WO2021006319A1 - Polymère hydrofuge et composition d'agent hydrofuge - Google Patents

Polymère hydrofuge et composition d'agent hydrofuge Download PDF

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WO2021006319A1
WO2021006319A1 PCT/JP2020/026918 JP2020026918W WO2021006319A1 WO 2021006319 A1 WO2021006319 A1 WO 2021006319A1 JP 2020026918 W JP2020026918 W JP 2020026918W WO 2021006319 A1 WO2021006319 A1 WO 2021006319A1
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water
group
monomer
repellent
weight
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PCT/JP2020/026918
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English (en)
Japanese (ja)
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礼奈 稲益
育男 山本
可奈子 高橋
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ダイキン工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

Definitions

  • the present disclosure relates to a water repellent polymer and a water repellent composition.
  • a fluorine-containing water-repellent oil-repellent agent containing a fluorine compound is known.
  • This water- and oil-repellent agent exhibits good water- and oil-repellent properties when treated on a base material such as a textile product.
  • telomers can produce PFOA by degradation or metabolism (telomers mean long-chain fluoroalkyl groups). It also announced that telomers are used in many products such as water and oil repellent, antifouling foam fire extinguishing agents, care products, cleaning products, carpets, textiles, paper and leather. There is. There is concern that fluorine-containing compounds will accumulate in the environment.
  • Patent Document 1 discloses that water repellency is imparted by a composition containing an amino alcohol having a fluoroalkyl group and a sulfonamide group.
  • Patent Document 2 is a water repellent agent made of a non-fluorine-based polymer containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester portion as a monomer unit.
  • a water repellent agent in which the composition ratio of the meta) acrylic acid ester is 80 to 100% by mass with respect to the total amount of the monomer units constituting the non-fluorinated polymer is disclosed.
  • Patent Document 3 describes both non-fluorinated polymers, nonionic surfactants and cationic surfactants having repeating units derived from long-chain (meth) acrylate ester monomers. Discloses a surfactant containing, and a surface treatment agent which is an aqueous emulsion containing water.
  • An object of the present disclosure is to provide a water-repellent polymer that provides excellent water repellency and does not have a fluorine atom.
  • the present disclosure relates to a polymer having no fluorine atom, that is, a non-fluorine polymer.
  • a polymer can be used as an active ingredient of a water repellent.
  • Such a polymer can form a water repellent composition.
  • the water-repellent polymer further has a repeating unit derived from a polymerizable monomer other than the sulfonamide group-containing acrylic monomer (a).
  • the water-repellent polymer according to any one of [1] to [3], which is a compound represented by.
  • the non-fluorinated crosslinkable monomer (c) is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group
  • the water-repellent polymer according to. [8] The water-repellent polymer according to [5], wherein the halogenated olefin monomer (d) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.
  • the amount of the repeating unit (b) is 0 to 20 parts by weight and the amount of the repeating unit (c) is 0 to 50 parts by weight with respect to 100 parts by weight of the repeating unit (a).
  • the water repellent composition according to [10] wherein the liquid medium (2) is water, an organic solvent, or a mixture of water and an organic solvent.
  • a method for treating a base material which comprises applying the water repellent composition according to any one of [10] to [12] to a base material and adhering a water repellent polymer to the base material.
  • a water-repellent polymer that imparts excellent water repellency to a base material such as a textile product can be obtained.
  • it has excellent spray water repellency and
  • water repellency The water-repellent polymer can provide excellent water repellency even to a cotton base material which is difficult to give water repellency with a normal water-repellent agent.
  • the water-repellent polymer is a polymer having a repeating unit derived from an acrylic monomer having a long-chain alkyl group having 7 to 40 or 7 to 30 carbon atoms and a sulfonamide group, and containing no fluorine atom.
  • the water repellent composition comprises (1) a water repellent polymer and (2) a liquid medium.
  • the water repellent composition may further contain (3) a surfactant.
  • Water-repellent polymer (or "polymer")
  • the water-repellent polymer is a non-fluorine polymer having no fluorine atom.
  • Water repellent polymers are generally (A) It has a repeating unit derived from a sulfonamide group-containing acrylic monomer.
  • the water-repellent polymer may further have a repeating unit derived from a non-fluorinated polymerizable monomer other than the sulfonamide group-containing acrylic monomer (a).
  • the non-fluorine-polymerizable monomer other than the monomer (a) may be a non-fluorine non-crosslinkable monomer or a non-fluorine crosslinkable monomer.
  • T is a hydrogen atom, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom), a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a chain or ring having an ester bond. It is an organic group having 2 to 41 carbon atoms. ] It may be a compound represented by.
  • chain or cyclic hydrocarbon groups having 1 to 40 carbon atoms are linear or branched saturated or unsaturated (eg, ethylenically unsaturated) aliphatic hydrocarbon groups having 1 to 40 carbon atoms. It is a saturated or unsaturated (for example, ethylenically unsaturated) cyclic aliphatic group having 4 to 40, an aromatic hydrocarbon group having 6 to 40 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 40 carbon atoms.
  • the non-fluorine crosslinkable monomer is as described later.
  • non-fluorine-polymerizable monomers other than the monomer (a) are as follows.
  • (B) (Meta) acrylate ester monomer,
  • the (c) non-fluorine crosslinkable monomer and (d) halogenated olefin monomer water-repellent polymer do not have a fluorine atom. That is, the water-repellent polymer is a non-fluorine polymer, and all the monomers constituting the water-repellent polymer are non-fluorine monomers.
  • A Sulfonamide Group-Containing Acrylic Monomer
  • a 1 is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or an iodine atom.
  • a 2 is -NH-SO 2- or -SO 2- NH-
  • R 1 is a hydrocarbon group having 1 to 5 carbon atoms.
  • R 2 is a hydrocarbon group having 7 to 40 carbon atoms.
  • a 1 is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or an iodine atom.
  • a 1 is preferably a hydrogen atom, a methyl group, or a chlorine atom.
  • a 2 is -NH-SO 2- or -SO 2- NH-, but A 2 is preferably -NH-SO 2- .
  • R 1 is a divalent hydrocarbon group having 1 to 5 carbon atoms.
  • the hydrocarbon group may be linear or branched.
  • the hydrocarbon group may be a saturated aliphatic hydrocarbon group, for example an alkylene group.
  • the hydrocarbon group preferably has 2 to 4 carbon atoms, particularly 2. Specific examples of R 1 are, but are not limited to, -CH 2- , -CH 2 CH 2- , -CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 CH 2- .
  • R 2 is a monovalent hydrocarbon group having from 7 to 40 or 7 to 30 carbon atoms.
  • the hydrocarbon group is preferably a linear or branched hydrocarbon group.
  • the hydrocarbon group may be a linear hydrocarbon group in particular.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, particularly an alkyl group. If the hydrocarbon group is short, the crystallinity of the side chains is lowered, and the water repellency is also lowered. If it is too long, problems such as a decrease in the solubility of the monomer and instability of emulsification may occur during polymerization. From these facts, the number of carbon atoms of the hydrocarbon group is preferably 12 to 30, for example, 16 to 26, particularly preferably 18 to 22.
  • the water repellent polymer may have repeating units derived from other (meth) acrylate ester monomers.
  • Examples of other (meth) acrylate ester monomers are as follows.
  • the water-repellent polymer is the monomer (b1) and It may have a repeating unit derived from at least one monomer selected from the group consisting of the monomer (b2).
  • the (meth) acrylate ester monomer water-repellent polymer having an aliphatic hydrocarbon group may have a repeating unit derived from the aliphatic hydrocarbon group-containing (meth) acrylate ester monomer. ..
  • the aliphatic hydrocarbon group-containing (meth) acrylate ester monomer is preferably a (meth) acrylate ester (ie, acrylate or methacrylate) in which the aliphatic hydrocarbon group forms an alcohol residue.
  • the aliphatic hydrocarbon group is preferably a linear or branched hydrocarbon group.
  • the aliphatic hydrocarbon group preferably does not have a cyclic hydrocarbon group.
  • a 11 is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 2 to 21 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, Alternatively, it is a substituted or unsubstituted phenyl group.
  • a 12 is a linear or branched aliphatic hydrocarbon group having 1 to 40 carbon atoms. ] It is a compound indicated by.
  • the aliphatic hydrocarbon group-containing (meth) acrylate ester monomer does not contain a fluorine atom.
  • a 11 is preferably a hydrogen atom, a methyl group or a chlorine atom, and particularly preferably a hydrogen atom or a methyl group.
  • a 12 is a linear or branched hydrocarbon group.
  • the linear or branched hydrocarbon group may be, in particular, a linear hydrocarbon group.
  • the linear or branched hydrocarbon group has 1 to 40 carbon atoms, for example 10 to 40, preferably 18 to 40 carbon atoms.
  • the linear or branched hydrocarbon group preferably has 18 to 28 carbon atoms, particularly 18 or 22, and is generally a saturated aliphatic hydrocarbon group, particularly an alkyl group.
  • aliphatic hydrocarbon group-containing (meth) acrylate ester monomer examples include lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.
  • lauryl (meth) acrylate cetyl (meth) acrylate
  • cetyl (meth) acrylate stearyl (meth) acrylate
  • behenyl (meth) acrylate behenyl (meth) acrylate.
  • the presence of the aliphatic hydrocarbon group-containing (meth) acrylate ester makes the texture more flexible.
  • the water repellent polymer may have a repeating unit derived from a cyclic hydrocarbon group-containing (meth) acrylate ester monomer.
  • a 22 is a cyclic hydrocarbon-containing group having 4 to 40 carbon atoms. ] It is preferably a compound represented by.
  • the cyclic hydrocarbon group-containing (meth) acrylate ester monomer is preferably a monomer having a high melting point of the homopolymer (for example, 50 ° C. or higher, particularly 80 ° C. or higher).
  • the cyclic hydrocarbon group-containing (meth) acrylate ester monomer does not contain a fluorine atom.
  • a 21 are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom and cyano group.
  • a 21 is preferably a hydrogen atom, a methyl group, or a chlorine atom, and is preferably a chlorine atom, for example.
  • Reference numeral A 22 is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include a monocyclic group, a polycyclic group, a bridging ring group, and the like, which are saturated or unsaturated. The cyclic hydrocarbon group is preferably saturated.
  • the cyclic hydrocarbon group has 4 to 40 carbon atoms, preferably 6 to 20 carbon atoms.
  • Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms.
  • the number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 12 or less.
  • the cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.
  • Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group.
  • cyclic hydrocarbon group-containing (meth) acrylate ester monomer examples include Cyclohexyl acrylate, t-butylcyclohexyl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate; and cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, dicyclopentanyl Examples thereof include methacrylate and dicyclopentenyl methacrylate.
  • the presence of the cyclic hydrocarbon group-containing (meth) acrylate ester monomer can improve processing stability and water repellency.
  • the water repellent polymer may have a repeating unit derived from the non-fluorine crosslinkable monomer.
  • the non-fluorine crosslinkable monomer is a monomer containing no fluorine atom.
  • the non-fluorine crosslinkable monomer may be a compound having at least two reactive groups and / or ethylenically unsaturated double bonds (preferably (meth) acrylate groups) and not containing a fluorine atom.
  • the non-fluorinated crosslinkable monomer is a compound having at least two ethylenically unsaturated double bonds (preferably (meth) acrylate groups), or at least one ethylenically unsaturated double bond and at least one reactivity. It may be a compound having a group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.
  • the non-fluorine crosslinkable monomer may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group.
  • the non-fluorine crosslinkable monomer may be a di (meth) acrylate.
  • non-fluorinated crosslinkable monomer is a vinyl monomer having a hydroxyl group.
  • examples of the non-fluorinated crosslinkable monomer include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 2,3.
  • the presence of the non-fluorine crosslinkable monomer enhances the washing durability provided by the water-repellent polymer.
  • the water-repellent polymer may have a repeating unit derived from the halogenated olefin monomer.
  • Halogenated olefin monomers do not have a fluorine atom.
  • the halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms.
  • the halogenated olefin monomer is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms.
  • halogenated olefin monomer Preferred specific examples of the halogenated olefin monomer are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide and vinylidene halides such as vinylidene chloride, vinylidene bromide and vinylidene iodide.
  • Vinyl chloride is preferable because it increases water repellency (particularly water repellency durability).
  • the presence of repeating units derived from the halogenated olefin monomer enhances the washing durability provided by the water repellent polymer.
  • examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate. , And vinyl alkyl ethers.
  • Other monomers are not limited to these examples.
  • the other monomer (e) does not have to be present in the water repellent polymer.
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acrylamide means acrylamide or methacrylamide
  • Each of the monomers (a) to (e) may be a single type or a mixture of two or more types.
  • the amount of the monomer (a) is 2 to 100% by weight with respect to the water-repellent polymer.
  • the lower limit of the amount of the monomer (a) may be 3% by weight, for example 5% by weight, particularly 10% by weight, particularly 15% by weight, based on the water-repellent polymer.
  • the lower limit of the amount of the monomer (a) may be 20% by weight, for example 25% by weight, particularly 30% by weight, particularly 40% by weight or 50% by weight, based on the water-repellent polymer.
  • the upper limit of the amount of the monomer (a) may be 95% by weight, for example, 80% by weight, 75% by weight, or 70% by weight, based on the water-repellent polymer.
  • the amount of the monomer (b) is 0 to 2000 parts by weight, preferably 0 to 200 parts by weight, more preferably 1 to 100 parts by weight, for example, 5 to 80 parts by weight.
  • the amount of the monomer (c) is 0 to 50 parts by weight, preferably 1 to 10 parts by weight, for example, 2 to 8 parts by weight.
  • the amount of the monomer (d) is 0 to 100 parts by weight, preferably 1 to 60 parts by weight, for example, 2 to 10 parts by weight.
  • the amount of the monomer (e) is 0 to 100 parts by weight, preferably 1 to 30 parts by weight, for example, 2 to 10 parts by weight. It may be.
  • the amounts of the monomer (b1) and the monomer (b2) are 0 to 150 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the monomer (a). It may be a part, for example, 2 to 50 parts by weight.
  • the amounts of the monomer (b), the monomer (c), the monomer (d) and the monomer (e) are (b) :( c): ( d): (e) is 0 to 80% by weight: 0 to 10% by weight: 0 to 40% by weight: 0 to 20% by weight, for example, 3 to 75% by weight: 0.5 to 5% by weight: 2 to 30% by weight.
  • the amount of the monomer (e) may be 0% by weight.
  • the number average molecular weight (Mn) of the water-repellent polymer may be generally 1000 to 1000000, for example 5000 to 500,000, particularly 3000 to 200,000.
  • the number average molecular weight (Mn) of the water-repellent polymer is generally measured by GPC (gel permeation chromatography).
  • the water-repellent polymer may be a random polymer or a block polymer, but is preferably a random polymer.
  • the crystallinity of the side chain of the water-repellent polymer is high.
  • the monomer is polymerized to obtain a water repellent composition in which the polymer is dispersed or dissolved in a liquid medium.
  • the monomers used in the present disclosure are as follows. Monomer (a), Monomer (a) + (b), Monomer (a) + (b) + (c), Monomer (a) + (b) + (d), or monomer (a) + (b) + (c) + (d).
  • the monomer (e) may be used.
  • the monomer (b) may be at least one of the monomer (b1) and the monomer (b2).
  • the water repellent composition contains the liquid medium (2).
  • the liquid medium (2) is water, an organic solvent, or a mixture of water and an organic solvent.
  • the water repellent composition is generally a solution or dispersion.
  • the solution is a solution in which the polymer is dissolved in an organic solvent.
  • the dispersion is an aqueous dispersion in which the polymer is dispersed in an aqueous medium (water or a mixture of water and an organic solvent).
  • organic solvents are esters (eg, esters with 2 to 30 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (eg, ketones with 2 to 30 carbon atoms, specifically, methyl ethyl ketone, diisobutyl).
  • the liquid medium may be water alone or a mixture of water and a (miscible) organic solvent.
  • the amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% by weight or more) with respect to the liquid medium.
  • the liquid medium is preferably water alone.
  • the amount of the liquid medium may be 0.2 to 100 parts by weight, for example 0.5 to 50 parts by weight, particularly 1 to 20 parts by weight, based on 1 part by weight of the water-repellent polymer.
  • the water repellent composition is an aqueous dispersion, it preferably contains the surfactant (3).
  • the surfactant (3) preferably contains a nonionic surfactant.
  • the surfactant (3) preferably contains one or more surfactants selected from a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.
  • Nonionic surfactants examples include ethers, esters, esther ethers, alkanolamides, polyhydric alcohols and amine oxides.
  • An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).
  • esters are alcohol and fatty acid esters.
  • An example of an alcohol is an alcohol having 1 to 6 valences (particularly 2 to 5 valences) and 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms) (for example, an aliphatic alcohol).
  • fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
  • an ester ether is a compound obtained by adding an alkylene oxide (particularly ethylene oxide) to an ester of an alcohol and a fatty acid.
  • An example of an alcohol is an alcohol having 1 to 6 valences (particularly 2 to 5 valences) and 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, an aliphatic alcohol).
  • Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
  • alkanolamides are formed from fatty acids and alkanolamines.
  • the alkanolamide may be a monoalkanolamide or a dialkanolamino.
  • fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
  • the alkanolamine may be an alkanol having 1 to 3 amino groups and 1 to 5 hydroxyl groups and having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
  • the polyhydric alcohol may be a dihydric to pentavalent alcohol having 10 to 50 carbon atoms.
  • the amine oxide may be an oxide (eg, 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).
  • the nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group).
  • the alkylene group in the oxyalkylene group preferably has 2 to 10 carbon atoms.
  • the number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100.
  • the nonionic surfactant is selected from the group consisting of ethers, esters, esther ethers, alkanolamides, polyhydric alcohols and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.
  • the nonionic surfactant may be one kind alone or a mixture of two or more kinds.
  • the cationic surfactant is preferably a compound having no amide group.
  • the cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene-added ammonium salt.
  • Specific examples of the cationic surfactant are not particularly limited, but are alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, etc. Examples thereof include quaternary ammonium salt-type surfactants such as alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt and benzethonium chloride.
  • Preferred examples of cationic surfactants are R 51 -N + (-R 52) (- R 53) (- R 54) X -
  • R 51 , R 52 , R 53 and R 54 are hydrocarbon groups having 1 to 30 carbon atoms.
  • X is an anionic group.
  • R 51 , R 52 , R 53 and R 54 are alkyl groups (eg, methyl group, butyl group, stearyl group, palmitic group).
  • Specific examples of X are halogens (eg, chlorine) and acids (eg, hydrochloric acid, acetic acid).
  • the cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).
  • the cationic surfactant is preferably an ammonium salt.
  • the carbon number of R 1 may be 12 to 50, for example, 12 to 30.
  • cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl. Included are di (hydropolyoxyethylene) ammonium chloride, benzyldodecyldi (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride.
  • amphoteric surfactant examples include alanines, imidazolinium betaines, amide betaines, betaine acetate and the like, and specific examples thereof include lauryl betaine, stearyl betaine, laurylcarboxymethyl hydroxyethyl imidazolinium betaine and lauryl dimethyl. Examples thereof include betaine aminoacetate and betaine fatty acid amide propyldimethylaminoacetate.
  • Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more.
  • the amount of the cationic surfactant may be 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, based on the total amount of the surfactant.
  • the weight ratio of the nonionic surfactant to the cationic surfactant is preferably 95: 5 to 20:80, more preferably 85: 15 to 40:60.
  • the amount of the cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight, based on 100 parts by weight of the polymer.
  • the total amount of the surfactant may be 0.1 to 20 parts by weight, for example 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer.
  • the water repellent composition may contain (4) additives in addition to the water repellent polymer (1), the liquid medium (2) and, if necessary, the (3) surfactant. ..
  • additive (4) include other water repellents, oil repellents, drying rate regulators, cross-linking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity regulators, UV absorbers, antioxidants. , PH adjusters, defoamers, texture adjusters, slipperiness adjusters, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, etc.
  • the additive (4) may be a fluorine-containing polymer.
  • the water-repellent composition may contain only the above-mentioned water-repellent polymer (particularly, non-fluorine polymer) as the polymer (active ingredient), but in addition to the above-mentioned non-fluorine polymer, the fluorine-containing weight It may contain coalescing.
  • a water repellent composition particularly, an aqueous emulsion
  • particles formed by a non-fluorinated polymer and particles formed by a fluorine-containing polymer are separately present. That is, it is preferable to separately produce the non-fluorine polymer and the fluorine-containing polymer, and then mix the non-fluorine polymer and the fluorine-containing polymer.
  • a non-fluorinated polymer emulsion particularly an aqueous emulsion
  • a fluorine-containing polymer emulsion particularly an aqueous emulsion
  • the non-fluorinated polymer emulsion and the fluorine-containing polymer emulsion are mixed. Is preferable.
  • the fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer.
  • Y is -O- or -NH-;
  • Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, or a cyclic aliphatic group.
  • R 1 is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms
  • R 2 CH OZ 1 ) CH 2 -group
  • Z 1 is a hydrogen atom or acetyl group
  • Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.
  • It is preferably an acrylate ester or acrylamide represented by.
  • the carbon number of the Rf group is preferably 1 to 6, particularly 4 to 6, and particularly preferably 6.
  • the fluorine-containing polymer is a repeat derived from at least one non-fluorine monomer selected from the group consisting of a halogenated olefin monomer, a non-fluorine non-crosslinkable monomer and a non-fluorine crosslinkable monomer. It may have a unit.
  • the halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms.
  • halogenated olefin monomer examples include vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide and vinylidene halides such as vinylidene chloride, vinylidene bromide and vinylidene iodide.
  • A is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom).
  • T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a chain or cyclic organic group having 1 to 20 carbon atoms having an ester bond.
  • non-fluorine non-crosslinkable monomer examples include alkyl (meth) acrylate ester, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth). Includes acrylates, methoxypolypropylene glycol (meth) acrylates, and vinyl alkyl ethers.
  • the non-fluorinated crosslinkable monomer has a compound having at least two carbon-carbon double bonds (eg, (meth) acrylic group), or at least one carbon-carbon double bond and at least one reactive group. It may be a compound.
  • the weight ratio of the non-fluorinated polymer to the fluorine-containing polymer in the water repellent composition may be 100: 0 to 10:90, for example, 90:10 to 20:80, preferably 80:20 to 30:70. ..
  • Each of the non-fluorine polymer and the fluorine-containing polymer may be one kind of polymer, or may be a combination of two or more kinds of polymers. When a combination of a non-fluorine polymer and a fluorine-containing polymer is used, performance (particularly, water repellency) equal to or higher than that when only the fluorine-containing polymer is used can be obtained.
  • the polymer (non-fluorine polymer and fluorinated polymer, particularly copolymer having a fluoroalkyl group) can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected.
  • a polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred.
  • the method for producing the polymer is not limited. For example, after producing a polymer by solution polymerization, a solvent can be removed and a surfactant and water can be added to obtain an aqueous emulsion.
  • solution polymerization a method is adopted in which the monomer is dissolved in an organic solvent in the presence of a polymerization initiator, replaced with nitrogen, and then heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours.
  • a polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxypivalate, diisopropylperoxydicarbonate and the like. Can be mentioned.
  • the polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
  • the organic solvent is inert to the monomer and dissolves them, for example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (for example, carbon). It may be a ketone having the number 2 to 30, specifically, a methyl ethyl ketone or a diisobutyl ketone), or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, an isopropyl alcohol).
  • an ester for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate
  • a ketone for example, carbon
  • It may be a ketone having the number 2 to 30, specifically, a methyl ethyl ketone or a diisobutyl ketone
  • an alcohol for example, an alcohol having 1 to 30 carbon atoms, specifically, an isopropyl alcohol
  • organic solvent examples include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, and the like.
  • Examples thereof include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane.
  • the organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the monomer in total.
  • emulsion polymerization a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, substituted with nitrogen, and then stirred and polymerized in the range of 50 to 80 ° C. for 1 to 10 hours.
  • the polymerization initiators are benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexylhydro peroxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutyamidine-dihydrochloride, and peroxide.
  • Water-soluble substances such as sodium oxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypi Oil-soluble substances such as valet and diisopropylperoxydicarbonate are used.
  • the polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
  • a monomer is atomized and polymerized in water using an emulsifying device such as a high-pressure homogenizer or an ultrasonic homogenizer that can apply strong crushing energy.
  • an emulsifying device such as a high-pressure homogenizer or an ultrasonic homogenizer that can apply strong crushing energy.
  • the emulsifier various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers.
  • compatibilizer that is sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. It is possible to improve emulsifying property and copolymerizability by adding a compatibilizer.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water.
  • the water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water.
  • the low molecular weight monomer examples include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate and the like, and 1 to 50 parts by weight, based on 100 parts by weight of the total amount of the monomer.
  • it may be used in the
  • a chain transfer agent may be used in the polymerization.
  • the molecular weight of the polymer can be changed according to the amount of the chain transfer agent used.
  • chain transfer agents are mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol (particularly alkyl mercaptans (eg, 1-30 carbon atoms)), inorganic salts such as sodium hypophosphite, sodium bisulfite. And so on.
  • the amount of the chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.
  • the water repellent composition may be in the form of a solution, emulsion (particularly an aqueous dispersion) or aerosol, but is preferably a solution or aqueous dispersion.
  • the water repellent composition comprises a polymer (the active ingredient of the water repellent composition) and a medium (particularly a liquid medium, such as an organic solvent and / or water).
  • the amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the water repellent composition.
  • the concentration of the polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.
  • the water repellent composition can be used as an external treatment agent (surface treatment agent) or an internal treatment agent.
  • the water repellent composition can be used as an oil repellent, an antifouling agent, a stain remover, a release agent or a mold release agent.
  • the water repellent composition When the water repellent composition is an external treatment agent, it can be applied to the object to be treated by a conventionally known method. Usually, a method in which the water repellent composition is dispersed in an organic solvent or water, diluted, adhered to the surface of an object to be treated by a known method such as immersion coating, spray coating, foam coating, etc., and dried. Is taken. If necessary, it may be applied together with a suitable cross-linking agent (for example, blocked isocyanate) for curing. Further, it is also possible to add an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent and the like to the water repellent composition and use them together.
  • the concentration of the polymer in the treatment liquid to be brought into contact with the base material may be 0.01 to 10% by weight (particularly in the case of dip coating), for example, 0.05 to 10% by weight.
  • the objects to be treated with the treatment agent composition include textile products, stone materials, filters (for example, electrostatic filters), dust masks, fuel cell parts (for example, gas diffusion electrodes and gas). Dust masks), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, coated surfaces, and plasters.
  • textile products For example, animal and vegetable natural fibers such as cotton, hemp, wool and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers and carbon fibers. , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.
  • the textile product may be in any form such as fiber or cloth.
  • the water repellent composition can also be used as an antifouling agent, a release agent, and a release agent (for example, an internal release agent or an external release agent).
  • a release agent for example, an internal release agent or an external release agent.
  • the surface of the base material can be easily peeled off from another surface (another surface on the base material or a surface on another base material).
  • the polymer can be applied to fibrous substrates (eg, textiles) by any of the methods known for treating textiles with liquids.
  • the textile is a cloth
  • the cloth may be dipped in the solution, or the solution may be attached or sprayed onto the cloth.
  • the treated textile product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop water repellency.
  • the polymer may be applied to textile products by a cleaning method, and may be applied to textile products by, for example, a washing application or a dry cleaning method.
  • the textile products to be processed are typically fabrics, which include textiles, knitted and non-woven fabrics, fabrics and carpets in the form of clothing, but textiles or yarns or intermediate textile products (eg, sliver or It may be blister yarn, etc.).
  • the textile material may be natural fibers (eg, cotton or wool), synthetic fibers (eg, biscorayon or leocell), or synthetic fibers (eg, polyester, polyamide or acrylic fibers), or , A mixture of fibers (eg, a mixture of natural and synthetic fibers).
  • the fibrous substrate may be leather.
  • Aqueous or aqueous emulsions of the polymer to make the leather hydrophobic and oleophobic at various stages of leather processing, for example during the moistening of the leather or during the finishing of the leather. May be applied to leather.
  • the fibrous substrate may be paper.
  • the polymer may be applied to preformed paper or at various stages of papermaking, for example during the drying period of the paper.
  • Treatment means applying the treatment agent to the object to be treated by dipping, spraying, coating, or the like.
  • the polymer which is the active ingredient of the treatment agent, permeates the inside of the object to be treated and / or adheres to the surface of the object to be treated.
  • the water repellent composition When the water repellent composition is an internal treatment agent, it can impart water repellency to the resin by adding it to a resin such as a thermoplastic resin.
  • a water repellent composition can be used in the production of resin moldings.
  • the liquid medium is removed from the liquid (solution or dispersion) containing the polymer to obtain a polymer.
  • a polymer can be obtained by reprecipitating a dispersion liquid (aqueous dispersion liquid or organic solvent dispersion liquid) of a polymer with water or an organic solvent and then drying the mixture.
  • a molded product can be produced by a production method including a step of mixing a resin and a polymer to obtain a resin composition and a step of molding the resin composition. It is preferable to produce a molded product by melt-kneading using an extruder or the like.
  • the thermoplastic resin and the polymer are compatible in the molten state. Kneading can be performed by a conventionally known method such as a uniaxial extruder, a twin extruder, a roll, or the like.
  • the resin composition thus obtained is molded by extrusion molding, injection molding, compression molding, blow molding, pressing or the like.
  • the resin composition is molded into molded bodies having various shapes.
  • the obtained molded product may be further heat-treated in an oven, a drying oven, or the like after the molding process.
  • the molded product may be a single layer, or may be a plurality of layers of 2 to 10 layers, for example, 3 to 5 layers.
  • the molded product can be used in applications where a thermoplastic resin is used, particularly in applications where it is preferable to have excellent wiping ease against dirt and excellent scratch resistance.
  • Molds are used in automobiles (exterior and interior parts) (eg bumpers, instrumental panels, door trims), household appliances (eg washing machines and refrigerators) (eg housings, doors in refrigerators, trays). , Vegetable room container), various cases, buildings (interior and parts) (for example, handrails, wallpaper, desks, chairs, toilet seats and toilet seat force bars, bathtubs), electronic devices (for example, smartphone housings), drains , Pipes, tableware, flooring materials, gasoline tanks, fuel hoses, OA equipment, etc. Of these, interior parts for automobiles, interior parts for home appliances, and buildings are even more preferable.
  • Spray water repellency test The water repellency of the cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). As shown in Table 1 below, the water repellent No. Represented by. The higher the score, the better the water repellency, and depending on the condition, an intermediate value (95, 85, 75) is given.
  • Example 2 (solvent-based, copolymerized with StA) With the composition shown in Table 2, polymerization was carried out in the same manner as in Example 1, and after polymerization, reprecipitation was performed and then diluted with toluene so as to have a solid content of 1.5% to prepare a treatment liquid (100 g). The polymer had the same composition ratio as the charged monomer. A cloth was dipped in the treatment liquid in the same manner as in Example 1 to perform a water repellency test. The results are shown in Table 2.
  • Comparative Example 1 (solvent type, StA only) With the composition shown in Table 2, polymerization was carried out in the same manner as in Example 1, and after polymerization, reprecipitation was performed and then diluted with toluene so as to have a solid content of 1.5% to prepare a treatment liquid (100 g). The polymer had the same composition ratio as the charged monomer. A cloth was dipped in the treatment liquid in the same manner as in Example 1 to perform a water repellency test. The results are shown in Table 2.
  • Example 3 (water-based, PVC copolymerization) Tripropylene glycol 10g, C18SAm 10g, N-methylolacrylamide 0.5g, pure water 60g, dimethyloctadecyl ammonium chloride 0.3g, polyoxyethylene tridecyl ether 1.0g, polyoxyethylene lauryl ether 1.0g in a 500ml plastic container was charged, heated to 80 ° C., stirred with a homomixer at 2000 rpm for 1 minute, and then emulsified and dispersed with ultrasonic waves for 15 minutes.
  • the emulsified dispersion is transferred to a 500 cc four-necked flask equipped with a nitrogen introduction tube, a thermometer, a stirring rod, and a reflux tube, and after nitrogen substitution, 0.1 g of lauryl mercaptan is charged and stirred, and then 2,2-azobis (2). -Amidinopropane) (0.6 g) dihydrochloride was added, the temperature was raised at 60 ° C., and the mixture was reacted for 4 hours to obtain an aqueous dispersion of the polymer. The polymer had the same composition ratio as the charged monomer. Then, pure water was added to prepare an aqueous dispersion having a solid content concentration of 20%.
  • Examples 4 to 6 and Comparative Examples 2 to 3 Polymerization was carried out in the same manner as in Example 3 with the compositions shown in Table 2, and pure water was added after the polymerization to prepare an aqueous dispersion having a solid content concentration of 20%.
  • the polymer had the same composition ratio as the charged monomer. Further, it was diluted with tap water to prepare a treatment solution having a solid content concentration of 1.5%. A cloth was dipped in the treatment liquid in the same manner as in Example 3 to perform a water repellency test. The results are shown in Table 2.
  • the water-repellent polymer can be used as an active ingredient of an external treatment agent (surface treatment agent) or an internal treatment agent.
  • the water repellent composition containing the water repellent polymer can be suitably used for a base material such as a textile product and a masonry, and imparts excellent water repellency to the base material.
  • excellent water repellency can be obtained for cotton, which is difficult to give water repellency with ordinary water and oil repellents.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un polymère hydrofuge qui fournit une excellente répulsion de l'eau et qui ne comprend pas d'atomes de fluor. Ce polymère hydrofuge ne comprend pas de fluor et a une unité de répétition dérivée de (a) un monomère acrylique ayant un groupe sulfonamide et un groupe alkyle à longue chaîne ayant de 7 à 40 atomes de carbone. Ledit monomère (a) est de préférence un composé représenté par la formule : CH2=CA1-C(=O)-O-R1-A2-R2 [dans la formule, A1 représente un atome d'hydrogène, un groupe méthyle, un atome de chlore, un atome de brome ou un atome d'iode, A2 représente -NH-SO2- ou -SO2-NH-, R1 représente un groupe hydrocarboné ayant de 1 à 5 atomes de carbone, et R2 représente un groupe hydrocarboné ayant de 7 à 40 atomes de carbone].
PCT/JP2020/026918 2019-07-10 2020-07-09 Polymère hydrofuge et composition d'agent hydrofuge WO2021006319A1 (fr)

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JP2023010656A (ja) * 2021-07-08 2023-01-20 ダイキン工業株式会社 耐油剤組成物

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EP4269456A1 (fr) 2020-12-23 2023-11-01 Techno-UMG Co., Ltd. Polymère greffé de polypropylène, composition de résine thermoplastique et article moulé correspondant

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JP2006328624A (ja) * 2005-04-28 2006-12-07 Nicca Chemical Co Ltd 撥水剤、撥水加工方法及び撥水性繊維製品
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JPH04350663A (ja) * 1991-05-28 1992-12-04 Fuji Photo Film Co Ltd 電子写真式平版印刷用原版
JP2002128829A (ja) * 2000-10-23 2002-05-09 Toray Ind Inc モノマー、ポリマーおよびそれを用いた眼用レンズ
JP2003313245A (ja) * 2002-04-25 2003-11-06 Mitsui Chemicals Inc スルホンアミド系有機重合体
JP2006328624A (ja) * 2005-04-28 2006-12-07 Nicca Chemical Co Ltd 撥水剤、撥水加工方法及び撥水性繊維製品
JP2007292859A (ja) * 2006-04-21 2007-11-08 Matsushita Electric Ind Co Ltd レジスト材料及びそれを用いたパターン形成方法

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JP2023010656A (ja) * 2021-07-08 2023-01-20 ダイキン工業株式会社 耐油剤組成物
JP7252502B2 (ja) 2021-07-08 2023-04-05 ダイキン工業株式会社 耐油剤組成物

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