Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
  • C09D5/1668—Vinyl-type polymers
• • 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
  • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
  • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D135/02—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • C—CHEMISTRY; METALLURGY
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
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  • 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
  • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
  • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
• • 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
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
  • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
• • 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
  • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
• • 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
  • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
• • D—TEXTILES; PAPER
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  • 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
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
• • 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
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/12—Esters of monocarboxylic acids with unsaturated alcohols containing three or more carbon atoms
• • D—TEXTILES; PAPER
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  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
• • 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
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
  • D06M2200/12—Hydrophobic properties

Definitions

• the present invention relates to a liquid repellent composition, a substrate treatment method, and an article.
• a fluorine-based liquid repellent agent containing a fluorine compound may impart liquid repellency to the surface of an article.
• the surface tension of an article treated with a fluorine-based liquid-repellent agent is lowered by the fluorine of the fluorine compound, and as a result, the liquid-repellent property can be imparted.
• fluorine-based liquid-repellent agents containing polymers having perfluoroalkyl groups as fluorine compounds are used in various fields.
• Patent Documents 1 to 3 disclose, as non-fluorine water repellents, hydrocarbon water repellents containing non-fluorine polymers having long-chain alkyl (meth)acrylate units.
• the present invention provides a liquid repellent composition that can impart excellent liquid repellency while being hydrocarbon-based; a method for treating a substrate using the liquid repellent composition; and a coating film that is hydrocarbon-based and yet has excellent liquid repellency. to provide an article comprising
• (R 1 -Q 1 -)HC CH(-Q 2 -R 2 ) formula (a)
• Q 1 and Q 2 each independently represent a divalent linking group
• R 1 and R 2 each independently represent a monovalent hydrocarbon group having 8 to 24 carbon atoms.
• R3 is an electron donating group.
• R4 represents an optionally substituted aliphatic hydrocarbon group.
• a liquid repellent composition capable of imparting excellent liquid repellency while being hydrocarbon; a method for treating a substrate using the liquid repellent composition; An article comprising a coating is provided.
• the monomer represented by formula (a) is also referred to as monomer (a).
• monomers represented by other formulas are similarly described.
• the compound represented by formula (1) is also referred to as compound (1).
• Compounds represented by other formulas are similarly described.
• the meanings and definitions of the terms used in the present invention are as follows.
• “Liquid repellency” means either one or both of water repellency and oil repellency.
• a unit based on a monomer is a general term for an atomic group directly formed by polymerization of one molecule of a monomer and an atomic group obtained by chemically converting a part of the atomic group.
• (Meth)acrylate is a generic term for acrylate and methacrylate.
• the number average molecular weight (Mn) and mass average molecular weight (Mw) of the polymer are polystyrene equivalent molecular weights obtained by GPC measurement using a calibration curve prepared using a standard polymethyl methacrylate sample.
• GPC is an abbreviation for gel permeation chromatography.
• Solid content concentration is the mass of the sample before heating, and the mass after drying the sample for 4 hours in a convection dryer at 120 ° C. is the solid content mass, (solid content mass / sample mass) ⁇ Calculated by 100.
• "ph” in the chemical formula represents a phenyl group.
• ⁇ indicating a numerical range means that the numerical values before and after it are included as lower and upper limits. Regarding the numerical ranges of the contents and various physical properties disclosed herein, new numerical ranges can be obtained by arbitrarily combining the lower and upper limits thereof.
• the liquid repellent agent composition of the present invention contains a polymer (A).
• the present composition may contain one type of polymer (A) alone, or may contain two or more types of polymer (A).
• the polymer (A) has units (hereinafter also referred to as "units (a)") based on the monomer (a).
• (R 1 -Q 1 -)HC CH(-Q 2 -R 2 ) formula (a)
• R 1 and R 2 each independently represent a monovalent hydrocarbon group having 8 to 24 carbon atoms.
• R 1 and R 2 may be the same or different. Since the monovalent hydrocarbon group in R 1 and R 2 has 8 or more carbon atoms, excellent liquid repellency is exhibited. Since the monovalent hydrocarbon group in R 1 and R 2 has 24 or less carbon atoms, the polymer (A) has excellent film-forming properties.
• R 1 and R 2 are each independently preferably a monovalent hydrocarbon group having 12 to 24 carbon atoms, more preferably a monovalent hydrocarbon group having 12 to 22 carbon atoms, and a monovalent hydrocarbon group having 14 to 20 carbon atoms. is more preferred.
• a monovalent hydrocarbon group is preferred.
• a monovalent aliphatic hydrocarbon group may be linear or branched.
• the monovalent aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
• the monovalent aliphatic hydrocarbon group is preferably a monovalent saturated hydrocarbon group, that is, an alkyl group, more preferably a linear alkyl group. Examples of monovalent hydrocarbon groups include lauryl, myristyl, cetyl, stearyl, arachidyl, behenyl, 2-ethylhexyl, isostearyl and oleyl groups.
• Q 1 and Q 2 each independently represent a divalent linking group.
• Q 1 and Q 2 may be the same or different.
• Q 1 and Q 2 are preferably the same.
• the monomer (a) the monomer (a1), the monomer (a2), the monomer (a3), and the monomer (a4) are preferable from the viewpoint of superior liquid repellency.
• (a2) is more preferred.
• two R 1 and R 2 may be the same or different. Further, the details and preferred aspects of R 1 and R 2 are the same as those described for formula (a).
• Examples of the monomer (a1) include trans-diastearoylethylene, cis-diastearoylethylene, trans-dilauryloylethylene, cis-dilauryloylethylene, trans-stearoyllauroylethylene, and cis-stearoyllauroylethylene.
• Examples of the monomer (a2) include distearyl fumarate, distearyl maleate, diisostearyl fumarate, diisostearyl maleate, dilauryl fumarate, dilauryl maleate, di-2-ethylhexyl fumarate, and malein.
• di-2-ethylhexyl acid di-2-ethylhexyl acid, stearyl-2-ethylhexyl maleate, stearyl-2-ethylhexyl fumarate, stearyl lauryl maleate, stearyl lauryl fumarate.
• the monomer (a3) include distearyl fumaric acid amide, distearyl maleic acid amide, diisostearyl fumaric acid amide, diisostearyl maleic acid amide, di-2-ethylhexyl fumaric acid amide, stearyl-2- Ethylhexyl fumaric acid amide, stearyl-2-ethylhexyl maleic acid amide can be mentioned.
• Examples of the monomer (a4) include vinylene distearate, vinylene dilaurylate, vinylene-2-ethylhexanoate, vinylene diisostearate, vinylene stearate laurylate, vinylene distearylate-2-ethyl hexanoate.
• the monomer (a1), monomer (a2), monomer (a3), and monomer (a4) may be commercially available products or may be prepared by synthesis. Moreover, each of these monomers may be used individually by 1 type, and may use 2 or more types together.
• the monomer (a1) can be produced, for example, by an alkylation reaction between a maleic acid ester, maleic acid amide, fumaric acid ester or fumaric acid amide and an organomagnesium reagent having an alkyl group having 8 to 24 carbon atoms.
• the monomer (a2) is, for example, a reaction (esterification It can be produced by a method of reacting).
• Y 1 and Y 2 each independently represent a chlorine atom or a hydroxyl group.
• the esterification reaction can be carried out, for example, by the method described in paragraphs 0053 and 0054 of JP-A-2009-84490. After the esterification reaction, the reaction product may be purified, etc., if necessary.
• the monomer (a3) can be produced, for example, by an amidation reaction between maleic acid or fumaric acid and an amine having an alkyl group of 8 to 24 carbon atoms.
• the monomer (a4) can be produced, for example, by an esterification reaction between glyoxal and an acid chloride having an alkyl group with 8 to 24 carbon atoms.
• the polymer (A) may be a copolymer further having units based on the following monomer (b) (hereinafter also referred to as "units (b)").
• Monomer (b) a monomer other than monomer (a) and having one polymerizable unsaturated group and an electron-donating group adjacent to the unsaturated group in one molecule Quantity.
• the monomer (b) Since the monomer (b) has one polymerizable unsaturated group and an electron-donating group adjacent to the unsaturated group in one molecule, it has excellent polymerization reactivity. When the monomer (b) is used in the polymerization reaction of the polymer (A), the polymerization reaction of the monomer (a) with relatively low polymerizability proceeds easily.
• the monomer (b) is not particularly limited as long as it can be copolymerized with the monomer (a).
• a non-fluorine monomer having no fluorine atom is preferred.
• the polymer (A) contains the unit (b)
• the unit (b) is based on a non-fluorine monomer, the polymer (A) can easily be made into a non-fluorine polymer.
• the following monomer (b1) is preferred.
• CH 2 CHR 3
• R3 is an electron donating group.
• the electron - donating group for R3 is not particularly limited as long as it can donate electrons to the unsaturated double bond of the monomer (b1).
• the electron-donating group for R 3 include a heteroatom-containing group in which a heteroatom is bonded to a carbon atom having a double bond, an optionally substituted aliphatic hydrocarbon group, and a substituted and aromatic hydrocarbon groups.
• heteroatom in the heteroatom-containing group examples include oxygen atom, nitrogen atom, phosphorus atom, sulfur atom, silicon atom, and boron atom.
• an oxygen atom and a nitrogen atom are preferable because they are easily available.
• the electron-donating heteroatom-containing group includes, for example, an ether group and an ester group.
• the electron-donating heteroatom-containing group includes, for example, an amide bond and an amine group.
• Examples of the aliphatic hydrocarbon group which may have a substituent include an alkyl group and an alkyl group having a substituent.
• the number of carbon atoms in the alkyl group is not particularly limited.
• the alkyl group may have 1 to 30 carbon atoms, 3 to 24 carbon atoms, or 4 to 20 carbon atoms.
• the aliphatic hydrocarbon group may be linear or branched.
• the substituted alkyl group at least one methylene unit is bound to the carbon atom having a double bond shown in formula (b1), and the position at which the substituent is introduced is not particularly limited.
• the substituent is not particularly limited. Examples of the substituent include hydroxyl group, ether group, carboxyl group, amino group and amide group.
• Substituents in the aromatic hydrocarbon group which may have a substituent include, for example, a phenyl group, a styrene group, a pyridine group, a phenyl group having a substituent, a styrene group having a substituent, and a pyridine group having a substituent. is mentioned.
• the aromatic hydrocarbon group having a substituent at least one unit of a methylene unit or a phenyl group may be bonded to the carbon atom having a double bond shown in formula (b1), and the position at which the substituent is introduced is It is not particularly limited. Also, the substituent is not particularly limited. Examples of the substituent include hydroxyl group, carboxyl group and ether group.
• monomers (b1) include, for example, vinyl esters, vinyl ethers, amides and silanes.
• Vinyl esters include, for example, vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl chloroacetate, divinyl adipate, vinyl trifluoroacetate, Examples include vinyl benzoate and vinyl 2-ethylhexanoate.
• Vinyl ethers include, for example, methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxybutyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, chloro Propyl vinyl ether, cyclohexyl vinyl ether, diethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether.
• Amides include, for example, N-vinylacetamide, 1-vinyl-2-pyrrolidone, N-vinyl- ⁇ -caprolactam, N-vinylphthalimide.
• Silanes include, for example, trimethylvinylsilane, dimethylphenylvinylsilane, and diphenylmethylvinylsilane.
• examples of the monomer (b1) include an optionally substituted ⁇ -olefin.
• ⁇ -olefins which may have a substituent include, for example, propylene, 1-hexene, 1-butene, 1-octadecene, allyl alcohol, allylamine, allyl ether, allyl ester, and derivatives thereof.
• examples of allyl ethers include diallyl ether and 1,3-diallyloxy-2-propanol. Allyl esters include, for example, allyl acetate and diallyl adipate.
• R 3 is an optionally substituted aromatic hydrocarbon group
• examples of the monomer (b1) include styrene, 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, 4- Vinyl benzoic acid can be mentioned.
• R4 represents an optionally substituted aliphatic hydrocarbon group. Examples of R4 include an alkyl group and an alkyl group having a substituent. The number of carbon atoms when R 4 is an alkyl group is not particularly limited. For example, the number of carbon atoms may be 1-24, 4-20, or 12-18. R4 may be linear or branched.
• the substituent for R 4 may be the same substituent as the “aliphatic hydrocarbon group optionally having substituent(s)” for R 3 in formula (b1). However, the substituent at R 4 may be electron withdrawing. Examples of electron-withdrawing groups include ester groups, amide groups, carbamoyl groups, urea groups, thiourea groups, and sulfonamide groups.
• vinyl esters and vinyl ethers are preferable, and vinyl acetate, vinyl pivalate, Vinyl laurate, vinyl stearate, methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether are more preferred, and vinyl acetate, vinyl laurate, vinyl stearate, 4- Hydroxybutyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether and cyclohexyl vinyl ether are more preferred, and vinyl acetate and vinyl stearate are particularly preferred.
• the monomer (b) may be used singly or in combination of two or more.
• the polymer (A) may be a copolymer further having units based on the following monomer (c) (hereinafter also referred to as "units (c)").
• CH2 CX1X2 ...
• Formula (c) In formula (c), X 1 and X 2 each independently represent a halogen atom or a hydrogen atom, and X 1 and X 2 are not hydrogen atoms at the same time.
• the film-forming properties of the polymer (A) on the substrate treated with the liquid repellent composition tend to be good.
• a chlorine atom is preferable as the halogen atom for X 1 and X 2 .
• Vinyl chloride and vinylidene chloride are preferable as the monomer (c).
• Monomer (c) may be used alone or in combination of two or more.
• the polymer (A) may be a copolymer further having units based on the monomer (d) below.
• R5 represents a hydrogen atom or a methyl group
• R6 represents a monovalent hydrocarbon group which may have a substituent. Details and preferred embodiments of the monovalent hydrocarbon group are the same as those described for R 1 and R 2 .
• the substituent that R 6 may have is not particularly limited as long as it is other than the crosslinkable functional group described later. Examples include aliphatic hydrocarbon groups and aromatic groups.
• a (meth)acrylate having an alkyl group of 1 to 24 carbon atoms is preferable, and a (meth)acrylate having an alkyl group of 4 to 22 carbon atoms is more preferable.
• (meth)acrylates include butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, ) acrylate, arachidyl (meth)acrylate, behenyl (meth)acrylate and other alkyl (meth)acrylates.
• Monomer (d) from the viewpoint of obtaining better liquid repellency, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth) Acrylates are preferred.
• Monomer (d) may be used individually by 1 type, and may use 2 or more types together.
• the polymer (A) may be a copolymer further having units based on the monomer (e) having a crosslinkable functional group.
• Monomer (e) is a monomer other than monomer (a), monomer (b), monomer (c) and monomer (d).
• the crosslinkable functional group of the monomer (e) is preferably a functional group having at least one bond selected from a covalent bond, an ionic bond and a hydrogen bond, and a functional group capable of forming a crosslinked structure through the interaction of said bond. .
• crosslinkable functional group from the viewpoint of excellent washing durability, isocyanate group, blocked isocyanate group, alkoxysilyl group, amino group, alkoxymethylamide group, methylol group, silanol group, ammonium group, amide group, epoxy group, A hydroxyl group, an oxazoline group, a carboxy group, an alkenyl group, and a sulfonic acid group are preferred. Among them, epoxy group, hydroxyl group, blocked isocyanate group, alkoxysilyl group, amino group and carboxy group are more preferable.
• monomer (e) include (meth)acrylate (excluding monomer (d)), acrylamide, vinyl ether, and vinyl ester.
• N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylamide, and 4-hydroxybutyl (meth)acrylamide are used because of their excellent washing durability.
• the polymer (A) preferably does not have a fluorine atom in order to use the present composition as a non-fluorine-based water repellent.
• the polymer (A) when it does not have a fluorine atom is a monomer (a) that does not have a fluorine atom and, if necessary, a monomer that does not have a fluorine atom other than the monomer (a). It is obtained by polymerizing the contained monomer components.
• Polymer (A) may be a homopolymer of monomer (a); monomer (a), monomer (b), monomer (c), monomer (d) and at least one selected from the group consisting of the monomer (e).
• Polymer (A) is preferably a copolymer of monomer (a), monomer (b), monomer (c), monomer (d) and monomer (e).
• the monomer (a), the monomer (b), the monomer (c), the monomer (d) and the monomer It may further have a unit derived from a monomer other than the body (e) (hereinafter referred to as "another monomer unit").
• Other monomers include, for example, norbornene, dicyclopentadiene, maleic anhydride.
• the proportion of unit (a) is preferably 60% by mass or more, more preferably 70% by mass or more, and may be 100% by mass, based on all structural units of polymer (A). If the proportion of the unit (a) is at least the above lower limit, the liquid repellency will be more excellent.
• the proportion of the unit (a) is preferably 5 to 80% by mass, preferably 8 to 70% by mass, based on the total structural units of the polymer (A). is more preferred, and 10 to 60% by mass is even more preferred. If the proportion of the unit (a) is equal to or higher than the lower limit of the numerical range, the liquid repellency will be more excellent. When the ratio of the units (a) is equal to or less than the upper limit of the above numerical range, it is easy to ensure the reactivity of the polymer (A) in the polymerization reaction.
• the proportion of the unit (b) is preferably 20 to 95% by mass, preferably 25 to 85% by mass, based on the total structural units of the polymer (A). is more preferred, and 30 to 80% by mass is even more preferred.
• the proportion of the units (b) is at least the lower limit of the numerical range, the reactivity of the polymer (A) in the polymerization reaction is more excellent. If the proportion of the unit (b) is equal to or less than the upper limit of the numerical range, it is easy to ensure liquid repellency.
• the proportion of the unit (c) is preferably 1 to 30% by mass, preferably 3 to 25% by mass, based on the total structural units of the polymer (A). is more preferred, and 5 to 20% by mass is even more preferred. If the ratio of the units (c) is at least the lower limit of the numerical range, the polymer (A) will have more excellent film-forming properties. If the proportion of the unit (c) is equal to or less than the upper limit of the numerical range, it is easy to ensure liquid repellency.
• the proportion of the unit (d) is preferably 0.1 to 25% by mass with respect to the total structural units of the polymer (A), and 0.5 ⁇ 20% by mass is more preferable, and 1 to 15% by mass is even more preferable. If the proportion of the unit (d) is equal to or higher than the lower limit of the numerical range, the water repellency will be more excellent. When the ratio of the units (d) is equal to or less than the upper limit of the above numerical range, the stability of the emulsified particles of the polymer formed by emulsion polymerization tends to be good.
• the proportion of the unit (e) is preferably 0.1 to 25% by mass with respect to the total structural units of the polymer (A), and 0.5 ⁇ 20% by mass is more preferable, and 1 to 15% by mass is even more preferable. If the proportion of the unit (e) is at least the lower limit of the above numerical range, the durability to washing will be more excellent. If the proportion of the unit (e) is equal to or less than the upper limit of the numerical range, the polymer (A) tends to have good film-forming properties.
• the ratio of the other monomer units is preferably 0 to 20% by mass, preferably 1 to 15% by mass, based on the total structural units of the polymer (A). is more preferred, and 5 to 10% by mass is even more preferred. If the proportion of other monomer units is at least the lower limit of the above numerical range, it is easy to impart the properties of the other monomer to the polymer (A). If the ratio of other monomer units is equal to or less than the upper limit of the above numerical range, the effects of the invention are less likely to be impaired.
• the ratio of each unit can be calculated from the reaction rate of each monomer component by 1 H-NMR and gas chromatography.
• the ratio of each unit based on the charged amount of the monomer component may be calculated.
• Mw of the polymer (A) is not particularly limited. For example, it may be from 5,000 to 100,000, from 7,000 to 80,000, or from 10,000 to 100,000. If the Mw of the polymer (A) is at least the lower limit of the numerical range, the liquid repellency will be more excellent. When the Mw of the polymer (A) is equal to or less than the upper limit of the numerical range, the solubility in liquid solvents is excellent.
• the Mn of the polymer (A) is preferably 2,500 to 50,000, more preferably 3,500 to 40,000, even more preferably 5,000 to 25,000. If the Mn of the polymer (A) is at least the lower limit of the numerical range, the liquid repellency will be more excellent. When the Mn of the polymer (A) is equal to or less than the upper limit value of the above numerical range, the film-forming properties of the polymer (A) are more excellent.
• the composition preferably further contains a liquid medium.
• liquid media include water, organic solvents, and aqueous media.
• organic solvents examples include water-soluble organic solvents, ketones, compounds having an amide bond, compounds having an ether bond and no hydroxyl group, and aromatic hydrocarbon compounds.
• a water-soluble organic solvent will be described later.
• Ketones include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
• Compounds having an amide bond include, for example, dimethylacetamide, 3-methoxy-dimethylpropanamide, 3-butoxydimethylpropanamide, and methylpyrrolidone.
• Examples of compounds having an ether bond and no hydroxyl group include tetrahydrofuran, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and cyclopentyl methyl ether.
• Examples of aromatic hydrocarbon compounds include toluene and xylene.
• An organic solvent may be used individually by 1 type, and may use 2 or more types together.
• the organic solvent is preferably one capable of dissolving or dispersing the polymer (A), more preferably one capable of dissolving the polymer (A).
• the organic solvent is preferably a ketone; a compound having an ether bond and having no hydroxyl group; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone. , tetrahydrofuran, and cyclopentyl methyl ether are more preferred.
• Aqueous media include water-soluble organic solvents and mixtures of water and water-soluble organic solvents.
• a water-soluble organic solvent is an organic solvent that is miscible with water in any proportion.
• the water-soluble organic solvent is a compound miscible with water in an arbitrary ratio, and consists of the above-mentioned ketones, compounds having an amide bond, compounds having an ether bond and not having a hydroxyl group, and aromatic hydrocarbon compounds. It may be a compound selected from the group.
• the water-soluble organic solvent is preferably at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols and aprotic polar solvents. Examples of alcohols include t-butanol and propylene glycol.
• Ether alcohols include, for example, 1-methoxy-2-propanol, 3-methoxymethylbutanol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol.
• aprotic polar solvents include N,N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, acetonitrile, acetone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-3-methyl-1-butanol, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether.
• One of the aqueous media may be used alone, or two or more thereof may be used in combination.
• the aqueous medium is a mixture of water and a water-soluble organic solvent
• the content of the water-soluble organic solvent is preferably 1-80 parts by mass, more preferably 5-60 parts by mass, relative to 100 parts by mass of water.
• the composition may further comprise a low molecular weight component with Mw less than 5000.
• a low-molecular-weight component having an Mw of less than 5,000 may contribute to development of liquid repellency.
• a component with Mw of 5000 or more is called a polymer component.
• Low-molecular-weight components include, for example, the above-described monomer (a), monomer (b), monomer (c), monomer (d), monomer (e), and A polymer (A) is mentioned. Details and preferred embodiments of each monomer are as described above.
• Each monomer and polymer (A) as a low-molecular-weight component may be used singly or in combination of two or more.
• the monomer (a) in the present composition and the monomer (a) forming the unit (a) of the polymer (A) may be the same or different.
• the Mw of the polymer (A) as the low-molecular-weight component is preferably 1,000 or more and less than 5,000, more preferably 1,200 to 4,800, even more preferably 1,500 to 3,000.
• Mn of the polymer (A) as a low-molecular-weight component is preferably 500-2,500, more preferably 750-1,500.
• the polymer (A) as a low-molecular-weight component may optionally further have at least one selected from the group consisting of units (b), units (c), units (d) and units (e). good.
• the ratio of each unit in the polymer (A) as a low-molecular-weight component, the details of the copolymer composition and preferred embodiments are the same as those described for the polymer (A).
• the present composition may further contain components other than the polymer (A), the low-molecular-weight component and the liquid medium, if necessary.
• Other components include, for example, surfactants, polymers other than the polymer (A), non-fluorine-based water and oil repellents, water-soluble polymer resins, cross-linking agents, catalysts, penetrants, antifoaming agents, Filming aids, insect repellents, flame retardants, antistatic agents, anti-wrinkle agents, softeners, pH adjusters, paper strength agents, waterproofing agents, sizing agents, organic fillers, inorganic fillers, support agents, flocculants, Buffers, bactericides, biocides, sequestering agents.
• JP-A-2006-328624, JP-A-2015-172198, JP-A-2017-025440 and the like can be mentioned without limitation.
• Other components may be used alone or in combination of two or more.
• surfactant a surfactant having no fluorine atom is preferred.
• Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These various surfactants may be used alone or in combination of two or more.
• a nonionic surfactant alone, a combination of a nonionic surfactant and a cationic surfactant, a nonionic
• a combined use of an amphoteric surfactant and an amphoteric surfactant and a single use of an anionic surfactant are preferred, and a combined use of a nonionic surfactant and a cationic surfactant is more preferred.
• the ratio of the nonionic surfactant to the cationic surfactant is preferably 100/0 to 40/60 (mass ratio), and 97/3 to 40/60. (mass ratio) is more preferable.
• the total amount of surfactants per 100 parts by mass of polymer (A) may be 5 parts by mass or less. In this case, it is easy to reduce the adverse effect of the surfactant on the liquid repellency of the article treated with the present composition.
• nonionic surfactants examples include surfactants s 1 to s 6 described in paragraphs [0067] to [0095] of JP-A-2009-215370.
• Polyoxyethylene alkyl ethers are preferred as the surfactant s1 .
• Acetylene glycol ethylene oxide adducts are preferred as the surfactant s2.
• As the surfactant s3 an ethylene oxide propylene oxide polymer is preferred.
• cationic surfactants examples include surfactant s7 described in paragraphs [0096] to [0100] of JP-A- 2009-215370 .
• Surfactant s7 is preferably an ammonium salt in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene chain having a terminal hydroxyl group, and compound (4) is more preferred.
• R 7 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a polyoxyalkylene chain having a terminal hydroxyl group.
• the four R7 's may be the same or different, but the four R7 's are not hydrogen atoms at the same time.
• Z ⁇ is a counterion.
• Z - includes, for example, chloride ion, ethyl sulfate ion, and acetate ion.
• Examples of compound (4) include monostearyltrimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono(stearyl)monomethyldi(polyethylene glycol)ammonium chloride, di(beef tallow alkyl)dimethylammonium chloride, and dimethylmonococonutamine. Acetate can be mentioned.
• amphoteric surfactants examples include surfactant s8 described in paragraphs [0101] to [0102] of JP-A- 2009-215370 .
• the surfactant s is preferred because it has little adverse effect on the liquid repellency of the article treated with the present composition and because the dispersion containing the polymer (A) has excellent dispersion stability.
• Surfactant s 2 and Surfactant s 7 Surfactant s 1 with Surfactant s 3 with Surfactant s 7
• Surfactant s 1 with Surfactant s 2 A combination of surfactant s3 and surfactant s7 is preferred. In these combinations, surfactant s7 is more preferably compound ( 4 ).
• polymers other than polymer (A) include, for example, at least one selected from the group consisting of units (b), units (c), units (d), units (e) and other monomer units. and having no unit (a) (hereinafter also referred to as "polymer (B)").
• the Mw of the polymer (B) may be from 5,000 to 100,000, or from 10,000 to 80,000.
• Mn of polymer (B) may be 2,500 to 50,000, or 5,000 to 40,000.
• water-soluble polymer resins examples include hydrophilic polyester and its derivatives, and hydrophilic polyethylene glycol and its derivatives.
• One of the water-soluble polymer resins may be used alone, or two or more of them may be used in combination.
• cross-linking agent examples include cross-linking agents described in paragraphs [0060] to [0063] of WO2019/172021.
• catalysts examples include cross-linking agents described in paragraph [0064] of WO2019/172021.
• the cross-linking agents and catalysts may be used singly or in combination of two or more.
• the content of the liquid medium can be appropriately selected according to the desired solid content concentration of the present composition.
• the solid content concentration of the composition is preferably 0.1 to 7% by mass, more preferably 0.2 to 5% by mass when the composition is used for treating articles.
• the content of the polymer (A) in the composition is preferably 60% by mass or more, more preferably 70% by mass or more, and may be 100% by mass with respect to 100% by mass of the solid content of the composition.
• the content of the polymer (A) is within the above numerical range, liquid repellency can be easily obtained when an article is treated with the present composition.
• the total content of the low-molecular-weight components in the present composition is preferably 0 to 30% by mass, more preferably 0.1-25% by mass, and 0.5-30% by mass, based on the total mass of the high-molecular-weight components and the low-molecular-weight components. 20% by mass is more preferred, and 1.0 to 15% by mass is particularly preferred.
• oil repellency can be easily obtained when an article is treated with the present composition.
• the content of the monomer (a) as the low-molecular-weight component is preferably 0-30% by mass, more preferably 0.1-25% by mass, and 0.1-25% by mass, based on the total mass of the high-molecular-weight component and the low-molecular-weight component. 5 to 20% by mass is more preferable, and 1.0 to 15% by mass is particularly preferable.
• the content of the monomer (a) is within the above numerical range, oil repellency can be easily obtained when an article is treated with the present composition.
• the content of the polymer (A) as a low-molecular component is preferably 0 to 30% by mass, more preferably 0.1 to 25% by mass, more preferably 0.5%, based on the total mass of the high-molecular component and the low-molecular component. ⁇ 20% by mass is more preferable, and 1.0 to 15% by mass is particularly preferable. If the content of the polymer (A) as the low-molecular-weight component is within the above numerical range, oil repellency can be easily obtained when an article is treated with the present composition.
• the total content of high-molecular-weight components and low-molecular-weight components is preferably 60% by mass or more, more preferably 70% by mass or more, and may be 100% by mass, relative to 100% by mass of the solid content of the composition.
• the content of the polymer (A) is preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, and even more preferably 0.1 to 35% by mass relative to 100% by mass of the present composition. .
• the content of the polymer (A) is at least the lower limit of the above numerical range, the present composition tends to impart liquid repellency to the article.
• the content of the polymer (A) is equal to or less than the upper limit of the above numerical range, the stability over time of the solution of the polymer (A) and the emulsified particles of the polymer (A) tends to be good.
• the present composition can be produced, for example, by a method of polymerizing a monomer component containing at least the monomer (a) in the presence of a polymerization initiator.
• the monomer component further contains at least one selected from the group consisting of monomer (b), monomer (c), monomer (d), monomer (e) and other monomers. You can
• each monomer is as described above. Further, the details and preferred aspects of the proportion of each monomer in the monomer component are the same as those described for the proportion of each unit in the polymer (A).
• polymerization initiators examples include thermal polymerization initiators, photopolymerization initiators, radiation polymerization initiators, radical polymerization initiators, and ionic polymerization initiators.
• a radical polymerization initiator is preferred.
• an azo polymerization initiator, a peroxide polymerization initiator, and a redox polymerization initiator are used depending on the polymerization temperature.
• an azo compound is preferable, and a salt of an azo compound is more preferable.
• the polymerization temperature is preferably 20 to 150°C.
• the amount of the polymerization initiator used is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the monomer component.
• a molecular weight modifier may be used when polymerizing the monomer component.
• molecular weight modifiers include aromatic compounds, mercaptoalcohols, mercaptocarboxylic acids, and alkylmercaptans. Among them, mercaptocarboxylic acid and alkyl mercaptan are preferable.
• Molecular weight modifiers include, for example, mercaptoethanol, mercaptopropionic acid, n-octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan, stearylmercaptan, ⁇ -methylstyrene dimer (CH 2 ⁇ C(Ph)CH 2 C( CH 3 ) 2 Ph).
• the amount of the molecular weight modifier used is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and may be 0 parts by mass with respect to 100 parts by mass of the monomer component.
• Examples of methods for polymerizing the monomer component include emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and the like. Among them, emulsion polymerization, solution polymerization, and bulk polymerization are preferred. Emulsion polymerization can be carried out, for example, by methods described in JP-A-8-3113, JP-A-2006-328624, JP-A-2015-172198, and JP-A-2017-025440. Solution polymerization can be carried out, for example, by the method described in WO2020/045407. After polymerization, if necessary, other components and liquid medium may be added.
• the monovalent hydrocarbon group with 8 to 24 carbon atoms which is the side chain of the unit (a) exists at a closer distance than in the case of polymerizing conventional long-chain alkyl (meth)acrylate units, resulting in excellent repellency. It is thought that liquid properties are expressed.
• Substrates include, for example, fibers, fabrics, textile products, glass, silicon wafers, paper substrates, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, porous quality goods.
• fabrics include woven fabrics, knitted fabrics, non-woven fabrics, and raised fabrics.
• textile products include clothing such as ski wear, rain wear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, and protective clothing, backpacks, bags, and tents.
• Paper includes, for example, paper, paperboard, pulp mold, synthetic paper using synthetic fibers as at least a portion of the raw material, and related products.
• Porous articles are used, for example, as filters.
• Materials for the porous article include, for example, polypropylene, polyethylene terephthalate, polytetrafluoroethylene, glass fiber, cellulose nanofiber, carbon fiber, and cellulose acetate.
• the type of fiber is not particularly limited.
• natural fibers such as cotton, wool, silk or cellulose
• synthetic fibers such as polyester, polyamide, acrylic or aramid
• regenerated fibers such as rayon, viscose rayon and lyocell
• blended fibers of natural and synthetic fibers and regenerated fibers
• materials when the substrate is a non-woven fabric include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, and rayon.
• the thickness of the fiber fabric is not particularly limited. For example, 0.01 to 5 mm.
• the treatment method may be any method as long as the present composition can adhere to the substrate.
• the substrate may be treated with the composition by various treatment methods such as coating, impregnation, immersion, spraying, brush-coated padding, size press, and roller, followed by drying. .
• the amount of solids in the composition that is deposited on the substrate is not particularly limited.
• the heating temperature is not particularly limited, but is, for example, 80 to 200.degree.
• Articles of the invention have a substrate treated with the composition. Therefore, the article of the present invention has a coating film with excellent liquid repellency.
• the details and preferred aspects of the substrate are the same as those described for the method of treating the substrate.
• the article of the present invention can be produced, for example, by the substrate treatment method described above.
• Poly-DSTF Poly distearyl fumarate (Mw: 14,000, Mn: 10,000)
• PMMA polymethyl methacrylate (Mw: 40,000, Mn: 28,000)
• Poly-STA polystearyl acrylate (Mw: 19,000, Mn: 11,000)
• Polymerization initiator VA-061A: 10 wt% aqueous solution of acetate of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] (VA-061, manufactured by Wako Pure Chemical Industries, Ltd.)
• Molecular weight modifier nStSH: n-octadecyl mercaptan
• Surfactant s 1 E-420: Polyoxyethylene (13) oleyl ether (manufactured by Kao Corporation, Emulgen 420)
• Surfactant s7 AQ-18: Stearyltrimethylammonium chloride (Lion Co., Ltd., Lipocard 18-63, active ingredient 63% by mass isopropyl alcohol solution)
• Liquid medium DPG: dipropylene glycol
• Cross-linking agent Makernate
• Test cloth for evaluation of water repellency and washing durability Dyed nylon cloth, PET cloth, and cotton were each immersed in the liquid repellent composition of each example, and squeezed so that the wet pick-up was 60% by mass. Subsequently, after drying at 110° C. for 90 seconds, it was dried at 170° C. for 60 seconds to obtain a test cloth.
• the test cloth was evaluated for water repellency according to the JIS L1092-2009 spray test.
• the water repellency was expressed in five grades from 1 to 5. A higher score indicates better water repellency.
• a "+" in the grade indicates that the respective property is slightly better than the standard in that grade.
• Grades marked with a "-" indicate that the respective property is slightly worse than the standard of the corresponding grade.
• washing durability The test cloth was washed 20 times or 50 times according to the washing method of JIS L0217 Appendix 103. After washing, the test fabric was air-dried overnight in a room at a room temperature of 25°C and a humidity of 60%, and the water repellency was evaluated as described above to evaluate the washing durability.
• the resulting reaction mixture was transferred to a 1 L separating funnel, and the organic layer was washed with a 1N hydrochloric acid aqueous solution and then with a saturated saline solution.
• the yield was 14.6 g and the yield was 25%.
• the 1 H-NMR spectrum of the obtained DSTF is shown below.
• Examples 1 to 6 A high-molecular-weight component and a low-molecular-weight component were dissolved in cyclopentyl methyl ether according to the formulation shown in Table 1 to obtain an oil repellent composition having a solid content concentration of 1% by mass.
• the oil repellent composition was applied by spin coating to the surface of a silicon wafer (3 cm long ⁇ 3 cm wide) washed with isopropyl alcohol, and dried at 40° C. for 1 hour to form a coating film.
• hexadecane contact angle The static contact angle with respect to n-hexadecane (hereinafter also referred to as “hexadecane contact angle”) is measured at three points, the center, left end, and right end of the formed coating film surface, and the average value of the three points is calculated. asked.
• the hexadecane contact angle conforms to JIS R 3257: 1999, and at 20°C, 2 ⁇ L of n-hexadecane droplets are placed at each point on the center, left edge, and right edge of the coating film surface. and measured by the sessile drop method for each drop. Table 1 shows the results.
• the coating films of the oil repellent compositions of Examples 1-3 had a larger hexadecane contact angle and superior oil repellency than those of Examples 4-6.
• Example 7 14.0 g of DSTF, 16.5 g of VSt, 1.1 g of MOI-BP, 0.3 g of StSH, 0.9 g of E-420, 0.2 g of P-204, AQ-18 in a polypropylene cup 0.3 g of , 10.3 g of DPG, and 57.7 g of deionized water were added and heated at 80° C. for 10 minutes. Then, they were mixed using a homomixer (manufactured by Nippon Seiki Seisakusho Co., Ltd., Biomixer) to obtain a mixed liquid.
• a homomixer manufactured by Nippon Seiki Seisakusho Co., Ltd., Biomixer
• the resulting mixture was treated at 40 MPa using a high-pressure emulsifier (MINILAB, manufactured by APV Lanier) to obtain an emulsion.
• a high-pressure emulsifier (MINILAB, manufactured by APV Lanier) to obtain an emulsion.
• 100 g of the obtained emulsion was placed in a glass ampoule and cooled to 40° C. or lower.
• 0.9 g of VA-061A was added, 2.6 g of VdCl was introduced, and a polymerization reaction was carried out with stirring at 60° C. for 15 hours to obtain a copolymer emulsion.
• About 10 g of acetone was added dropwise to 1 g of the obtained emulsion, and the mixture was heated and stirred at 50° C. and cooled to precipitate a solid.
• the resulting solid was collected by filtration under reduced pressure to obtain a copolymer. Mw and Mn were measured for the copolymer thus obtained.
• the resulting copolymer emulsion was diluted with distilled water to adjust the solid content concentration to 0.5% by mass, 1.0% by mass and 1.5% by mass, respectively. Thereafter, Makernate TP-10 was added to each concentration of emulsion so that the concentration was 1.5% by mass to prepare liquid repellent compositions.
• the liquid repellent composition was evaluated for water repellency (water repellency after air drying) and water repellency after washing.
• Example 8-12 A copolymer emulsion was obtained in the same manner as in Example 7, except that the amount of each raw material charged was changed to the amount shown in Table 2. Mw and Mn were measured from each emulsion in the same manner as in Example 7. In Example 8, STA was placed in a polypropylene cup as the initial monomer component of the reaction. For the emulsion of the copolymer obtained in each example, a liquid repellent composition was prepared in the same manner as in Example 7, and water repellency (water repellency after air drying) and water repellency after washing were evaluated.
• Table 2 shows the measurement results of Mw, Mn, and Mw/Mn of the copolymer of each example together with the ratio of each monomer in the monomer component.
• Table 3 shows the evaluation results of water repellency and washing durability of each example. In Examples 7 to 11, water repellency and washing durability equal to or higher than those in Example 12 were obtained.
• a liquid repellent composition capable of imparting excellent liquid repellency while being hydrocarbon; a method for treating a substrate using the liquid repellent composition; An article comprising a coating is provided.

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• 2022
  • 2022-04-08 JP JP2023514631A patent/JPWO2022220198A1/ja active Pending
  • 2022-04-08 WO PCT/JP2022/017385 patent/WO2022220198A1/ja not_active Ceased
  • 2022-04-08 EP EP22788123.2A patent/EP4324860A4/en active Pending
  • 2022-04-08 CN CN202280028129.6A patent/CN117120577A/zh active Pending
• 2023
  • 2023-09-05 US US18/461,085 patent/US20230407107A1/en active Pending

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