CN112513220A - Water repellent agent, method for producing water repellent fiber product, and water repellent fiber product - Google Patents
Water repellent agent, method for producing water repellent fiber product, and water repellent fiber product Download PDFInfo
- Publication number
- CN112513220A CN112513220A CN201980049510.9A CN201980049510A CN112513220A CN 112513220 A CN112513220 A CN 112513220A CN 201980049510 A CN201980049510 A CN 201980049510A CN 112513220 A CN112513220 A CN 112513220A
- Authority
- CN
- China
- Prior art keywords
- water
- repellent
- mass
- water repellent
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Public Health (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention provides a water repellent agent which does not contain fluorine and has excellent water repellency. In order to achieve the above object, the water repellent of the present invention is characterized by having 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 (b) an isocyanate having an aliphatic group having 8 or more carbon atoms.
Description
Technical Field
The invention relates to a water repellent agent, a method for producing a water repellent fiber product, and a water repellent fiber product.
Background
As a water repellent agent used for fibers and the like, a fluorine-based water repellent agent containing a fluorine element is widely used (patent document 1 and the like).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-262970
Disclosure of Invention
Technical problem to be solved by the invention
Fluorine compounds such as perfluorooctanoic acid (hereinafter referred to as "PFOA") and perfluorooctane sulfonic acid (hereinafter referred to as "PFOS") contained in fluorine-based water repellents may have an influence on living environments, living organisms, and the like. Therefore, in recent years, a non-fluorine water repellent containing no fluorine element has been proposed.
However, the water repellency of a non-fluorine-based water repellent is lower than that of a fluorine-based water repellent, and particularly the water repellency after washing tends to be lowered. Therefore, a non-fluorine water repellent agent having excellent water repellency is required.
Accordingly, an object of the present invention is to provide a water repellent agent containing no fluorine element and having excellent water repellency, a method for producing a water repellent fiber product using the water repellent agent, and a water repellent fiber product.
Means for solving the technical problem
In order to achieve the above object, a water repellent of the present invention comprises 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;
(b) an isocyanate having an aliphatic group having 8 or more carbon atoms.
The method for producing a water-repellent fiber product of the present invention is characterized by comprising a water-repellent treatment step of water-repellent 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 a crosslinked product of the adduct (a) in the water-repellent agent of the present invention is attached to a fiber.
Effects of the invention
According to the present invention, a water repellent agent containing no fluorine element and having excellent water repellency, a method for producing a water repellent fiber product using the water repellent agent, and a water repellent fiber product can be provided.
Detailed Description
The present invention will be described below by way of example. However, the present invention is not limited to the following description.
The water repellent of the present invention may further contain a surfactant (B) and water (C), for example.
The water repellent agent of the present invention may further contain, for example, an organic solvent (D) in which the adduct (a) is dissolved.
In the water repellent agent of the present invention, for example, the component (a) may be at least one selected from the group consisting of polyvinyl alcohol, a vinyl alcohol-vinyl acetate copolymer, an ethylene-vinyl alcohol-vinyl acetate copolymer, polyallylamine, and polyethyleneimine.
In the water repellent of the present invention, for example, the ratio of the sum of the numbers of hydroxyl groups, amino groups, and imino groups in the component (a) to the number of isocyanate groups in the component (b) may be 4/1 to 1/1.
The water repellent agent of the present invention may further contain an amino-modified silicone (E), for example.
In the method for producing a water-repellent fiber product of the present invention, for example, the treatment liquid may contain isocyanate (F) in the water-repellent treatment step, and the adduct (a) may be crosslinked by the isocyanate (F).
In the present invention, the "water repellent composition" refers to a composition of water repellents.
In the present invention, "isocyanate" refers to a compound having an isocyanate group (isocyanate group) -N ═ C ═ O in the molecule. "monoisocyanate" means an isocyanate having only 1 isocyanate group in 1 molecule. "polyisocyanate" refers to an isocyanate having a plurality of isocyanate groups in 1 molecule.
In the present invention, the "alkyl group" includes, for example, a linear or branched alkyl group. In the present invention, the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl.
In the present invention, the "alkylene group" includes, for example, a linear alkylene group (methylene group or polymethylene group) or a branched alkylene group. In the present invention, the alkylene group is not particularly limited, and examples thereof include methylene, dimethylene (vinyl), ethylene, trimethylene, 1-methylethenyl (propenyl), tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1-dimethylethenyl, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene.
The following further specifically describes embodiments of the present invention. However, the present invention is not limited to the following embodiments.
[ 1 ] Water repellant
As described above, the water repellent agent 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 (isocyanate group) in the following component (b). When the component (a) is a vinyl polymer having a hydroxyl group, the adduct (a) is, for example, urethane. The "urethane" refers to a compound having a urethane bond (-NH-CO-O-). When the component (b) is a vinyl polymer having at least one of an amino group and an imino group, the adduct (a) is, for example, urea. In addition, in the present invention, the "urea" is not urea itself, but a urea derivative compound having a urea bond (-NH-CO-NH-).
(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;
(b) an isocyanate having an aliphatic group having 8 or more carbon atoms.
[ 1-1 ] adduct (A) ]
The component (a) is a vinyl polymer as described above. The vinyl polymer is, for example, a polymer having a terminal double bond (vinyl CH)2CH-or vinylidene CH2C ═ C) monomers. 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, vinyl palmitate, vinyl stearate, vinyl oleate, and vinyl benzoate. The vinyl polymer may have a structure of a copolymer of the monomer and another monomer, for example. Examples of the other monomer include ethylene, propylene, 1-butene, isobutylene, and 1-hexene. In addition, in the vinyl polymer, there may be copolymerized unsaturated carboxylic acids such as acrylamide, methacrylamide, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and esters thereof, sulfonic acid monomers such as amides, anhydrides, and vinylsulfonic acids, dimethylaminoethyl methacrylate, vinylimidazole, vinylpyridine, and vinylsuccinimide.
The component (a) is a vinyl polymer having at least one substituent selected from the group consisting of a hydroxyl group, an amino group and an imino group, as described above, and may be a vinyl polymer having a hydroxyl group. Examples of the vinyl polymer having the hydroxyl group include polyvinyl alcohol, a vinyl alcohol-vinyl acetate copolymer, an ethylene-vinyl alcohol-vinyl acetate copolymer, and the like. When the component (a) is an ethylene-vinyl alcohol copolymer, the content of the vinyl alcohol structural unit is not particularly limited, and is, for example, 10 to 80 mol%, 40 to 80 mol%, or 40 to 70 mol%. The average polymerization degree of the ethylene-vinyl alcohol copolymer is not particularly limited, and is, for example, 100 or more, 500 or more, or 800 or more, for example, 3000 or less, 2500 or less, or 1500 or less. Examples of the commercially available product of the ethylene-vinyl alcohol copolymer include the product name Eval: grades E-171B, E-151B, E-105B, E-171A, E-151A, E-105A; soarnol manufactured by Nippon synthetic chemical industries, Ltd: grades AT4403, AT4406, A4412, and the like. Further, an ethylene-vinyl alcohol copolymer to which ethylene oxide is added, which is synthesized by addition polymerization of ethylene oxide to a vinyl group of the ethylene-vinyl alcohol copolymer, may also be used. Examples of the commercially available products include a product name Sumiguard grade 300K and a product name Sumiguard grade 300G manufactured by sumitomo chemical co. When the component (a) is polyvinyl alcohol, the average degree of polymerization is not particularly limited, and is, for example, 100 to 3000 or 150 to 2000. The saponification degree of the polyvinyl alcohol is not particularly limited, and is, for example, 70% or more, 80% or more, or 90 to 100%.
The 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 may be 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, polyethyleneimine, and the like. The molecular weight of the polyallylamine and the polyethyleneimine is not particularly limited, and is, for example, 300 to 100000.
The component (a) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. As described above, the component (a) may be at least one selected from the group consisting of polyvinyl alcohol, a vinyl alcohol-vinyl acetate copolymer, an ethylene-vinyl alcohol-vinyl acetate copolymer, polyallylamine, and polyethyleneimine.
The 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. Examples of 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, and 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 octadecyl isocyanate (stearyl isocyanate) is particularly preferable. As for the octadecyl isocyanate, for example, a commercially available mixture of monoalkyl isocyanates having 12, 14, 16, 17, 18, and 20 carbon atoms and an alkyl group may be used. The content ratio of each component in the mixture is preferably a mixture of 1 to 10% by mass of an isocyanate having an alkyl group with 16 carbon atoms, 0.5 to 4% by mass of an isocyanate having an alkyl group with 17 carbon atoms, and 80 to 98% by mass of an alkyl group with 18 carbon atoms. The mixture is, for example, a mixture in which the mixing ratio of the main components is 8 to 9 mass% of isocyanate having an alkyl group and 16 carbon atoms, 3 to 4 mass% of isocyanate having an alkyl group and 17 carbon atoms, and 85 to 87 mass% of isocyanate having a carbon number 18. Examples of commercially available products of such mixtures include Millionate O, a product of Sago chemical Co. In the present invention, only 1 kind of the component (b) may be used, or 2 or more kinds may be used in combination.
In the adduct (A), the ratio of the sum of the 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, and may be, for example, 4/1 to 1/1, and may be, for example, 4/3 to 1/1 or 2/1 to 1/1, as described above.
The method for producing the adduct (a) is not particularly limited, and for example, the same as or reference to the addition reaction between a general hydroxyl group-containing polymer or imino group-containing polymer and isocyanate may be used. The process for producing the adduct (A) can be specifically carried out as follows, for example.
First, the component (a) (polymer) may or may not be dehydrated as necessary. The dehydration is not particularly limited, and for example, the particle-shaped component (a) is dispersed in a nonpolar solvent such as toluene to conduct azeotropic dehydration. In addition, for example, a method of removing water by a dryer or the like is exemplified. From the viewpoint of efficiency, azeotropic dehydration is preferable industrially. The azeotropic dehydration may be performed, for example, by refluxing and separating and removing water in the middle of a reflux apparatus. The solvent to be used is not particularly limited as long as it is azeotropic with water, but toluene and xylene are preferable in view of solubility with the water repellent of the present invention. The moisture content in the component (a) after the moisture removal step is not particularly limited, and is preferably 150ppm or less.
Next, as the component (a), a catalyst used in a urethane-forming reaction by a general isocyanate can be used as needed, and for example, 1 or 2 or more kinds of a weakly acidic alkali metal salt having high water solubility, an organotin salt (e.g., dibutyltin dilaurate), a zinc salt, a zirconium complex, a bismuth salt, a tertiary amine and a salt thereof (e.g., trade name DBU, DBN, UCASTA102 manufactured by San-Apro corporation) and the like can be added as a reaction catalyst. In this case, a water-soluble solvent such as dimethyl sulfoxide or a water-insoluble solvent such as toluene may be added as necessary. Then, component (b) (isocyanate) was added and reacted. As described above, the catalyst may be added before the reaction, during the reaction, or in multiple portions. The reaction temperature and the reaction time are not particularly limited, and may be the same as or referred to as the addition reaction between a general hydroxyl group-containing polymer or imino group-containing polymer and isocyanate, for example. The reaction temperature is not particularly limited as described above, and may be, for example, 50 to 150 ℃ or 75 to 140 ℃. The reaction time may be, for example, 100 to 240 minutes or 120 to 200 minutes. The end point of the reaction can be confirmed by, for example, measuring the remaining amount of the unreacted isocyanate compound in the reaction mixture with an infrared spectrophotometer.
After the completion of the reaction, for example, water is added to separate an oil layer and an aqueous layer, and the catalyst can be removed by transferring it to the aqueous layer. In addition, this operation may be omitted, for example, when the catalyst does not need to be removed. On the other hand, the adduct (A) of the target product was transferred to the oil layer. The oil layer is filtered through a filter to remove by-products such as diurea. In addition, this operation may be omitted, for example, when it is not necessary to remove the above-mentioned by-products. The filter is not particularly limited, and a closed-type pressure filter is preferable for the purpose of removing by-products insoluble in an organic solvent such as toluene. The filtration method is not particularly limited, and any method may be used, for example, a method of receiving the solution from the container to which the solution is added through a filter by using another receiver, or a circulation method of returning the solution from the container to which the solution is added through the filter to the container to which the solution is added.
Further, the oil layer containing the adduct (a) is added to a vessel in which methanol is previously placed, and the precipitated adduct (a) is separated by filtration to be used for the water repellent of the present invention. For example, when the separation operation of the catalyst and the by-product is omitted, the mixture after the completion of the reaction may be directly added to methanol to precipitate the adduct (a).
[ 1-2 ] Water repellent agent and Process for producing the same
The water repellent of the present invention may contain a surfactant (B) and water (C) in addition to the adduct (a), for example, as described above. The water repellent agent of the present invention may contain an organic solvent (D) in addition to the adduct (a), and the adduct (a) is dissolved in the organic solvent (D), for example, as described above. Hereinafter, the former is sometimes referred to as "water-based water repellent" and the latter is sometimes referred to as "solvent-based water repellent".
The method for producing the aqueous water repellent of the present invention is not particularly limited, and, for example, a general mechanical emulsification method can be used. The machine used in the mechanical emulsification method is not particularly limited, and examples of the batch system include a Nauta mixer (Nauta mixer), an Anchor mixer (Anchor mixer), a homomixer (Homo mixer), a homodisperser (Homo disper), a Planetary mixer (Planetary mixer), and a multiaxial emulsification dispersion apparatus combining these, and examples thereof may include Combi Mix series manufactured by seimiksi corporation. In the continuous system, for example, a line homogenizer (line homogenizer) or the like is mentioned, or a combination thereof may be used. Particularly, a high-temperature high-pressure emulsification and dispersion apparatus capable of increasing the pressure in the apparatus is preferable.
In the water repellent of the present invention, the surfactant (B) is not particularly limited, and may be, for example, a general surfactant. The surfactant may be any of a nonionic (nonion) type surfactant, a cationic (cation) type surfactant, an anionic (anion) type surfactant, and an amphoteric surfactant, for example. Examples of the nonionic surfactant include polyoxyalkylene alkyl ether surfactants such as polyoxyethylene alkyl ether surfactants, and polyoxyalkylene alkylamines. Examples of the polyoxyalkylene alkyl ether surfactant include Blaunon 230 and Finesurf1502.2, which are trade names of those manufactured by Rauwolfia oil and fat industries, Ltd. Examples of the cationic surfactant include quaternary ammonium salts, tertiary amines, and salts thereof. Examples of the quaternary ammonium salt include Lipoquad18-63, which is a trade name of Shiwang specialty Chemicals. Examples of the anionic surfactant include alkylbenzenesulfonic acid, salts thereof, and fatty acid salts. Examples of the amphoteric surfactant include fatty acid amide propyldimethylamino acetic acid betaine and the like. The surfactant (B) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The content of the surfactant (B) in the water repellent of the present invention is not particularly limited, and is, for example, 1 mass% or more, 3 mass% or more, or 5 mass% or more, for example, 200 mass% or less, 150 mass% or less, or 100 mass% or less, based on the mass of the adduct (a).
The aqueous water repellent of the present invention may contain an organic compound such as a hydrocarbon oil or a higher alcohol. The organic compound such as a hydrocarbon oil or a higher alcohol is a component different from the organic solvent mixed with water (C) in the aqueous water repellent agent described later. Specific examples of the hydrocarbon oil include squalene, squalane, liquid paraffin, liquid isoparaffin, heavy liquid isoparaffin, α -olefin oligomer, naphthene, polybutene, vaseline, paraffin, microcrystalline wax, polyethylene wax, and ozokerite. Examples of the higher alcohol include higher alcohols having 6 to 30 carbon atoms, such as hexanol, 2-ethylhexanol, octanol, decanol, isodecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, eicosanol, and docosanol. The content of the organic compound is not particularly limited, and is, for example, 1 mass% or more, 3 mass% or more, or 5 mass% or more, for example, 200 mass% or less, 150 mass% or less, or 100 mass% or less, based on the mass of the adduct (a). The organic compound has, for example, an effect of reducing the viscosity of the aqueous water repellent. For example, in the production of the aqueous water repellent of the present invention, by adding an organic compound having an action of reducing the viscosity of the aqueous water repellent, the behavior of increasing the viscosity can be controlled and emulsification and dispersion can be easily performed.
In the water repellent of the present invention, water (C) is not particularly limited, and examples thereof include tap water, distilled water, ion-exchanged water, and the like. Further, water (C) and an organic solvent may be mixed as necessary. The organic solvent used in this case is not particularly limited as long as it is an organic solvent miscible with water, and examples thereof include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, glycols such as propylene glycol, dipropylene glycol and tripropylene glycol, and glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether. The ratio of water to the organic solvent is not particularly limited.
In the water repellent of the present invention, the content of the adduct (a) is not particularly limited, and is, for example, 0.5 mass% or more, 1 mass% or more, or 3 mass% or more, for example, 90 mass% or less, 70 mass% or less, or 50 mass% or less, with respect to the mass of the water (C).
In the solvent-based water repellent of the present invention, the organic solvent (D) is not particularly limited, but a solvent in which the adduct (a) is easily dissolved is preferable. Examples of the organic solvent (D) include hydrocarbon solvents such as aromatic hydrocarbons and aliphatic hydrocarbons (e.g., n-hexane), alcohol solvents (e.g., methanol and ethanol), glycol solvents (e.g., ethylene glycol), amide solvents (e.g., Dimethylformamide (DMF) and dimethylacetamide), sulfoxide solvents (e.g., dimethyl sulfoxide), ketone solvents (e.g., Methyl Ethyl Ketone (MEK)), aromatic solvents (e.g., toluene and xylene), ether solvents (e.g., dioxane and tetrahydrofuran), and ester solvents (e.g., ethyl acetate and butyl acetate). Examples of the aromatic hydrocarbon include toluene, benzene, xylene, 1,3, 5-trimethylbenzene, and the like. The organic solvent (D) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
In the solvent-based water repellent agent of the present invention, the content of the adduct (a) is not particularly limited, and is, for example, 0.1 mass% or more, 0.5 mass% or more, or 1.0 mass% or more, for example, 90 mass% or less, 80 mass% or less, or 70 mass% or less, based on the mass of the organic solvent (D).
The water repellent of the present invention may or may not contain any other components other than the above-mentioned components (a) to (D). Examples of the optional component include the amino-modified silicone (E). That is, the aqueous water repellent or solvent water repellent of the present invention may further contain an amino-modified silicone (E) as described above. By containing the amino-modified silicone (E), the water repellency of, for example, the water-repellent treated fiber or fiber product is further improved, or the hand becomes softer. Examples of the amino group-modified silicone (E) include side chain type amino group-modified silicone, both-terminal type amino group-modified silicone, single-terminal type amino group-modified silicone, both-terminal type amino group-modified silicone in a side chain, and the like, and may have different reactive groups such as polyether groups in the same molecule. Examples of the amino-modified silicone include those having a trade name of SM-8709SR manufactured by Tolliken Corning. In the amino-modified silicone, the functional group equivalent of the amino group is not particularly limited, and is, for example, 100 to 20000g/mol, 200 to 18000g/mol, or 500 to 16000 g/mol.
The content of the amino-modified silicone (E) in the aqueous or solvent-based water repellent of the present invention is not particularly limited, and is, for example, 0.5 mass% or more, 1 mass% or more, or 2 mass% or more, for example, 200 mass% or less, 150 mass% or less, or 100 mass% or less, based on the mass of the adduct (a).
In the aqueous water repellent or solvent water repellent of the present invention, examples of the optional component other than the amino-modified silicone (E) include a linear silicone oil (Straight silicone oil) such as dimethylsilicone oil or methylhydrogen-containing silicone oil, a reactive silicone oil such as polyether-modified silicone oil or epoxy-modified silicone oil, and the like.
The method for producing the aqueous water repellent or the solvent water repellent of the present invention is not particularly limited, and for example, all the components may be mixed and dissolved or dispersed. In addition, each component may be dissolved or dispersed by heating appropriately so as to be easily dissolved or dispersed. For example, in the case of an aqueous water repellent, 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 disperse the adduct (a) and the surfactant (B) in the water (C), whereby the aqueous water repellent can be produced. The heating temperature in this case is not particularly limited, and is, for example, 30 ℃ or more, or 50 ℃ or more, or 180 ℃ or less, or 160 ℃ or less. The time for heating and stirring is not particularly limited, and may be, for example, a time that allows all the components to be uniformly mixed.
[ 2] method for using water-repellent agent, method for producing water-repellent fiber product, and water-repellent fiber product
The method of using the water repellent of the present invention is not particularly limited, and for example, the same method as or the same method as the method of using a general water repellent, particularly a fiber water repellent can be used. The water repellent agent of the present invention can be used for, for example, water repellent treatment (water repellent processing) of fibers or fiber products, and can be used for, for example, the method for producing the water repellent fiber product of the present invention and the water repellent fiber product of the present invention. The method for producing the water-repellent fiber product of the present invention is not particularly limited, but the water-repellent fiber product can be produced by the method for producing the water-repellent fiber product of the present invention. In the method for producing a water-repellent fiber product of the present invention, the "fiber" to be subjected to water-repellent treatment (water-repellent treatment) is not particularly limited, and may be any fiber product, for example. The fiber or fiber product is not particularly limited, and may be any fiber or fiber product, for example, clothing, daily necessities, interior decoration, automobile seats, and the like.
The method for producing the water-repellent fiber product of the present invention is not particularly limited except for the step of water-repellent treatment using the water-repellent agent of the present invention, and may be, for example, the same as or similar to a general method for water-repellent treatment of fibers or fiber products.
The method for producing the waterproof fiber product of the present invention can be specifically performed, for example, as follows.
First, a treatment liquid containing the water repellent of the present invention is prepared. For example, the water repellent agent of the present invention may be used as the treatment liquid as it is, or may be diluted with water or an organic solvent. For example, in the case of an aqueous water repellent, the treatment liquid may be diluted with water, and in the case of a solvent-based water repellent, the treatment liquid may be diluted with an organic solvent or the like of the same kind as or different kind from the organic solvent (D). The concentration of the treatment liquid is not particularly limited, and the concentration of the adduct (a) is, for example, 0.1 mass% or more, 0.3 mass% or more, or 0.5 mass% or more, for example, 30 mass% or less, 20 mass% or less, or 10 mass% or less, with respect to the dispersant or the solvent (for example, the water or the organic solvent) of the treatment liquid. In addition, for example, a water-repellent auxiliary agent or the like may be added to the treatment liquid. The water-repellent auxiliary is not particularly limited, and examples thereof include linear silicone oils such as amino-modified silicone oil, dimethyl silicone oil, and methyl hydrogen silicone oil, and reactive silicone oils such as polyether-modified silicone oil and epoxy-modified silicone oil. The amount of the water-repellent auxiliary is not particularly limited, and is, for example, 0.5 mass% or more, 1 mass% or more, or 2 mass% or more, for example, 200 mass% or less, 150 mass% or less, or 100 mass% or less, based on the adduct (a).
Next, the water-repellent treatment step of water-repellent treating the fibers in the treatment liquid is performed. The water-repellent treatment step may be the same as or similar to a general water-repellent treatment method for fibers or fiber products, for example, as described above. Specifically, for example, the treatment liquid may be allowed to permeate into fibers or fiber products to be subjected to water repellent treatment, and then the fibers or fiber products may be dried. In this way, the method for producing the 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 or may not include a step other than the water-repellent treatment step. The other step is, for example, a dry heat treatment described later.
The water-repellent treatment step may be performed by, for example, a continuous method or a batch method.
In the continuous method, for example, first, fibers or fiber products as a treatment object are continuously fed into an impregnation apparatus filled with the treatment liquid to impregnate the treatment object with the water-repellent treatment liquid, and thereafter, unnecessary water-repellent treatment liquid is removed. The impregnation device is not particularly limited, but a padding machine type applicator, a roll lick type applicator, a gravure coater type applicator, a spray type applicator, a molding type applicator, and a coating type applicator are particularly preferable, and a padding machine type applicator is particularly preferable. Subsequently, water, organic solvents, and the like remaining in the object to be treated are removed using a dryer. The dryer is not particularly limited, but is preferably a spreading dryer such as a hot air dryer or a tenter. The continuous method is preferably used when the object to be treated is in the form of a fabric such as a woven fabric.
For example, the method includes an immersion step of immersing fibers or fiber products as a treatment object in the treatment liquid, and a liquid removal step of removing water, an organic solvent, and the like remaining in the treatment object immersed in the water repellent treatment liquid. The batch method is preferably used, for example, when the object to be treated is not suitable for treatment by a continuous method. More specifically, the case where the object to be treated is not in the form of a fabric is mentioned, and examples thereof include the case where the object to be treated is loose wool, wool top, sliver (sliver), skein, tow, yarn, or the like, and the case where the object to be treated is a woven fabric. In the impregnation step, for example, a cotton dyeing machine, a bobbin dyeing machine, a jet dyeing machine, an industrial washing machine, a beam dyeing machine, or the like can be used. In the liquid removing step, a hot air dryer such as a bobbin dryer, a beam dryer, or a drum dryer, a high frequency dryer, or the like can be used.
For example, as described above, the treatment liquid may contain isocyanate (F) in the water-repellent treatment step, and the adduct (a) may be crosslinked by the isocyanate (F). For example, when the treatment liquid contains the amino-modified silicone (E), the amino group of the amino-modified silicone (E) and the isocyanate (F) may be crosslinked. By adding the isocyanate (F), for example, the water repellency after washing (washing durability) of the produced water-repellent fiber product is further improved. The isocyanate (F) is not particularly limited, and for example, an organic compound having 2 or more isocyanate functional groups in the molecule can be used. Specific examples of the isocyanate (F) include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, triphenyltriisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, trimethylolpropane trimethylbenzene diisocyanate adduct, glycerol trimethylbenzene diisocyanate adduct, biuret of hexamethylene diisocyanate, trimethylolpropane trihexylene diisocyanate adduct, and glycerol trihexylene diisocaprylate adduct. Further, as the isocyanate (F), there are further exemplified an organic compound containing a blocked isocyanate functional group which is obtained by reacting phenol, diethyl maleate, methyl ethyl ketoxime, sodium hydrogen sulfite, epsilon-caprolactam, etc. regenerated by an isocyanate group which is dissociated by heating and is active, with an organic compound containing the isocyanate functional group, etc. to block the isocyanate group. Specific examples of the isocyanate (F) include, for example, a solvent system such as Coronate B-45E, Coronate HX, Duranate D101, Duranate D201, manufactured by Asahi Kasei corporation; examples of the water system include the trade name "Aquanate" series manufactured by Tosoh corporation, the trade name Duranate WB 40-100 manufactured by Asahi Kasei corporation, Duranate WT 20-100, Duranate WE 50-100, and the trade name "Elastron" series manufactured by first Industrial pharmaceutical Co. The amount of the isocyanate (F) added is also not particularly limited, and is, for example, 0.5 mass% or more, 1 mass% or more, or 3 mass% or more, for example, 200 mass% or less, 150 mass% or less, or 100 mass% or less, relative to the adduct (a). In the crosslinking reaction in which the adduct (A) is crosslinked by the isocyanate (F), the reaction temperature is not particularly limited, but is, for example, 100 ℃ or more or 120 ℃ or more, for example, 200 ℃ or less or 180 ℃ or less. The reaction time is not particularly limited, and is, for example, 0.1 minute or more or 0.3 minute or more, for example, 20 minutes or less or 15 minutes or less.
Further, the object to be treated to which the water repellent of the present invention is attached is preferably subjected to dry heat treatment. This is because the active ingredient of the 1 st water-repellent agent or the 2 nd water-repellent agent of the present invention is likely to adhere more strongly to the object to be treated when the dry heat treatment is performed. However, the present invention may be carried out without dry heat treatment. In addition, the water repellent agent of the present invention can also be used for paper products, wooden boards (e.g., chipboards, MDF boards, etc.), and the like.
As described above, the water repellent of the present invention is excellent in water repellency. Thus, for example, a water-repellent fiber product having excellent water repellency can be produced. Further, according to the water repellent agent of the present invention, for example, a waterproof product excellent in water repellency after washing (washing durability) can be produced. The water repellent of the present invention can exhibit water repellency or washing durability equivalent to those of a fluorine-based water repellent, for example.
In addition, the water repellent agent of the present invention can provide, for example, excellent oil repellency. This enables, for example, production of a water-repellent fiber product having excellent oil repellency. In addition, the water repellent agent of the present invention can provide excellent oil repellency, and for example, it is expected that sebum dirt will not easily adhere to a textile product. In general, a non-fluorine water repellent agent has inferior oil repellency compared to a fluorine water repellent agent, and sebum dirt is easily adhered. However, according to the present invention, a water repellent and a water repellent fiber product having excellent oil repellency can be obtained even when the water repellent is a non-fluorine-based water repellent.
The water repellent of the present invention can be used efficiently at low cost, and is excellent in water repellency, processing bath stability, storage stability, and the like. The water repellent of the present invention is not particularly limited in its application as described above, and can be used for fiber products such as clothing, umbrellas, raincoats, tent cloths, daily necessities, interior decorations, automobile seats, and the like, and further can be widely applied to water repellent paper, water repellent boards, and the like. Further, the use of the water repellent of the present invention is not limited to the above-described uses, and the water repellent can be widely applied to any use.
Examples
Examples of the present invention are explained below. In addition, the present invention is not limited to these examples.
[ Synthesis example 1 ]
The adduct (a) was produced as follows. First, a reaction vessel capable of heating and cooling while including a stirrer having a Faerdra blade, a reflux condenser, a thermometer, a nitrogen introduction tube, and a dropping funnel was prepared. Next, 57 parts by mass of octadecyl isocyanate (component (b), the content of aliphatic groups having 17 or less carbon atoms being 2.0%) was charged into the reaction vessel, and 10 parts by mass of an ethylene/vinyl alcohol copolymer (component (a), the copolymerization ratio of ethylene being 32 mol%, the average polymerization degree being 1500) as a raw polymer was added thereto and stirred to disperse the mixture. The mass ratio of the octadecyl isocyanate (component (b)) to the ethylene/vinyl alcohol copolymer (component (a)) was adjusted so that the molar ratio of isocyanate to hydroxyl groups was 1/1. The solution was heated to 80 ℃ over about 30 minutes, and 0.036 parts by mass of dibutyltin (Sn) dilaurate was gradually added thereto and dissolved by stirring. While the solution was further stirred and heated, 10 parts by mass of dimethyl sulfoxide (hereinafter referred to as "DMSO") took about 30 minutes to be added dropwise. After completion of the dropwise addition, the reaction temperature was raised to 140 ℃ over 60 minutes from the temperature at the end of the dropwise addition of DMSO (about 90 ℃ C.) while stirring. After the reaction temperature reached 140 ℃, the reaction was further continued with sufficient stirring. The completion of the reaction was confirmed by stirring at about 140 ℃ for about 120 minutes while confirming the progress of the reaction. The progress of the reaction was examined by sampling an appropriate reaction solution and measuring the amount of the octadecyl isocyanate compound in the reaction solution by infrared spectroscopy. After the reaction, the reaction mixture was cooled to 80 ℃ and poured into methanol in an amount of 5 times the total amount of the reaction mixture to obtain a white precipitate. Since DMSO in the reaction solution was dissolved in methanol, DMSO was removed from the precipitate by filtration. Therefore, the white precipitate was separated by filtration, washed with methanol, dried, and then pulverized to obtain a polymer urethane product (adduct (a) of components (a) and (b)) as a target product.
[ Synthesis example 2]
A polymer urethane product (adduct (a) of components (a) and (b)) was obtained in the same manner as in synthesis example 1, except that polyvinyl alcohol having the same number of hydroxyl groups (degree of saponification: 99%, average degree of polymerization: 2000) was used as component (a) instead of the ethylene/vinyl alcohol copolymer.
[ Synthesis example 3 ]
A polymer urethane product (adduct (a) of components (a) and (b)) was obtained in the same manner as in synthesis example 1, except that polyethyleneimine (average polymerization degree 700) was used as component (a) instead of the ethylene/vinyl alcohol copolymer, and the amount of polyethyleneimine was adjusted so that the sum of the numbers of amino groups and imino groups of the polyethyleneimine was equal to the number of hydroxyl groups of the ethylene/vinyl alcohol copolymer.
[ Synthesis example 4 ]
A polymer urethane product (adduct (a) of components (a) and (b)) was obtained in the same manner as in synthesis example 1, except that polyvinyl alcohol (degree of saponification: 99%, average degree of polymerization: 300) having 1.2 times the number of hydroxyl groups was used as component (a) instead of the ethylene/vinyl alcohol copolymer.
[ Synthesis example 5 ]
A polymer urethane product (adduct (a) of components (a) and (b)) was obtained in the same manner as in synthesis example 1, except that polyethyleneimine (average polymerization degree 500) was used as component (a) instead of the ethylene/vinyl alcohol copolymer, and the amount of polyethyleneimine was adjusted so that the sum of the numbers of amino groups and imino groups of the polyethyleneimine was 1.1 times the number of hydroxyl groups of the ethylene/vinyl alcohol copolymer.
[ Synthesis example 6 ]
A polymer urethane product (adduct (a) of components (a) and (b)) was obtained in the same manner as in synthesis example 1, except that polyallylamine (average polymerization degree 400) was used as component (a) instead of the ethylene/vinyl alcohol copolymer, and the amount of polyallylamine was adjusted so that the number of amino groups of the polyallylamine was 1.1 times the number of hydroxyl groups of the ethylene/vinyl alcohol copolymer.
[ Synthesis example 7 ]
A polymer urethane product (adduct (a) of components (a) and (b)) was obtained in the same manner as in synthesis example 1, except that DBU (trade name, manufactured by San-Apro corporation) as a tertiary amine or a salt thereof was used as component (a) instead of the dibutyltin (Sn) dilaurate.
[ example 1 ]
The water repellent of this example was produced by dissolving 2.0 parts by mass of the polymer urethane (adduct (a)) obtained in synthesis example 1 in 98.0 parts by mass of toluene. The water repellent agent is used as it is as a treatment liquid for producing a water repellent fiber product.
Further, after each of a nylon 100% fabric and a polyester 100% fabric was impregnated with the water repellent agent (treatment liquid) of this example (liquid-carrying rate: 50 mass%), it was dried at 130 ℃ for 2 minutes to conduct water repellency treatment (water repellency treatment step), and the water repellent fiber product (water repellent-treated fabric) of this example was obtained. Further, the water-repellent fiber product (water-repellent treated cloth) was heat-treated at 170 ℃ for 1 minute to obtain a heat-treated water-repellent fiber product (water-repellent treated cloth) of this example. The "liquid carrying rate" represents a ratio of the mass of the treatment liquid absorbed by the cloth to the mass of the cloth before the impregnation.
[ example 2]
The water repellent of this example was produced by dissolving 2.0 parts by mass of the polymer urethane (adduct (a)) obtained in synthesis example 2 in 98.0 parts by mass of toluene. Further, the same operation as in example 1 was carried out except that the water-repellent agent of this example was used as a treatment liquid in place of the water-repellent agent of example 1, whereby the water-repellent fiber product (water-repellent treated fabric) of this example and the heat-treated water-repellent fiber product (water-repellent treated fabric) of this example were obtained.
[ example 3 ]
The water repellent of this example was produced by dissolving 2.0 parts by mass of the polymer urethane (adduct (a)) obtained in synthesis example 3 in 98.0 parts by mass of toluene. Further, the same operation as in example 1 was carried out except that the water-repellent agent of this example was used as a treatment liquid in place of the water-repellent agent of example 1, whereby the water-repellent fiber product (water-repellent treated fabric) of this example and the heat-treated water-repellent fiber product (water-repellent treated fabric) of this example were obtained.
[ example 4 ]
The water repellent of this example was produced by dissolving 2.0 parts by mass of the polymer urethane (adduct (a)) obtained in synthesis example 1 and 1.0 part by mass of Coronate B-45E (isocyanate (F)) produced by tokyo co. Further, the same operation as in example 1 was carried out except that the water-repellent agent of this example was used as a treatment liquid in place of the water-repellent agent of example 1, whereby the water-repellent fiber product (water-repellent treated fabric) of this example and the heat-treated water-repellent fiber product (water-repellent treated fabric) of this example were obtained.
[ example 5 ]
30.0 parts by mass of the polymer urethane (adduct (A)) obtained in Synthesis example 1, 0.5 parts by mass of Lipoquad18-63 (quaternary ammonium salt, cationic surfactant, surfactant (B)) which is a trade name produced by Shiwang specialty Chemicals, 1.5 parts by mass of Blaunon 230 (polyoxyalkylene alkyl ether surfactant, nonionic surfactant, surfactant (B)) which is a trade name produced by Kazuki oil and fat industries, and 3.0 parts by mass of Finesurf1502.2 (polyoxyalkylene alkyl ether surfactant, nonionic surfactant, surfactant (B)) which is a trade name produced by Kazuki oil and fat industries, were charged into a high-pressure multi-shaft disperser having an anchor mixer, homomixer, and homodisperser, sealed, melt-mixed at 120 ℃ and then kept at 110 ℃ or higher, and 87.0 parts by mass of hot water having a temperature of 95 ℃ or higher was mixed while continuing stirring, thereby producing the water repellent of the present embodiment. Further, the same operation as in example 1 was carried out except that 9.0 parts by mass of the water repellent agent (emulsion) of this example and 91.0 parts by mass of water were mixed and used as a treatment liquid in place of the treatment liquid of example 1, to obtain a water-repellent fiber product (water-repellent treated fabric) of this example and a heat-treated water-repellent fiber product (water-repellent treated fabric) of this example.
[ example 6 ]
The same operation as in example 1 was carried out except that 9.0 parts by mass of the water-repellent agent obtained in example 5, 3.0 parts by mass of an amino-modified silicone (E) having a trade name SM-8709SR manufactured by tokyo ken corporation, and 88.0 parts by mass of water were mixed and used as the treatment liquid, to obtain a water-repellent fiber product (water-repellent treated cloth) of this example and a heat-treated water-repellent fiber product (water-repellent treated cloth) of this example.
[ example 7 ]
The same operation as in example 1 was carried out except that 9.0 parts by mass of the water repellent agent obtained in example 5, 3.0 parts by mass of an amino-modified silicone (E) having a trade name SM-8709SR manufactured by tokyo corporation, 1.0 part by mass of a Coronate AQ-140 (isocyanate (F)) manufactured by tokyo corporation, and 87.0 parts by mass of water were mixed and used as the treatment liquid, to obtain a water repellent fiber product (water-repellent treated fabric) of this example and a heat-treated water repellent fiber product (water-repellent treated fabric) of this example.
[ example 8 ]
The same procedures as in example 5 were carried out except that the polymer urethane product (adduct (a)) obtained in synthesis example 4 was used instead of the polymer urethane product (adduct (a)) obtained in synthesis example 1, to obtain a water-repellent fiber product (water-repellent treated fabric) of this example and a water-repellent fiber product (water-repellent treated fabric) of this example after heat treatment.
[ example 9 ]
The same procedures as in example 5 were carried out except that the polymer urethane product (adduct (a)) obtained in synthesis example 5 was used instead of the polymer urethane product (adduct (a)) obtained in synthesis example 1, to obtain the water-repellent fiber product (water-repellent treated fabric) of this example and the water-repellent fiber product (water-repellent treated fabric) of this example after heat treatment.
[ example 10 ]
The same procedures as in example 5 were carried out except that the polymer urethane product (adduct (a)) obtained in synthesis example 6 was used instead of the polymer urethane product (adduct (a)) obtained in synthesis example 1, to obtain the water-repellent agent, the water-repellent fiber product (water-repellent treated fabric) according to the present example, and the water-repellent fiber product (water-repellent treated fabric) according to the present example after the heat treatment.
[ example 11 ]
30.0 parts by mass of the polymer urethane (adduct (A)) obtained in Synthesis example 1, 0.5 parts by mass of Lipoquad18-63 (quaternary ammonium salt, cationic surfactant, surfactant (B)) which is a trade name produced by Shiwang specialty Chemicals, 1.5 parts by mass of Blaunon 230 (polyoxyalkylene alkyl ether surfactant, nonionic surfactant, surfactant (B)) which is a trade name produced by Kazuki oil and fat industries, 3.0 parts by mass of Finesulf1502.2 (polyoxyalkylene alkyl ether surfactant, nonionic surfactant, surfactant (B)) which is a trade name produced by Kazuki oil and fat industries, 4.0 parts by mass of stearyl alcohol are put into a vessel having an anchor blade, melt-mixed at 100 ℃ and then mixed with stirring under normal pressure with 8.0 parts by mass of hot water at 90 ℃ or higher, thereby producing the water repellent of the present example. Further, the same operation as in example 1 was carried out except that 9.0 parts by mass of the water repellent agent (emulsion) of this example and 91.0 parts by mass of water were mixed and used as a treatment liquid in place of the treatment liquid in example 1, to obtain the water repellent fiber product (water-repellent treated fabric) of this example and the heat-treated water repellent fiber product (water-repellent treated fabric) of this example.
[ example 12]
The same procedures as in example 11 were carried out except that 130 ° F paraffin of the same quality was used instead of stearyl alcohol, thereby obtaining a water-repellent agent, a water-repellent fiber product (water-repellent treated fabric) of the present example, and a heat-treated water-repellent fiber product (water-repellent treated fabric) of the present example.
[ example 13 ]
The same procedures as in example 5 were carried out except that the polymer urethane product (adduct (a)) obtained in synthesis example 7 was used instead of the polymer urethane product (adduct (a)) obtained in synthesis example 1, to obtain the water repellent agent, the water repellent fiber product (water-repellent treated fabric) of the present example, and the water repellent fiber product (water-repellent treated fabric) of the present example after the heat treatment.
[ COMPARATIVE EXAMPLE 1 ]
A reaction vessel was prepared which was equipped with a stirrer having a Faerdra blade, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel and which was capable of heating and cooling. In the reaction vessel, 2.0 parts by mass of an emulsifier (polyoxyethylene [ EO ═ 12] alkyl [ C ═ 12 to 14, branched ether) and 14.0 parts by mass of water were added and dissolved, and the inside of the system was replaced with nitrogen gas. In addition, a mixture of 49.0 parts by mass of octadecyl acrylate and 1.0 part by mass of 2-ethylhexyl acrylate was prepared, and 2 parts by mass of the mixture was charged into the reaction vessel and emulsified at 70 ℃ for 30 minutes. Next, 0.2 parts by mass of 2, 2' -azobis (2-methylpropionamidine) hydrochloride as a polymerization initiator was dissolved in 0.4 parts by mass of water and added to the reaction vessel, and immediately, the residual polymerization initiator was continuously added dropwise to the reaction vessel over 90 minutes, and polymerization was carried out at 70 ℃. After completion of the dropwise addition, the mixture was aged at 70 ℃ for 90 minutes. And cooling the mixture to room temperature to obtain the water repellent. A water-repellent fiber product (water-repellent treated fabric) of this comparative example and a heat-treated water-repellent fiber product (water-repellent treated fabric) of this comparative example were obtained in the same manner as in example 1, except that 96 parts by mass of water was used as the treatment liquid of this comparative example by mixing 4 parts by mass of the obtained water-repellent agent (emulsion).
[ COMPARATIVE EXAMPLE 2]
30.0 parts by mass of a product name X-22-4515 (silicone oil) manufactured by shin Etsu chemical Co., Ltd. and 2.0 parts by mass of a 5-mole adduct of ethylene oxide of a branched alcohol having 12 to 14 carbon atoms were mixed. Next, to the obtained mixture, 68.0 parts by mass of water was gradually added while mixing in small amounts, to obtain a water repellent containing 30 mass% of polyether silicone. A water-repellent fiber product (water-repellent treated fabric) of this comparative example and a heat-treated water-repellent fiber product (water-repellent treated fabric) of this comparative example were obtained in the same manner as in example 1, except that 6 parts by mass of the obtained water-repellent agent (emulsion) and 94 parts by mass of water were mixed and used as the treatment liquid of this comparative example.
[ COMPARATIVE EXAMPLE 3 ]
The same operation as in example 1 was carried out except that 8.0 parts by mass of a commercially available fluorine-based water repellent agent (product name: Aashiguard AG-E081, manufactured by Asahi glass company Co., Ltd.), 1.0 part by mass of a crosslinking agent (product name: Meikanate FM-1, manufactured by Minghua chemical Co., Ltd.) and 91.0 parts by mass of water were mixed as a treatment liquid, to obtain a water repellent fiber product (water-repellent treated fabric) of this comparative example and a water repellent fiber product (water-repellent treated fabric) of this comparative example after heat treatment.
The water repellency, washing durability (water repellency after washing), and hand feeling of the water repellent fiber products (water-repellent treated fabrics) of examples 1 to 13 and comparative examples 1 to 3 obtained as described above and the water repellent fiber products (water-repellent treated fabrics) after heat treatment were evaluated by the following methods. The evaluation results are summarized in tables 1 and 2 below.
[ evaluation of Water repellency ]
The test was carried out with the shower water temperature being 23 ℃ according to the water repellency test (spray test) of JISL1092 (2009). The results were evaluated visually by 5-stage rating as described below. The evaluation was that the water repellency was better as the value of the grade in the following 5 stages was larger.
Water repellency: status of state
5: no wetting on the surface;
4: slightly adherent wetting on the surface;
3: partial wetting of the surface is shown;
2: showing wetness on the surface;
1: showing wetting over the entire surface.
[ evaluation of oil repellency ]
The following evaluation solution was dropped on 5 spots on the test cloth in accordance with AATCC118-1997, and the state of the evaluation solution after 30 seconds was visually observed, and the oil repellency was evaluated on the following 9-stage scale of 0 to 8. Specifically, of the following evaluation liquids that did not permeate the test cloth after 30 seconds, the numerical value of the evaluation liquid having the largest numerical value was set as the rating of the evaluation. The oil repellency was evaluated to be better as the numerical value of the following 9-stage scale was larger. The following "Kaydol" is a trade name of white mineral oil from Witco Chemical Company, which is also sometimes referred to as "KYDOL".
Evaluation liquid
8: n-heptane
7: n-hexane
6: n-decane
5: n-dodecane
4: n-tetradecane
3: n-hexadecane
2: mixed solution of n-hexadecane and Kaydol (mass ratio 65/35)
1：Kaydol
0: less than 1
[ evaluation of stitch slippage resistance ]
According to JISL 1096: 8.23 slippage resistance of 2010 8.23.1 stitch slippage method B) stitch slippage resistance was measured by method B). The evaluation was that the smaller the value, the better the stitch slippage (stitch slippage resistance).
[ Wash durability (Water repellency after washing) ]
The water repellency of the cloth washed 10 times (L-10) by method 103 according to JIS L0217(1995) was evaluated in the same manner as the above-mentioned water repellency evaluation method.
[ evaluation of hand feeling ]
The softness of the cloth was evaluated in 5 stages of 1 to 5 by hand feeling (hand touch). As described below, the softness of the unprocessed cloth (which was not subjected to the water repellent treatment and the heat treatment) was evaluated as 5, and the softness was the softest in evaluation 5 and the hardness was the hardest in evaluation 1.
1: hard-5: soft (with unprocessed cloth 5)
[ TABLE 1 ]
[ TABLE 2]
As shown in tables 1 and 2, the fabrics (water-repellent fiber products) of examples 1 to 13 in which the water-repellent agent contained the adduct (a) of the components (a) and (b) were excellent in water repellency and oil repellency before washing and water repellency after washing (washing durability) of 100% nylon, 100% polyester, 100% non-heat-treated fabric and heat-treated fabric, and also comparable to the fluorine-based water-repellent agent (comparative example 3). The fabrics (water repellent fiber products) of examples 1 to 13 exhibited sufficient flexibility even in the evaluation of hand feeling. In particular, examples 6 and 7, in which the amino-modified silicone (E) was added, exhibited comparable flexibility to the fluorine-based water repellent (comparative example 3). Further, regarding the evaluation of hand feeling, in all of examples and comparative examples, since the evaluation results of the water-repellent fiber product without heat treatment (water-repellent treated cloth) and the water-repellent fiber product heat-treated at 170 ℃ for 1 minute (water-repellent treated cloth) were the same, the evaluation results of both were collectively shown in tables 1 and 2. Furthermore, the fabrics (water-repellent fiber products) of examples 1 to 13 were also excellent in stitch slippage resistance. On the other hand, in comparative examples 1 and 2 in which the water repellent agent does not contain the adduct (a) of the components (a) and (b), although the hand was soft, the water repellency and oil repellency before washing and the water repellency after washing (washing durability) were significantly deteriorated compared to the examples. The fabric (water-repellent fiber product) of comparative example 1 was excellent in stitch slippage resistance, but in comparative example 2, the resistance was greatly deteriorated compared to the other examples and comparative examples. In addition, comparative example 3 (fluorine-based water repellent) is excellent in water repellency, oil repellency, washing durability and hand feeling, but has a problem in that it contains fluorine element. As described above, the water repellent agents of examples 1 to 13 not only did not contain fluorine, but also exhibited performance comparable to that of comparative example 3 (fluorine-based water repellent agent).
The present application claims priority based on Japanese patent application laid-open at 2018, 7, 25 and 2019, 1, 29, 2018, 139574 and 2019, 013679, the entire disclosures of which are incorporated herein by reference.
Claims (9)
1. A water repellent agent characterized by comprising 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;
(b) an isocyanate having an aliphatic group having 8 or more carbon atoms.
2. The water repellent according to claim 1, wherein the water repellent further contains a surfactant (B) and water (C).
3. The water repellent agent according to claim 1, further comprising an organic solvent (D) in which the adduct (a) is dissolved.
4. The water repellent agent according to any one of claims 1 to 3, wherein the component (a) is at least one selected from polyvinyl alcohol, a vinyl alcohol-vinyl acetate copolymer, an ethylene-vinyl alcohol-vinyl acetate copolymer, polyallylamine, and polyethyleneimine.
5. The water repellent according to any one of claims 1 to 4, wherein the ratio of the sum of the numbers 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 to 1/1.
6. The water repellent agent according to any one of claims 1 to 5, further comprising an amino-modified silicone (E).
7. A method for producing a water-repellent fiber product, characterized by comprising a water-repellent treatment step of subjecting fibers to a water-repellent treatment with a treatment liquid containing the water-repellent agent according to any one of claims 1 to 6.
8. The method for producing a water-repellent fiber product according to claim 7, wherein in the water-repellent treatment step, the treatment liquid contains isocyanate (F), and the adduct (A) is crosslinked by the isocyanate (F).
9. A water-repellent fiber product characterized in that the adduct (A) or a crosslinked product of the adduct (A) in the water-repellent agent according to any one of claims 1 to 6 is attached to a fiber.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-139574 | 2018-07-25 | ||
| JP2018139574 | 2018-07-25 | ||
| JP2019-013679 | 2019-01-29 | ||
| JP2019013679 | 2019-01-29 | ||
| PCT/JP2019/028956 WO2020022367A1 (en) | 2018-07-25 | 2019-07-24 | Water repellent agent, method for manufacturing water repellent fiber product, and water repellent fiber product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112513220A true CN112513220A (en) | 2021-03-16 |
| CN112513220B CN112513220B (en) | 2023-10-10 |
Family
ID=69181579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980049510.9A Active CN112513220B (en) | 2018-07-25 | 2019-07-24 | Water repellent agent, method for producing water repellent fiber product, and water repellent fiber product |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2020022367A1 (en) |
| CN (1) | CN112513220B (en) |
| WO (1) | WO2020022367A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7284410B2 (en) | 2021-06-09 | 2023-05-31 | ダイキン工業株式会社 | Oil resistant agents and paper products |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2532011A (en) * | 1946-09-07 | 1950-11-28 | Minnesota Mining & Mfg | Liners and adhesive tapes having low adhesion polyvinyl carbamate coatings |
| JPS5951855A (en) * | 1982-09-18 | 1984-03-26 | 日東電工株式会社 | Adhesive tape fixed to living body |
| JPS602779A (en) * | 1983-06-13 | 1985-01-09 | 保土谷化学工業株式会社 | Water repellent and waterproof processing of fiber product |
| JPH06184947A (en) * | 1992-12-08 | 1994-07-05 | Nippon Unicar Co Ltd | Softening agent composition |
| CN103492522A (en) * | 2011-04-27 | 2014-01-01 | 旭硝子株式会社 | Water-repelling, oil-repelling agent composition, method for producing same, and article |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS297333B1 (en) * | 1951-09-30 | 1954-11-09 | ||
| JP2802112B2 (en) * | 1989-08-31 | 1998-09-24 | 株式会社日本触媒 | Aqueous release agent and method for producing the same |
| JP3133256B2 (en) * | 1996-05-10 | 2001-02-05 | 大日精化工業株式会社 | Modified polyvinyl alcohol-based copolymer, method for producing the same, and coating composition for plasticized vinyl chloride-based resin molded article |
| JP4392086B2 (en) * | 1998-10-22 | 2009-12-24 | 株式会社日本触媒 | Polymer aqueous dispersion, method for producing the same, and aqueous release agent |
| DE10124387A1 (en) * | 2001-05-18 | 2002-11-28 | Basf Ag | Hydrophobically modified polyethyleneimine and polyvinylamine as anticrease agents for treatment of cellulose containing textiles, useful as textile finishing agents in both solid and liquid formulations |
| JP4236538B2 (en) * | 2002-08-20 | 2009-03-11 | 東レ株式会社 | Biosensor |
| JP2004183159A (en) * | 2002-12-04 | 2004-07-02 | Toray Ind Inc | Stainproof fiber |
| JP2005281870A (en) * | 2004-03-26 | 2005-10-13 | Lintec Corp | Water-disintegrating water repellent paper and method for producing the same |
| JP6693110B2 (en) * | 2015-12-14 | 2020-05-13 | 三菱ケミカル株式会社 | Laminated polyester film |
-
2019
- 2019-07-24 WO PCT/JP2019/028956 patent/WO2020022367A1/en active Application Filing
- 2019-07-24 CN CN201980049510.9A patent/CN112513220B/en active Active
- 2019-07-24 JP JP2020532434A patent/JPWO2020022367A1/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2532011A (en) * | 1946-09-07 | 1950-11-28 | Minnesota Mining & Mfg | Liners and adhesive tapes having low adhesion polyvinyl carbamate coatings |
| JPS5951855A (en) * | 1982-09-18 | 1984-03-26 | 日東電工株式会社 | Adhesive tape fixed to living body |
| JPS602779A (en) * | 1983-06-13 | 1985-01-09 | 保土谷化学工業株式会社 | Water repellent and waterproof processing of fiber product |
| JPH06184947A (en) * | 1992-12-08 | 1994-07-05 | Nippon Unicar Co Ltd | Softening agent composition |
| CN103492522A (en) * | 2011-04-27 | 2014-01-01 | 旭硝子株式会社 | Water-repelling, oil-repelling agent composition, method for producing same, and article |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020022367A1 (en) | 2020-01-30 |
| JPWO2020022367A1 (en) | 2021-08-05 |
| CN112513220B (en) | 2023-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6608804B2 (en) | Non-fluorinated urethane coating | |
| CN111386327B (en) | Water repellent composition and process for producing water repellent fiber product | |
| JP6272588B1 (en) | Water repellent agent and method for producing the same | |
| TWI668243B (en) | Wax and urethane based extender blends for surface effect compositions | |
| US10941315B2 (en) | Water repellent agent composition and method for producing water repellent fiber product | |
| JP4280325B2 (en) | Reaction products of isocyanates and hydroxy compounds used in finishing fiber materials | |
| CN109563339B (en) | Fluorine-free fiber treatment composition, treated substrate, and treatment method | |
| KR20150136114A (en) | Urethane based polymeric extenders for compositions to modify the surface properties of substrates | |
| US20160090560A1 (en) | Method of imparting water repellency with non-fluorinated laundry treatment compositions | |
| CN109988264A (en) | A kind of no fluoro water proofing agent and its preparation method and application | |
| KR20120092557A (en) | Composition for oil- and /or water-repellent finishing of fiber materials | |
| JP2005519176A (en) | Water dispersible finishing composition for fibrous substrates | |
| CN112513220B (en) | Water repellent agent, method for producing water repellent fiber product, and water repellent fiber product | |
| KR102437958B1 (en) | Fluorine-free hydrophobization | |
| CN100471889C (en) | Extender for treatment of fiber materials | |
| CN113227486B (en) | Water repellent composition and method for producing water repellent fiber product | |
| JP2024072903A (en) | Water repellent, water repellent treatment liquid, and method for producing water repellent textile product using the water repellent treatment liquid | |
| WO2024095652A1 (en) | Non-fluorine water-repellent composition and method for producing water-repellent fiber product | |
| JP6046525B2 (en) | Water / oil repellent composition, water / oil repellent fiber product, and method for producing water / oil repellent fiber product | |
| JP2001107031A (en) | Water- and oil-repellent composition having low dynamic surface tension and water- and oil-repellent treatment process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |