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
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
  • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
  • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • 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
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D171/02—Polyalkylene oxides
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • 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
  • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
  • C09D5/1637—Macromolecular compounds
• • 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
  • 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
• • 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
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
• • 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
  • B05D2202/00—Metallic substrate
  • B05D2202/10—Metallic substrate based on Fe
• • 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
  • B05D5/083—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 involving the use of fluoropolymers

Definitions

• the present invention relates to a fluorine-containing coating agent for use on wet articles (i.e., articles that come into intermittent contact with tap water or rainwater) that comprises a composition in which a polymer and/or a partial (hydrolyzed) condensate thereof having a hydrolyzable silyl group or hydroxysilyl group in the molecule and a fluoropolyether group (structure consisting of repeating fluorooxyalkylene units) with a specific molar mass (number average molecular weight) and a specific fluorine content is uniformly dissolved in an organic solvent that does not have fluorine atoms in the molecule, and the fluorine-containing coating agent is preferably used on wet articles that can form a cured coating film with excellent water/oil repellency and abrasion resistance on the surface of the article by wet coating such as dip coating or brush coating, and also relates to an article for use in wet areas that has a layer made of the cured product of the coating agent,
• the surfaces of semiconductor manufacturing process components, mold components, precision equipment components, medical equipment parts, automobile parts, building materials, home appliances, office equipment, and household goods are generally treated to be water- and oil-repellent. This has created a demand for anti-fouling properties that make it difficult for water droplets, oil droplets, dust, water stains, fingerprints, sebum, processing residues, and other contaminants to adhere, or that make it easier to remove adhering contaminants.
• fluoropolyether group-containing compounds have very low surface free energy and therefore have water and oil repellency, chemical resistance, lubricity, release properties, and stain resistance. Taking advantage of these properties, they are widely used industrially as water and oil repellent and stain resistant agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, and more. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and although they can be applied to the surface of a substrate, it has been difficult to make the coating adhere to it.
• silane coupling agents are well known as agents that bond organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as coating agents for the surfaces of various substrates.
• Silane coupling agents have an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule.
• the hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating.
• the coating becomes a strong and durable coating as the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.
• compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, and that can form coatings on the substrate surface that are easily adhered to the substrate surface and have water and oil repellency, chemical resistance, lubricity, releasability, and stain resistance (Patent Documents 1 to 6: JP-T-2008-534696, JP-T-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, and JP-A-2015-199906).
• dry coating and wet coating are shown as methods for applying (coating) fluoropolyether group-containing polymers to substrates.
• a coating agent is used in which the fluoropolyether group-containing polymer is dissolved (diluted) in an organic solvent containing fluorine atoms in the molecule (fluorine-based organic solvent).
• the fluoropolyether group-containing polymer has a long-chain fluoropolyether structure, which improves the water- and oil-repellency of the surface after coating treatment.
• fluorine-based solvents are expensive compared to general non-fluorine-based organic solvents, and there is a demand to reduce the amount of fluorine-based solvents used from the perspective of cost as well.
• Patent Document 7 JP Patent Publication No. 9-326240
• a hardened coating is formed using a coating liquid in which a perfluoropolyether group-containing silane compound with a number-average molecular weight of about 2,000 (i.e., a molar mass of about 2,000 Da) is dissolved in an organic solvent that does not contain fluorine atoms in the molecule, but the scale removability and abrasion resistance of the hardened coating are insufficient.
• Patent Document 8 JP Patent Publication No. 4363388
• Patent Document 9 JP Patent Publication No. 2022-118099
• hardened coatings are formed on embossed stainless steel substrates and chrome-plated metal substrates, respectively, using a coating liquid containing a perfluoropolyether group-containing silane compound, but the coating liquid uses an organic solvent that contains fluorine atoms in the molecule.
• the present invention has been made in consideration of the above circumstances, and aims to provide a fluorine-containing coating agent for use on articles used in wet environments, which comprises a fluoropolyether group-containing polymer composition uniformly dissolved (diluted) with a non-fluorine-based organic solvent and is capable of forming a cured coating film with excellent stain resistance and abrasion resistance, as well as an article for use in wet environments having a layer made of a cured product of a specific fluoropolyether group-containing polymer contained in the fluorine-containing coating agent, and a method for surface modification of an article for use in wet environments, which includes a step of applying the coating agent and curing it to form a layer.
• a fluorine-containing coating agent comprising a fluoropolyether group-containing polymer having a specific hydrolyzable silyl group or hydroxysilyl group described below and/or a partial (hydrolyzed) condensate thereof, in which the molar mass of the fluoropolyether group in the polymer is 2,500 Da or more and the fluorine content of the polymer (excluding trifluoromethyl groups present in the branched chains of the fluoropolyether group) is 50 mass% or less, can be dissolved uniformly in a non-fluorine-based organic solvent and can form a cured coating film that is excellent in stain resistance and abrasion resistance, thereby completing the present invention.
• a fluorine-containing coating agent for use on articles used in wet environments comprising a composition in which a fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group and/or a partial (hydrolyzed) condensate thereof is uniformly dissolved in an organic solvent having no fluorine atoms in the molecule, wherein the molar mass of the fluoropolyether group in the polymer is 2,500 Da or more and the fluorine content of the polymer (excluding trifluoromethyl groups present in the branched chains of the fluoropolyether group) is 50 mass% or less.
• the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group is represented by the following formula (1):
• Rf is a divalent fluoropolyether group having a molar mass of 2,500 Da or more
• A1 is a fluorine atom, a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or D, each D being independently a monovalent group represented by the following formula (2):
• m is 1 or 2
• G is a single bond or a trivalent organic group
• Q is independently a single bond, an oxygen atom, or a divalent organic group
• Z is independently a single bond or a tri- to octavalent group
• ⁇ is independently an integer of 1 to 7
• Y is independently a single bond or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon
• G is a single bond or the following formula: (In the formula, the bond on the left side is bonded to Rf, and the other bond is bonded to Q.) is a trivalent group represented by Q is a divalent group having an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms which may contain a single bond, an oxygen atom, an amide bond, an ether bond, a carbonyl bond, an ester bond, or one or more bonds selected from the group consisting of an amide bond, an ether bond, a carbonyl bond, an ester bond, a sulfide bond, a urethane bond, a siloxane bond, a triazine bond, a diorganosilylene bond, a silphenylene bond, and a silal
• X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.
• the fluorine-containing coating agent according to any one of [1] to [5], wherein the organic solvent having no fluorine atoms in the molecule is one or more organic solvents selected from isopropyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, hexane, n-heptane, ethyl acetate, isopropyl acetate, butyl acetate, tetrahydrofuran, isononane, isooctane, cyclopentanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
• the organic solvent having no fluorine atoms in the molecule is one or more organic solvents selected from isopropyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, hexane, n-heptane, ethyl acetate, isopropyl acetate
• An article for use in wet areas comprising a layer made of a cured product of a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group and/or a partial (hydrolyzed) condensate thereof, which is contained in the fluorine-containing coating agent according to any one of [1] to [6].
• Test environment conditions 25°C, humidity 50% RH
• the water contact angle of the friction-wear portion was measured every 2,500 reciprocating friction cycles, and the number of reciprocating friction cycles at which the water contact angle was maintained at 100° or more was defined as the number of reciprocating friction cycles for which the water contact angle was maintained at 100° or more.
• a surface modification method for an article for use in wet environments comprising a step of applying a fluorine-containing coating agent according to any one of [1] to [6] to the entire or part of the surface of the article by a dry or wet method, and curing the fluorine-containing coating agent to form a layer made of a cured product of a fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group and/or a partial (hydrolyzed) condensate thereof, contained in the fluorine-containing coating agent.
• the fluorine-containing coating agent of the present invention for use on articles for use in wet environments has a molar mass of fluoropolyether groups in the polymer having hydrolyzable silyl or hydroxysilyl groups and/or a partial (hydrolyzed) condensate thereof of 2,500 Da or more, and the fluorine content of the polymer (excluding trifluoromethyl groups present in the branched chains of the fluoropolyether groups) is 50 mass% or less.
• articles for housing facilities such as articles for use in wet environments having a layer made of a cured product such as a fluoropolyether group-containing polymer produced using the fluorine-containing coating agent of the present invention have excellent stain resistance and high abrasion resistance.
• the fluorine-containing coating agent of the present invention for use in articles used in wet areas comprises a composition in which a fluoropolyether group-containing polymer having a specific hydrolyzable silyl group or hydroxysilyl group and/or a partial (hydrolyzed) condensate thereof is uniformly dissolved in an organic solvent having no fluorine atoms in the molecule (non-fluorine-based organic solvent), and is characterized in that the molar mass of the fluoropolyether group in the polymer is 2,500 Da or more and the fluorine content of the polymer (excluding trifluoromethyl groups present in the branched chains of the fluoropolyether group) is 50 mass% or less.
• partial (hydrolysis) condensate refers to a partial condensate or a partial hydrolysis condensate.
• the molar mass (unit Da) of the fluoropolyether group is synonymous with the number average molecular weight of the fluoropolyether group.
• the molar mass (number average molecular weight) of the fluoropolyether group can be determined as the number average molecular weight (or number average degree of polymerization) of the polymethyl methacrylic acid resin by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent, but is preferably calculated from the characteristic peak intensity ratio of the terminal structure and main chain structure of the fluoropolyether group-containing polymer based on 1 H-NMR analysis and 19 F-NMR analysis (hereinafter the same).
• GPC gel permeation chromatography
• the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group is preferably one containing a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the following formula (1) and/or a partial (hydrolyzed) condensate thereof, and in particular, it is preferable that all of the fluoropolyether group-containing polymers having a hydrolyzable silyl group or a hydroxysilyl group are a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the formula (1) and/or a partial (hydrolyzed) condensate thereof.
• the fluorine-containing coating agent may contain a partial condensate obtained by partially condensing the hydroxyl groups of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the formula (1) or a partial hydrolyzed condensate obtained by condensing the hydroxyl groups obtained by partially hydrolyzing the hydrolyzable groups in the terminal hydrolyzable silyl groups of the fluoropolyether group-containing polymer in advance by a known method.
• Rf is a divalent fluoropolyether group having a molar mass of 2,500 Da or more
• A1 is a fluorine atom, a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or D, each D being independently a monovalent group represented by the following formula (2):
• m is 1 or 2
• G is a single bond or a trivalent organic group
• Q is independently a single bond, an oxygen atom, or a divalent organic group
• Z is independently a single bond or a tri- to octavalent group
• ⁇ is independently an integer of 1 to 7
• Y is independently a single bond or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond
• R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms
• X is independently
• the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the following formula (1), will be described.
• Rf is a divalent fluoropolyether group having a molar mass of 2,500 Da or more, and is preferably a divalent polyfluorooxyalkylene structure ( fluoropolyether structure consisting of repeating fluorooxyalkylene units)-containing group represented by -CdF2d - O-( CF2O ) p (C2F4O) q ( C3F6O) r ( C4F8O ) s ( C5F10O ) t ( C6F12O) u (WO) v - CdF2d- .
• fluoropolyether structure consisting of repeating fluorooxyalkylene units
• d is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, independently for each unit.
• p, q, r, s, t, u and v are each independently an integer of 0 to 150, preferably an integer of 0 to 100, more preferably an integer of 0 to 60, and the sum of p, q, r, s, t, u and v is an integer of 8 to 250, preferably an integer of 8 to 140, more preferably an integer of 8 to 70, and an integer such that the molar mass of the Rf is 2,500 Da or more.
• each of these units may be linear or branched.
• each repeating unit shown in parentheses with p, q, r, s, t, u and v may be randomly bonded.
• W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, and examples thereof include perfluoroalkylene groups such as CF2 units, C2F4 units, C3F6 units , C4F8 units , C5F10 units , and C6F12 units in which one or two fluorine atoms have been replaced by hydrogen atoms.
• the divalent fluoropolyether group of Rf can specifically be represented by the following structure.
• p', q', q2', r', and s' are each an integer of 1 to 150
• r2' and r3' are each an integer of 1 or more
• the sum of r2' and r3' is an integer of 2 to 150
• the sum of p', q', q2', r', r2', r3', and s' is each an integer of 8 to 250 and an integer such that the molar mass of Rf is 2,500 Da or more.
• each repeating unit shown in parentheses with p', q', r', and s' may be randomly bonded.
• A1 is a fluorine atom, a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or D (i.e., a monovalent group represented by formula (2) described below).
• the monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom is preferably a fluoroalkyl group or fluorooxyalkyl group having 1 to 7 carbon atoms, and particularly preferably a fluoroalkyl group having 1 to 4 carbon atoms or a fluorooxyalkyl group having 4 to 7 carbon atoms and whose polymer terminal is CF3- or CF2H- .
• Examples of such monovalent fluorine-containing hydrocarbon groups in which A 1 has a terminal CF 3 -- or CF 2 H-- and which may contain an oxygen atom include the following groups.
• a 1 is preferably a fluorine atom or D.
• D is independently a monovalent group represented by the following formula (2).
• G is a single bond or a trivalent organic group
• the trivalent organic group is Examples include the following groups: In the following structures, it is preferable that the bond on the left side is bonded to Rf, and the other bond is bonded to Q.
• Q is independently a single bond, an oxygen atom, or a divalent organic group
• Q other than a single bond or an oxygen atom is preferably an amide bond (e.g., an unsubstituted amide bond, an N-methyl substituted amide bond, an N-phenyl substituted amide bond), an ether bond, a carbonyl bond, an ester bond, or an amide bond (e.g., an unsubstituted amide bond, an N-methyl substituted amide bond, an N-phenyl substituted amide bond), an ether bond, a carbonyl bond, an ester bond, a sulfide bond, a urethane bond, a siloxane bond, a trivalent organic group, a It is an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms, preferably 2 to 15 carbon atoms, which may contain one or more bonds selected from the group consisting of an azine bond,
• examples of the silalkylene bond and silarylene bond include those shown below.
• R 1 is an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably an alkyl group having 1 to 4 carbon atoms, such as a phenyl group, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group, and R 1 may be the same or different.
• R 2 is an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, or a propylene group (trimethylene group, methylethylene group), or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.
• Examples of Q other than a single bond or an oxygen atom include the following groups: In the following structure, it is preferable that the left bond is bonded to Rf and the right bond is bonded to Z. (In the formula, t is an integer from 2 to 4.)
• Z is independently a single bond or a trivalent to octavalent group, preferably a single bond or a trivalent to octavalent, preferably a tri- or tetravalent group selected from trivalent to octavalent organopolysiloxane residues having silicon atoms, nitrogen atoms, and siloxane bonds, preferably linear, branched, or cyclic organopolysiloxane residues having 3 to 13 silicon atoms, more preferably 3 to 5 silicon atoms.
• silalkylene structure such as a silethylene structure in which two silicon atoms are bonded by an alkylene group such as an ethylene group (i.e., the silalkylene bond exemplified by Q above).
• Examples of the trivalent to octavalent organopolysiloxane residue having a siloxane bond include the linear, cyclic and branched organopolysiloxane residues shown below.
• R 1 is the same as above.
• g1 is an integer of 3 to 8, preferably 3 or 4.
• g2 is an integer of 3 to 8, preferably 3 or 4
• h1 is an integer of 0 to 8, preferably 0 or 1
• g2+h1 is an integer of 3 to 13, preferably an integer of 3 to 5, and each repeating unit shown in the parentheses enclosed by g2 and h1 may be randomly bonded.
• R 3 is R 1 or a group represented by the following formula (6): (In the formula, R1 is the same as above, h2 is an integer of 1 to 6, preferably 1, and the left bond is bonded to Si.)
• R 4 is a single bond or a group represented by the following formula (7): (In the formula, R 2 and R 3 are the same as above, j1 is an integer of 0 to 6, preferably an integer of 0 to 3, j2 is an integer of 0 to 6, preferably an integer of 0 to 2, j1+j2 is an integer of 1 to 10, preferably an integer of 1 to 3, and each repeating unit shown in the parentheses enclosed by j1 and j2 may be bonded randomly, and the bond on the left side is bonded to Si.) wherein, among all R 3 in the organopolysiloxane residue, 1 to 6 R 3 are groups represented by formula (6) and have 3 to 13 silicon atoms.
• Z other than a single bond examples include the following: In the following structure, it is preferable that the left bond is bonded to Q, and the other bond is bonded to Y.
• Y is independently a single bond, or a divalent hydrocarbon group which may have one or more selected from fluorine atoms, silicon atoms, and siloxane bonds.
• the divalent hydrocarbon group which may have one or more selected from fluorine atoms, silicon atoms, and siloxane bonds is a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms and containing a fluorine atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms (alkylene-arylene group), a divalent group in which alkylene groups are mutually bonded via a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cycl
• Y other than a single bond include the following: In the following structure, it is preferable that the left bond is bonded to Z and the right bond is bonded to a silicon atom.
• At least one of G, Q, Z, and Y is not a single bond.
• R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, of which the methyl group and the ethyl group are preferred.
• X is independently a hydroxyl group or a hydrolyzable group.
• hydrolyzable groups for X include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy groups; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy groups; acyloxy groups having 2 to 10 carbon atoms, such as acetoxy and propionoxy groups; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy, allyloxy, propenoxy, and isopropenoxy groups; and halogen groups, such as chlorine, bromo, and iodine groups. Among these, methoxy, ethoxy, isopropenoxy, and chlorine groups are preferred.
• a is independently 2 or 3 for each silicon atom to which it is bonded, and is preferably 3 from the viewpoints of reactivity and adhesion to the substrate.
• ⁇ which indicates the number of hydrolyzable silyl groups or hydroxysilyl groups, is independently an integer of 1 to 7, and preferably an integer of 1 to 5.
• m is 1 or 2.
• Examples of the group represented by the above formula (2) include those shown below.
• fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group represented by the above formula (1), include the following. (In the formula, A 1 and Rf are the same as above.)
• the molar mass of the fluoropolyether group (Rf) in the fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group represented by the above formula (1) is 2,500 Da or more, preferably 3,000 Da or more (i.e., the number average molecular weight of the fluoropolyether group (Rf) is 2,500 or more, preferably 3,000 or more). If the molar mass of the fluoropolyether group (Rf) is less than 2,500 Da (number average molecular weight is less than 2,500), a cured coating having excellent stain resistance and abrasion resistance cannot be obtained.
• the upper limit of the molar mass (number average molecular weight) of the fluoropolyether group (Rf) can usually be 10,000 Da, preferably about 6,000 Da (i.e., the upper limit of the number average molecular weight of the fluoropolyether group (Rf) is 10,000, preferably about 6,000).
• the fluorine content (excluding trifluoromethyl group atoms present in the branched chains of the fluoropolyether group) in the fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group represented by the above formula (1) is 50% by mass or less, preferably 45% by mass or less. If the fluorine content (excluding trifluoromethyl group atoms present in the branched chains of the fluoropolyether group) exceeds 50% by mass, the polymer cannot be dissolved uniformly in an organic solvent that does not have fluorine atoms in the molecule (non-fluorine-based organic solvent), and therefore a uniform cured coating cannot be formed.
• the lower limit of the fluorine content (excluding trifluoromethyl group atoms present in the branched chains of the fluoropolyether group) can usually be about 35% by mass, preferably about 38% by mass.
• fluorine content means the content (mass %) of fluorine atoms in the entire molecular formula of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group, represented by the above formula (1), provided that, in the case where a branched chain is present in the repeating unit (fluorooxyalkylene unit) constituting the fluoropolyether group Rf in the above formula (1), it means the content (mass %) of fluorine atoms in the molecular formula in which the trifluoromethyl group ( CF3 ) contained in the branched chain has been excluded (deleted) from the entire molecule.
• Such a fluorine content can be obtained, for example, by calculating the F atom content value (theoretical value) in elemental analysis of a molecular formula obtained by calculating the number of repetitions of each repeating unit (fluorooxyalkylene unit) constituting the fluoropolyether group Rf in a fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group represented by formula (1) from the intensity ratio of the characteristic peaks of the terminal structure and main chain structure of the fluoropolyether group-containing polymer based on 1 H-NMR analysis and 19 F-NMR analysis, or, in the case where the repeating unit (fluorooxyalkylene unit) has a branched chain, by assuming a molecular formula excluding (deleting) the trifluoromethyl group (CF 3 ) contained in the branched chain and calculating the F atom content value (theoretical value) in elemental analysis of a molecular formula excluding the contribution of the
• Methods for preparing a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group represented by formula (1) include, for example, the methods disclosed in JP 2022-19577 A (Patent Document 10), JP 2014-214194 A (Patent Document 11), and WO 2021/065537 A (Patent Document 12).
• the fluorine-containing coating agent of the present invention comprises a composition in which the above-mentioned fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group and/or its partial (hydrolyzed) condensate is uniformly dissolved in an organic solvent that does not have fluorine atoms in the molecule, and preferably consists of the composition.
• Examples of the organic solvent having no fluorine atom in the molecule include one or more organic solvents selected from isopropyl alcohol (also known as isopropanol), methyl isobutyl ketone, methyl ethyl ketone, hexane, n-heptane, ethyl acetate, isopropyl acetate, butyl acetate, tetrahydrofuran, isononane, isooctane, cyclopentanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
• isopropyl alcohol also known as isopropanol
• methyl isobutyl ketone methyl ethyl ketone
• hexane n-heptane
• n-heptane ethyl acetate
• isopropyl acetate butyl acetate
• tetrahydrofuran is
• the organic solvent may be a mixture of two or more of these, and is preferably one that uniformly dissolves the fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate.
• uniformly dissolved means that when the fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate is mixed with an organic solvent having no fluorine atoms in the molecule, the mixture is transparent with the naked eye and does not produce any turbidity or precipitate.
• the optimal concentration of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group and/or its partial (hydrolyzed) condensate to be dissolved in the organic solvent varies depending on the processing method, and may be any amount that is easy to weigh.
• direct coating it is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of the organic solvent and the fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group and/or its partial (hydrolyzed) condensate
• vapor deposition processing it is preferably 1 to 80 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the organic solvent and the fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group and/or its partial (hydrolyzed) condensate.
• the fluorine-containing coating agent of the present invention in which the fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate and the organic solvent having no fluorine atoms in the molecule are uniformly dissolved, may optionally be further blended with an organic solvent having fluorine atoms in the molecule (fluorine-containing organic solvent) as necessary, within a range that does not impair the effects of the present invention.
• organic solvent having fluorine atoms examples include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), etc.
• the ratio of the organic solvent that does not have fluorine atoms in its molecule to the total organic solvents in the fluorine-containing coating agent is 40% by mass or more and less than 100% by mass, and particularly 60 to 99% by mass.
• a hydrolysis and condensation catalyst such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.) may be added to the fluorine-containing coating agent of the present invention.
• an organotin compound dibutyltin dimethoxide, dibutyltin dilaurate, etc.
• an organotitanium compound tetra n-butyl titanate, etc.
• an organic acid acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.
• an inorganic acid hydroochloric acid, sulfuric acid, etc.
• the amount of the hydrolysis and condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or hydroxysilyl group and/or its partial (hydrolysis) condensate.
• Additives can be added to the fluorine-containing coating agent of the present invention as long as they do not impair the effects of the present invention.
• Specific examples include rust inhibitors, surfactants, antioxidants, antistatic agents, antibacterial agents, silane coupling agents, and primer components. Many of these additives can be dissolved uniformly in organic solvents that do not contain fluorine atoms in the molecule.
• the article of the present invention is characterized in that it is for use in wet areas and has a layer (also referred to as a cured layer or cured coating layer) made of a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or a cured product of its partial (hydrolysis) condensate, which is contained in the above-mentioned fluorine-containing coating agent.
• a layer also referred to as a cured layer or cured coating layer
• a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or a cured product of its partial (hydrolysis) condensate, which is contained in the above-mentioned fluorine-containing coating agent.
• the article is for use in wet areas and has a substrate and a cured layer (cured coating layer) made of the above-mentioned fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or a partial (hydrolysis) condensate, which is formed on the surface of the substrate.
• a cured layer cured coating layer
• the surface of the article of the present invention preferably has the following initial water contact angle, stain resistance, and abrasion resistance.
• the initial water contact angle (initial contact angle) on the surface of the article is preferably 105° or more, and more preferably 110° or more. If the water contact angle is equal to or greater than the above lower limit, sufficient initial antifouling properties can be ensured.
• the water contact angle on the surface of the article is measured by a method conforming to JIS R3257.
• the soil-resistant property of the surface of the article is preferably good or better, more preferably excellent, under the test conditions described below. If the test result is poor, the soil-resistant property of the cured coating is insufficient, and water-derived scale adhering to the surface of the article is difficult to remove.
• [Anti-soiling test conditions] - Removability of scale derived from tap water on the surface of the cured material layer provided on a SUS304 (preferably SUS304BA finish) substrate: 0.2 mL of tap water was dropped onto the surface of the cured material layer, and dried for 24 hours under an environment of 25°C and 50% RH to form scale derived from tap water on the surface of the cured material layer.
• the scale was then removed by scrubbing with a Bemcot (M-3II, manufactured by Ozu Sangyo Co., Ltd.) moistened with pure water at a pressure of 200 g/ cm2 .
• the surface was visually inspected, and the scale was removed if the number of scrubbing attempts required to remove the scale was 3 or less, which was excellent, 5 or less, good, 20 or less, and unacceptable if more than 20.
• the abrasion durability (friction durability) on the surface of the article is preferably 10,000 times or more, more preferably 15,000 times or more, and even more preferably 20,000 times or more under the test conditions described below. If the abrasion durability (friction durability) is less than 10,000 times, the cured coating easily deteriorates due to cleaning, etc., and the water/oil repellency and stain resistance are not maintained for a long period of time.
• [Wear durability test conditions] Evaluation of wet cloth abrasion resistance using a reciprocating abrasion tester on the surface of a SUS304 substrate.
• Substrate material of the article SUS304 (preferably SUS304BA finish) Rubbing material: Bemcot (M-3II, Ozu Sangyo Co., Ltd.) moistened with pure water Load: 1 kgf Round trip distance: 40mm Reciprocating speed: 60 reciprocations/min. Test environment conditions: 25°C, humidity 50% RH The water contact angle of the friction-wear portion was measured every 2,500 reciprocating friction cycles, and the number of reciprocating friction cycles at which the water contact angle was maintained at 100° or more was defined as the number of reciprocating friction cycles for which the water contact angle was maintained at 100° or more.
• the soil resistance of the surface of the article can be made good or better and the abrasion resistance can be made the above value (friction durability of 10,000 times) or more.
• the surface modification method of the present invention (or the manufacturing method of the present invention) for an article is characterized by comprising a step of applying the above-mentioned fluorine-containing coating agent of the present invention to the whole or part of the surface of an article by a dry method or a wet method, and curing the agent to form a layer (also referred to as a cured layer or a cured coating layer) consisting of a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or a partial (hydrolyzed) condensate thereof, contained in the fluorine-containing coating agent.
• the fluorine-containing coating agent used in the present invention for wet-use articles can be applied (coated) to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition.
• the heating method during vapor deposition can be either resistance heating or electron beam heating, and is not particularly limited.
• the curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferable to apply the coating at 25 to 200°C, especially 25 to 80°C, for 30 minutes to 36 hours, especially 1 to 24 hours.
• the coating In the case of application by vapor deposition, it is preferable to apply the coating at a temperature range of 20 to 200°C, especially 25 to 80°C, for 30 minutes to 36 hours, especially 30 minutes to 24 hours. It may also be cured under humid conditions.
• the coating is diluted in a fluorine-based solvent to which moisture has been added beforehand, and hydrolyzed, i.e., Si-OH is generated, and then spray coating is performed, which results in rapid curing after coating.
• the thickness of the cured coating is selected appropriately depending on the type of substrate, but is usually 0.1 to 100 nm, and particularly 1 to 20 nm.
• the thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, X-ray fluorescence measurement, etc.
• the substrate of the article to be treated with the fluorine-containing coating agent used for the article for use in wet areas of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc.
• the fluorine-containing coating agent of the present invention can impart water and oil repellency, stain resistance, and abrasion resistance (wet abrasion resistance) to the substrate.
• a substrate treated with SiO2 can be preferably used as a base layer for the coating.
• the fluorine-containing coating agent of the present invention can be applied to the entire or part of the surface of an article for use in wet environments by a dry method (vapor deposition treatment) or a wet method (brushing, dipping, spraying, etc.), and then cured to form a layer, thereby modifying the surface of the article in terms of water and oil repellency, stain resistance, and abrasion resistance (wet abrasion resistance).
• the surface modification method of the present invention (method of manufacturing an article) is useful for surface modification of articles that come into intermittent contact with tap water or rainwater, particularly for anti-soiling coatings for sanitary products such as bathtubs, wash basins, and toilets, for anti-soiling coatings for window glass or tempered glass in automobiles, trains, and aircraft, for headlamp covers, and for anti-soiling coatings for exterior wall building materials and for kitchen building materials.
• the number average molecular weight of the fluoropolyether group in the fluoropolyether group-containing polymer is a value calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether group-containing polymer based on 1 H-NMR analysis and 19 F-NMR analysis
• the fluorine content is the content of fluorine atoms (mass%, theoretical value) in elemental analysis of the molecular formula in which the number of repeating units (fluorooxyalkylene groups) constituting the fluoropolyether group is calculated based on 1 H-NMR analysis and 19 F-NMR analysis, provided that, in the case where the repeating unit (fluorooxyalkylene group) has a branched chain, the content of fluorine atoms (mass%, theoretical value) in elemental analysis of the molecular formula in which the contribution of the trifluor
• Example 1 A coating agent was prepared by dissolving the compound (A) shown in the following formula in hexane to a concentration of 0.1% by mass. Visual observation showed that the compound (A) was transparently and uniformly dissolved in hexane.
• the coating agent was spray-coated on a stainless steel plate (SUS304BA) with a BA (bright annealing) surface finish, and left for 30 minutes in an atmosphere of 80°C and 80% RH humidity, and then held for 12 hours or more in an atmosphere of 25°C and 50% RH humidity to harden, forming a hardened coating layer (thickness 15 nm) of a fluoropolyether group-containing polymer.
• Example 2 A cured coating layer (film thickness 15 nm) was formed and evaluated in the same manner as in Example 1, except that the compound (B) shown in the following formula was dissolved in isopropyl acetate to a concentration of 0.1 mass % to prepare a coating agent. When visually observed, the compound (B) was transparent and uniformly dissolved in isopropyl acetate. The evaluation results of the initial contact angle, antifouling property, and abrasion durability are shown in Table 1.
• Example 3 A cured coating layer (film thickness 15 nm) was formed and evaluated in the same manner as in Example 1, except that the compound (C) shown in the following formula was dissolved in isopropyl alcohol to a concentration of 0.1 mass% to prepare a coating agent. When visually observed, the compound (C) was transparent and uniformly dissolved in isopropyl alcohol. The evaluation results of the initial contact angle, antifouling property, and abrasion durability are shown in Table 1.
• Example 1 A cured coating layer (thickness 15 nm) was formed and evaluated in the same manner as in Example 1, except that the compound (D) shown in the following formula was dissolved in isopropyl alcohol to a concentration of 0.1 mass% to prepare a coating agent. When visually observed, the compound (D) was transparent and uniformly dissolved in isopropyl alcohol. The evaluation results of the initial contact angle, antifouling property, and abrasion durability are shown in Table 1.
• a coating agent was prepared by mixing the compound (E) shown in the following formula with methyl ethyl ketone to a concentration of 0.1% by mass, but the mixture of compound (E) and methyl ethyl ketone became cloudy. It was not possible to form a cured coating by spray coating or to evaluate it.
• a coating agent was prepared by mixing compound (F) shown in the following formula with methyl ethyl ketone to a concentration of 0.1% by mass, but the mixture of compound (F) and methyl ethyl ketone became cloudy. It was not possible to form a cured coating by spray coating or to evaluate it.
• Example 4 A cured coating layer (film thickness 15 nm) was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving the compound (G) shown in the following formula in methyl ethyl ketone to a concentration of 0.1 mass %. When visually observed, the compound (G) was dissolved transparently and uniformly in methyl ethyl ketone. The evaluation results of the initial contact angle, antifouling property, and abrasion durability are shown in Table 1.

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