WO2019240162A1 - Agent hydrofuge, produit fibreux hydrofuge, et procédé de fabrication associé - Google Patents

Agent hydrofuge, produit fibreux hydrofuge, et procédé de fabrication associé Download PDF

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Publication number
WO2019240162A1
WO2019240162A1 PCT/JP2019/023256 JP2019023256W WO2019240162A1 WO 2019240162 A1 WO2019240162 A1 WO 2019240162A1 JP 2019023256 W JP2019023256 W JP 2019023256W WO 2019240162 A1 WO2019240162 A1 WO 2019240162A1
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Prior art keywords
group
isocyanate
water
agent
water repellent
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PCT/JP2019/023256
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English (en)
Japanese (ja)
Inventor
達也 松村
知樹 藤田
橋本　貴史
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明成化学工業株式会社
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Priority to JP2019554581A priority Critical patent/JP6633265B1/ja
Publication of WO2019240162A1 publication Critical patent/WO2019240162A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M13/10—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 oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • the present invention relates to a water repellent, a water repellent fiber product, and a method for producing the same.
  • these products are not satisfied only by being excellent in flame retardancy, but are also required to have functionality such as water repellency, antifouling properties, and antibacterial properties.
  • water repellency for example, shower curtains used in hotel bathrooms For example, high water repellency is required.
  • Patent Document 1 As a technique for suppressing the decrease in flame retardancy due to a water repellent, for example, in Patent Document 1, flame retardant yarn is used to increase the flame retardancy of a fiber, and a very small amount of C8 fluorine-based repellent is used as a water repellent. A method for treating a flame retardant yarn with a liquid is disclosed. Since the C8 fluorine-based water repellent can impart strong water repellency, it can impart water repellency even with a small amount of treatment.
  • C6 fluorine-based water repellents and fluorine-free water repellents are inferior in water repellency compared to C8 fluorine-based water repellents. For this reason, in order to impart sufficient water repellency to textile products, it is necessary to increase the amount used, while flame retardance decreases with increasing amount used, so excellent flame resistance and water repellency It is difficult to achieve both.
  • Patent Document 2 describes that both flame retardancy and water repellency can be achieved by using a flame retardant yarn to increase the flame retardancy of a fiber and treating a small amount of a wax-based water repellent as a water repellent. ing. However, it is difficult to impart sufficient water repellency to the fiber with a wax-based water repellent.
  • the main object of the present invention is to provide a water-repellent agent that imparts excellent water repellency to a fiber and that hardly inhibits the flame retardancy of the fiber.
  • Another object of the present invention is to provide a water repellent fiber product using the water repellent and a method for producing the same.
  • the present inventors have intensively studied to solve the above problems.
  • at least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group and an aqueous dispersion in which the isocyanate compound is dispersed in water, the isocyanate compound relative to the number of moles of the functional group of the hydrocarbon compound.
  • Item 1 At least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, and an aqueous dispersion in which the isocyanate compound is dispersed in water, A water repellent, wherein the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the hydrocarbon compound is 0.3 or more.
  • Item 2. Item 2. The water repellent according to Item 1, wherein the hydrocarbon compound having a functional group capable of reacting with the isocyanate group is a compound represented by the following general formula (1).
  • W is an (a + b) -valent organic group.
  • A is bonded to W and is —X—Y— or —Y—.
  • B is bonded to W and is —XZ or —Z.
  • a is an integer of 1 or more.
  • b is an integer of 1 or more.
  • (A + b) is 3 to 8.
  • X is a divalent polyalkylene ether group.
  • Y is a divalent group, and is an ether group, an ester group, an amide group, a urethane group, a urea group, or a thiourethane group.
  • R is a straight-chain or branched monovalent hydrocarbon group having 6 to 30 carbon atoms which may optionally contain at least one unsaturated bond.
  • Z is a hydroxy group, an amino group, a carboxy group or a thiol group. However, when B is -XZ, Z is a hydroxy group.
  • Item 3. The water repellent according to Item 1 or 2, wherein the isocyanate compound is a blocked isocyanate.
  • Item 4. The water repellent according to any one of Items 1 to 3, further comprising a surfactant.
  • Item 5. The water repellent according to any one of Items 1 to 4, further comprising an acrylic polymer.
  • Item 6. Item 6.
  • the water repellent according to Item 5 wherein the content of the acrylic polymer is 0.1 to 99 parts by mass with respect to a total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound in the water repellent.
  • Item 7. Item 7. The water repellent according to Item 5 or 6, wherein the acrylic polymer is an acrylic polymer containing a halogen element.
  • Item 8. Item 8. The water repellent according to any one of Items 5 to 7, wherein the acrylic polymer is an acrylic polymer containing no fluorine atom.
  • Item 10. Item 10.
  • a first agent comprising at least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group;
  • a kit for preparing a water repellent used as an aqueous dispersion in which the first agent and the second agent are dispersed in water The kit whose molar ratio of the crosslinkable functional group of the said isocyanate compound of the said 2nd agent with respect to the functional group of the said hydrocarbon compound of the said 1st agent is 0.3 or more.
  • a first agent comprising at least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group;
  • At least a third agent comprising an acrylic polymer;
  • a kit for preparing a water repellent used as an aqueous dispersion in which the first agent, the second agent, and the third agent are dispersed in water The kit whose molar ratio of the crosslinkable functional group of the said isocyanate compound of the said 2nd agent with respect to the functional group of the said hydrocarbon compound of the said 1st agent is 0.3 or more.
  • the present invention it is possible to provide a water-repellent agent that imparts excellent water repellency to fibers and hardly inhibits the flame retardancy of the fibers. Moreover, according to this invention, the water-repellent fiber product using the said water-repellent agent and its manufacturing method can also be provided.
  • the water-repellent agent of the present invention comprises a hydrocarbon compound having a functional group capable of reacting with an isocyanate group (hereinafter sometimes referred to as “isocyanate-reactive hydrocarbon compound”) and an isocyanate compound dispersed in water.
  • the ratio of the number of moles of crosslinkable functional groups of the isocyanate compound to the number of moles of the functional groups of the hydrocarbon compound is 0.3 or more.
  • the water repellent of the present invention is provided with such a configuration, thereby imparting excellent water repellency to the fiber, and further inhibiting the inhibition of the flame retardancy of the fiber.
  • the water repellent of the present invention will be described in detail.
  • a one-component type water repellent composed of an aqueous dispersion in which an isocyanate-reactive hydrocarbon compound and an isocyanate compound are dispersed in water.
  • a two-component kit comprising a first agent containing an isocyanate-reactive hydrocarbon compound and a second agent containing an isocyanate compound, and in use, the first agent and the second agent are dispersed in water, It is good also as a form of the kit which prepares the water repellent of this invention as a dispersion.
  • the 3 liquid type kit provided with the 1st agent containing an isocyanate-reactive hydrocarbon compound, the 2nd agent containing an isocyanate compound, and the 3rd agent containing an acrylic polymer,
  • the agent, the second agent, and the third agent may be dispersed in water to form a kit for preparing the water repellent of the present invention as an aqueous dispersion.
  • the hydrocarbon compound having a functional group capable of reacting with an isocyanate group is a hydrocarbon compound in which a functional group capable of reacting with an isocyanate group is bonded to a hydrocarbon skeleton. Only one type of isocyanate-reactive hydrocarbon compound may be used, or two or more types may be mixed and used.
  • Preferred examples of the functional group capable of reacting with an isocyanate group include a hydroxy group, an amino group, a carboxy group, and a thiol group.
  • Examples of the isocyanate-reactive hydrocarbon compound include compounds represented by the following general formula (1). W [-A-R] a [-B] b (1)
  • W is an (a + b) -valent organic group.
  • A is bonded to W and is —X—Y— or —Y—.
  • B is bonded to W and is —XZ or —Z.
  • a is an integer of 1 or more.
  • b is an integer of 1 or more.
  • (A + b) is 3 to 8.
  • X is a divalent polyalkylene ether group.
  • Y is a divalent group, and is an ether group, an ester group, an amide group, a urethane group, a urea group, or a thiourethane group.
  • R is a straight-chain or branched monovalent hydrocarbon group having 6 to 30 carbon atoms which may optionally contain at least one unsaturated bond.
  • Z is a hydroxy group, an amino group, a carboxy group or a thiol group. However, when B is -XZ, Z is a hydroxy group.
  • the hydroxy group, amino group, carboxy group or thiol group of the group Z is a functional group capable of reacting with the isocyanate group.
  • the isocyanate-reactive hydrocarbon compound is a compound having a hydrocarbon group derived from the group R.
  • the group W is an (a + b) -valent organic group and is preferably a residue of a polyfunctional compound.
  • a group A and a group B are bonded to the group W.
  • a is an integer of 1 or more
  • b is an integer of 1 or more
  • (a + b) is 3 to 8. That is, the valence of the group W is 3-8.
  • a polyfunctional compound Preferably, a polyhydric alcohol compound, a polyvalent amine compound, a polyvalent carboxylic acid compound, and a polyvalent thiol compound are mentioned.
  • the polyhydric alcohol compound is not limited, and can be selected from, for example, trimethylolethane, trimethylolpropane, ditrimethylolpropane, 1,2,4-butanetriol, glycerin, and sugar alcohol.
  • Sugar alcohols include, but are not limited to, compounds derived from aldoses and ketoses such as tetroses, pentoses, hexoses and heptoses.
  • polyvalent amine compound examples include, but are not limited to, diethylenetriamine, triethylenetetramine, aminoethylethanolamine, diethanolamine, and triethanolamine.
  • polyvalent carboxylic acid compound examples include, but are not limited to, malic acid and citric acid.
  • polyvalent thiol compound examples include, but are not limited to, trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropio And dipentaerythritol hexakis (3-mercaptopropionate).
  • the group X is a divalent polyalkylene ether group (that is, a polyoxyalkylene group).
  • Specific examples of the group X include single polymers such as ethylene oxide, propylene oxide, and butylene oxide, block copolymers obtained by combining two or more of these, and random copolymers.
  • the group Y is a divalent group, and is an ether group, an ester group, an amide group, a urethane group, a urea group, or a thiourethane group.
  • the group R is a linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, which is bonded to the group Y and may optionally contain at least one unsaturated bond.
  • the lower limit of the number of carbon atoms of the hydrocarbon group is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and the upper limit is preferably 28 or less, more preferably 26 or less, even more preferably.
  • Is 24 or less, and preferred ranges are 6 to 28, 6 to 26, 6 to 24, 8 to 30, 8 to 28, 8 to 26, 8 to 24, 10 to 30, 10 to 28, 10 to 26. 10-24, 12-30, 12-28, 12-26, 12-24, and 12-24 are particularly preferable.
  • hydrocarbon group examples include decyl group, undecyl group, dodecyl group (lauryl group), myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, eicosyl group, heneicosyl group, behenyl group, oleyl Groups and the like.
  • higher fatty acids (note that the carbon number includes carbon of the carbonyl group), higher aliphatic alcohols, higher aliphatic monoisocyanates, higher aliphatic amines. , Alkyl halides, fatty acid chlorides, and the like, and a method of reacting the hydroxy group, carboxy group, thiol group, amino group and the like of the polyfunctional compound can be employed.
  • group Y and group R can be formed, and group R can be introduce
  • higher fatty acids examples include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, and erucic acid. Can be mentioned.
  • higher aliphatic alcohols examples include lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, stearyl alcohol, eicosanol, heneicosanol, behenyl alcohol, and oleyl alcohol.
  • Examples of the higher aliphatic monoisocyanate include decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, myristyl isocyanate, pentadecyl isocyanate, cetyl isocyanate, stearyl isocyanate, eicosyl isocyanate, and behenyl isocyanate.
  • higher aliphatic amines examples include decylamine, laurylamine, myristylamine, stearylamine, behenylamine, and oleylamine.
  • alkyl halide examples include dodecyl chloride, hexadecyl chloride, octadecyl chloride, dodecyl bromide, hexadecyl bromide, octadecyl bromide and the like.
  • fatty acid chloride examples include caprylic acid chloride, capric acid chloride, lauric acid chloride, myristic acid chloride, palmitic acid chloride, stearic acid chloride, and oleic acid chloride.
  • the isocyanate-reactive hydrocarbon compound is preferably selected from the group consisting of the polyfunctional compound and the higher fatty acid, higher aliphatic alcohol, higher aliphatic monoisocyanate, higher aliphatic amine, alkyl halide, and fatty acid chloride.
  • the reaction product with at least one selected from the above is preferable.
  • the reaction product has a hydrocarbon skeleton derived from the polyfunctional compound and includes a functional group (preferably a hydroxy group, an amino group, a carboxy group, or a thiol group) that can react with an isocyanate group. Yes.
  • the number of functional groups capable of reacting with an isocyanate group in one molecule is preferably 1 or more for the lower limit, preferably 7 or less, more preferably 5 or less for the upper limit. More preferably, it is 3 or less, and the range is preferably 1 to 7, more preferably 1 to 5, and further preferably 1 to 3.
  • isocyanate compound As an isocyanate compound, the well-known isocyanate compound (polyfunctional isocyanate compound) which has a 2 or more crosslinkable functional group in 1 molecule can be used individually by 1 type or in combination of 2 or more types as appropriate.
  • the crosslinkable functional group of the isocyanate compound is specifically an isocyanate group or a blocked isocyanate group. Therefore, in the water repellent of the present invention, the total molar ratio of the isocyanate group of the isocyanate compound and the blocked isocyanate group to the functional group of the hydrocarbon compound is 0.3 or more.
  • a blocked isocyanate in which 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more of the isocyanate group is blocked with a blocking agent can be suitably used.
  • a blocked isocyanate various known blocked isocyanates can be used.
  • the blocked isocyanate can be prepared by reacting various known isocyanate compounds with various known blocking agents.
  • Isocyanate compounds may have self-emulsifying properties.
  • isocyanate compounds having self-emulsifying properties include nonionic hydrophilic groups, cationic hydrophilic groups, and anionic properties in part of isocyanate compounds.
  • an isocyanate compound into which a nonionic hydrophilic group having an oxyethylene group is preferably used can be used.
  • Monoalkyl ethers ethylene glycol or (poly) ethylene glycols such as diethylene glycol, triethylene glycol, and polyethylene glycol; block copolymers, random copolymers, and ethylene oxides of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol And propylene oxide, ethylene oxide and butyleneo Random copolymers or block copolymers of the side; polyoxyalkylene monoamines, polyoxyalkylene diamines; and the like, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether and the like are preferably used.
  • the said nonionic hydrophilic compound may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the introduction amount of these compounds is preferably 1 mol% or more for the lower limit with respect to the isocyanate group, and preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less for the upper limit.
  • the range is preferably about 1 to 50 mol%, more preferably about 1 to 40 mol%, and still more preferably about 1 to 30 mol%.
  • Examples of the isocyanate compound include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate.
  • Examples of the aliphatic polyisocyanate include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate and the like.
  • alicyclic polyisocyanate examples include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate), bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI), norbornane diisocyanate, etc.
  • aromatic polyisocyanate examples include 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, crude MDI, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
  • examples include diisocyanate, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, and the like.
  • aliphatic polyisocyanate examples include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate, and the reaction of these compounds.
  • adduct type polyisocyanate and urea It is also preferable to use an isocyanate-modified product obtained by a todionization reaction, an isocyanuration reaction, a carbodiimidization reaction, a ureton iminization reaction, a biuretization reaction, or a mixture thereof.
  • the blocking agent introduced into the isocyanate compound is a compound having at least one active hydrogen in the molecule, and can be used alone or in combination of two or more.
  • the blocking agent include alcohol compounds, alkylphenol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, imidazoline compounds, triazole compounds, Examples thereof include carbamic acid compounds, urea compounds, oxime compounds, amine compounds, imide compounds, imine compounds, pyrazole compounds, and bisulfites.
  • acid amide compounds active methylene compounds, oxime compounds, and pyrazole compounds are preferable, and ⁇ -caprolactam, acetylacetone, diethyl malonate, methyl ethyl ketone oxime, cyclohexanone oxime, 3-methylpyrazole, 3,5-dimethylpyrazole, and the like.
  • ⁇ -caprolactam acetylacetone, diethyl malonate
  • methyl ethyl ketone oxime cyclohexanone oxime
  • 3-methylpyrazole 3,5-dimethylpyrazole, and the like.
  • the ratio (molar ratio) of the number of moles of the crosslinkable functional group of the isocyanate compound to the number of moles of the functional group of the isocyanate-reactive hydrocarbon compound may be 0.3 or more, From the viewpoint of effectively suppressing the inhibition of the flame retardancy of the fiber while suitably imparting excellent water repellency to the fiber, the molar ratio is preferably about 0.4 or more, more preferably The upper limit is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. Preferred ranges are about 0.3 to 8, about 0.3 to 6, About 3-4, about 0.4-8, about 0.4-6, about 0.4-4, about 0.5-8, about 0.5-6, about 0.5-4, In particular, about 0.5 to 4 is preferable.
  • the mass ratio of the isocyanate-reactive hydrocarbon compound to the isocyanate compound is not particularly limited, but preferably has excellent water repellency for the fiber. From the viewpoint of effectively suppressing the inhibition of the flame retardancy of the fiber while being applied, it is preferably 1: 0.001 to 1000, more preferably 1: 0.05 to 20, further preferably 1: 0.1 to 10 is mentioned.
  • the water repellent of the present invention may be a processing solution having a concentration for treating a fiber product as it is, or a stock solution (for example, 5 to 1000 times the stock solution) used by diluting with water before being used for treating a textile product. It may be used as a processing liquid after dilution).
  • the lower limit of the content (solid content) of the isocyanate-reactive hydrocarbon compound is preferably 0.01% by mass or more, more preferably 0.5% by mass or more.
  • the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and a preferable range is 0.01% by mass or more. ⁇ 60 mass%, 0.01 ⁇ 50 mass%, 0.01 ⁇ 40 mass%, 0.5 ⁇ 60 mass%, 0.5 ⁇ 50 mass%, 0.5 ⁇ 40 mass% About 1.0 to 60% by mass, about 1.0 to 50% by mass, and about 1.0 to 40% by mass, and particularly preferably about 1.0 to 40% by mass.
  • the lower limit of the isocyanate compound content is preferably 0.01% by mass or more, more preferably 0.5% by mass or more. More preferably, it is 1.0% by mass or more, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.
  • the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.
  • the isocyanate-reactive hydrocarbon compound and the isocyanate compound may be an aqueous dispersion dispersed in water. More specifically, the water repellent of the present invention may be, for example, an aqueous dispersion in which particles of an isocyanate-reactive hydrocarbon compound and particles of an isocyanate compound are dispersed in water, or an isocyanate-reactive carbonization agent. An aqueous dispersion of particles in which a hydrogen compound and an isocyanate compound are contained in one particle may be used.
  • the aqueous dispersion in which the isocyanate-reactive hydrocarbon compound particles and the isocyanate compound particles are dispersed in water is obtained by mixing the aqueous dispersion of the isocyanate-reactive hydrocarbon compound and the aqueous dispersion of the isocyanate compound. It can be easily prepared. Also, an aqueous dispersion of particles in which an isocyanate-reactive hydrocarbon compound and an isocyanate compound are contained in one particle is also prepared by mixing the isocyanate-reactive hydrocarbon compound and the isocyanate compound and then dispersing in water. Can do.
  • the water repellent of the present invention may contain other components in addition to the isocyanate-reactive hydrocarbon compound, the isocyanate compound, and water.
  • Other components preferably include acrylic polymers, surfactants, flame retardants, silicone compounds, and other additives. Only one type of other components may be used, or two or more types may be mixed and used. However, it is preferable that the water repellent of the present invention does not contain a C8 fluorine-based water repellent (a compound having a perfluoroalkyl group having 8 or more carbon atoms).
  • an acrylic polymer can be suitably prepared as an aqueous dispersion, so that it can be blended even when the water repellent of the present invention is a stock solution, or the water repellent of the present invention is diluted with water.
  • the processing liquid it may be blended with water when the processing liquid is prepared.
  • the surfactant is preferably used to disperse the isocyanate-reactive hydrocarbon compound and isocyanate compound in water when the water-repellent agent of the present invention is used as an aqueous dispersion. It is also preferable to mix the liquid medicine when it is a stock solution. What is necessary is just to select suitably about the timing which adds another component to a water repellent.
  • other components will be described in detail.
  • the water repellent of the present invention may contain an acrylic polymer as necessary from the viewpoint of water repellency and flame retardancy. Only one type of acrylic polymer may be used, or two or more types may be mixed and used.
  • acrylic polymer those known as an aqueous dispersion can be used.
  • an acrylic polymer containing a fluorine atom is preferable from the viewpoint of imparting further excellent water repellency to the fiber.
  • an acrylic polymer containing a chlorine atom is preferable.
  • an acrylic polymer that does not contain a halogen element is also preferable.
  • the acrylic polymer is a polymer obtained by polymerizing at least a (meth) acrylate monomer.
  • an acrylic polymer containing a halogen atom is obtained by copolymerizing a monomer containing a halogen atom with a (meth) acrylate monomer.
  • the (meth) acrylate monomer preferably has an ester moiety having 12 or more carbon atoms, and the ester moiety is preferably a hydrocarbon group other than the ester group.
  • This hydrocarbon group may be linear or branched, may be saturated or unsaturated, and has an alicyclic or aromatic ring. You may do it. Among these, those that are linear are preferable, and those that are linear alkyl groups are more preferable.
  • the ester moiety preferably has 12 or more carbon atoms, more preferably 30 or less, and more preferably 12 to 30 carbon atoms.
  • the number of carbon atoms in the ester moiety is more preferably 21 or less, and further preferably 12 to 21. When the carbon number is within this range, the water repellency and texture are particularly excellent.
  • Particularly preferred as the ester moiety is a linear alkyl group having 12 to 18 carbon atoms.
  • Examples of the (meth) acrylate monomer include lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, and the like. One or more types can be used.
  • (meth) acrylate monomer having a cyclic structure in the ester moiety benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, naphthyl (meth) Acrylate, 4-morpholinoethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, glycidyl ( (Meth) acrylate etc. are mentioned, These 1 type or multiple can be used.
  • the (meth) acrylate monomer preferably contains a functional group having crosslinkability.
  • the functional group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group.
  • examples of the (meth) acrylate monomer include a radical reactive organopolysiloxane macromonomer.
  • the acrylic polymer when the radical-reactive organopolysiloxane macromonomer is copolymerized, the acrylic polymer becomes an acrylic-silicone polymer.
  • the radical-reactive organopolysiloxane macromonomer may have one or more radical-reactive groups in one molecule, and particularly preferably one.
  • the radical reactive group include an azo group, a mercapto group, a vinyl group, a styryl group, and a (meth) acryloyl group, and at least one of these can be used.
  • the reactive group is preferably a (meth) acryloyl group from the viewpoint of easiness of radical copolymerization, easiness of synthesis, and availability of commercially available products.
  • a commercially available product can be selected and used.
  • X-22-174ASX, X-22-174BX, X-22-2426, KF-2012, etc. manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • Other monomers that can be copolymerized with the (meth) acrylate monomer include other polymerizable monomers that are not (meth) acrylate monomers, organopolysiloxanes having radical reactive groups, and Are different macromonomers.
  • examples of other monomers include styrene, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, vinyl alkyl ether, acrylonitrile, alkylol acrylamide, maleic acid diester, methoxypolyalkylene glycol (meth) acrylate, and the like. .
  • Other monomers are not limited to these examples.
  • an acrylic polymer containing chlorine atoms can be obtained by copolymerizing vinyl chloride or vinylidene chloride with a (meth) acrylate monomer.
  • an acrylic polymer containing a fluorine atom is obtained by copolymerizing a fluorine-containing monomer having a perfluoroalkyl group and an ethylenically unsaturated double bond with a (meth) acrylate monomer.
  • the carbon number of the perfluoroalkyl group is preferably 1 or more, preferably 6 or less, and preferably 1 to 6.
  • acrylic polymer examples include, for example, Japanese Patent No. 5572385, Japanese Patent No. 5585078, Japanese Patent No. 5678660, Japanese Patent Publication No. 2017-534713, Japanese Patent Publication No. 2017-536439, Japanese Patent Publication No. 2017-538793, Japanese Patent No. 4927760, Japanese Patent No. 5398723, Japanese Patent No. 5500368, Japanese Patent No. 5626337, Japanese Patent No. 6015003, Japanese Patent No. 6249048, Japanese Patent No. 6280298, Japanese Patent No. 4996875, etc. Can also be suitably used.
  • the acrylic polymer may be an acrylic polymer containing a halogen atom or an acrylic polymer not containing a halogen atom.
  • an acrylic polymer containing a fluorine atom is preferable.
  • an acrylic polymer containing a chlorine atom is preferable.
  • the acrylic polymer can be suitably prepared as an aqueous dispersion by, for example, emulsion polymerization. For this reason, a water repellent is simply obtained by mixing the isocyanate-reactive hydrocarbon compound and isocyanate compound prepared as an aqueous dispersion and the acrylic polymer prepared as an aqueous dispersion.
  • the content of the acrylic polymer is preferably 0.1 parts by mass or more with respect to the lower limit with respect to a total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound.
  • the upper limit is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and the upper limit is preferably 99 parts by mass or less, more preferably 55 parts by mass or less, and further preferably 35 parts by mass or less.
  • the preferred range is 0.1 to 99 parts by weight, 0.1 to 55 parts by weight, 0.1 to 35 parts by weight, 0.5 to 99 parts by weight, 0.5 to 55 parts by weight, 0.5 They are ⁇ 35 parts by mass, 1.0 to 99 parts by mass, 1.0 to 55 parts by mass, 1.0 to 35 parts by mass, and particularly preferably 1.0 to 35 parts by mass.
  • surfactant As the surfactant, one or more of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used.
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylol amide, alkyl alkanol amide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene And glycol polypropylene glycol block copolymer.
  • anionic surfactant examples include sulfate esters of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfone salts.
  • examples include succinate.
  • cationic surfactant examples include amine salts, amidoamine salts, quaternary ammonium salts, and imidazolinium salts. Specific examples include, but are not limited to, alkylamine salts, polyoxyethylene alkylamine salts, alkylamidoamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, And quaternary ammonium salt type surfactants such as dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, alkylisoquinolinium salt, benzethonium chloride, and the like.
  • amphoteric surfactants include alkylamine oxides, alanines, imidazolinium betaines, amide betaines, betaine acetate, and the like. Specific examples include long-chain amine oxides, lauryl betaines, stearyl betaines, lauryl carboxy. Examples include methylhydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.
  • the content of the surfactant is preferably 0.5 parts by mass or more, more preferably about the lower limit with respect to 100 parts by mass of the water repellent solid content.
  • the upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less.
  • the ranges are about 0.5 to 30 parts by weight, about 0.5 to 20 parts by weight, about 0.5 to 10 parts by weight, about 1 to 30 parts by weight, about 1 to 20 parts by weight, and 1 to 10 parts by weight.
  • the water repellent of the present invention may further contain a flame retardant from the viewpoint of further improving the flame retardancy of the fiber.
  • the flame retardant is not particularly limited.
  • a known flame retardant such as a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, a metal salt flame retardant, a silicon flame retardant, or an inorganic flame retardant is used. can do.
  • the fiber product to be treated by the water repellent of the present invention may be subjected to a flame retardant treatment in advance, and these flame retardants can be used for the flame retardant treatment.
  • the content (solid content) of the flame retardant in the working fluid is preferably 1% by mass or more for the lower limit, and preferably 40 for the upper limit. % By mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. The range is preferably about 1 to 40% by mass, more preferably about 1 to 30% by mass, and further preferably 1 to About 25 mass% is mentioned.
  • siliconeone compound One or more silicone compounds can be used in the water repellent of the present invention.
  • amino-modified silicone can be used as the silicone compound.
  • any of those having an amino group introduced into the side chain of the siloxane structure, those having an amino group introduced into the terminal of the siloxane structure, or a mixture thereof may be used.
  • a diamine or a partly blocked diamine may be used.
  • the amine equivalent is preferably 300 g / mol or more, and preferably 20000 g / mol or less, more preferably about 300 to 20000 g / mol.
  • Such amino-modified silicone can be selected from commercial products.
  • WACKER FINISH WR301, WR1100, WR1200, WR1300, WR1600 manufactured by Asahi Kasei Wacker Silicone, KF-867, KF-869 and KF-8004 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • Carbinol-modified silicone can also be used.
  • the carbinol-modified silicone any of those having a hydroxyl group introduced into the side chain of the siloxane structure, those having a hydroxyl group introduced into the terminal of the siloxane structure, or a mixture thereof may be used.
  • Such carbinol-modified silicone can be selected from commercial products. For example, X-22-4039, X-22-4015, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002, KF-6003 etc. manufactured by Shin-Etsu Chemical Co., Ltd. are used. Can do.
  • Diol-modified silicone can also be used.
  • the diol-modified silicone any of those having a diol group introduced into the side chain of the siloxane structure, those having a diol group introduced into the terminal of the siloxane structure, or a mixture thereof may be used.
  • Such a diol-modified silicone can be selected from commercial products. For example, X-22-176DX, X-22-176F, X-22-176GX-A manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • phenol-modified silicone can be used.
  • any of those having a phenolic hydroxyl group introduced into the side chain of the siloxane structure, those having a phenolic hydroxyl group introduced to the terminal of the siloxane structure, or a mixture thereof may be used.
  • Such a phenol-modified silicone can be selected from commercial products. For example, KF-2201 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • carboxyl-modified silicone can be used.
  • carboxyl-modified silicone any of those having a carboxyl group introduced into the side chain of the siloxane structure, those having a carboxyl group introduced into the terminal of the siloxane structure, or a mixture thereof may be used.
  • Such carboxyl-modified silicone can be selected from commercial products. For example, X-22-3701E and X-22-162C manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • Mercapto-modified silicone can also be used.
  • the mercapto-modified silicone any of those having a mercapto group introduced into the side chain of the siloxane structure, those having a mercapto group introduced into the terminal of the siloxane structure, or a mixture thereof may be used.
  • Such mercapto-modified silicone can be selected from commercial products. For example, KF-2001, KF-2004, X-22-167B, X-22-167C, etc. manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • Epoxy-modified silicone can also be used.
  • the epoxy-modified silicone any of those having an epoxy group introduced into the side chain of the siloxane structure, those having an epoxy group introduced to the terminal of the siloxane structure, or a mixture thereof may be used.
  • Such epoxy-modified silicone can be selected from commercial products. For example, X-22-343, KF-101, KF-1001, X-22-163, X-22-163A, X-22-163B, X-22-163C, KF-105, X manufactured by Shin-Etsu Chemical Co., Ltd. -22-169AS, X-22-169B, X-22-173BX, X-22-173DX, and the like can be used.
  • Fluoroalkyl-modified silicone can also be used.
  • the fluoroalkyl-modified silicone can be selected from commercially available products, and examples thereof include Fluorosil J15, Fluorosil D2, Fluorosil H418, and Fluorosil L118 manufactured by SILTECH.
  • long chain alkyl-modified silicones can be used.
  • the long-chain alkyl-modified silicone can be selected from commercially available products, such as KF-412, KF-413, KF-414, KF-415, KF-4003, KF-4701, manufactured by Shin-Etsu Chemical Co., Ltd. KF-4917, KF-7235B, X-22-7322, BELSIL CDM 3526 VP, BELSIL CM 7026 VP, BELSIL SDM 5055 VP manufactured by Asahi Kasei Wacker Silicone Co., Ltd. can be used.
  • long-chain alkyl / aralkyl-modified silicones can be used.
  • the long-chain alkyl / aralkyl-modified silicone can be selected from commercially available products, for example, X-22-1877 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • long chain alkyl / polyether-modified silicones can be used.
  • the long-chain alkyl / polyether-modified silicone can be selected from commercially available products, and examples thereof include Silube T308-16, Silube T310-A16, Silube J208-812, etc. manufactured by SILTECH.
  • higher fatty acid amide-modified silicones can be used.
  • the higher fatty acid amide-modified silicone can be selected from commercially available products. For example, KF-3935 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • dimethyl silicone and methylphenyl silicone can be used.
  • Commercially available products can be selected and used as dimethyl silicone and methylphenyl silicone.
  • KF-96, KF-965, KF-968, KF-995 manufactured by Shin-Etsu Chemical Co., Ltd. are used for dimethyl silicone
  • KF-50, KF-54 manufactured by Shin-Etsu Chemical Co., Ltd. are used for methylphenyl silicone.
  • KF-56 or the like can be used.
  • Silanol-terminated silicone can also be used.
  • the silanol-terminated silicone can be selected from commercially available products, such as X-21-5841 and KF-9701 manufactured by Shin-Etsu Chemical Co., Ltd.
  • a silicone resin compound can also be used from a viewpoint of provision of slip prevention property.
  • the silicone resin known materials can be used.
  • Siloxane is preferred.
  • M, D, T, and Q represent (R ′) 3 SiO 0.5 unit, (R ′) 2 SiO unit, R′SiO 1.5 unit, and SiO 2 unit, respectively.
  • R ′ represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
  • Silicone resins are commonly known as MQ resins, MT resins, or MDT resins, and may have portions designated as MDQ, MTQ, or MDTQ.
  • the silicone resin can also be obtained as a solution in which it is dissolved in an appropriate solvent.
  • the solvent include relatively low molecular weight methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and mixtures of these solvents. Etc.
  • Such a silicone resin can be selected from commercial products.
  • KF-7312J, KF-7312K, KF-7312L, KF-7312T, KF-9021L manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • the silicone resin alone include KR-220L and KR-216 manufactured by Shin-Etsu Chemical Co., Ltd., DOWSIL MQ-1600 Solid Resin manufactured by Toray Dow Corning Co., Ltd., DOWSIL MQ-1640 Flask Resin, and SILRES MK POWDER manufactured by Asahi Kasei Silicone. SILRES MK FLAKE, SILRES 604, etc. can be used.
  • silane coupling agent examples include silane coupling agents containing an epoxy group, an amino group, a mercapto group, an isocyanate group, and the like.
  • a commercial item can be selected and used for such a silane coupling agent.
  • a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • the epoxy group-containing silane coupling agent examples include KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, etc.
  • silane coupling agents examples include KBM-602, KBM-608, KBM-903, KBE-903, and KBM-573.
  • mercapto group-containing silane coupling agents examples include KBM-802, KBM-803, and isocyanate groups.
  • KBE-9007 or the like can be used.
  • the content of the silicone compound is preferably 0.01 parts by mass or more with respect to the lower limit with respect to 100 parts by mass in total of the hydrocarbon compound and the isocyanate compound.
  • the upper limit is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 45 parts by mass or less, and the range is preferably about 0.01 to 100 parts by mass, more preferably 0.
  • the amount is about 01 to 70 parts by mass, more preferably about 0.01 to 45 parts by mass.
  • the water repellent of the present invention may contain any additive as long as the effects of the present invention are produced, in addition to the other components described above.
  • additives include various sorbitan derivatives described in International Publication No. 2014/190905, fatty acid esters such as alkyl citrate derivatives and pentaerythritol derivatives, hydrophobic compounds described in US Publication No.
  • Hydrophobic compounds such as wax-based compounds, water-repellent auxiliary components, crosslinking agents (compounds different from isocyanate compounds), anti-slip agents, anti-wrinkle agents, flame retardants, anti-static agents, heat resistance
  • additives such as textile agents such as agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, deodorants, and antibacterial agents.
  • examples of the water-repellent auxiliary component include zirconium compounds, and zirconium acetate, zirconium hydrochloride, and zirconium nitrate are particularly preferable. These additives can be used singly or in appropriate combination of two or more.
  • the isocyanate-reactive hydrocarbon compound and the isocyanate compound may be an aqueous dispersion dispersed in water.
  • the isocyanate-reactive hydrocarbon compound particles, the isocyanate compound particles, An aqueous dispersion in which is dispersed in water can be easily produced by mixing an aqueous dispersion of an isocyanate-reactive hydrocarbon compound and an aqueous dispersion of an isocyanate compound.
  • the water repellent which further contains an acrylic polymer by mixing the aqueous dispersion of an acrylic polymer can also be manufactured easily.
  • An aqueous dispersion of particles containing an isocyanate-reactive hydrocarbon compound and an isocyanate compound in one particle can be produced by producing the isocyanate-reactive hydrocarbon compound and the isocyanate compound in the same water.
  • various aqueous dispersions may be produced by a known method. For example, after mixing various components and a surfactant, water is added and dispersed, or a known disperser or the like is used. For example, a dispersion method. As a disperser, a homomixer, a homogenizer, a colloid mill, a line mixer, a bead mill, or the like can be used. Moreover, when carrying out aqueous dispersion, you may add a well-known organic solvent.
  • a two-component kit including a first agent containing an isocyanate-reactive hydrocarbon compound and a second agent containing an isocyanate compound is used, and the first agent and the second agent are used at the time of use. It is good also as a kit form which prepares the water repellent of this invention as water-based dispersion.
  • the 3 liquid type kit provided with the 1st agent containing an isocyanate-reactive hydrocarbon compound, the 2nd agent containing an isocyanate compound, and the 3rd agent containing an acrylic polymer,
  • the agent, the second agent, and the third agent may be dispersed in water to form a kit for preparing the water repellent of the present invention as an aqueous dispersion.
  • the two-pack type kit of the present invention comprises at least a first agent containing a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, and at least a second agent containing an isocyanate compound,
  • the molar ratio of the crosslinkable functional group is 0.3 or more.
  • the three-component type kit of the present invention includes at least a first agent containing a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, at least a second agent containing an isocyanate compound, and at least an acrylic polymer.
  • the molar ratio of the crosslinkable functional group of the isocyanate compound of the second agent to the functional group of the hydrogen compound is 0.3 or more.
  • the two-component type kit and the three-component type kit of the present invention are each used for preparing the above-described water repellent of the present invention. Therefore, the kind and content of the isocyanate-reactive hydrocarbon compound, isocyanate compound, acrylic polymer, and other components are the same as the water repellent of the present invention described above.
  • at least one of the acrylic polymer and other components can be blended with the first agent and the second agent.
  • another component can be mix
  • Water-repellent fiber product The water-repellent fiber product of the present invention is treated with the above-described water-repellent agent of the present invention. That is, the water-repellent fiber product of the present invention is produced by bringing the water-repellent agent of the present invention into contact with the fiber product. The details of the water repellent of the present invention are as described above.
  • the fiber product treated with the water repellent of the present invention is not particularly limited as long as it is an article composed of fibers, for example, natural fibers such as cotton, silk, hemp, wool, polyester, nylon, acrylic, Examples thereof include synthetic fibers such as spandex and fiber products using them.
  • natural fibers such as cotton, silk, hemp, wool, polyester, nylon, acrylic
  • synthetic fibers such as spandex and fiber products using them.
  • the form and shape of the textile product there are no restrictions on the form and shape of the textile product, and not only the shape of raw materials such as staples, filaments, tows, and yarns, but also various processes such as woven fabrics, knitted fabrics, stuffed cotton, non-woven fabrics, paper, sheets, and films. It may be in the form.
  • the flame retardant treatment may be applied to the textile product in advance.
  • flame retardancy treatment can be performed by appropriately selecting from the above-mentioned flame retardants in consideration of compatibility with the yarn-making property.
  • the treatment method using a flame retardant is not particularly limited, and may be mixed by a method of simply adding to a polymer or a method of copolymerizing with polyester at a molecular level.
  • a water repellent treatment can be performed on a fiber product (cloth or the like) by a known method.
  • Examples of the method for treating a fiber product with the water repellent of the present invention include a continuous method or a batch method. If the water repellent of the present invention is a stock solution, the concentration suitable for treatment (for example, the solid content concentration is 0.01% by mass or more, or 6% by mass or less, preferably 0.01 to 6% by mass).
  • the processing liquid is prepared by diluting the water repellent with water so as to be approximately%.
  • an object to be processed (that is, a fiber product) is continuously fed into the impregnation apparatus filled with the processing liquid, and the processing object is impregnated with the processing liquid, and then the unnecessary processing liquid is removed.
  • the impregnation device is not particularly limited, and a padder, a kiss roll type applicator, a gravure coater type applicator, a spray type applicator, a foam type applicator, a coating type applicator, etc. can be preferably employed, and a padder type is particularly preferable.
  • a dryer is not particularly limited, and a spread dryer such as a hot fluid or a tenter is preferable.
  • the continuous method is preferably employed when the object to be treated is a fabric such as a woven fabric.
  • the batch method includes a step of immersing the object to be processed in a processing liquid and a step of removing water remaining on the object to be processed.
  • the batch method is preferably employed when the object to be treated is not in the form of a fabric, for example, in the case of loose hair, top, sliver, skein, tow, yarn or the like, or when it is not suitable for continuous methods such as knitting.
  • a cotton dyeing machine, a cheese dyeing machine, a liquid dyeing machine, an industrial washing machine, a beam dyeing machine or the like can be used.
  • a hot air dryer such as a cheese dryer, a beam dryer or a tumble dryer, a high-frequency dryer or the like can be used. It is preferable to perform a dry heat treatment on the workpiece to which the water repellent of the present invention is attached.
  • the lower limit is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, and the upper limit is preferably 180 ° C. or lower, and the range is preferably 120 to 180 ° C. In particular, 160 to 180 ° C. is preferable.
  • the time for the dry heat treatment the lower limit is preferably 10 seconds or more, more preferably 1 minute or more, and the upper limit is preferably 3 minutes or less, more preferably 2 minutes or less. For 10 seconds to 3 minutes, 10 seconds to 2 minutes, 1 to 3 minutes, and 1 to 2 minutes.
  • the method for the dry heat treatment is not particularly limited, but a tenter is preferable when the object to be processed is in the form of a fabric.
  • the reaction was stirred for 1 hour and cooled to room temperature. Vacuum filtration was performed and the collected solid was dried in an oven under reduced pressure overnight.
  • the obtained isocyanate-reactive hydrocarbon compound had a hydroxyl value of 123.2 mgKOH / g.
  • aqueous dispersion of isocyanate-reactive hydrocarbon compound was prepared by the following procedure using the composition shown in Table 1. To the flask, 20 g of an isocyanate-reactive hydrocarbon compound and 20 g of methyl isobutyl ketone were added and melted at 80 ° C.
  • Stearylamine 30EO adduct 1.0 g and acetic acid (90% aqueous solution) 0.3 g were dissolved in 78.7 g of ion-exchanged water at 80 ° C. and added dropwise.
  • the mixture was emulsified with a high-pressure homogenizer (400 bar) while maintaining the temperature. Thereafter, methyl isobutyl ketone was distilled off under reduced pressure, and ion-exchanged water was added to obtain an aqueous dispersion having a solid content concentration of 21%.
  • the content of the isocyanate-reactive functional group in each aqueous dispersion was calculated. Each average particle size was measured.
  • the average particle diameter is a particle diameter (median particle diameter) having a percentage integrated value (volume basis) of 50% measured by a laser diffraction / scattering particle diameter distribution measuring apparatus LA-300 (manufactured by Horiba, Ltd.). (The same applies to the following production examples).
  • the obtained mixed liquid was treated with a high-pressure homogenizer (400 bar) while maintaining the temperature at 50 ° C. to obtain an emulsion.
  • the obtained emulsion was put in an autoclave and cooled to 30 ° C. or lower.
  • VA-061 2,2′-azobis [2- (2-imidazolin-2-yl) propane]
  • the polymerization reaction was carried out at 65 ° C. for 15 hours with stirring, and ion exchange water was added to obtain an aqueous dispersion of an acrylic polymer having a solid content concentration of 20.7%.
  • the average particle size of this aqueous dispersion was 0.10 ⁇ m.
  • the obtained acrylic polymer contains a perfluoroal
  • the emulsion was processed by the high pressure homogenizer (400 bar), keeping at 40 degreeC, and obtained the emulsion.
  • 0.3 g of azobis (isobutylamidine) dihydrochloride was added and reacted at 60 ° C. for 10 hours in a nitrogen atmosphere.
  • Ion exchange water was added to adjust the solid content concentration to 21.8% to obtain an aqueous dispersion of an acrylic polymer.
  • the average particle size of this aqueous dispersion was 0.18 ⁇ m.
  • the resulting acrylic polymer is an acrylic-silicone polymer and does not contain halogen atoms.
  • the obtained acrylic polymer contains a perfluoroalkyl group and a fluorine atom and a chlorine atom derived from vinyl chloride.
  • Paragit ZS wax-zirconium-based water repellent; solid concentration 24%; manufactured by Meisei Chemical Co., Ltd.
  • Petrox P-200 wax-based water repellent; solid content concentration 34%; Meisei Chemical Industries
  • ⁇ Evaluation of water repellency and flame retardancy> As a test cloth, a PET tropical cloth (weighing 138 g / m 2 , undyed, flame retardant untreated) was prepared. Next, using the water repellent as a processing liquid, the test cloth is passed through the processing liquid by a continuous method, and an unnecessary solution is squeezed with a mangle at a constant pressure, dried at 110 ° C. for 1.5 minutes, and 170 ° C. And cured for 1 minute to obtain a processed cloth. The pickup was 92%.
  • Paragit ZS wax-zirconium-based water repellent; solid content concentration 24%; manufactured by Meisei Chemical Co., Ltd.
  • Petrox P-200 wax-based water repellent
  • solid content concentration 34% manufactured by Meisei Chemical Industry Co., Ltd.
  • the test cloth was passed through the processing liquid in a continuous manner in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5, and a mangle with a constant pressure was used.
  • the unnecessary solution was squeezed, dried at 110 ° C. for 1.5 minutes, and cured at 170 ° C. for 1 minute to obtain a processed cloth.
  • the pickup was 92%.
  • the water repellents of Examples 20 to 26 contain an acrylic polymer, but, as in Example 19, which does not contain an acrylic polymer, excellent water repellency for fibers. Further, it is understood that the inhibition of the flame retardancy of the fiber is effectively suppressed. On the other hand, the water repellents of Comparative Examples 6 to 8 were unable to achieve both excellent water repellency and flame retardance inhibiting effect.
  • a PET shower curtain (weighing 125 g / m 2 , undyed, using flame-retardant yarn) was prepared. Next, the following flame retardant treatment was performed on the PET shower curtain to obtain a test cloth.
  • test cloth was passed through the working fluid in a continuous manner in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5, and then with a mangle of constant pressure.
  • the unnecessary solution was squeezed, dried at 110 ° C. for 1.5 minutes, and cured at 170 ° C. for 1 minute to obtain a processed cloth.
  • the pickup was 42%.
  • Example 32 and Comparative Examples 13 to 15 ⁇ Preparation of water repellent> 100% by mass of an aqueous dispersion of an isocyanate-reactive hydrocarbon compound, an aqueous dispersion of an isocyanate compound, an aqueous dispersion of an acrylic polymer, and a phosphorus flame retardant together with water so as to have the composition shown in Table 6.
  • a water repellent was prepared by diluting and mixing.
  • Table 6 shows the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the isocyanate reactive hydrocarbon compound.
  • Table 6 shows the content (parts by mass) of the acrylic polymer with respect to 100 parts by mass in total of the hydrocarbon compound and the isocyanate compound.
  • K-19A phosphorus flame retardant; solid content concentration: 100%; manufactured by Meisei Chemical Industry Co., Ltd.
  • Comparative Example 13 a commercially available C6 fluorine-based water repellent, AsahiGuard E-SERIES AG-E550D (C6 fluorine-based water repellent; manufactured by Asahi Glass Co., Ltd.) and a phosphorus flame retardant were used in combination.
  • Nylon high-density taffeta (weighing 60 g / m 2 , dyed, flame retardant untreated (treated with a phosphorus flame retardant when treated with a water repellent)) was prepared as a test cloth.
  • the test cloth was passed through the processing liquid by a continuous method, and unnecessary solution was squeezed with a mangle at a constant pressure, and dried at 110 ° C. for 1.5 minutes, 170 A processed cloth was obtained by curing at 0 ° C. for 1 minute. The pickup was 42%.
  • the water repellent of Example 32 imparts excellent water repellency to the fiber, and further, the inhibition of the flame retardancy of the fiber is effectively suppressed. I understand. On the other hand, the water repellents of Comparative Examples 13 and 14 were unable to achieve both excellent water repellency and flame retardancy inhibiting effect.
  • Examples 33 to 34 ⁇ Preparation of water repellent> Dilute the aqueous dispersion of the isocyanate-reactive hydrocarbon compound, the aqueous dispersion of the isocyanate compound, and the aqueous dispersion of the acrylic polymer to 100% by mass with water so as to have the composition shown in Table 7.
  • Table 7 shows the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the isocyanate reactive hydrocarbon compound.
  • Table 7 shows the acrylic polymer content (parts by mass) with respect to 100 parts by mass in total of the hydrocarbon compound and the isocyanate compound.
  • test cloth was passed through the working fluid in a continuous manner in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5, and then with a mangle of constant pressure.
  • the unnecessary solution was squeezed, dried at 110 ° C. for 1.5 minutes, and cured at 170 ° C. for 1 minute to obtain a processed cloth.
  • the pickup was 92%.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

L'invention concerne un agent hydrofuge qui confère un excellent caractère hydrofuge à des fibres sans réduire considérablement leur effet retardateur de flamme. L'agent hydrofuge est une dispersion aqueuse contenant au moins : un composé hydrocarboné ayant un groupe fonctionnel susceptible de réagir avec un groupe isocyanate ; et un composé isocyanate dispersé dans l'eau, le rapport en moles du groupe fonctionnel réticulable du composé isocyanate au groupe fonctionnel du composé hydrocarboné étant d'au moins 0,3.
PCT/JP2019/023256 2018-06-12 2019-06-12 Agent hydrofuge, produit fibreux hydrofuge, et procédé de fabrication associé WO2019240162A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021132172A1 (fr) * 2019-12-24 2021-07-01
JP7307788B1 (ja) 2021-12-28 2023-07-12 日華化学株式会社 撥水剤組成物及びその製造方法、並びに撥水性繊維製品及びその製造方法
WO2024095652A1 (fr) * 2022-10-31 2024-05-10 日華化学株式会社 Composition hydrofuge sans fluor et procédé de production d'un produit fibreux hydrofuge
JP7555355B2 (ja) 2019-12-24 2024-09-24 三井化学株式会社 撥水剤組成物、撥水剤組成物の製造方法、および、繊維製品

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220163486A (ko) * 2020-06-03 2022-12-09 메이세이 카가쿠고교 가부시키가이샤 발수제 조성물, 키트, 발수성 섬유 제품 및 그 제조 방법
JP6830710B1 (ja) * 2020-09-09 2021-02-17 竹本油脂株式会社 ポリオレフィン系合成繊維用処理剤、ポリオレフィン系合成繊維、及びサーマルボンド不織布

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016522330A (ja) * 2013-03-29 2016-07-28 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー 基材の表面特性を改質する組成物のためのウレタン性ポリマーエクステンダー
JP2016524628A (ja) * 2013-03-29 2016-08-18 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー 非フッ素化ウレタン系コーティング
WO2017199726A1 (fr) * 2016-05-17 2017-11-23 明成化学工業株式会社 Agent d'hydrofugation, et procédé de fabrication de celui-ci
JP2017222827A (ja) * 2016-06-17 2017-12-21 日華化学株式会社 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法
JP2018062720A (ja) * 2016-10-14 2018-04-19 松本油脂製薬株式会社 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5922706B2 (ja) * 2014-05-23 2016-05-24 明成化学工業株式会社 フッ素を含まないはっ水剤組成物及びはっ水加工方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016522330A (ja) * 2013-03-29 2016-07-28 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー 基材の表面特性を改質する組成物のためのウレタン性ポリマーエクステンダー
JP2016524628A (ja) * 2013-03-29 2016-08-18 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー 非フッ素化ウレタン系コーティング
WO2017199726A1 (fr) * 2016-05-17 2017-11-23 明成化学工業株式会社 Agent d'hydrofugation, et procédé de fabrication de celui-ci
JP2017222827A (ja) * 2016-06-17 2017-12-21 日華化学株式会社 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法
JP2018062720A (ja) * 2016-10-14 2018-04-19 松本油脂製薬株式会社 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021132172A1 (fr) * 2019-12-24 2021-07-01
WO2021132172A1 (fr) * 2019-12-24 2021-07-01 三井化学株式会社 Composition hydrofuge, procédé de fabrication de composition hydrofuge et produit textile
JP7555355B2 (ja) 2019-12-24 2024-09-24 三井化学株式会社 撥水剤組成物、撥水剤組成物の製造方法、および、繊維製品
JP7307788B1 (ja) 2021-12-28 2023-07-12 日華化学株式会社 撥水剤組成物及びその製造方法、並びに撥水性繊維製品及びその製造方法
JP2023101422A (ja) * 2021-12-28 2023-07-21 日華化学株式会社 撥水剤組成物及びその製造方法、並びに撥水性繊維製品及びその製造方法
WO2024095652A1 (fr) * 2022-10-31 2024-05-10 日華化学株式会社 Composition hydrofuge sans fluor et procédé de production d'un produit fibreux hydrofuge

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