, and may be, for example, the same as or similar to a general addition reaction of a hydroxyl group-containing polymer or an imino group-containing polymer with an isocyanate.
• the reaction temperature is not particularly limited as described above, but may be, for example, 50 to 150 ° C or 75 to 140 ° C.
• the reaction time may be, for example, 100 to 240 minutes, or may be 120 to 200 minutes.
• the end point of the reaction can be confirmed, for example, by measuring the remaining amount of the unreacted isocyanate compound in the reaction mixture using an infrared spectrophotometer.
• water can be added to separate the oil layer and the aqueous layer, and the catalyst can be transferred to the aqueous layer and removed.
• this operation may be omitted.
• the adduct (A) of the target product moves to the oil layer.
• This oil layer may be filtered through a filter (filter) to remove a by-product (for example, a bisurea compound).
• a filter for example, a closed pressure filter is preferable because it is intended to remove by-products insoluble in organic solvents such as toluene.
• the method of filtration is not particularly limited.For example, a method of receiving a solution in a separate receiver through a filter from a vessel containing a solution, or a vessel in which a solution is again filled through a filter from a vessel containing a solution. It is possible to use either of the recirculation methods.
• the oil layer containing the adduct (A) is put into a vessel in which methanol has been put in advance, and the precipitated adduct (A) is separated by filtration and used as the water repellent of the present invention.
• the mixture after the reaction may be directly put into methanol to precipitate the adduct (A).
• the water repellent of the present invention may further include a surfactant (B) and water (C) in addition to the additive (A).
• the water repellent of the present invention contains, for example, an organic solvent (D) in addition to the adduct (A) as described above, and the adduct (A) is dissolved in the organic solvent (D). It may be.
• the former may be referred to as “water-based water repellent”, and the latter may be referred to as “solvent-based water repellent”.
• the method for producing the water-based water repellent of the present invention is not particularly limited, and for example, a general mechanical emulsification method can be used.
• the machine used for the mechanical emulsification method is not particularly limited, but in the batch method, for example, a Nauter mixer, an anchor mixer, a homomixer, a homodisper, a planetary mixer, and the like, and a multiaxial emulsifying and dispersing apparatus combining them.
• a combi mix series manufactured by Primix Co., Ltd. may be used.
• a line homomixer or the like may be used, or an apparatus combining them may be used.
• a high-temperature high-pressure emulsifying and dispersing apparatus capable of increasing the pressure in the apparatus is preferable.
• the surfactant (B) is not particularly limited, and may be, for example, a general surfactant.
• the surfactant may be, for example, any of a nonionic (nonionic) surfactant, a cationic (cationic) surfactant, an anionic (anionic) surfactant, and an amphoteric surfactant.
• the nonionic surfactant include a polyoxyalkylene alkyl ether surfactant such as a polyoxyethylene alkyl ether surfactant, and a polyoxyalkylene alkylamine.
• Examples of the polyoxyalkylene alkyl ether surfactant include Brownon 230 and Fine Surf 1502.2 (trade names, manufactured by Aoki Yushi Kogyo Co., Ltd.).
• Examples of the cationic surfactant include a quaternary ammonium salt, a tertiary amine or a salt thereof, and the like.
• Examples of the quaternary ammonium salt include Lipocard 18-63 (trade name, manufactured by Lion Specialty Chemicals Co., Ltd.).
• Examples of the anionic surfactant include alkylbenzenesulfonic acid and salts thereof, and fatty acid salts.
• Examples of the amphoteric surfactant include fatty acid amidopropyldimethylaminoacetic acid betaine.
• the surfactant (B) may be used alone or in combination of two or more.
• the content of the surfactant (B) is not particularly limited, but is, for example, 1% by mass or more, 3% by mass or more, or 5% by mass based on the mass of the adduct (A).
• the content is 200% by mass or less, 150% by mass or less, or 100% by mass or less.
• the water-based water repellent of the present invention may further contain an organic compound such as a hydrocarbon oil or a higher alcohol.
• Organic compounds such as hydrocarbon oils and higher alcohols are components that are different from the organic solvent mixed with water (C) in the water-based water repellent described below.
• Specific examples of the hydrocarbon oil include, for example, squalene, squalane, liquid paraffin, liquid isoparaffin, heavy liquid isoparaffin, ⁇ -olefin oligomer, cycloparaffin, polybutene, petrolatum, paraffin wax, microcrystalline wax, polyethylene wax, and Ceresin.
• the higher alcohol is a higher alcohol having 6 to 30 carbon atoms.
• Specific examples include hexyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, decyl alcohol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, and palmityl. Alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, icosyl alcohol, and behenyl alcohol.
• the content of the organic compound is not particularly limited, but is, for example, 1% by mass or more, 3% by mass or more, or 5% by mass or more, for example, 200% by mass or less, 150% by mass with respect to the mass of the adduct (A). % By mass or less, or 100% by mass or less.
• the above organic compound has, for example, an action of reducing the viscosity of an aqueous water repellent.
• an organic compound having an effect of reducing the viscosity of the water-based water repellent by adding an organic compound having an effect of reducing the viscosity of the water-based water repellent, the behavior of increasing the viscosity can be controlled, and the emulsification and dispersion can be easily performed. Become.
• water (C) is not particularly limited, and examples thereof include tap water, distilled water, and ion-exchanged water. If necessary, water (C) and an organic solvent may be mixed. The organic solvent at this time is not particularly limited as long as it is an organic solvent miscible with water.
• alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, propylene glycol, dipropylene glycol, and tripropylene glycol Glycols such as propylene glycol, and glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether.
• the ratio between water and the organic solvent is not particularly limited.
• the content of the adduct (A) is not particularly limited, but is, for example, 0.5% by mass or more, 1% by mass or more, or 3% by mass with respect to the mass of water (C). It is at least 90 mass%, for example, at most 90 mass%, at most 70 mass%, or at most 50 mass%.
• the organic solvent (D) is not particularly limited, but a solvent that easily dissolves the adduct (A) is preferable.
• the organic solvent (D) include hydrocarbon solvents such as aromatic hydrocarbons and aliphatic hydrocarbons (such as normal hexane), alcohol solvents (such as methanol and ethanol), glycol solvents (such as ethylene glycol), and amides.
• Solvents (dimethylformamide (DMF), dimethylacetamide, etc.), sulfoxide solvents (dimethylsulfoxide, etc.), ketone solvents (methylethylketone (MEK), etc.), aromatic solvents (toluene, xylene, etc.), ether solvents (dioxane) , Tetrahydrofuran, etc.) and ester solvents (ethyl acetate, butyl acetate, etc.).
• the aromatic hydrocarbon include toluene, benzene, xylene, and 1,3,5-trimethylbenzene.
• the organic solvent (D) may be used alone or in combination of two or more.
• the content of the adduct (A) is not particularly limited, but is, for example, 0.1% by mass or more and 0.5% by mass with respect to the mass of the organic solvent (D). Or more, or 1.0% by mass or more, for example, 90% by mass or less, 80% by mass or less, or 70% by mass or less.
• the water repellent of the present invention may or may not contain any other components other than the components (A) to (D).
• the optional component include the amino-modified silicone (E) described above. That is, the water-based water repellent or the solvent-based water repellent of the present invention may further contain an amino-modified silicone (E) as described above.
• the amino-modified silicone (E) for example, the water repellency of the water-repellent treated fiber or fiber product is further improved, or the texture is further softened.
• Examples of the amino-modified silicone (E) include a side-chain type amino-modified silicone, a double-terminal type amino-modified silicone, a single-terminal type amino-modified silicone, a side-chain double-terminal type amino-modified silicone, and the like. It may have a different reactive group such as an ether group.
• the amino-modified silicone includes, for example, SM-8709SR (trade name, manufactured by Dow Corning Toray Co., Ltd.).
• the functional group equivalent of the amino group is not particularly limited, but is, for example, 100 to 20,000 g / mol, 200 to 18,000 g / mol, or 500 to 16,000 g / mol.
• the content of the amino-modified silicone (E) is not particularly limited, but is, for example, 0.5% by mass or more, It is at least 200 mass%, or at least 2 mass%, for example, at most 200 mass%, at most 150 mass%, or at most 100 mass%.
• the optional component in addition to the amino-modified silicone (E), for example, straight silicone oils such as dimethyl silicone oil and methyl hydrogen silicone oil, and Reactive silicone oils such as polyether-modified silicone oil and epoxy-modified silicone oil are exemplified.
• the method for producing the water-based water-repellent or the solvent-based water-repellent of the present invention is not particularly limited.
• all the components may be mixed and dissolved or dispersed.
• each component may be dissolved or dispersed while appropriately heating or the like so that each component is easily dissolved or dispersed.
• the adduct (A) and the surfactant (B) are mixed while heating and stirring, and then water (C) is added while continuing heating and stirring to add the adduct (A) and the surfactant.
• the activator (B) may be dispersed in water (C) to produce a water-based water repellent.
• the heating temperature in this case is not particularly limited, but is, for example, 30 ° C. or higher, or 50 ° C. or higher, for example, 180 ° C. or lower, or 160 ° C. or lower.
• the heating and stirring time is not particularly limited, but may be, for example, until all the components are uniformly mixed.
• the method of using the water repellent of the present invention is not particularly limited, and for example, may be the same as or similar to the method of using a general water repellent, especially a fiber water repellent.
• the water-repellent agent of the present invention can be used, for example, for water-repellent treatment (water-repellent processing) of fibers or textile products.
• the above-described method for producing the water-repellent fiber product of the present invention and the water-repellent fiber of the present invention Can be used for products.
• the method for producing the water-repellent fiber product of the present invention is not particularly limited, it can be produced by the method for producing a water-repellent fiber product of the present invention.
• the “fiber” to be subjected to the water-repellent treatment is not particularly limited and is arbitrary, and may be, for example, a fiber product.
• the fiber or fiber product is not particularly limited, and may be any fiber or fiber product, such as clothes, daily necessities, interiors, and car seats.
• the method for producing a water-repellent fiber product of the present invention is not particularly limited except that the water-repellent treatment step is performed using the water-repellent agent of the present invention. It may be the same as or similar thereto.
• the method for producing a water-repellent fiber product of the present invention can be carried out, for example, as follows.
• a treatment liquid containing the water repellent of the present invention is prepared.
• the water repellent of the present invention may be used as the processing liquid as it is, or may be diluted with water or an organic solvent to obtain the processing liquid.
• the treatment liquid may be diluted with water, or in the case of a solvent-based water repellent, the treatment liquid may be diluted with an organic solvent of the same or different type as the organic solvent (D). It may be.
• the concentration of the treatment liquid is not particularly limited, but the concentration of the adduct (A) is, for example, 0.1% by mass or more based on the dispersion medium or the solvent (eg, the water or organic solvent) of the treatment liquid.
• the content is 3% by mass or more, or 0.5% by mass or more, for example, 30% by mass or less, 20% by mass or less, or 10% by mass or less.
• a water-repellent auxiliary agent or the like may be added to the treatment liquid.
• the water-repellent auxiliary is not particularly limited.
• straight silicone oils such as amino-modified silicone oil, dimethyl silicone oil and methyl hydrogen silicone oil, and reactive silicones such as polyether-modified silicone oil and epoxy-modified silicone oil Oil and the like.
• the addition amount of the water-repellent auxiliary is not particularly limited either, but is, for example, 0.5% by mass or more, 1% by mass or more, or 2% by mass or more based on the adduct (A), for example, 200% by mass or less, 150% by mass or less. % By mass or less, or 100% by mass or less.
• the water-repellent treatment step of treating the fibers with the treatment liquid is performed.
• This water-repellent treatment step may be, for example, the same as or similar to a general water-repellent treatment method for fibers or textile products, as described above.
• the fiber or fiber product may be dried after the treatment liquid is impregnated into the fiber or fiber product to be subjected to the water-repellent treatment.
• the method for producing a water-repellent fiber product of the present invention can be performed.
• the method for producing a water-repellent fiber product of the present invention may include other steps other than the water-repellent treatment step, but may not include the other steps. As the other step, for example, a dry heat treatment described later is given.
• the water-repellent treatment step may be performed by, for example, a continuous method or a batch method.
• a fiber or a fiber product as an object to be treated is continuously fed to an impregnation device filled with the treatment liquid, and then the object to be treated is impregnated with the water-repellent treatment liquid. And unnecessary water-repellent treatment liquid is removed.
• the impregnation device is not particularly limited, but a padder type application device, a kiss roll type application device, a gravure coater type application device, a spray type application device, a foam type application device, and a coating type application device are preferable, and a padder type application device is particularly preferable.
• water, an organic solvent, and the like remaining on the object to be treated are removed using a dryer.
• the dryer is not particularly limited, but a spread dryer such as a hot flue or a tenter is preferable.
• the continuous method is preferably used, for example, when the object to be treated is a fabric such as a woven fabric.
• the batch method is preferably used, for example, when the object is not suitable for processing by a continuous method. More specifically, when the object to be processed is not a cloth, for example, when the object to be processed is rose hair, top, sliver, skein, tow, thread, or the like, or when the object to be processed is a knitted fabric. There are some cases.
• a cotton dyeing machine, a cheese dyeing machine, a liquid jet dyeing machine, an industrial washing machine, a beam dyeing machine, or the like can be used.
• a hot air drier such as a cheese drier, a beam drier, a tumble drier, or a high-frequency drier can be used.
• the treatment liquid may contain isocyanate (F), and the isocyanate (F) may be used to crosslink the adduct (A).
• the treatment liquid contains the amino-modified silicone (E)
• the amino group of the amino-modified silicone (E) may be crosslinked with the isocyanate (F).
• the isocyanate (F) is not particularly limited, for example, an organic compound containing two or more isocyanate functional groups in a molecule can be used.
• isocyanate (F) examples include, for example, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, triphenyl triisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, and trimethylolpropane tolylene diisocyanate adduct.
• Glycerin tolylene diisocyanate adduct uret of hexamethylene diisocyanate, trimethylolpropane trihexamethylene diisocyanate adduct, glycerin trihexamethylene diisocyanate adduct, and the like.
• isocyanate (F) phenol, malonic acid diethyl ester, methyl ethyl ketoxime, sodium bisulfite, ⁇ which dissociates upon heating and regenerates an active isocyanate group with the organic compound containing an isocyanate functional group, etc.
• An organic compound containing a blocked isocyanate functional group obtained by reacting caprolactam or the like to block an isocyanate group.
• isocyanate (F) examples include, for example, Coronate B-45E and Coronate HX (trade names, manufactured by Tosoh Corporation) as solvent systems, and Duranate D101 and Duranate D201 (trade names, manufactured by Asahi Kasei Corporation).
• Coronate B-45E and Coronate HX trade names, manufactured by Tosoh Corporation
• Duranate D101 and Duranate D201 trade names, manufactured by Asahi Kasei Corporation.
• “Aquanate” series manufactured by the company Duranate WB40-100, Duranate WT20-100, Duranate WE50-100 manufactured by Asahi Kasei Corporation, "Elastron” series manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
• the amount of the isocyanate (F) to be added is not particularly limited either, but is, for example, 0.5% by mass or more, 1% by mass or more, or 3% by mass or more based on the adduct (A), for example, 200% by mass or less, 150% by mass or less. % Or less, or 100% by mass or less.
• the reaction temperature is not particularly limited, and is, for example, 100 ° C. or higher, or 120 ° C. or higher, for example, 200 ° C. or lower, or 180 ° C. or lower. is there.
• the reaction time is not particularly limited, but is, for example, 0.1 minutes or more, or 0.3 minutes or more, for example, 20 minutes or less, or 15 minutes or less.
• the dry heat treatment it is preferable to perform a dry heat treatment on the object to which the water repellent of the present invention is attached. This is because, when the dry heat treatment is performed, the active ingredient of the first water repellent or the second water repellent of the present invention is more likely to adhere to the object to be processed. However, in the present invention, the dry heat treatment may not be performed.
• the water repellent of the present invention can also be used for paper products, wood boards (eg, particle board, MDF board, etc.).
• the water repellent of the present invention has excellent water repellency.
• a water-repellent fiber product excellent in water repellency can be manufactured.
• a water repellent product having excellent water repellency (washing durability) after washing can be produced.
• the water repellent of the present invention for example, excellent oil repellency can be obtained.
• a water-repellent fiber product excellent in oil repellency can be manufactured.
• excellent oil repellency can be obtained by the water repellent of the present invention, and for example, it can be expected that sebum stains are less likely to adhere to textiles.
• non-fluorine-based water repellents are inferior in oil repellency and easily adhere to sebum stains as compared with fluorine-based water repellents.
• the water repellent of the present invention can be used efficiently at a low cost, for example, and is excellent in water repellency, processing bath stability, storage stability and the like.
• the use of the water repellent of the present invention is not particularly limited, and textiles such as clothes, umbrellas, raincoats, tents, daily necessities, interiors, car seats, and further, water repellent paper, water repellent boards, and the like. Widely applicable to Further, the use of the water repellent of the present invention is not limited to the above-mentioned respective uses, and can be widely used for any use.
• the adduct (A) was produced as follows. First, a reaction vessel equipped with a stirrer having a Faudler blade, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel, and capable of heating and cooling was prepared. Next, 57 parts by mass of stearyl isocyanate (component (b), the content of an aliphatic group having 17 or less carbon atoms of 2.0%) was placed in the reaction vessel, and ethylene / vinyl alcohol was used as a raw material polymer.
• component (b) stearyl isocyanate
• DMSO dimethyl sulfoxide
• the reaction solution was cooled to 80 ° C., and the reaction mixture was poured into methanol five times the total amount of the reaction mixture to obtain a white precipitate. Since DMSO in the reaction solution is dissolved in methanol, DMSO can be removed from the precipitate by filtration. Therefore, the white precipitate is separated by filtration, and the white precipitate is washed with methanol, dried, and pulverized to obtain a high-molecular-weight urethane compound (the components (a) and (b)). Adduct (A)) was obtained.
• Example 1 2.0 parts by mass of the high molecular urethane compound (adduct (A)) obtained in Synthesis Example 1 was dissolved in 98.0 parts by mass of toluene to produce a water repellent of this example. This water repellent was used as it was as a treatment liquid for producing a water-repellent fiber product.
• a 100% nylon cloth and a 100% polyester cloth are each immersed (pickup ratio: 50% by mass) in the water repellent (treatment liquid) of the present embodiment, and then dried at 130 ° C. for 2 minutes to obtain water repellency.
• the water-repellent fiber product (water-repellent treated cloth) of this example was obtained by performing the treatment (water-repellent treatment step).
• the water-repellent fiber product (water-repellent cloth) was further heat-treated at 170 ° C. for 1 minute to obtain a heat-treated water-repellent fiber product of this example (water-repellent cloth).
• the “pickup ratio” represents the ratio of the mass of the treatment liquid absorbed by the cloth to the mass of the cloth before immersion.
• Example 2 2.0 parts by mass of the polymer urethane compound (adduct (A)) obtained in Synthesis Example 2 was dissolved in 98.0 parts by mass of toluene to produce a water repellent of this example. Further, except that the water repellent of the present example was used as a treatment liquid instead of the water repellent of Example 1, the water repellent fiber product of the present example (the cloth treated for water repellency) was used in the same manner as in Example 1. ) And heat-treated water-repellent fiber product of this example (water-repellent treated cloth).
• Example 3 2.0 parts by mass of the polymeric urea compound (adduct (A)) obtained in Synthesis Example 3 was dissolved in 98.0 parts by mass of toluene to produce a water repellent of this example. Further, except that the water repellent of the present example was used as a treatment liquid instead of the water repellent of Example 1, the water repellent fiber product of the present example (the cloth treated for water repellency) was used in the same manner as in Example 1. ) And heat-treated water-repellent fiber product of this example (water-repellent treated cloth).
• Example 4 2.0 parts by mass of the high molecular urethane compound (adduct (A)) obtained in Synthesis Example 1 and 1.0 parts by mass of Coronate B-45E (isocyanate (F)) (trade name, manufactured by Tosoh Corporation) were dissolved in toluene. This was dissolved in 97.0 parts by mass to produce a water repellent of this example. Further, except that the water repellent of the present example was used as a treatment liquid instead of the water repellent of Example 1, the water repellent fiber product of the present example (the cloth treated for water repellency) was used in the same manner as in Example 1. ) And heat-treated water-repellent fiber product of this example (water-repellent treated cloth).
• Example 5 30.0 parts by mass of the polymer urethane compound (adduct (A)) obtained in Synthesis Example 1 and a trade name of Lipocard 18-63 (a quaternary ammonium salt, a cationic interface, manufactured by Lion Specialty Chemicals Co., Ltd.)
• Surfactant, surfactant (B)) 0.5 parts by mass, trade name Brownon 230 (polyoxyalkylene alkyl ether-based surfactant, nonionic surfactant, surfactant (B) manufactured by Aoki Yushi Kogyo Co., Ltd.)
• Fine Surf 1502.2 polyoxyalkylene alkyl ether surfactant, nonionic surfactant, surfactant (B)) manufactured by Aoki Yushi Kogyo Co., Ltd.
• Example 1 0 parts by mass, sealed in a container of a high-pressure multi-screw disperser having an anchor mixer, a homomixer, and a homodisper, sealed, and melt-mixed at 120 ° C. Maintaining the 10 ° C. or more, to produce a water repellent by mixing 87.0 parts by weight 95 ° C. or more hot water with continued stirring this embodiment. Further, Example 1 was repeated except that 9.0 parts by mass of the water repellent (emulsion) of this example and 91.0 parts by mass of water were mixed and used as the treatment liquid instead of the treatment liquid of Example 1.
• Example 6 9.0 parts by mass of the water repellent obtained in Example 5, 3.0 parts by mass of SM-8709SR (amino-modified silicone (E)) (trade name, manufactured by Dow Corning Toray Co., Ltd.), and 88.0 parts by mass of water Are mixed and used as a treatment liquid, in the same manner as in Example 1, except that the water-repellent fiber product (the cloth subjected to the water-repellent treatment) and the heat-treated water-repellent fiber product (the water-repellent cloth) of the present example are used. Treated cloth).
• SM-8709SR amino-modified silicone (E))
• Example 7 9.0 parts by mass of the water repellent obtained in Example 5, 3.0 parts by mass of SM-8709SR (amino-modified silicone (E)) manufactured by Dow Corning Toray Co., Ltd., and 3.0 parts by mass of product manufactured by Tosoh Corporation
• the water-repellent fiber product of this example was prepared in the same manner as in Example 1 except that 1.0 part by mass of Coronate AQ-140 (isocyanate (F)) and 87.0 parts by mass of water were mixed and used as a treatment liquid.
• Coronate AQ-140 isocyanate (F)
• Example 8 Example 5 was repeated except that the high molecular urethane compound (adduct (A)) obtained in Synthesis Example 4 was used instead of the high molecular urethane compound (adduct (A)) obtained in Synthesis Example 1.
• a water-repellent fiber product of this example a cloth subjected to a water-repellent treatment
• a heat-treated water-repellent fiber product of the present example a cloth subjected to a water-repellent treatment
• Example 5 was the same as Example 5 except that the polymer urea compound (adduct (A)) obtained in Synthesis Example 5 was used instead of the polymer urethane compound (adduct (A)) obtained in Synthesis Example 1. Similarly, a water-repellent fiber product of this example (a cloth subjected to a water-repellent treatment) and a heat-treated water-repellent fiber product of the present example (a cloth subjected to a water-repellent treatment) were obtained.
• Example 10 Example 5 was repeated except that the polymer urea compound (adduct (A)) obtained in Synthesis Example 6 was used in place of the polymer urethan compound (adduct (A)) obtained in Synthesis Example 1.
• the water-repellent agent, water-repellent fiber product (water-repellent treated cloth) of this example and heat-treated water-repellent fiber product of this example (water-repellent treated cloth) were obtained in the same manner as described above.
• Example 11 30.0 parts by mass of the polymer urethane compound (adduct (A)) obtained in Synthesis Example 1 and a trade name of Lipocard 18-63 (a quaternary ammonium salt, a cationic interface, manufactured by Lion Specialty Chemicals Co., Ltd.)
• Surfactant, surfactant (B)) 0.5 parts by mass, trade name Brownon 230 (polyoxyalkylene alkyl ether-based surfactant, nonionic surfactant, surfactant (B) manufactured by Aoki Yushi Kogyo Co., Ltd.)
• Fine Surf 1502.2 polyoxyalkylene alkyl ether surfactant, nonionic surfactant, surfactant (B)) manufactured by Aoki Yushi Kogyo Co., Ltd.
• Example 1 Example 1 was repeated except that 9.0 parts by mass of the water repellent (emulsion) of this example and 91.0 parts by mass of water were mixed and used as the treatment liquid instead of the treatment liquid of Example 1.
• Example 12 A water-repellent agent, a water-repellent fiber product (a cloth subjected to water-repellent treatment), and a heat-treated book of this example were carried out in the same manner as in Example 11 except that the same mass of 130 ° F paraffin was used instead of stearyl alcohol. A water-repellent fiber product (a cloth subjected to a water-repellent treatment) of an example was obtained.
• Example 13 Example 5 was repeated except that the polymer urea compound (adduct (A)) obtained in Synthesis Example 7 was used instead of the polymer urethan compound (adduct (A)) obtained in Synthesis Example 1.
• the water-repellent agent, water-repellent fiber product (water-repellent treated cloth) of this example and heat-treated water-repellent fiber product of this example (water-repellent treated cloth) were obtained in the same manner as described above.
• the water repellent fiber product of this comparative example is prepared in the same manner as in Example 1.
• a water-repellent treated fabric) and a heat-treated water-repellent fiber product of this comparative example (water-repellent treated fabric) were obtained.
• Comparative Example 3 8.0 parts by mass of a commercially available fluorine-based water repellent (manufactured by Asahi Glass Co., Ltd., trade name: Asahi Guard AG-E081) and 1.0 part by mass of a crosslinking agent (manufactured by Meisei Chemical Industry Co., Ltd., trade name: Mecanate FM-1) And water-repellent fiber product (water-repellent treated cloth) of this comparative example and heat-treated this comparative example in the same manner as in Example 1 except that water was mixed with 91.0 parts by mass of water and used as a treatment liquid. (Water-repellent treated cloth) was obtained.
• a commercially available fluorine-based water repellent manufactured by Asahi Glass Co., Ltd., trade name: Asahi Guard AG-E081
• a crosslinking agent manufactured by Meisei Chemical Industry Co., Ltd., trade name: Mecanate FM-1
• Water-repellent fiber product water-repellent treated cloth
• Evaluation solution 8 n-heptane 7: n-hexane 6: n-decane 5: n-dodecane 4: n-tetradecane 3: n-hexadecane 2: n-hexadecane / kaidol (mass ratio 65/35) mixed solution 1: Something less than 0: 1
• seam slippage resistance was measured by the 8.23 slippage resistance 8.28.23.1 seam slippage method of JIS L 1096: 2010 b) Method B. The smaller the value, the better the seam slippage property (seam slippage resistance) was evaluated.
• the cloths (water-repellent fiber products) of Examples 1 to 13 in which the water-repellent agent contains the adduct (A) of the components (a) and (b) were 100% nylon and 100% polyester.
• Both heat-treated and non-heat-treated fabrics are extremely excellent in water repellency and oil repellency before washing and water repellency after washing (washing durability), and are based on fluorine-based water repellent (Comparative Example). Compared to 3), there was no inferiority. Further, the cloths (water-repellent fiber products) of Examples 1 to 13 also showed sufficient softness in the evaluation of the hand.
• Examples 6 and 7 to which the amino-modified silicone (E) was added exhibited softness comparable to that of the fluorine-based water repellent (Comparative Example 3).
• the evaluation of the texture was made of a water-repellent fiber product without heat treatment (water-repellent treated cloth) and a water-repellent fiber product heat-treated at 170 ° C. for 1 minute (water-repellent treatment). Since the evaluation results were the same, the evaluation results of both were collectively shown in Tables 1 and 2. Further, the fabrics (water-repellent fiber products) of Examples 1 to 13 were also excellent in seam slippage resistance.
• Comparative Examples 1 and 2 in which the water repellent did not contain the additive (A) of the components (a) and (b), although the texture was soft, the water repellency and oil repellency before washing were improved.
• the water repellency (washing durability) after washing was significantly inferior to the examples.
• the cloth (water-repellent fiber product) of Comparative Example 1 was excellent, but Comparative Example 2 was significantly inferior to the other Examples and Comparative Examples.
• Comparative Example 3 (fluorine-based water repellent) is excellent in water repellency, oil repellency, washing durability and texture, but has a problem in that it contains elemental fluorine.
• the water repellents of Examples 1 to 13 exhibited the same performance as Comparative Example 3 (fluorine-based water repellent) as a water repellent despite not containing the elemental fluorine.

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