WO2024095652A1 - Composition hydrofuge sans fluor et procédé de production d'un produit fibreux hydrofuge - Google Patents

Composition hydrofuge sans fluor et procédé de production d'un produit fibreux hydrofuge Download PDF

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Publication number
WO2024095652A1
WO2024095652A1 PCT/JP2023/035738 JP2023035738W WO2024095652A1 WO 2024095652 A1 WO2024095652 A1 WO 2024095652A1 JP 2023035738 W JP2023035738 W JP 2023035738W WO 2024095652 A1 WO2024095652 A1 WO 2024095652A1
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group
mass
parts
compound
polyisocyanate
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PCT/JP2023/035738
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English (en)
Japanese (ja)
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由枝 南嶋
圭一郎 定
君之 末定
高輔 前田
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日華化学株式会社
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Publication of WO2024095652A1 publication Critical patent/WO2024095652A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • 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
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • This application discloses a non-fluorine-based water repellent composition and a method for producing a water-repellent textile product.
  • Fluorine-based water repellents containing fluorine-based compounds are produced, for example, by polymerizing a monomer having a fluoroalkyl group. Articles treated with such fluorine-based water repellents have excellent water repellency. However, monomers having a fluoroalkyl group are an environmental burden. For this reason, non-fluorine-based water repellents that exhibit excellent water repellency have been internationally sought.
  • Patent Document 1 discloses a water-based water repellent treatment agent that contains a non-fluorine-based water repellent component and a crosslinking component that can react with the water repellent component, and is composed of a hybrid emulsion in which the water repellent component and the crosslinking component are contained in one particle.
  • Patent Document 2 also discloses a water repellent composition that contains an amino-modified silicone, a silicone resin, and a polyfunctional isocyanate compound.
  • A at least one non-fluorine-based water-repellent component selected from the group consisting of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound;
  • B an alicyclic polyisocyanate;
  • a non-fluorine-based water repellent composition comprising:
  • the alicyclic polyisocyanate is at least one of isophorone diisocyanate and hydrogenated MDI;
  • a method for producing a water-repellent textile product comprising:
  • the articles can have excellent initial water repellency, washing-durable water repellency, and also excellent water repellency during actual use (abrasion-resistant water repellency).
  • Non-fluorinated water repellent composition contains (A) at least one non-fluorinated water repellent component selected from the group consisting of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound, and (B) an alicyclic polyisocyanate.
  • the non-fluorine-based water repellent composition includes, as the non-fluorine-based water repellent component (A), at least one selected from the group consisting of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound.
  • the non-fluorine-based compound (A) may be at least one of an acrylic compound and a silicone compound, or may be at least one of a wax compound, a urethane compound, and a dendrimer compound. In particular, when the non-fluorine-based compound (A) is at least one of an acrylic compound and a silicone compound, better performance can be expected.
  • the acrylic compound has, for example, a structural unit derived from a (meth)acrylic acid ester monomer (hereinafter also referred to as "(A1) component”) represented by the following general formula (A1).
  • the acrylic compound may further have a structural unit derived from a compound (hereinafter also referred to as "(A2) component”) represented by the following general formula (A2).
  • (meth)acrylic acid ester means “acrylic acid ester” or the corresponding "methacrylic acid ester”, and the same applies to "(meth)acrylic acid", "(meth)acrylamide", etc.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent.
  • R 11 is hydrogen or a methyl group
  • R 12 is a divalent hydrocarbon group having 1 to 6 carbon atoms
  • Z is an ester group or an amide group
  • W is a group represented by -CO-R 13 (R 13 is a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH 2 , or a group represented by the following formula (W1):
  • the component (A1) has a monovalent hydrocarbon group having 12 to 30 carbon atoms, which may have a substituent.
  • the hydrocarbon group may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may have an alicyclic or aromatic ring structure.
  • a linear one is preferable, and a linear alkyl group is more preferable. In this case, the water repellency is more excellent.
  • the substituent may be one or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group.
  • R 2 is preferably an unsubstituted hydrocarbon group.
  • the number of carbon atoms in the hydrocarbon group is preferably 12 to 24, and more preferably 12 to 22. When the number of carbon atoms is within this range, the water repellency and texture are particularly excellent.
  • a linear alkyl group having 18 to 22 carbon atoms is particularly preferred as the hydrocarbon group.
  • Examples of the (A1) component include at least one selected from stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, and behenyl (meth)acrylate.
  • the (A1) component may have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent.
  • the durable water repellency can be further improved.
  • the isocyanate group may be protected with a blocking agent to form a blocked isocyanate group.
  • the texture can be further improved.
  • the above component (A1) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.
  • the above (A1) component may be used alone or in combination of two or more types.
  • R 12 may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic ring structure.
  • R 12 when Z is an ester group, R 12 is preferably a hydrocarbon group having 2 to 4 carbon atoms, and W is preferably a group represented by -NH-CO- NH2 or a group represented by the above formula (W1).
  • W is preferably a group represented by -CO-R 13 , and R 13 preferably has 1 to 2 carbon atoms.
  • the above-mentioned (A2) component is not particularly limited, but examples thereof include diacetone acrylamide, 2-methylpropenoic acid [2-(2-oxo-2-imidazolidinyl)ethyl], and N-[2-(2-oxoimidazolidin-3-yl)ethyl]methacrylamide.
  • diacetone acrylamide and 2-methylpropenoic acid [2-(2-oxo-2-imidazolidinyl)ethyl] are preferred as the above-mentioned (A2) component.
  • the above (A2) component may be used alone or in combination of two or more types.
  • the content ratio of the structural units derived from component (A1) and the structural units derived from component (A2) in the acrylic compound is preferably the ratio (A1)/(A2) of the mass of component (A1) to the mass of component (A2) to be blended, 100/0 to 70/30, more preferably 99.9/0.1 to 70/30, even more preferably 99.8/0.2 to 80/20, and particularly preferably 99.7/0.3 to 90/10. If (A1)/(A2) is within the above range, durable water repellency and water repellency will be better.
  • the total mass of the (A1) component and the (A2) component is preferably 60 to 100% by mass, more preferably 70 to 99% by mass, and even more preferably 80 to 98% by mass, based on the total amount of the monomer components constituting the acrylic compound.
  • the acrylic compound preferably contains, in addition to the (A1) component and the optional (A2) component, at least one monomer (A3) selected from vinyl chloride and vinylidene chloride (hereinafter also referred to as "(A3) component") as a monomer component.
  • A3 component at least one monomer selected from vinyl chloride and vinylidene chloride
  • the (A3) component is preferably vinyl chloride from the viewpoint of maintaining the texture of the textile product.
  • the mass of the (A3) component to be blended is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, based on the total mass of the (A1) and (A2) components to be blended (100), from the viewpoints of water repellency, durable water repellency, and peel strength.
  • the mass of the (A3) component to be blended is preferably 100 parts by mass or less, and more preferably 75 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, based on the total mass of the (A1) and (A2) components to be blended (100), from the viewpoints of water repellency, durable water repellency, and texture.
  • the acrylic compound preferably contains, in addition to component (A1) and any component (A2), at least one reactive emulsifier (A4) (hereinafter also referred to as "component (A4)") selected from compounds having an HLB of 7 to 18 and represented by the following general formula (A4-1), compounds having an HLB of 7 to 18 and represented by the following general formula (A4-2), and compounds (A4-3) having an HLB of 7 to 18 and formed by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group.
  • component (A4) at least one reactive emulsifier
  • R3 is hydrogen or a methyl group
  • X is a linear or branched alkylene group having 1 to 6 carbon atoms
  • Y1 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.
  • R4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group
  • Y2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.
  • reactive emulsifier refers to an emulsifying dispersant having radical reactivity, i.e., a surfactant having one or more polymerizable unsaturated groups in the molecule, which can be copolymerized with a monomer such as a (meth)acrylic acid ester.
  • HLB refers to the HLB value calculated using the Griffin method, assuming that the ethyleneoxy group is a hydrophilic group and all other groups are lipophilic groups.
  • the HLB of the above compounds (A4-1) to (A4-3) is 7 to 18, and from the viewpoint of emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the acrylic compound (hereinafter simply referred to as emulsion stability), it is preferably 9 to 15. Furthermore, from the viewpoint of storage stability of the water repellent composition, it is more preferable to use two or more reactive emulsifiers (A4) having different HLBs within the above range in combination.
  • R 3 is hydrogen or a methyl group, and is more preferably a methyl group in terms of copolymerizability with the (A1) component and/or the (A2) component.
  • X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the acrylic compound.
  • Y 1 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination and number of additions of the alkyleneoxy group in Y 1 can be appropriately selected so as to be within the above HLB range. In addition, when there are two or more types of alkyleneoxy groups, they can have a block addition structure or a random addition structure.
  • R 3 is hydrogen or a methyl group
  • X is a linear or branched alkylene group having 1 to 6 carbon atoms
  • a 1 O is an alkyleneoxy group having 2 to 4 carbon atoms
  • m can be appropriately selected so as to be within the above-mentioned HLB range, and specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A 1 O may be the same or different.
  • R 3 is hydrogen or a methyl group, and is more preferably a methyl group in terms of copolymerizability with the (A1) component and/or the (A2) component.
  • X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the acrylic compound.
  • a 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. The type and combination of A 1 O and the number of m can be appropriately selected so as to be within the above HLB range.
  • m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60.
  • m A 1 O may be the same or different.
  • they can have a block addition structure or a random addition structure.
  • the reactive emulsifier represented by the above general formula (A4-1-1) can be obtained by a conventionally known method and is not particularly limited. It can also be easily obtained from commercial products, such as "Latemul PD-420", “Latemul PD-430", and “Latemul PD-450” manufactured by Kao Corporation.
  • R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group.
  • the unsaturated hydrocarbon group include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group.
  • R 4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.
  • Y2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.
  • the type, combination and number of added alkyleneoxy groups in Y2 can be appropriately selected so as to fall within the above-mentioned HLB range.
  • they can have a block addition structure or a random addition structure.
  • the alkyleneoxy group is an ethyleneoxy group.
  • R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group
  • a 2 O is an alkyleneoxy group having 2 to 4 carbon atoms
  • n can be appropriately selected so as to be within the above-mentioned HLB range, and specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, the n A 2 O may be the same or different.
  • R 4 in the compound represented by the above general formula (A4-2-1) include the same as R 4 in the above general formula (A4-2).
  • a 2 O is an alkyleneoxy group having 2 to 4 carbon atoms.
  • the type and combination of A 2 O and the number of n can be appropriately selected so as to be within the above HLB range.
  • a 2 O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and even more preferably an integer of 8 to 14.
  • n is 2 or more, the n A 2 O may be the same or different.
  • they may have a block addition structure or a random addition structure.
  • the reactive emulsifier represented by the above general formula (A4-2-1) can be synthesized, for example, by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group, but is not limited to this.
  • it can be synthesized by adding a predetermined amount of alkylene oxide under pressure at 120 to 170°C using an alkaline catalyst such as caustic soda or caustic potassium.
  • Phenols having the corresponding unsaturated hydrocarbon group include pure products or mixtures produced industrially, as well as those that exist as pure products or mixtures extracted and purified from plants, etc. Examples include 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc., which are extracted from cashew nut shells, etc. and are collectively known as cardanol.
  • Compound (A4-3) is an oil having an HLB of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group to which an alkylene oxide having 2 to 4 carbon atoms has been added.
  • oils having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids that may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, ⁇ -linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.).
  • alkylene oxide adducts of triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid are preferred
  • alkylene oxide adducts of castor oil (triglycerides of fatty acids containing ricinoleic acid) having 2 to 4 carbon atoms are more preferred
  • ethylene oxide adducts of castor oil are even more preferred.
  • the number of moles of alkylene oxide added can be appropriately selected so as to fall within the above HLB range, and from the viewpoint of emulsion stability of the acrylic compound, 20 to 50 moles is more preferable, and 25 to 45 moles is even more preferable.
  • they can have a block addition structure or a random addition structure.
  • Compound (A4-3) can be synthesized, for example, by adding an alkylene oxide to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, but is not limited to this.
  • it can be synthesized by adding a predetermined amount of alkylene oxide to a triglyceride of a fatty acid containing ricinoleic acid, i.e., castor oil, using an alkaline catalyst such as caustic soda or caustic potassium, under pressure at 120 to 170°C.
  • the monomer composition ratio of the above component (A4) in the acrylic compound is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass, based on the total amount of monomer components constituting the acrylic compound, from the viewpoint of improving water repellency and emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the acrylic compound.
  • the acrylic compound may contain, in addition to the (A1) component and the optional (A2) component, at least one second (meth)acrylic acid ester monomer (A5) (hereinafter also referred to as "A5 component") selected from the group consisting of a monomer represented by the following general formula (A5-1), a monomer represented by the following general formula (A5-2), a monomer represented by the following general formula (A5-3), and a monomer represented by the following general formula (A5-4) as a monomer component.
  • A5 component selected from the group consisting of a monomer represented by the following general formula (A5-1), a monomer represented by the following general formula (A5-2), a monomer represented by the following general formula (A5-3), and a monomer represented by the following general formula (A5-4) as a monomer component.
  • R5 is hydrogen or a methyl group
  • R6 is a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group, provided that the number of (meth)acryloyloxy groups in the molecule is 2 or less.
  • R7 is a hydrogen atom or a methyl group
  • R8 is a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.
  • R 9 is an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.
  • R 10 is hydrogen or a methyl group
  • p is an integer of 2 or more
  • S is a (p+1)-valent organic group
  • T is a monovalent organic group having a polymerizable unsaturated group.
  • the monomer (A5-1) is a (meth)acrylic acid ester monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms, which has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester portion.
  • the monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group.
  • the isocyanate group may be a blocked isocyanate group protected by a blocking agent.
  • the chain-like hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group.
  • the chain-like hydrocarbon group may further have a substituent in addition to the functional group. Of these, it is preferable that the chain-like hydrocarbon group is linear and/or that the chain-like hydrocarbon group is a saturated hydrocarbon group, in terms of improving durable water repellency.
  • the monomer (A5-1) examples include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred in terms of improving durable water repellency. Furthermore, dimethylaminoethyl (meth)acrylate is preferred in terms of improving texture.
  • the mass of the (A5-1) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined mass of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the mass of the (A5-1) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined mass of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the monomer (A5-2) is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester portion.
  • the cyclic hydrocarbon group include isobornyl, cyclohexyl, and dicyclopentanyl groups. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group is selected in which the total number of carbon atoms in the substituent and the cyclic hydrocarbon group is 11 or less. In addition, from the viewpoint of improving durable water repellency, it is preferable that these cyclic hydrocarbon groups are directly bonded to an ester bond.
  • the cyclic hydrocarbon group may be alicyclic or aromatic, and when it is alicyclic, it may be a saturated or unsaturated hydrocarbon group.
  • Specific examples of the monomer include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers may be used alone or in combination of two or more. Among these, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred, with isobornyl methacrylate being more preferred, in terms of improving durable water repellency.
  • the mass of the (A5-2) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the mass of the (A5-2) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the monomer (A5-3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety.
  • chain hydrocarbon group having 1 to 4 carbon atoms a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable.
  • chain hydrocarbon group having 1 to 4 carbon atoms for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, etc. are mentioned.
  • Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used alone or in combination of two or more. Among them, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable in terms of improving durable water repellency, and methyl methacrylate is more preferable.
  • the mass of the (A5-3) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the mass of the (A5-3) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the monomer (A5-4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule.
  • T is a (meth)acryloyloxy group, and a polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule is preferred.
  • the p Ts may be the same or different.
  • compounds include ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.
  • These monomers may be used alone or in combination of two or more.
  • tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred because they can improve durable water repellency.
  • the mass of the (A5-4) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the mass of the (A5-4) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the total composition ratio of the monomers of the above-mentioned (A5) component in the acrylic compound is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, based on the total amount of the monomer components constituting the acrylic compound, from the viewpoints of water repellency and texture.
  • the mass of the (A5) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the mass of the (A5) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the acrylic compound may contain, in addition to the (A1) component and the optional (A2) component, a monofunctional monomer (A6) (hereinafter also referred to as "(A6) component”) that is copolymerizable with these components, within a range that does not impair the effects of the present invention.
  • a monofunctional monomer (A6) (hereinafter also referred to as "(A6) component") that is copolymerizable with these components, within a range that does not impair the effects of the present invention.
  • Examples of the (A6) component include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group other than the above (A1), (A2), and (A5), (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylol acrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other fluorine-free vinyl monomers other than the (A3) component.
  • the (meth)acrylic acid esters having a hydrocarbon group other than the (A1), (A2), and (A5) components may have substituents such as vinyl groups, hydroxyl groups, amino groups, epoxy groups, isocyanate groups, and blocked isocyanate groups in the hydrocarbon group, and may have substituents other than groups that can react with crosslinking agents, such as quaternary ammonium groups, and may have ether bonds, ester bonds, amide bonds, urethane bonds, and the like.
  • Examples of (meth)acrylic acid esters other than components (A1), (A2), and (A5) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, etc.
  • (meth)acryloylmorpholine is more preferred in that it can improve the peel strength of the resulting textile product against coating.
  • the mass of the (A6) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the mass of the (A6) monomer to be blended is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less, per 100 parts by mass of the combined total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.
  • the acrylic compound has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent, as this improves durable water repellency.
  • the isocyanate group may be protected with a blocking agent to form a blocked isocyanate group.
  • the acrylic compound has an amino group, as this improves the texture.
  • the weight-average molecular weight of the acrylic compound is preferably 30,000 or more. When the weight-average molecular weight is 30,000 or more, water repellency tends to be further improved. Furthermore, the weight-average molecular weight of the acrylic compound is more preferably 50,000 or more. In this case, water repellency can be more fully exerted.
  • the upper limit of the weight-average molecular weight of the acrylic compound is preferably about 5 million.
  • the weight average molecular weight of acrylic compounds is measured using a GPC device (Tosoh Corporation's GPC "HLC-8020") at a column temperature of 40°C and a flow rate of 1.0 ml/min, using tetrahydrofuran as the eluent, and is expressed in terms of standard polystyrene.
  • the columns used are three connected columns manufactured by Tosoh Corporation under the trade names TSK-GELG5000HHR, G4000HHR, and G3000HHR.
  • the melt viscosity of the acrylic compound at 105°C is preferably 1000 Pa ⁇ s or less.
  • the texture tends to be easily maintained.
  • the melt viscosity of the acrylic compound is 1000 Pa ⁇ s or less, when the acrylic compound is emulsified or dispersed to form a water repellent composition, the acrylic compound can be prevented from precipitating or settling, and therefore the storage stability of the water repellent composition tends to be easily maintained.
  • the melt viscosity at 105°C is 500 Pa ⁇ s or less. In this case, the texture is more excellent while sufficient water repellency is exhibited.
  • the "melt viscosity at 105°C” refers to the viscosity measured using an elevated flow tester (e.g., CFT-500 manufactured by Shimadzu Corporation) by placing 1 g of a non-fluorinated polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm), holding the temperature at 105°C for 6 minutes, and applying a load of 100 kg f/ cm2 with a plunger.
  • an elevated flow tester e.g., CFT-500 manufactured by Shimadzu Corporation
  • the silicone-based compound is, for example, at least one of silicone resin and silicone oil.
  • silicone resin is preferred from the viewpoint of water repellency.
  • the silicone-based compound may be used alone or in combination of two or more kinds.
  • the silicone resin may be an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT or MDTQ as a constituent, being solid at 25° C. and having a three-dimensional structure, where M, D, T and Q respectively represent (R′′) 3 SiO 0.5 units, (R′′) 2 SiO units, R′′SiO 1.5 units and SiO 2 units.
  • 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 also have moieties designated as MDQ, MTQ or MDTQ.
  • Silicone resins can also be obtained as solutions in suitable solvents.
  • suitable solvents include relatively low molecular weight methylpolysiloxanes, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and mixtures of these solvents.
  • silicone resin solutions examples include KF7312J (a 50:50 mixture of trimethylsilyl-containing polysiloxane: decamethylcyclopentasiloxane), KF7312F (a 50:50 mixture of trimethylsilyl-containing polysiloxane: octamethylcyclotetrasiloxane), KF9021L (a 50:50 mixture of trimethylsilyl-containing polysiloxane: low-viscosity methylpolysiloxane), and KF7312L (a 50:50 mixture of trimethylsilyl-containing polysiloxane: low-viscosity methylpolysiloxane), all of which are commercially available from Shin-Etsu Chemical Co., Ltd.
  • silicone resins alone include MQ-1600 solid Resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 Flake Resin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane), both of which are commercially available from Toray Dow Corning Co., Ltd.
  • the above commercially available products contain trimethylsilyl group-containing polysiloxane, and include MQ, MDQ, MT, MTQ, MDT, or MDTQ.
  • the silicone oil is a linear organopolysiloxane, and may have an organic group at least in one of the side chains and the terminals of the organopolysiloxane.
  • Such silicone oils can be the same as hydrophobic silicone oils and functionalized silicone oils, and examples of such silicone oils include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil; modified silicone oils such as amino-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil, carboxyl-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, aralkyl-modified silicone oil, alkylaralkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, and higher aliphatic amide-modified silicone oil.
  • the amino-modified silicone oil may be a compound having an organic group containing an amino group and/or an imino group at least on the side chain or end of the organopolysiloxane.
  • Such an organic group may be an organic group represented by -R- NH2 or an organic group represented by -R-NH-R'- NH2 .
  • R and R' include divalent groups such as an ethylene group and a propylene group.
  • a part or all of the amino group and/or imino group may be a blocked amino group and/or imino group. The blocked amino group and/or imino group may be obtained, for example, by treating the amino group and/or imino group with a blocking agent.
  • the blocking agent examples include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms.
  • the functional group equivalent of the amino-modified silicone oil is preferably 100 to 20,000 g/mol, more preferably 150 to 12,000 g/mol, and even more preferably 200 to 4,000 g/mol.
  • the amino-modified silicone oil is preferably liquid at 25° C.
  • the kinetic viscosity of the amino-modified silicone oil at 25° C. is preferably 10 to 100,000 mm 2 /s, more preferably 10 to 30,000 mm 2 /s, and even more preferably 10 to 5,000 mm 2 /s. If the kinetic viscosity at 25° C. is greater than 100,000 mm 2 /s, the viscosity is too high and workability tends to deteriorate.
  • the kinetic viscosity at 25° C. refers to a value measured by the method described in JIS K2283:2000 (Ubbelohde viscometer).
  • Amino-modified silicone oils are readily available as commercial products.
  • commercial products include KF8005, KF-868, KF-864, KF-393, and KF-8021 (all of which are product names manufactured by Shin-Etsu Chemical Co., Ltd.), TSF-4709 and XF42-B1989 (product names manufactured by Momentive Performance Materials Japan Co., Ltd.), BY16-872, SF-8417, BY16-853U, and BY16-892 (product names manufactured by Dow Corning Toray Co., Ltd.), KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), and WACKER (registered trademark) FINISH WR 301 (manufactured by Asahi Kasei Wacker Silicone).
  • Silicone oils other than amino-modified silicone oils are also readily available as commercially available products.
  • Examples of commercially available products include KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., product name: epoxy-modified silicone oil), X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd., product name: carboxyl-modified silicone oil), SF8428 (manufactured by Dow Corning Toray Co., Ltd., product name: carbinol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., product name: methyl hydrogen silicone oil), and X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd., product name: methyl hydrogen silicone oil).
  • the silicone compound may be an organo-modified silicone represented by the following general formula (1).
  • the structural units may be arranged in a block, random, or alternating fashion.
  • R 20 , R 21 and R 22 are each independently a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms
  • R 23 is a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 8 to 40 carbon atoms
  • R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms
  • a is an integer of 0 or more
  • b is an integer of 1 or more
  • (a+b) is 10 to 200, when a is 2 or more, the multiple R 20 and R 21 may be the same or different, and when b is 2 or more, the multiple R 22 and R 23 may be the same or
  • the alkoxyl group having 1 to 4 carbon atoms may be linear or branched.
  • the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • R 20 , R 21 , and R 22 are each preferably independently a hydrogen atom or a methyl group, and more preferably a methyl group.
  • Examples of the above-mentioned hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring include aralkyl groups having 8 to 40 carbon atoms and groups represented by the following general formula (2) or (3).
  • R 40 is an alkylene group having 2 to 6 carbon atoms
  • R 41 is a single bond or an alkylene group having 1 to 4 carbon atoms
  • c is an integer of 0 to 3.
  • the multiple R 41s may be the same or different.
  • the above alkylene groups may be linear or branched.
  • R 42 is an alkylene group having 2 to 6 carbon atoms
  • R 43 is a single bond or an alkylene group having 1 to 4 carbon atoms
  • d is an integer of 0 to 3.
  • d is 2 or 3
  • the multiple R 43s may be the same or different.
  • the above alkylene groups may be linear or branched.
  • Examples of the aralkyl group having 8 to 40 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, and a naphthylethyl group.
  • the phenylethyl group and the phenylpropyl group are preferred because they are easy to produce industrially and are readily available.
  • R 40 is preferably an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, and more preferably 0.
  • R 42 is preferably an alkylene group having 2 to 4 carbon atoms, and d is preferably 0 or 1, and more preferably 0.
  • the above-mentioned hydrocarbon group having an aromatic ring and a carbon number of 8 to 40 the above-mentioned aralkyl group having a carbon number of 8 to 40 and the group represented by the above-mentioned general formula (2) are preferred in that they are easy to produce industrially and are readily available, and the above-mentioned aralkyl group having a carbon number of 8 to 40 is more preferred in that it can improve water repellency.
  • the alkyl group having 8 to 40 carbon atoms may be linear or branched.
  • Examples of the alkyl group having 8 to 40 carbon atoms include octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, stearyl, behenyl, hexacosyl, octacosyl, triacontyl, and dotriacontyl.
  • an alkyl group having 12 to 36 carbon atoms is preferred, and an alkyl group having 16 to 34 carbon atoms is more preferred, in terms of improving water repellency.
  • R 30 , R 31 , R 32 , R 33 , R 34 , and R 35 are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms, or an alkyl group having 3 to 22 carbon atoms.
  • R 30 , R 31 , R 32 , R 33 , R 34 , and R 35 are each independently a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and among these, a methyl group is more preferable.
  • a is an integer of 0 or more. In terms of ease of industrial production, availability, and superior peel strength, a is preferably 40 or less, and more preferably 30 or less.
  • (a+b) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a+b) is preferably 20 to 100, and more preferably 40 to 60. When (a+b) is within the above range, the silicone itself tends to be easier to produce and handle.
  • Organo-modified silicones can be synthesized by conventional methods.
  • organo-modified silicones can be obtained by subjecting silicones having SiH groups to a hydrosilylation reaction with aromatic compounds and/or ⁇ -olefins having vinyl groups.
  • silicones having SiH groups include methylhydrogensilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane.
  • methylhydrogensilicones are preferred because they are easy to manufacture industrially and are readily available.
  • the aromatic compound having a vinyl group is a compound from which the hydrocarbon group having an aromatic ring and 8 to 40 carbon atoms in R 23 in the above general formula (1) is derived.
  • aromatic compounds having a vinyl group include styrene, ⁇ -methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl phenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.
  • the above ⁇ -olefin is a compound from which the alkyl group having 8 to 40 carbon atoms in R 23 in the above general formula (1) is derived.
  • the ⁇ -olefin include ⁇ -olefins having 8 to 40 carbon atoms such as 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexacosene (C26), 1-octacosene (C28), 1-triacontene (C30), and 1-dotriacontene (C32).
  • the hydrosilylation reaction may be carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group and the ⁇ -olefin in a stepwise or all-at-once reaction, if necessary, in the presence of a catalyst.
  • the amounts of the silicone having a SiH group, the aromatic compound having a vinyl group, and the ⁇ -olefin used in the hydrosilylation reaction can be appropriately selected according to the SiH group equivalent weight of the silicone having a SiH group, the number average molecular weight, etc.
  • Catalysts used in hydrosilylation reactions include, for example, platinum and palladium compounds, with platinum compounds being preferred.
  • platinum compounds include platinum(IV) chloride.
  • the reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted as appropriate.
  • the reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C.
  • the reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C.
  • the hydrosilylation reaction is preferably carried out in an inert gas atmosphere.
  • inert gas include nitrogen and argon.
  • the reaction proceeds without a solvent, but a solvent may be used.
  • solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.
  • the water repellent component it is preferable to use the above acrylic compound and the above silicone compound in combination from the viewpoint of water repellency and chalk marks.
  • the mass ratio of the acrylic compound ( ⁇ ) and the silicone compound ( ⁇ ) is not particularly limited.
  • the silicone compound ( ⁇ ) when the silicone compound ( ⁇ ) is a silicone resin, the silicone compound ( ⁇ ) may occupy 1 to 99 parts by mass, assuming that the total of the acrylic compound ( ⁇ ) and the silicone compound ( ⁇ ) is 100 parts by mass. It is preferably 5 to 98 parts by mass, more preferably 10 to 97 parts by mass, and even more preferably 15 to 95 parts by mass.
  • the silicone compound ( ⁇ ) when the silicone compound ( ⁇ ) is an organo-modified silicone, the silicone compound ( ⁇ ) may occupy 10 to 90 parts by mass, assuming that the total of the acrylic compound ( ⁇ ) and the silicone compound ( ⁇ ) is 100 parts by mass. It is preferably 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 60 parts by mass. By keeping the proportion of silicone compound ( ⁇ ) within this range, the coating has excellent water repellency and is less likely to produce chalk marks.
  • the wax-based compound is, for example, at least one type selected from paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, animal and vegetable waxes, and mineral waxes. From the viewpoints of water repellency, durable water repellency, and texture, paraffin wax is preferable.
  • the wax-based compound may be, for example, one or both of a normal alkane and a normal alkene. From the viewpoints of water repellency, durable water repellency, and texture, the wax-based compound is preferably a normal alkane.
  • the normal alkane may be, for example, at least one selected from tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane.
  • the normal alkane is preferably triacontane, hentriacontane, or dotriacontane.
  • the normal alkene may be, for example, at least one selected from 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosene, triacontene, hentriacontene, dotriacontene, tritriacontene, tetratriacontene, pentatriacontene, and hexatriacontene. From the viewpoints of water repellency, durable water repellency, and texture, it is preferable that the normal alkene is at least one selected from triacontene, hentriacontene, and dotriacontene.
  • the number of carbon atoms in the wax-based compound is not particularly limited, but may be 20 to 60, and from the standpoint of water repellency, durable water repellency, and texture, it is preferably 25 to 45.
  • the weight average molecular weight of the wax-based compound is not particularly limited, but may be from 300 to 850, and from the viewpoints of water repellency, durable water repellency, and texture, it is preferably from 300 to 700.
  • the melting point of the wax-based compound is preferably 35 to 90°C, more preferably 40 to 85°C, more preferably 45 to 80°C, and even more preferably 50 to 75°C.
  • the melting point of the wax-based compound refers to a value measured using the same method as JIS K2235-1991.
  • the penetration of the wax-based compound is not particularly limited, but may be, for example, 30 or less, and from the viewpoint of water repellency and durable water repellency, is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the penetration of the wax-based compound is not particularly limited, but may be, for example, 0.1 or more, or 1 or more.
  • the penetration of the wax-based compound refers to a value measured by the same method as JIS K2235-1991.
  • the urethane-based compound is, for example, a reaction product of an aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound. More specifically, for example, (U1) an aliphatic polyisocyanate derivative having an average number of isocyanate groups of 2 or more; (U2) a long-chain active hydrogen compound having both a hydrocarbon group and an active hydrogen group and having from 12 to 30 carbon atoms; (U3) a cationic active hydrogen compound having both an active hydrogen group and a cationic group; (U4) an acid compound that forms a salt with a cationic group;
  • the concentration of the hydrocarbon group may be 30% or more and 85% or less.
  • the aliphatic polyisocyanate derivative may contain an isocyanurate derivative of an aliphatic polyisocyanate.
  • the cationic group may be a tertiary amino group
  • the active hydrogen group may be a hydroxyl group
  • the cationic active hydrogen compound may have two or more hydroxyl groups per molecule.
  • Examples of the aliphatic polyisocyanate constituting the aliphatic polyisocyanate derivative (U1) include aliphatic diisocyanates such as hexamethylene diisocyanate (hexane diisocyanate) (HDI), pentamethylene diisocyanate (pentane diisocyanate) (PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate.
  • the term "aliphatic polyisocyanate” is a concept that includes alicyclic polyisocyanates.
  • alicyclic polyisocyanates include alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'-, or 2,2'-methylene bis(cyclohexyl isocyanate) or mixtures thereof (H12MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.
  • alicyclic diisocyanates such as 3-isocyanatomethyl-3,
  • the aliphatic polyisocyanate is preferably one or both of hexamethylene diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane (hereinafter simply referred to as bis(isocyanatomethyl)cyclohexane), and more preferably hexamethylene diisocyanate.
  • aliphatic polyisocyanate derivatives examples include polymers of the above-mentioned aliphatic polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (e.g., allophanate derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanates with monohydric alcohols or dihydric alcohols), polyol derivatives (e.g., polyol derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanates with trihydric alcohols (e.g., trimethylolpropane, etc.) (alcohol adducts, preferably trimethylolpropane, etc.), Pan adducts), biuret derivatives (for example, biuret derivatives produced by the reaction of the above-mentioned
  • the aliphatic polyisocyanate derivative is preferably at least one of an isocyanurate derivative, a trimethylolpropane adduct, an allophanate derivative, and a biuret derivative, and is more preferably an isocyanurate derivative.
  • an isocyanurate derivative When the aliphatic polyisocyanate derivative contains an isocyanurate derivative, the texture becomes good.
  • the aliphatic polyisocyanate derivative is more preferably at least one of an isocyanurate derivative of hexamethylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, a biuret derivative of hexamethylene diisocyanate, and an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, and is even more preferably an isocyanurate derivative of hexamethylene diisocyanate.
  • the aliphatic polyisocyanate derivatives may be used alone or in combination of two or more.
  • an isocyanurate derivative of hexamethylene diisocyanate is used alone, or an isocyanurate derivative of hexamethylene diisocyanate is used in combination with at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate.
  • the mixing ratio of the isocyanurate derivative of hexamethylene diisocyanate is, for example, 60 parts by mass or more relative to 100 parts by mass of the total amount of the isocyanurate derivative of hexamethylene diisocyanate and at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate.
  • hexamethylene diisocyanate preferably 70 parts by mass or more, and for example, 85 parts by mass or less, and the blending ratio of at least one selected from the group consisting of isocyanurate derivatives of bis(isocyanatomethyl)cyclohexane, trimethylolpropane adducts of hexamethylene diisocyanate, allophanate derivatives of hexamethylene diisocyanate, and biuret derivatives of hexamethylene diisocyanate is, for example, 15 parts by mass or more, and for example, 40 parts by mass or less, preferably 30 parts by mass or less.
  • Aliphatic polyisocyanate derivatives can be produced by known methods.
  • the average number of isocyanate groups of the aliphatic polyisocyanate derivative is 2 or more, preferably 2.5, more preferably 2.9, and for example, 3.8 or less. If the average number of isocyanate groups is equal to or greater than the lower limit, the water repellency can be further improved.
  • the average number of isocyanate groups is calculated from the isocyanate group concentration A of the aliphatic polyisocyanate derivative, the solid content concentration B, and the number average molecular weight C of gel permeation chromatography measured using the following device and conditions, according to the following formula (1). When two or more types of aliphatic polyisocyanate derivatives are used in combination, the average number of isocyanate groups is calculated from the weight ratio of the aliphatic polyisocyanate derivatives and their average number of isocyanate functional groups.
  • Average isocyanate functionality A/B ⁇ C/42.02 (1) (In the formula, A represents the isocyanate group concentration of the aliphatic polyisocyanate derivative, B represents the solid content concentration, and C represents the number average molecular weight.)
  • Apparatus HLC-8220GPC (manufactured by Tosoh) Column: TSKgel G1000HXL, TSKgel G2000HXL, and TSKgel G3000HXL (manufactured by Tosoh) connected in series Detector: differential refractometer Injection volume: 100 ⁇ L Eluent: tetrahydrofuran Flow rate: 0.8 mL/min Temperature: 40°C Calibration curve: Standard polyethylene oxide in the range of 106 to 22450 (manufactured by Tosoh Corporation, product name: TSK Standard Polyethylene Oxide)
  • Long-chain active hydrogen compounds have both a hydrocarbon group with 12 to 30 carbon atoms and an active hydrogen group that reacts with an aliphatic polyisocyanate derivative.
  • the hydrocarbon group having 12 to 30 carbon atoms may be, for example, a linear or branched saturated hydrocarbon group having 12 to 30 carbon atoms (e.g., an alkyl group, etc.), or a linear or branched unsaturated hydrocarbon group having 12 to 30 carbon atoms (e.g., an alkenyl group, etc.).
  • the active hydrogen group may be, for example, a hydroxyl group.
  • the long-chain active hydrogen compound having both a hydrocarbon group and an active hydrogen group may be, for example, at least one of a linear saturated hydrocarbon group-containing active hydrogen compound, a branched saturated hydrocarbon group-containing active hydrogen compound, a linear unsaturated hydrocarbon group-containing active hydrogen compound, and a branched unsaturated hydrocarbon group-containing active hydrogen compound.
  • the linear saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound that contains a linear saturated hydrocarbon group having 12 to 30 carbon atoms, and examples of such compounds include linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol, and linear saturated hydrocarbon group-containing sorbitan esters such as sorbitan tristearate.
  • linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecan
  • the branched chain saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound that contains a branched chain saturated hydrocarbon group having 12 to 30 carbon atoms, and examples of such compounds include branched chain saturated hydrocarbon group-containing alcohols such as isomyristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol.
  • the linear unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound that contains a linear unsaturated hydrocarbon group having 12 to 30 carbon atoms, and examples of such compounds include linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacosenyl alcohol, and octacosenyl alcohol.
  • linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacosenyl alcohol, and octacosenyl alcohol.
  • the branched unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound that contains a branched unsaturated hydrocarbon group having 12 to 30 carbon atoms, and examples thereof include phytol.
  • the long-chain active hydrogen compound is preferably one or both of a linear saturated hydrocarbon group-containing active hydrogen compound and a linear unsaturated hydrocarbon group-containing active hydrogen compound.
  • the long-chain active hydrogen compound can be used alone or in combination of two or more types.
  • a linear saturated hydrocarbon group-containing active hydrogen compound When using a long-chain active hydrogen compound alone, it is preferable to use a linear saturated hydrocarbon group-containing active hydrogen compound alone, more preferably to use a linear saturated hydrocarbon group-containing alcohol alone, and even more preferably to use stearyl alcohol alone.
  • two or more long-chain active hydrogen compounds in combination it is preferable to use a linear saturated hydrocarbon group-containing active hydrogen compound in combination with a linear unsaturated hydrocarbon group-containing active hydrogen compound, more preferably to use a linear saturated hydrocarbon group-containing alcohol in combination with a linear unsaturated hydrocarbon group-containing alcohol, or to use a linear saturated hydrocarbon group-containing alcohol in combination with a linear saturated hydrocarbon group-containing sorbitan ester and a linear unsaturated hydrocarbon group-containing alcohol.
  • the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, and more preferably 70 parts by mass or more, relative to 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol.
  • the blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 60 parts by mass or less, preferably 45 parts by mass or less, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. If the blending ratio of the linear saturated hydrocarbon group-containing alcohol is equal to or more than the above lower limit, the crystallinity of the hydrocarbon group is improved, and as a result, the water repellency can be improved.
  • the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 30 parts by mass or more and, for example, 60 parts by mass or less, per 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol.
  • the blending ratio of the linear saturated hydrocarbon group-containing sorbitan ester is, for example, 20 parts by mass or more and, for example, 50 parts by mass or less, per 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol.
  • the blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by mass or more and, for example, 20 parts by mass or less, per 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol.
  • Cationic active hydrogen compounds have both active hydrogen groups and cationic groups. Cationic active hydrogen compounds can be used alone or in combination of two or more types.
  • the active hydrogen group is an active hydrogen group that reacts with an aliphatic polyisocyanate derivative, and examples of the active hydrogen group include hydroxyl groups.
  • the cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule.
  • the cationic group may also be a tertiary amino group.
  • the cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule as the active hydrogen group, and a tertiary amino group as the cationic group. More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as the active hydrogen group, and a tertiary amino group as the cationic group.
  • Such a cationic active hydrogen compound can impart good dispersibility in water, and can also introduce cationic groups that have affinity for fibers, thereby improving washing durability.
  • Such cationic active hydrogen compounds include, for example, alkyl dialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine, and preferably N-methyldiethanolamine.
  • the acid compound is a compound that forms a salt with a cationic group.
  • the acid compound include one or both of an organic acid and an inorganic acid.
  • the organic acid include acetic acid, lactic acid, tartaric acid, malic acid, etc., and preferably acetic acid or lactic acid, and more preferably acetic acid.
  • the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, etc., and preferably hydrochloric acid.
  • the acid compound is preferably an organic acid. When the acid compound contains an organic acid, the acid is volatilized by heat treatment, which reduces the ionicity and improves water resistance, thereby improving water repellency. In addition, the acid is volatilized by heat treatment, which makes it easier for the cationic group to adsorb to the fiber, and improves washing durability.
  • the acid compounds can be used alone or in combination of two or more types.
  • the above-mentioned aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound are reacted to obtain a urethane-based compound as a reaction product.
  • the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound first, the aliphatic polyisocyanate derivative is mixed with the long-chain active hydrogen compound, and the aliphatic polyisocyanate derivative is reacted with the long-chain active hydrogen compound.
  • the long-chain active hydrogen compound is preferably mixed so that two isocyanate groups of the isocyanurate derivative of the aliphatic polyisocyanate are modified by the long-chain active hydrogen compound to a hydrocarbon group having 12 to 30 carbon atoms, and one isocyanate group remains in the isocyanurate derivative of the aliphatic polyisocyanate, and no unreacted isocyanurate derivative of the aliphatic polyisocyanate remains.
  • the long-chain active hydrogen compound is blended with the aliphatic polyisocyanate derivative so that the equivalent ratio of isocyanate groups to active hydrogen groups (isocyanate groups/active hydrogen groups) is, for example, 1.2 or more, preferably 1.5 or more, and, for example, 2.0 or less.
  • the molecular terminals of the reaction product of the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound (hereinafter referred to as the first intermediate reaction product) become hydrocarbon groups and isocyanate groups having 12 to 30 carbon atoms.
  • the above reaction is carried out under a nitrogen atmosphere.
  • the reaction conditions are, for example, a reaction temperature of 70°C to 120°C and a reaction time of 1 hour to 6 hours.
  • the above reaction is carried out until the isocyanate concentration of the first intermediate reaction product reaches a predetermined calculated value.
  • the isocyanate concentration can be measured using a potentiometric titration device by the n-dibutylamine method in accordance with JIS K-1556.
  • a known solvent such as methyl ethyl ketone can be added in an appropriate ratio.
  • a cationic active hydrogen compound is added to the reaction liquid containing the first intermediate reaction product, and the first intermediate reaction product is reacted with the cationic active hydrogen compound.
  • the cationic active hydrogen compound is added to the first intermediate reaction product so that the equivalent ratio of isocyanate groups to active hydrogen groups of the cationic active hydrogen compound (isocyanate groups/active hydrogen groups) is, for example, 0.95 or more and, for example, 1.05 or less.
  • the above reaction is carried out under a nitrogen atmosphere.
  • the reaction conditions are, for example, a reaction temperature of 70°C to 120°C and a reaction time of 0.5 to 4 hours.
  • the above reaction is carried out until the reaction between the first intermediate reaction product and the cationic active hydrogen compound is completed.
  • a known solvent such as methyl ethyl ketone can also be added in an appropriate ratio.
  • the second intermediate reaction product has a hydrocarbon group having 12 to 30 carbon atoms and a cationic group.
  • an acid compound is mixed with the second intermediate reaction product.
  • the mixing ratio of the acid compound is, for example, 0.5 moles or more, preferably 3 moles or more, and for example, 10 moles or less, preferably 4 moles or less, per mole of the cationic group of the cationic active hydrogen compound.
  • the acid compound forms a salt with the cationic group of the second intermediate reaction product, and a reaction liquid containing a reaction product (i.e., a urethane-based compound) of the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound is obtained.
  • the above reaction product has a hydrocarbon group having a carbon number of 12 to 30 and has a cationic group.
  • the above reaction product since the above reaction product has a hydrocarbon group having a carbon number of 12 to 30, it can self-disperse (self-emulsify) in water without relying on a dispersant (emulsifier). In other words, the above reaction product can be internally emulsified.
  • aqueous dispersion containing the above-mentioned reaction product (i.e., a urethane-based compound).
  • the solids concentration of the aqueous dispersion is, for example, 10% by mass or higher and, for example, 30% by mass or lower.
  • urethane compounds are reaction products obtained using long-chain active hydrogen compounds, they have excellent water repellency, oil repellency, oil resistance, and stain resistance. Furthermore, since such urethane compounds are reaction products obtained using cationic active hydrogen compounds, they have improved affinity with fibers, resulting in excellent washing durability for fibers.
  • the concentration of the hydrocarbon group is 30% or more and 85% or less, preferably 50%. If the concentration of the hydrocarbon group is equal to or more than the above-mentioned lower limit, the water repellency can be improved. If the concentration of the hydrocarbon group is equal to or less than the above-mentioned upper limit, the stability of the urethane-based compound can be improved.
  • the concentration of the hydrocarbon group can be calculated from the amount of each component charged.
  • the aliphatic polyisocyanate derivative is reacted with a long-chain active hydrogen compound to obtain a reaction liquid containing a first intermediate reaction product, then the first intermediate reaction product is reacted with a cationic active hydrogen compound to obtain a reaction liquid containing a second intermediate reaction product, and then the second intermediate reaction product is reacted with an acid compound.
  • the order of the reactions is not particularly limited, and for example, the aliphatic polyisocyanate derivative can be reacted with a cationic active hydrogen compound, and then the long-chain active hydrogen compound can be reacted with an acid compound.
  • the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound can be mixed together and reacted.
  • the dendrimer-based compounds may be, for example, dendritic polymer compounds having a structure that is radially and regularly branched from the center. In order to obtain water repellency, the dendritic polymer compounds may have linear or branched hydrocarbon groups having one or more carbon atoms at the terminal branches.
  • the dendritic polymer compound for example, the "apolymerextender" disclosed in International Publication WO 2014/160906 can be used.
  • a compound obtained by reacting at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or a mixture thereof with at least one isocyanate-reactive compound selected from the following formula (Ia), (Ib), or (Ic) can be used.
  • R 50 is each independently -H, R 51 , -C(O)R 51 , -(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 52 , or -(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 51 , each n is independently 0 to 20, each m is independently 0 to 20, and m + n exceeds 0.
  • Each R 51 is independently a linear or branched alkyl group having 5 to 29 carbon atoms which may contain one or more unsaturated bonds
  • each R 52 is independently -H or a linear or branched alkyl group having 6 to 30 carbon atoms which may contain one or more unsaturated bonds.
  • R 50 or R 52 is —H.
  • R 53 is independently -H, -R 51 , -C(O)R 51 , -(CH 2 CH 2 O(CH(CH 3 )CH 2 O) m R 52 , or -(CH 2 CH 2 O(CH(CH 3 )CH 2 OC(O)R 51
  • R 54 is independently -H, or a linear or branched alkyl group having 6 to 30 carbon atoms which may contain one or more unsaturated bonds, -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' R 52 , or -(CH 2 CH 2 O(CH(CH 3 )CH 2 OC(O)R 51 , each n' is independently 0 to 20, each m' is independently 0 to 20, and m+n is greater than 0.
  • R 52 , R 53 and R 54 is —H.
  • R 55 is -H, -C(O)R 51 , or -CH 2 C[CH 2 OR 50 ] 3 .
  • At least one of R 55 or R 50 is —H.
  • the isocyanate group-containing compound is not particularly limited, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified polyisocyanates such as dimers and trimers thereof.
  • Commercially available products such as "DESMODURN-100” (product name, manufactured by Bayer), "Duranate THA-100” (product name, manufactured by Asahi Kasei Corporation), and “Duranate 24A-100” (product name, manufactured by Asahi Kasei Corporation) can be used.
  • the reaction can be carried out, for example, at 80°C for 1 hour or more.
  • polyisocyanates examples include polyisocyanate monomers and polyisocyanate derivatives.
  • Polyisocyanate refers to an isocyanate compound having multiple isocyanate groups in the compound molecule.
  • diisocyanate compound refers to an isocyanate compound having two isocyanate groups in the compound molecule.
  • the polyisocyanate monomer is not particularly limited, and examples thereof include aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyisocyanate monomers can be used alone or in combination of two or more types.
  • the polyisocyanate derivative is not particularly limited, and examples thereof include polymers of polyisocyanate monomers (e.g., dimers, trimers (e.g., isocyanurate modified products, iminooxadiazinedione modified products), pentamers, heptamers, etc.), allophanate modified products (e.g., allophanate modified products produced by further adding an isocyanate group of a polyisocyanate monomer to a urethane group formed by the reaction of the above-mentioned polyisocyanate monomer with a low molecular weight polyol described later), adducts (e.g., adducts (alcohol adducts) produced by the reaction of a polyisocyanate monomer with a low molecular weight polyol described later), biuret modified products (e.g., , biuret modified products produced by the reaction of the above-mentioned polyisocyanate monomer with water or amine
  • the non-fluorinated water repellent composition contains an alicyclic polyisocyanate as a polyisocyanate.
  • the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate), trans, trans thereof, and the like.
  • the isocyanate may be at least one selected from the group consisting of methyl cyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof) (H6XDI, hydrogenated XDI), and the like.
  • NBDI norbornane diisocyanate
  • H6XDI bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof)
  • the (B) alicyclic polyisocyanate is preferably at least one of isophorone diisocyanate (IPDI), hydrogenated MDI, and hydrogenated XDI, more preferably at least one of isophorone diisocyanate (IPDI) and hydrogenated MDI, and even more preferably isophorone diisocyanate (IPDI).
  • the alicyclic polyisocyanate is preferably a polymer of the above-mentioned monomers.
  • the alicyclic polyisocyanate is a trimer
  • the abrasion resistance and water repellency are more likely to be improved.
  • the alicyclic polyisocyanate is a trimer
  • the initial Bundesmann and abrasion resistance Bundesmann are more improved.
  • the polyisocyanate may be composed of only the above-mentioned alicyclic isocyanate, or may be a combination of an alicyclic isocyanate and another polyisocyanate. Alternatively, the alicyclic isocyanate may be reacted with another isocyanate.
  • the non-fluorinated water repellent composition may contain an aliphatic polyisocyanate in addition to the alicyclic polyisocyanate (B).
  • the aliphatic polyisocyanate may be at least one selected from, for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, lysine diisocyanate, dimer acid diisocyanate, and the like.
  • 1,6-hexamethylene diisocyanate 1,2-propylene diisocyanate
  • the non-fluorinated water repellent composition may contain an aromatic polyisocyanate in addition to the alicyclic polyisocyanate (B).
  • the aromatic polyisocyanate may be at least one selected from, for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, and the like.
  • TKI tolylene diisocyanate
  • the non-fluorinated water repellent composition may contain an araliphatic polyisocyanate in addition to the alicyclic polyisocyanate (B).
  • the araliphatic polyisocyanate may be at least one selected from, for example, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or 1,4-tetramethyl xylylene diisocyanate or a mixture thereof) (TMXDI), ⁇ , ⁇ '-diisocyanato-1,4-diethylbenzene, and the like.
  • the non-fluorine-based water repellent composition may contain at least one of an aliphatic polyisocyanate, an aromatic polyisocyanate, and an araliphatic polyisocyanate in addition to the alicyclic polyisocyanate (B).
  • the mass ratio of the alicyclic polyisocyanate to the other polyisocyanates may be 99/1 to 1/99, 95/5 to 5/95, 90/10 to 10/90, or 85/15 to 25/75.
  • the above polyisocyanate may be blocked with a blocking agent.
  • the blocked polyisocyanate can be obtained by reacting the above polyisocyanate with a blocking agent.
  • the blocking agent may be used alone or in combination of two or more.
  • the blocking agent may be, for example, a compound having one or more active hydrogen atoms in the molecule.
  • the blocking agent may be, for example, at least one selected from alcohol compounds, alkylphenol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, imidazoline compounds, triazole compounds, carbamic acid compounds, urea compounds, oxime compounds, amine compounds, imide compounds, imine compounds, pyrazole compounds, and bisulfites.
  • At least one selected from acid amide compounds, active methylene compounds, oxime compounds, and pyrazole compounds is preferred, for example, at least one selected from ⁇ -caprolactam, acetylacetone, diethyl malonate, methyl ethyl ketone oxime, cyclohexanone oxime, 3-methylpyrazole, and 3,5-dimethylpyrazole is preferred, and among them, one or both of dimethylpyrazole and malonic acid diester are more preferred from the viewpoint of washing durability and water repellency.
  • the above polyisocyanates may or may not have self-emulsifying property. From the viewpoint of initial water pressure resistance, polyisocyanates without self-emulsifying property are more preferable than those with self-emulsifying property. Examples of polyisocyanates with self-emulsifying property include polyisocyanates with nonionic hydrophilic groups, cationic hydrophilic groups, and anionic hydrophilic groups introduced into a part of the polyisocyanate. From the viewpoint of water repellency, polyisocyanates with nonionic hydrophilic groups having oxyethylene groups can be preferably used.
  • the non-fluorinated water repellent composition may contain the above-mentioned non-fluorinated water repellent component and alicyclic polyisocyanate, and may further contain other components.
  • the non-fluorinated water repellent composition according to one embodiment may contain an aqueous medium, an emulsifier, etc.
  • the non-fluorinated water repellent composition may contain an aqueous medium.
  • the aqueous medium may be water or a mixture of water and an organic solvent.
  • the amount of the organic solvent may be, for example, 0.1% by mass or more and 30% by mass or less, or 0.1% by mass or more and 10% by mass or less, relative to the aqueous medium. It is preferable that the aqueous medium consists of water only.
  • the amount of the aqueous medium may be 30 to 99% by mass, or 50 to 90% by mass, with the entire non-fluorinated water repellent composition being 100% by mass.
  • the non-fluorinated water repellent composition may contain an emulsifier to improve the dispersibility of the composition in an aqueous medium.
  • the emulsifier may be at least one selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
  • the emulsifier is preferably a nonionic surfactant alone, or a combination of a nonionic surfactant and a cationic surfactant.
  • the mass ratio of the nonionic surfactant to the cationic surfactant may be, for example, 99.5:0.5 to 50:50, or 99:1 to 90:10.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylol amides, alkyl alkanol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, etc.
  • anionic surfactants include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylate salts, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinate, polyoxyalkylene alkyl ether phosphates, etc.
  • cationic surfactants include amine salts, amidoamine salts, quaternary ammonium salts, and imidazolinium salts, etc.
  • alkylamine salts include, but are not limited to, alkylamine salts, polyoxyethylene alkylamine salts, alkylamide amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt surfactants such as imidazoline, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, alkyl pyridinium salts, alkyl isoquinolinium salts, quaternary ammonium salt surfactants such as benzethonium chloride, etc.
  • alkylamine salts such as imidazoline, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, alkyl pyridinium salts, alkyl isoquinolinium salts, quaternary ammonium salt surfactants such as benzethonium chloride, etc.
  • amphoteric surfactants include alkylamine oxides, alanines, imidazolinium betaines, amido betaines, and betaine acetate, and more specifically, long-chain amine oxides, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethyl amino acetate betaine, fatty acid amido propyl dimethyl amino acetate betaine, etc.
  • the amount of these surfactants used is not particularly limited, but is preferably 1 to 20% by mass, more preferably 1.5 to 10% by mass, of the solid content of the emulsion.
  • the hydrophilic-lipophilic balance (HLB) of the emulsifier is not particularly limited.
  • the average HLB of the nonionic emulsifier in the non-fluorinated water repellent composition according to one embodiment is preferably 6.0 to 16.0, 6.5 to 15.5, 7.0 to 15.0, or 7.5 to 14.5. If the HLB is outside this range, the initial Heilmann, Farbmann after abrasion, and initial water pressure resistance tend to decrease.
  • the ratio of the non-fluorine-based water repellent component to the crosslinking component (polyisocyanate) in the solid content contained in the composition is preferably 20 to 90% by mass of the non-fluorine-based water repellent component and 10 to 80% by mass of the crosslinking component.
  • the non-fluorine-based water repellent component is 30 to 85% by mass
  • the crosslinking component is 15 to 70% by mass, even more preferably, the non-fluorine-based water repellent component is 40 to 80% by mass
  • the crosslinking component is 20 to 60% by mass, and particularly preferably, the non-fluorine-based water repellent component is 55 to 80% by mass
  • the crosslinking component is 20 to 45% by mass.
  • the particle size in the aqueous emulsion is not particularly limited, but the average particle size is preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and particularly preferably 50 to 500 nm. If the average particle size is too large, the stability of the emulsion tends to decrease.
  • the average particle size is measured by a laser diffraction/scattering type particle size distribution measuring device, and means the particle size (median particle size) at a percentage integrated value (volume basis) of 50%.
  • the non-fluorine-based water repellent composition can be obtained by mixing the non-fluorine-based water repellent component and the polyisocyanate.
  • the ratio of the non-fluorine-based water repellent component to the polyisocyanate in the non-fluorine-based water repellent composition can be the preferred ratio described above.
  • the non-fluorine-based water repellent composition may be, for example, a one-component type in which the non-fluorine-based water repellent component and the polyisocyanate are premixed, or a two-component type in which one component contains at least one of the above components and one component contains the other component. From the viewpoint of ease of handling, it is preferable that the non-fluorine-based water repellent composition has each component dispersed (including emulsified and dissolved) in an aqueous medium.
  • a one-component non-fluorinated water repellent composition containing each component can be obtained, for example, by simultaneously dispersing (including emulsifying and dissolving) each component in an aqueous medium, or by mixing a dispersion in which at least one of the components is dispersed in an aqueous medium with a dispersion in which the other component is dispersed in an aqueous medium.
  • a method for dispersing each of the above components in an aqueous medium can be, for example, mixing and stirring each component with the aqueous medium and, if necessary, a dispersant.
  • a conventionally known emulsifying and dispersing machine such as a Milder, high-speed agitator, homogenizer, ultrasonic homogenizer, homomixer, bead mill, pearl mill, dyno mill, aspek mill, basket mill, ball mill, nanomizer, 8%zer, or starburst may be used.
  • emulsifying and dispersing machines can be used alone or in combination of two or more types.
  • aqueous media and emulsifiers are as described above.
  • the non-fluorinated water repellent composition prepared as a dispersion as described above may be used as a treatment liquid as is, or may be further diluted with an aqueous medium or a hydrophobic organic solvent to prepare a treatment liquid.
  • the non-fluorinated water repellent composition of the present disclosure may be produced, for example, by the following procedure.
  • a polyisocyanate is reacted with a hydrophilic compound capable of reacting with an isocyanate group of the polyisocyanate, and a blocking agent capable of reacting with an isocyanate group of the polyisocyanate until the NCO content becomes 0%, to obtain a blocked isocyanate.
  • a non-fluorine-based water-repellent component and water are added to and mixed with the liquid containing the blocked isocyanate obtained in (I) above to obtain an emulsion.
  • the organic solvent is optionally removed from the emulsion obtained in (II) above to obtain an aqueous emulsion.
  • the polyisocyanate may be any of those mentioned above, and the hydrophilic compound capable of reacting with the isocyanate group may be polyethylene glycol monoalkyl ether or the like.
  • the reaction between the polyisocyanate and the hydrophilic compound or blocking agent may be carried out by a known method, and may be carried out regardless of the presence or absence of a solvent. When a solvent is used, it is necessary to use a solvent that is inactive against the isocyanate group.
  • an organic metal salt of tin, zinc, lead, or the like, a metal alcoholate, a tertiary amine, or the like may be used as a catalyst.
  • the blocking reaction can generally be carried out at -20 to 150°C, but preferably 0 to 100°C. If the temperature exceeds 150°C, a side reaction may occur, and if the temperature is too low, the reaction rate becomes slow, which is disadvantageous.
  • 50 mol% or more of the isocyanate group may be blocked with the blocking agent, preferably 75 mol% or more, and particularly preferably 90 mol% or more.
  • the hydrophilic compound is introduced in an amount of 1 to 50 mol% relative to the isocyanate group.
  • the blocked isocyanate has self-emulsifying properties, and a water-repellent treatment agent containing a water-repellent component and a crosslinking component in one particle can be obtained without using a surfactant or with a small amount of surfactant. It is preferable to carry out the reaction in step (I) until the NCO content becomes 0%.
  • the NCO content can be measured by a known method such as the method described in JIS K6806:2003, 5.10 NCO content, and 0% may be a level at which it is judged that substantially all of the NCO groups have disappeared, and may be below the detection limit in a known measurement method or in a range that is considered to be equivalent thereto.
  • solvent for the above reaction system examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, n-butyl acetate, cellosolve acetate, toluene, etc. These solvents can be used alone or in combination of two or more.
  • the water-repellent component may be any of those mentioned above.
  • An organic solvent may be added together with the water-repellent component. It is preferable to add water after confirming that the reaction liquid (liquid containing blocked isocyanate) of step (I), the water-repellent component, and the organic solvent are uniformly mixed. An emulsion can be obtained by stirring while adding water dropwise.
  • the method for removing the organic solvent from the emulsion may be appropriately selected from known methods, for example, evaporation under reduced pressure.
  • the non-fluorinated water repellent composition of the present disclosure further comprises: (a) reacting a polyisocyanate with a blocking agent capable of reacting with an isocyanate group of the polyisocyanate until the NCO content becomes 0%, thereby obtaining a blocked isocyanate; (b) adding a water-repellent component, a surfactant, and water to the liquid containing the blocked isocyanate obtained in the step (a) and mixing them to obtain an emulsion; and (c) removing the organic solvent from the emulsion obtained in the step (b) to obtain an aqueous emulsion;
  • the water repellent treatment agent can also be obtained by a method for producing the water repellent treatment agent, which includes the steps of:
  • the polyisocyanate and blocking agent used in the above step (a) are as described above.
  • the NCO content can be measured by a known method such as the method described in JIS K6806:2003, 5.10 NCO content, and 0% is sufficient if it is determined that substantially all NCO groups have disappeared, and may be below the detection limit in a known measurement method or in a range that is considered to be equivalent thereto.
  • the solvent used in the reaction system is not particularly limited as long as it is possible to uniformly proceed with the reaction in the reaction system, and for example, the same solvent as that used in the above step (I) can be used.
  • the water-repellent component and the surfactant may be the same as those mentioned above.
  • An organic solvent may be added together with the water-repellent component.
  • the surfactant may be dissolved or dispersed in water beforehand and added by a method such as dropwise addition, or may be dissolved or dispersed in the organic solvent together with the water-repellent component beforehand.
  • a known emulsifying device may be used for mixing, such as a homomixer, homogenizer, colloid mill, or line mixer.
  • the mixed solution of the water-repellent component and the crosslinking component is forcibly emulsified using a surfactant, so that the emulsion contains both the water-repellent component and the crosslinking component in one particle, resulting in a hybrid emulsion.
  • the method for removing the organic solvent from the emulsion may be appropriately selected from known methods, for example, evaporation under reduced pressure.
  • the non-fluorinated water repellent composition of the present disclosure can impart water repellency (abrasion-resistant water repellency) to textile products during actual use, for example.
  • water repellency abrasion-resistant water repellency
  • the non-fluorinated water repellent composition of the present disclosure may be able to impart excellent abrasion-resistant water repellency to various articles other than textile products.
  • a method for producing a water-repellent textile product includes treating textiles with a treatment liquid containing the non-fluorinated water repellent composition of the present disclosure. Through this process, a water-repellent textile product is obtained.
  • the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as nylon, polyester, polyurethane, polypropylene, and acrylic; and composite and blended fibers of these.
  • the form of the fiber is not particularly limited, and is not limited to raw material forms such as staple, filament, tow, and thread, but may be in any form such as woven fabric, knitted fabric, wadding, nonwoven fabric, paper, sheet, and film.
  • the fiber may be a textile product.
  • Methods for treating fibers with the treatment liquid include, for example, immersion, spraying, coating, and other processing methods.
  • the non-fluorine-based water repellent composition contains water, it is preferable to dry the composition after it has been applied to the fibers in order to remove the water.
  • the amount of non-fluorine-based water repellent composition applied to the fiber can be adjusted as appropriate depending on the level of water repellency required, but it is preferable to adjust the amount of non-fluorine-based water repellent composition applied to 100 g of fiber to 0.1 to 5 g, and more preferably 0.1 to 3 g. If the amount of non-fluorine-based water repellent composition applied is too small, the fiber will tend not to exhibit sufficient water repellency, and if it is too large, the texture of the fiber will tend to become rough and hard, and it will also be economically disadvantageous.
  • the treatment with the treatment liquid may be performed by a continuous method or a batch method.
  • the water repellent composition is first diluted with water to prepare the treatment liquid.
  • the treated object textile product
  • the treated object is continuously sent to an impregnation device filled with the treatment liquid, and the treated object is impregnated with the treatment liquid, and then unnecessary treatment liquid is removed.
  • the impregnation device is not particularly limited, and a padder, a kiss roll type application device, a gravure coater type application device, a spray type application device, a foam type application device, a coating type application device, etc. can be preferably used, and a padder type is particularly preferred.
  • an operation is performed to remove the water remaining in the treated object using a dryer.
  • the dryer is not particularly limited, and a hot flue, a tenter, or other spread dryer is preferred.
  • the continuous method is preferably used when the treated object is in the form of a fabric such as a woven fabric.
  • the batch method includes, for example, a process of immersing the treated object in the treatment liquid and a process of removing the water remaining in the treated object after the treatment.
  • the batch method is preferably used when the object to be treated is not in the form of a fabric, for example, loose fibers, tops, slivers, skeins, tows, yarns, etc., or when the object is not suitable for the continuous method, such as knitted fabrics.
  • a cotton dyeing machine, a cheese dyeing machine, a liquid jet dyeing machine, an industrial washing machine, a beam dyeing machine, etc. can be used.
  • a hot air dryer such as a cheese dryer, a beam dryer, a tumble dryer, a high frequency dryer, etc.
  • the temperature of the dry heat treatment is preferably 100 to 200°C, particularly preferably 120 to 180°C.
  • the time of the dry heat treatment is preferably 10 seconds to 3 minutes, particularly preferably 1 to 2 minutes.
  • the method of dry heat treatment is not particularly limited, but when the object to be treated is in the form of a fabric, a tenter is preferable.
  • water-repellent textile products have excellent abrasion resistance and water repellency, they are ideally suited for a variety of uses, including clothing and non-clothing items, such as down jacket coverings, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, futon coverings, futon drying covers, curtains, and tents.
  • clothing and non-clothing items such as down jacket coverings, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, futon coverings, futon drying covers, curtains, and tents.
  • the mixed liquid was irradiated with ultrasonic waves to emulsify and disperse all the monomers.
  • 0.2 parts by mass of azobis (isobutylamidine) dihydrochloride was added to the dispersion, and under a nitrogen atmosphere, 4.0 parts by mass of vinyl chloride was continuously pressed into the autoclave so that the internal pressure of the autoclave was maintained at 0.3 MPa, and radical polymerization was performed at 60 ° C. for 6 hours to obtain a dispersion containing 20% by mass of acrylic resin.
  • the inside of the kettle was heated to 120°C, and an addition reaction was carried out for 6 hours to obtain an alkyl-modified silicone in which R 20 , R 21 and R 22 are CH 3 , R 23 is C 26 H 53 , a is 60, b is 90, a:b is 2:3, and R 30 to R 35 are CH 3 in the above formula (1).
  • Completion of the addition reaction was confirmed by subjecting the resulting alkyl-modified silicone to Fourier transform infrared (FT-IR) spectroscopic analysis and confirming that the absorption spectrum derived from the SiH group of the methylhydrogen silicone had disappeared.
  • FT-IR Fourier transform infrared
  • the inside of the kettle was heated to 120°C, and an addition reaction was carried out for 6 hours to obtain an alkyl-modified silicone in which R 20 , R 21 , and R 22 are CH 3 , R 23 is C 32 H 65 , a is 140, b is 60, a:b is 7.3, and R 30 to R 35 are CH 3 in the above formula (1).
  • Completion of the addition reaction was confirmed by subjecting the resulting alkyl-modified silicone to Fourier transform infrared (FT-IR) spectroscopic analysis and confirming that the absorption spectrum derived from the SiH group of the methylhydrogen silicone had disappeared.
  • FT-IR Fourier transform infrared
  • compositions of Preparation Examples A-4 to A-6 and the average HLB of the nonionic surfactants are summarized in Table 2 below.
  • the nonionic surfactants are SPAN65: HLB 2.1 (manufactured by Croda), Noigen XL-160: HLB 16.3 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and NIKKOL BC-30: HLB 19.5 (manufactured by Nikko Chemicals Co., Ltd.).
  • Noigen XL-40 is as described above.
  • this reaction mixture was passed through a thin-film distillation apparatus (temperature 150°C, degree of vacuum 93.3 Pa) and distilled until the amount of remaining HDI monomer was 0.5% or less, thereby obtaining an aliphatic polyisocyanate derivative (isocyanurate derivative of hexamethylene diisocyanate).
  • the obtained aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average number of isocyanate functional groups of 3.0.
  • methyl ethyl ketone 50 parts by mass of methyl ethyl ketone was added as a solvent and reacted at 80°C until it was confirmed by infrared absorption spectrum that the isocyanate group had disappeared.
  • MEK methyl ethyl ketone
  • Preparation Example B-2 DMP Blocked IPDI Trimer
  • 150 parts by mass (NCO equivalent: 0.62 mol) of Vestanat 1890/100 isophorone diisocyanate trimer, manufactured by Evonik, NCO group content: 17.3%, NV: 100%
  • DMP dimethylpyrazole
  • Preparation Example B-3 DMP blocked IPDI trimer
  • 150 parts by mass (NCO equivalent: 0.62 mol) of Vestanat 1890/100 isophorone diisocyanate trimer, manufactured by Evonik, NCO group content: 17.3%, NV: 100%
  • DMP dimethylpyrazole
  • Preparation Example B-4 DMP blocked IPDI trimer
  • 150 parts by mass (NCO equivalent: 0.62 mol) of Vestanat 1890/100 isophorone diisocyanate trimer, manufactured by Evonik, NCO group content: 17.3%, NV: 100%
  • DMP dimethylpyrazole
  • Preparation Example B-6 MEKO blocked IPDI trimer
  • polyisocyanate 150 parts by mass (NCO equivalent: 0.62 mol) of Vestanat 1890/100 (isophorone diisocyanate trimer, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) was used.
  • the blocking agent 54.0 parts by mass (0.62 mol) of 2-Butanone Oxime (methyl ethyl ketoxime, MEKO, Tokyo Chemical Industry) was used. The same preparation as in Preparation Example B-1 was used.
  • Preparation Example B-8 DMP Blocked Product of Hydrogenated MDI Monomer
  • polyisocyanate 167 parts by mass (NCO equivalent: 1.27 mol) of dicyclohexylmethane 4,4'-diisocyanate (hydrogenated MDI monomer, Tokyo Chemical Industry, NCO group content: 32.0%, NV: 90%) and 122 parts by mass (1.27 mol) of dimethylpyrazole (DMP) were used as the blocking agent, but the same preparation as in Preparation Example B-1 was used.
  • NCO equivalent 1.27 mol
  • DMP dimethylpyrazole
  • Preparation Example B-9 DMP blocked product of HDI monomer Except for using 150 parts by mass (NCO equivalent: 1.78 mol) of hexamethylene diisocyanate (hexamethylene diisocyanate monomer, Tokyo Chemical Industry Co., Ltd., NCO group content: 49.9%, NV: 100%) as the polyisocyanate and 171 parts by mass (1.78 mol) of dimethylpyrazole (DMP) as the blocking agent, it was prepared in the same manner as in Preparation Example B-1.
  • NCO equivalent 1.78 mol
  • DMP dimethylpyrazole
  • Preparation Example B-10 DMP Blocked HDI Trimer (Biuret Type)
  • DMP dimethylpyrazole
  • Preparation Example B-11 DMP Blocked Product of HDI Trimer (Isocyanurate Type)
  • polyisocyanate 150 parts by mass (NCO equivalent: 0.825 mol) of Duranate TPA-100 (isocyanurate type of hexamethylene diisocyanate, Asahi Kasei, NCO group content: 23.1%, NV: 100%) and 79.3 parts by mass (0.825 mol) of dimethylpyrazole (DMP) were used as the blocking agent, except that it was prepared in the same manner as in Preparation Example B-1.
  • NCO equivalent 0.825 mol
  • DMP dimethylpyrazole
  • Preparation Example B-12 MEKO Blocked HDI Trimer (Isocyanurate Type)
  • the polyisocyanate 150 parts by mass (NCO equivalent: 0.825 mol) of Duranate TPA-100 (isocyanurate type of hexamethylene diisocyanate, Asahi Kasei, NCO group content: 23.1%, NV: 100%) and 71.87 parts by mass (0.825 mol) of 2-Butanone Oxime (methyl ethyl ketoxime, MEKO, Tokyo Kasei) were used as the blocking agent. Except for this, the same preparation as in Preparation Example B-1 was used.
  • DMP dimethylpyrazole
  • the emulsion of Preparation Example B-15 is a hybrid emulsion containing silicone and blocked isocyanate, which are water-repellent components, in a ratio of 59:41 (parts by mass).
  • IPDI trimer In a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, 150 parts by mass (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890/100, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) as a polyisocyanate and propylene glycol diacetate (Dowanol (registered trademark) PGDA, Ando Parachemie Co., Ltd.) as a solvent were mixed at room temperature to completely dissolve the polyisocyanate, thereby obtaining a PGDA solution of IPDI trimer.
  • IPDI trimer isophorone diisocyanate trimer
  • Uniox M-2000 polyethylene glycol monomethyl ether with average molecular weight of 2000, manufactured by NOF Corporation, solid content 100%
  • 0.001 parts by mass of diazabicycloundecene and 4.5 parts by mass of acetone were added and reacted at 60 ° C. for 2 hours, and it was confirmed that the NCO content became 0%, and the mixture was cooled with water to 40 ° C.
  • WACKER FINISH WR 301 amino-modified silicone, manufactured by Asahi Kasei Wacker Silicone Co., Ltd., amine equivalent 3700, solid content 100%
  • acetone 24.1 parts by mass of acetone
  • 110 parts by mass of ion-exchanged water was slowly dropped to emulsify.
  • the solvent was distilled off under reduced pressure, and 0.74 parts by mass of 90% acetic acid and 109 parts by mass of ion-exchanged water were added to obtain an emulsion with a total concentration of amino-modified silicone and blocked isocyanate of 20%.
  • This emulsion is a hybrid emulsion containing amino-modified silicone and blocked isocyanate, which are water-repellent components, in a ratio of 5:2 (by mass).
  • this blocked isocyanate has polyethylene glycol monomethyl ether introduced into a part of its structure, and has self-emulsifying properties.
  • Preparation Example C-2 Except for changing the amounts of ingredients, the same operation as in Preparation Example C-1 was carried out to obtain a hybrid emulsion containing water-repellent components, amino-modified silicone and blocked isocyanate, in a ratio of 5:1 (mass ratio) (the total concentration of amino-modified silicone and blocked isocyanate was 20%.
  • This blocked isocyanate has polyethylene glycol monomethyl ether introduced into part of its structure and has self-emulsifying properties).
  • Emazol S-30V sorbitan tristearate, manufactured by Kao Corporation, hydroxyl value 68.6 mgKOH/g
  • MIBK MIBK
  • emulsion is a hybrid emulsion containing sorbitan tristearate and blocked isocyanate, which are water-repellent components, in a ratio of 5:2 (mass ratio).
  • This preparation example is a hybrid emulsion in which the water-repellent component and the cross-linking component are emulsified with Tergitol TMN-10, a nonionic surfactant, and dimethylstearylamine acetate, a cationic surfactant.
  • the non-fluorine-based water repellent composition is used to impart water repellency to textile products, but the technology of the present disclosure is not limited to this form.
  • the non-fluorine-based water repellent composition of the present disclosure is believed to be capable of imparting water repellency and abrasion-resistant water repellency to various articles other than textile products, but is particularly suitable for imparting water repellency and abrasion-resistant water repellency to textile products, as shown in the above examples.

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  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne une composition hydrofuge sans fluor qui permet d'améliorer l'effet déperlant lors de l'utilisation réelle de divers articles. Une composition hydrofuge sans fluor selon la présente divulgation contient : (A) au moins un composant hydrofuge sans fluor choisi dans le groupe constitué de composés acryliques, de composés de silicone, de composés de cire, de composés d'uréthane et de composés dendrimères ; et (B) un polyisocyanate alicyclique.
PCT/JP2023/035738 2022-10-31 2023-09-29 Composition hydrofuge sans fluor et procédé de production d'un produit fibreux hydrofuge WO2024095652A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006143866A (ja) * 2004-11-19 2006-06-08 Kansai Paint Co Ltd 撥水剤、その撥水剤を用いた撥水性被膜形成方法及びその撥水性被膜形成物
CN1844282A (zh) * 2005-04-08 2006-10-11 厚生股份有限公司 具优异泼水性的涂料及其涂层制造方法
JP2019026998A (ja) * 2017-08-02 2019-02-21 株式会社ミマキエンジニアリング メディアの着色方法及び撥水剤
WO2019240162A1 (fr) * 2018-06-12 2019-12-19 明成化学工業株式会社 Agent hydrofuge, produit fibreux hydrofuge, et procédé de fabrication associé
WO2021132170A1 (fr) * 2019-12-24 2021-07-01 三井化学株式会社 Composition de résine de polyuréthane, répulsif, hydrofuge pour fibres, et agent de revêtement résistant aux tâches
JP2023117014A (ja) * 2022-02-10 2023-08-23 日本ペイント・オートモーティブコーティングス株式会社 塗料用組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006143866A (ja) * 2004-11-19 2006-06-08 Kansai Paint Co Ltd 撥水剤、その撥水剤を用いた撥水性被膜形成方法及びその撥水性被膜形成物
CN1844282A (zh) * 2005-04-08 2006-10-11 厚生股份有限公司 具优异泼水性的涂料及其涂层制造方法
JP2019026998A (ja) * 2017-08-02 2019-02-21 株式会社ミマキエンジニアリング メディアの着色方法及び撥水剤
WO2019240162A1 (fr) * 2018-06-12 2019-12-19 明成化学工業株式会社 Agent hydrofuge, produit fibreux hydrofuge, et procédé de fabrication associé
WO2021132170A1 (fr) * 2019-12-24 2021-07-01 三井化学株式会社 Composition de résine de polyuréthane, répulsif, hydrofuge pour fibres, et agent de revêtement résistant aux tâches
JP2023117014A (ja) * 2022-02-10 2023-08-23 日本ペイント・オートモーティブコーティングス株式会社 塗料用組成物

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