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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/001—General methods for coating; Devices therefor
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
• • 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
  • 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
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • 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
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

• the present invention relates to an article having a hardened coating layer formed on the surface of a fluoropolyether group-containing polymer (a compound having a fluorooxyalkylene group in the molecule) having a hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or a partial (hydrolyzed) condensate thereof, and a method for modifying the surface of the article.
• a fluoropolyether group-containing polymer a compound having a fluorooxyalkylene group in the molecule
• hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or a partial (hydrolyzed) condensate thereof and a method for modifying the surface of the article.
• the surface of the article has excellent stain resistance, abrasion resistance, and retention (slip resistance) of a fastener using a suction cup or the like.
• 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 small 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-, oil-, 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 objects, and although they can be applied to the surface of objects, it has been difficult to make the coating adhere to them.
• silane coupling agents are well known as agents that bond organic compounds to the surfaces of articles such as glass and cloth, and are widely used as coating agents for the surfaces of various articles.
• 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 hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc., resulting in a strong and durable coating.
• 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 surface of articles that are easily adhered to the 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).
• the present invention has been made in consideration of the above circumstances, and aims to provide an article having excellent slip resistance, stain resistance, and abrasion resistance, on the surface of which a cured coating layer of a fluoropolyether group-containing polymer (a compound having a fluorooxyalkylene group in the molecule) having a specific hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or a partial (hydrolyzed) condensate thereof is formed, and which is resistant to misalignment of an adhesive tape or suction cup; and a method for surface modification of an article, which includes a step of applying and curing a fluorine-containing coating agent containing the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or a partial (hydrolyzed) condensate thereof to form a cured coating layer having excellent slip resistance, stain resistance, and abrasion resistance.
• the present invention provides an article having a cured coating layer of the following fluoropolyether group-containing polymer and/or partial (hydrolyzed) condensate thereof formed on its surface, and a method for modifying the surface of the article.
• An article having a substrate and a cured coating layer 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 formed on the surface of the substrate The fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group is represented by the following formula (1): [In the formula, Rf is a divalent fluoropolyether group containing --(C 3 F 6 O) r -- (the repeating unit C 3 F 6 O has a branched structure, and the average of r is an integer of 30 to 200) and having a molar mass of 5,000 Da or more, and D is independently a monovalent organic group having a hydrolyzable silyl group or a hydroxyl-containing silyl group at the terminal.] The static friction coefficient of the article surface is 0.30 or more,
• 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.
• D independently represents the following formula (2): (In the formula, m is an integer of 1 to 3; G is a single bond or a trivalent or tetravalent organic group; Q is independently a single bond, an oxygen atom, or a divalent organic group; Z is independently a single bond or a trivalent 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 fluorine atoms, silicon atoms, and siloxane bonds; R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms; X is independently a hydroxyl group or a hydrolyzable group; and a is independently 2 or 3 for each silicon atom to which it is bonded.
• 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.) wherein Q is a single bond, an oxygen atom, an amide bond, an ether bond, a carbonyl bond, an ester bond, or a divalent group having an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms which may contain 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 silalkylene bond;
• 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.
• Rf is a divalent fluoropolyether group containing --(C 3 F 6 O) r -- (the repeating unit C 3 F 6 O has a branched structure, and the average of r is an integer of 30 to 200) and having a molar mass of 5,000 Da or more
• D is independently a monovalent organic group having a hydrolyzable silyl group or a hydroxyl-containing silyl group at the terminal.
• Rf is a divalent fluoropolyether group containing --(C 3 F 6 O) r -- (the repeating unit C 3 F 6 O has a branched structure, and the average of r is an integer of 30 to 200) and having a molar mass of 5,000 Da or more
• D is independently a monovalent organic group having a hydrolyzable silyl group or a hydroxyl-containing silyl group at the terminal.
• a partial (hydrolyzed) condensate thereof and then curing the fluorine-containing coating agent to
• D independently represents the following formula (2): (In the formula, m is an integer of 1 to 3; G is a single bond or a trivalent or tetravalent organic group; Q is independently a single bond, an oxygen atom, or a divalent organic group; Z is independently a single bond or a trivalent 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 fluorine atoms, silicon atoms, and siloxane bonds; R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms; X is independently a hydroxyl group or a hydrolyzable group; and a is independently 2 or 3 for each silicon atom to which it is bonded.
• 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.) wherein Q is a single bond, an oxygen atom, an amide bond, an ether bond, a carbonyl bond, an ester bond, or a divalent group having an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms which may contain 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 group, a silpheny
• 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. [8] or [9].
• the article of the present invention has a cured coating layer of a specific fluoropolyether group-containing polymer or its partial (hydrolyzed) condensate on its surface, and the cured coating has a high surface friction coefficient and excellent water and oil repellency and abrasion resistance, so it is also excellent in slip resistance, stain resistance, and abrasion resistance.
• the article having the cured coating of the present invention has excellent stain resistance, abrasion resistance, and retention (slip resistance) of fasteners such as adhesive tapes and suction cups.
• the article of the present invention is an article having a substrate and a cured coating layer 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 formed on the surface of the substrate, wherein the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group is represented by the following formula (1), and the article surface has a static friction coefficient of 0.30 or more, a dynamic friction coefficient of 0.25 or more, a water contact angle of 105° or more, and an abrasion durability count of 10,000 or more in the abrasion durability test described below.
• Rf is a divalent fluoropolyether group containing --(C 3 F 6 O) r -- (the repeating unit C 3 F 6 O has a branched structure, and the average of r is an integer of 30 to 200) and having a molar mass of 5,000 Da or more, and D is independently a monovalent organic group having a hydrolyzable silyl group or a hydroxyl-containing silyl group at the terminal.
• Substrate material of article chemically strengthened glass.
• Abrasive material nonwoven fabric moistened with pure water (Bencotto M-3II, manufactured by Ozu Sangyo Co., Ltd.). 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 term "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) converted into 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 used in the cured coating layer of the fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate of the present invention has hydrolyzable silyl groups or hydroxyl group-containing silyl groups at both ends of the polymer main chain containing fluoropolyether groups, the molar mass of the main chain fluoropolyether group is 5,000 Da or more, and the fluoropolyether group contains a specific fluoropolyether group containing a repeating structure of oxyalkylene units having a branched structure.
• the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group of the present invention includes a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group represented by the following formula (1), and it is particularly preferable that all of the fluoropolyether group-containing polymers having a hydrolyzable silyl group or a hydroxyl group-containing silyl group are the fluoropolyether group-containing polymers having a hydrolyzable silyl group or a hydroxyl group-containing silyl group represented by the formula (1).
• Rf is a divalent perfluoropolyether group containing -(C3F6O ) r- (the repeating unit C3F6O has a branched structure and the average of r is an integer of 30 to 200) and having a molar mass of 5,000 Da or more
• D is independently a monovalent organic group having a hydrolyzable silyl group or a hydroxyl-containing silyl group at the end, preferably a monovalent group represented by the following formula (2):
• m is an integer of 1 to 3;
• G is a single bond or a trivalent or tetravalent organic group;
• Q is independently a single bond, an oxygen atom, or a divalent organic group;
• Z is independently a single bond or a trivalent 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
• Rf is a divalent fluoropolyether group containing -(C3F6O ) r- (the repeating unit C3F6O has a branched structure and the average of r is an integer of 30 to 200), and is preferably a divalent polyfluorooxyalkylene structure-containing group represented by -CdF2d - O-( CF2O ) p ( C2F4O ) q ( C3F6O) r ( C4F8O ) s ( C5F10O ) t ( C6F12O ) u (WO) v -CdF2d- (perfluoropolyether structure containing a repeating structure of perfluorooxyalkylene 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, 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 r is an integer of 30 to 200, preferably an integer of 30 to 150, more preferably an integer of 30 to 120.
• the sum of p, q, r, s, t, u and v is an integer of 30 to 200, preferably an integer of 30 to 140, more preferably an integer of 30 to 100, and the molar mass of Rf is 5,000 Da or more.
• the C3F6O unit has a branched structure, and each unit other than the C3F6O unit may be linear or branched.
• the repeating units shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.
• 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.
• Rf the following is preferable. (In the formula, q1, r1, and r2 are each an integer of 1 or more, and the sum of r1 and r2 is an integer of 30 to 200.)
• Rf is more preferably as shown below. (In the formula, r1 and r2 are each an integer of 1 or more, and the sum of r1 and r2 is an integer of 30 to 200.)
• the molar mass of Rf which represents the main chain fluoropolyether group in the above formula (1), must be 5,000 Da or more, but is usually 5,000 to 35,000 Da, preferably 5,000 to 25,000 Da, and more preferably about 5,000 to 20,000 Da. If the molar mass (number average molecular weight) of the main chain fluoropolyether group (Rf) is less than 5,000 Da, a hardened coating layer (surface treatment layer) with excellent abrasion resistance cannot be obtained.
• D-Rf-D D is independently a monovalent organic group having a hydrolyzable silyl group or a hydroxyl-containing silyl group at its terminal, and is preferably a monovalent group represented by the following formula (2):
• G is a single bond or a trivalent or tetravalent organic group, and examples of the trivalent or tetravalent organic group include the following groups:
• 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 a trivalent to octavalent organopolysiloxane residue having a silicon atom, a nitrogen atom, and a siloxane bond, preferably a linear organopolysiloxane residue having 3 to 13 silicon atoms, more preferably 3 to 5 silicon atoms, or a branched or cyclic organopolysiloxane residue 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 those shown below.
• the left bond is bonded to Z and the right bond is bonded to a silicon atom.
• 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 from 1 to 7, and preferably an integer from 1 to 5.
• m is an integer from 1 to 3, preferably 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 a hydroxyl group-containing silyl group represented by the above formula (1) examples include the following. (In the formula, Rf is the same as above.)
• Examples of 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 the methods disclosed in JP-A-2022-019577 and JP-A-2014-214194.
• a cured coating layer is formed on the surface of a substrate using a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group represented by the above formula (1).
• the substrate in 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., but glass or metal is particularly preferred.
• a substrate treated with SiO2 can be suitably used as a base layer for the coating. That is, it is preferred to have an intermediate layer of silicon oxide between the substrate and the hardened coating layer of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or its partial (hydrolysis) condensate.
• the surface of the article of the present invention is characterized by having the following friction coefficients (static and kinetic friction coefficients), water contact angles, and abrasion resistance.
• the static friction coefficient and dynamic friction coefficient on the surface of the article are 0.3 (0.30) or more and 0.25 or more, respectively, under the test conditions described below, preferably 0.35 or more and 0.28 or more, more preferably 0.50 or more and 0.32 or more.
• the upper limits of the static friction coefficient and dynamic friction coefficient on the surface of the article are not particularly limited, but are, for example, 0.80 or less and 0.50 or less, respectively. If the static friction coefficient and dynamic friction coefficient are each equal to or greater than the above lower limits, sufficient slip resistance is ensured, and the retention of adhesive tapes, suction cups, and other fasteners is improved.
• the initial water contact angle (immediately after the formation of the cured coating) on the surface of the article is 105° or more, and preferably 110° or more. If the water contact angle is equal to or greater than the above lower limit, sufficient initial stain resistance can be ensured.
• the water contact angle on the surface of the article is measured by a method conforming to JIS R3257.
• the abrasion durability (friction durability) of the surface of the article is 10,000 times or more, preferably 15,000 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.
• Material of the article's substrate chemically strengthened glass.
• Abrasive nonwoven fabric moistened with pure water (Bencotto M-3II, manufactured by Ozu Sangyo Co., Ltd.). 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.
• this can be achieved by using a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group represented by the above formula (1) as the fluoropolyether group-containing polymer in the fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate for forming a cured coating (i.e., a polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group at both ends of the polymer main chain containing a fluoropolyether group, the molar mass of the main chain fluoropolyether group being 5,000 Da or more, and the fluoropolyether group having a specific fluoropolyether group containing a repeating structure of oxyalkylene
• the surface modification method of the present invention for an article is characterized by comprising a step of applying a fluorine-containing coating agent containing the above-mentioned fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or a partial (hydrolyzed) condensate thereof to the whole or part of the surface of the article by a dry method or a wet method, and curing the applied agent to form a cured coating layer.
• the fluorine-containing coating agent for forming the cured coating layer used in the present invention may contain a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group represented by the above formula (1) and/or a partial (hydrolyzed) condensate thereof, and a suitable solvent.
• an organic solvent containing fluorine is preferred, and examples of such a solvent include organic solvents of one or more mixtures selected from 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.), and fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.).
• fluorine-modified aliphatic hydrocarbon solvents perfluoroheptane, perfluorooctane, etc.
• fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benz
• the above solvents may be used in combination of two or more kinds, and it is preferable that the solvent is capable of uniformly dissolving the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group and/or its partial (hydrolyzed) condensate.
• the optimal concentration of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group (fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate) to be dissolved in the solvent varies depending on the processing method, and may be any amount that is easy to weigh.
• the concentration is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of the solvent and the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group (fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate).
• the concentration is preferably 1 to 100 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the solvent and the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group (fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate).
• a hydrolysis and condensation catalyst such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium 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.
• an organic tin compound dibutyltin dimethoxide, dibutyltin dilaurate, etc.
• an organic titanium 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 a hydroxyl group-containing silyl group represented by the above formula (1) and/or its partial (hydrolysis) condensate.
• the above-mentioned fluorine-containing coating agent can be applied (coated) to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition.
• the heating method during vapor deposition may 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 thickness of the cured coating is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, especially 1 to 20 nm.
• the resin when spray coating, the resin is diluted in a fluorine-based solvent to which moisture has been added beforehand, and then hydrolyzed, that is, Si-OH is generated, before spray coating, which results in quick curing after coating.
• the above-mentioned fluorine-containing coating agent is applied to the entire surface or a part of the surface of an article by a dry method (vapor deposition treatment) or a wet method (brushing, dipping, spraying, etc.), and then cured to form a cured coating layer, thereby modifying the surface of the article in terms of slip resistance, stain resistance, and abrasion resistance.
• the fluorine-containing coating agent used in the present invention can impart stain resistance and abrasion resistance to the above-mentioned substrate while maintaining the surface's slip resistance.
• Articles having the cured coating layer of the present invention include semiconductor manufacturing process parts, molds, electronic device housings such as smartphones and tablets, display panels, medical instruments, automobile interiors, building materials, household electrical appliances, office automation equipment, furniture, etc.
• the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
• the number average molecular weight of the fluoropolyether group in the fluoropolyether group-containing polymer was 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.
• a coating agent was prepared by dissolving compound (A) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20% by mass.
• a chemically strengthened glass substrate (GORILLA, Corning) having a SiO 2 film formed on the surface with a thickness of 10 nm was set in a resistance heating type vacuum deposition apparatus (VTR-350M, ULVAC Kiko Co., Ltd.), and 8 ⁇ L of the coating agent prepared above was dropped onto the resistance heating part, and the pressure was reduced. When the pressure inside the container was reduced to 3 ⁇ 10 -3 Pa or less, resistance heating was started.
• the power of resistance heating was adjusted so that the maximum evaporation rate in a quartz crystal film thickness gauge installed at a position about 20 cm away from the resistance heating part was 1.0 nm / sec. Resistance heating was continued for 100 seconds after the evaporation rate in the quartz crystal film thickness gauge decreased to 0.1 nm / sec. After waiting for 5 minutes to cool the apparatus, it was opened to the atmosphere to obtain a substrate having a coating film of a fluoropolyether group-containing polymer.
• the substrate with the coating film was aged for 12 hours or more in an environment of 25°C and 50% RH to harden the coating film, obtaining a substrate with a hardened coating layer made of a fluoropolyether group-containing polymer.
• Example 2 A cured film was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (B) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (B) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 3 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (C) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (C) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 4 A cured film was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (D) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (D) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 5 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (E) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (E) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 6 A cured film was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (F) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (F) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 7 A cured film was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (G) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (G) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 8 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (H) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (H) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 9 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (I) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20% by mass.
• a coating agent was prepared by dissolving compound (I) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20% by mass.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 10 A cured film was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (J) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (J) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 11 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (K) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• K dissolving compound represented by the following formula in ethyl perfluorobutyl ether
• Example 1 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (L) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (L) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 2 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (M) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• M dissolving compound represented by the following formula in ethyl perfluorobutyl ether
• Example 3 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (N) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (N) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 4 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (O) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• a coating agent was prepared by dissolving compound (O) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• the evaluation results for initial contact angle, friction coefficient, abrasion resistance, antifouling property, and retention of fixture are shown in Table 1.
• Example 5 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (P) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• P dissolving compound represented by the following formula in ethyl perfluorobutyl ether
• Novec 7200 manufactured by 3M
• Example 6 A cured coating was formed and evaluated in the same manner as in Example 1, except that a coating agent was prepared by dissolving compound (Q) represented by the following formula in ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to a concentration of 20 mass %.
• Q dissolving compound represented by the following formula in ethyl perfluorobutyl ether
• the number-average molecular weight of the fluoropolyether group portion is 5,000 or more (i.e., the molar mass is 5,000 Da or more), and the fluoropolyether group-containing polymer has hydrolytically decomposable groups at both ends of the fluoropolyether group, and/or a cured coating made from the partial (hydrolyzed) condensate thereof exhibited excellent stain resistance, abrasion resistance, and retention of fasteners such as suction cups.

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