Fluorine-containing coating agent, article, and method for modifying surface of article

Abstract

A fluorine-containing coating agent which contains a composition in which a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group and / or a partial (hydrolyzed) condensation product thereof are uniformly dissolved in an organic solvent having no fluorine atoms in the molecule, and wherein the molar mass of the fluoropolyether group in the polymer is 2500 Da or more; the fluorine content (excluding the trifluoromethyl group present in the branched chain of the fluoropolyether group) of the polymer is 50 mass% or less, and the polymer can form a cured coating film having excellent antifouling properties and wear durability when used in an article for use in a water site.

Description

Technical Field

[0001] The present invention relates to a fluorine-containing coating agent for use in articles intended for use in water areas (i.e., articles that come into intermittent contact with tap water or rainwater) comprising a fluorine-containing polymer composition uniformly dissolved (diluted) in an organic solvent having no fluorine atoms in its molecules, and in particular, comprising a composition comprising a polymer having a hydrolyzable silyl group or a hydroxysilyl group in its molecule and a fluorine-containing polyether group (a structure composed of repeating fluorooxyalkylene units) having a specific molar mass (number average molecular weight) and a specific fluorine content and / or a partial (hydrolyzed) condensate thereof, uniformly dissolved in an organic solvent having no fluorine atoms in its molecules. The present invention relates to a fluorine-containing coating agent for use in articles intended for use in water areas (i.e., articles that come into intermittent contact with tap water or rainwater), preferably capable of forming a cured film having excellent water- and oil-repellency and abrasion resistance on the surface of the article by wet coating such as dipping or brush coating, an article intended for use in water areas having a layer composed of a cured product of the coating agent, and a method for surface modification of an article intended for use in water areas comprising the steps of applying and curing the coating agent to form the layer. Background Art

[0002] Components for semiconductor manufacturing processes, mold components, precision equipment components, medical equipment parts, automotive parts, building materials, home appliances, OA equipment, and household goods are generally treated with water and oil repellent treatments. Therefore, they require antifouling properties that prevent the adhesion of dirt such as water droplets, oil droplets, dust, scale, fingerprints, sebum, and processing residues, or that facilitate the removal of adhered dirt.

[0003] Generally, the compound that contains fluoropolyether group is because its surface free energy is very little, therefore has water and oil repellency, chemical resistance, lubricity, demoulding property, antifouling property etc.Utilize its character, industrially, be widely utilized in the water and oil repellent antifouling agent of paper fiber etc., the lubricant of magnetic recording medium, oil repellent, releasing agent, cosmetics, protective film etc. of precision equipment.But its character also means non-adhesiveness, non-adhesiveness for other base materials, even can be coated on substrate surface, also be difficult to make its tunic close.

[0004] Silane coupling agents, on the other hand, are well-known for bonding organic compounds to the surfaces of substrates such as glass and cloth. They are widely used as coating agents for various substrate surfaces. Silane coupling agents contain an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) within a single molecule. The hydrolyzable silyl group undergoes a self-condensation reaction with moisture in the air, forming a film. This film chemically and physically bonds to the surface of glass, metal, etc. through the hydrolyzable silyl group, resulting in a durable and strong film.

[0005] Therefore, a composition is disclosed that uses a fluoropolyether group-containing polymer obtained by introducing a hydrolyzable silyl group into a fluoropolyether group-containing compound, thereby easily adhering to the surface of a substrate and forming a film having water and oil repellency, chemical resistance, lubricity, mold release properties, antifouling properties, etc. on the surface of the substrate (Patent Documents 1 to 6: JP-A-2008-534696, JP-A-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, JP-A-2015-199906).

[0006] About these prior arts, as the coating (coating) method of the polymer containing fluoropolyether group on the substrate, dry coating and wet coating are shown. In the case of wet coating, a coating agent for dissolving (diluting) the polymer containing fluoropolyether group in an organic solvent (fluorine-based organic solvent) containing fluorine atoms in the molecule is used. When the polymer containing fluoropolyether group has a long-chain fluoropolyether structure, the water- and oil-repellent properties of the surface after the film treatment are improved, but because the fluorine content in the polymer increases, the solubility in the organic solvent (non-fluorine-based organic solvent) not containing fluorine atoms in the molecule is extremely poor. When uniformly coating the surface of the material, it is necessary to dissolve (dilute) the low-molecular volatile organic solvent containing fluorine atoms in the molecule.

[0007] In recent years, due to environmental concerns, concerns about bioaccumulation, and toxicity, regulations on low-molecular-weight fluorinated compounds, such as PFOS (perfluorooctanesulfonic acid) and PFOA (perfluorooctanoic acid), have been tightened. The use of fluorinated solvents requires specialized removal equipment, unlike general non-fluorinated organic solvents, and enhanced safety measures for workers. Furthermore, fluorinated organic solvents are more expensive than general non-fluorinated organic solvents, and from a cost perspective, there is a need to reduce the amount of fluorinated solvents used.

[0008] In this social context, the amount of fluorinated solvents that can be used and the working environment have tended to be greatly restricted in recent years. There is a demand for compounds that can impart excellent properties (such as antifouling properties and wear durability) derived from fluorinated polymers (compounds containing fluoropolyether groups) to the surface of cured products without using fluorinated solvents.

[0009] About the article of water-using part purpose, the technology of preventing the dirt (dirt) of the metal salt of metal (that is, alkaline earth metals such as calcium and magnesium) contained in water from being precipitated is known so far.For example, in patent document 7 (Japanese Patent Publication No. 9-326240), a coating liquid in which a silane compound containing a perfluoropolyether group with a number average molecular weight of about 2000 (that is, a molar mass of about 2000Da) is dissolved in an organic solvent without fluorine atoms in the molecule is used to form a cured film, but the dirt removal and wear durability of the cured film are insufficient. In addition, in patent document 8 (Japanese Patent Publication No. 4363388) and patent document 9 (Japanese Patent Publication No. 2022-118099), respectively, for a stainless steel substrate that has been embossed and a metal substrate that has been chromium-plated, a coating liquid comprising a silane compound containing a perfluoropolyether group is formed, and an organic solvent comprising fluorine atoms in the molecule is used in the coating liquid.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Application No. 2008-534696

[0013] Patent Document 2: Japanese Patent Application No. 2008-537557

[0014] Patent Document 3: Japanese Patent Application Laid-Open No. 2012-072272

[0015] Patent Document 4: Japanese Patent Application Laid-Open No. 2012-157856

[0016] Patent Document 5: Japanese Patent Application Laid-Open No. 2013-136833

[0017] Patent Document 6: Japanese Patent Application Laid-Open No. 2015-199906

[0018] Patent Document 7: Japanese Patent Application Laid-Open No. 9-326240

[0019] Patent Document 8: Japanese Patent No. 4363388

[0020] Patent Document 9: Japanese Patent Application Laid-Open No. 2022-118099

[0021] Patent Document 10: Japanese Patent Application Laid-Open No. 2022-019577

[0022] Patent Document 11: Japanese Patent Application Laid-Open No. 2014-214194

[0023] Patent Document 12: International Publication No. 2021 / 065537 Summary of the Invention

[0024] Problems to be solved by the invention

[0025] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a fluorine-containing coating agent for use in articles for use in water areas, comprising a fluoropolyether group-containing polymer composition uniformly dissolved (diluted) in a non-fluorine-based organic solvent, capable of forming a cured film having excellent antifouling properties and abrasion durability; an article for use in water areas having a layer composed of a cured product of a specific fluoropolyether group-containing polymer contained in the fluorine-containing coating agent; and a surface modification method for an article for use in water areas, comprising the steps of applying and curing the coating agent to form a layer.

[0026] Means for solving problems

[0027] To achieve the above-mentioned object, the present inventors conducted intensive studies and, as a result, discovered that a fluorine-containing coating agent comprising a fluoropolyether group-containing polymer having a specific hydrolyzable silyl group or hydroxysilyl group and / or a partial (hydrolyzed) condensate thereof, wherein the molar mass of the fluoropolyether group in the polymer is 2500 Da or more and the fluorine content of the polymer (excluding trifluoromethyl groups present in the branched chains of the fluoropolyether groups) is 50% by mass or less, can be uniformly dissolved in a non-fluorine-based organic solvent and can form a cured film having excellent antifouling properties and abrasion durability, thereby completing the present invention.

[0028] Therefore, the present invention provides the following fluorine-containing coating agent, article, and method for modifying the surface of an article.

[0029] [1] A fluorine-containing coating agent comprising a composition in which a polymer containing a fluoropolyether group and having a hydrolyzable silyl group or a 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 2500 Da or more and the fluorine content of the polymer is 50% by mass or less, excluding trifluoromethyl groups present in the branched chains of the fluoropolyether group, and is used in articles for use in water-using areas.

[0030] [2] The fluorine-containing coating agent according to [1], wherein the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group is represented by the following formula (1):

[0031] [Chemistry 1]

[0032] A 1 —Rf—D (1)

[0033] Wherein, Rf is a divalent fluoropolyether group with a molar mass of 2500Da or more, A 1is a fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and optionally containing an oxygen atom, or D, D being independently a monovalent group represented by the following formula (2),

[0034] [Chemistry 2]

[0035]

[0036] In the formula, 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 trivalent to octavalent group, α is independently an integer from 1 to 7, Y is independently a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and a is independently 2 or 3 for each bonded silicon atom. However, at least one of G, Q, Z and Y is not a single bond.

[0037] [3] The fluorine-containing coating agent according to [2], wherein Rf in the formula (1) is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u (WO) v -C d F 2d -, wherein W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, d is independently an integer of 0 to 5 in each unit, p, q, r, s, t, u and v are each independently an integer of 0 to 150, the sum of p, q, r, s, t, u and v is an integer of 8 to 250 and an integer such that the molar mass of Rf is 2500 Da or more, each of these units may be linear or branched, and the repeating units represented by p, q, r, s, t, u and v may be randomly bonded.

[0038] [4] The fluorine-containing coating agent according to [2] or [3], wherein in the formula (2), G is a single bond or a trivalent group represented by the following formula; 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; and Z is a single bond or a trivalent to octavalent group selected from a silicon atom, a nitrogen atom, and a trivalent to octavalent organopolysiloxane residue having a siloxane bond.

[0039] [Chemistry 3]

[0040]

[0041] In the formula, the left-side binding end is bound to Rf, and the other binding ends are bound to Q.

[0042] [5] The fluorine-containing coating agent according to any one of [2] to [4], wherein in the formula (2), X is independently a group selected from 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.

[0043] [6] 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.

[0044] [7] An article for use in water-containing areas, comprising a layer composed 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 contained in the fluorine-containing coating agent according to any one of [1] to [6].

[0045] [8] The article for use in water-using areas according to [7], wherein the antifouling property of the surface of the cured product layer is good or better under the test conditions described below,

[0046] [Antifouling test conditions]

[0047] - Removability of scale from tap water on the surface of the cured layer provided on the SUS304 substrate

[0048] 0.2 mL of tap water was dropped onto the surface of the cured layer and dried for 24 hours under an environment of 25°C and 50% RH to form a scale derived from tap water on the surface of the cured layer. BEMCOT (M-3II, manufactured by Ozu Sangyo Co., Ltd.) moistened with pure water was used to measure the scale with a 200 g / cm 2 Rub with pressure to remove the scale, visually check the surface, and if the scale can be removed within 3 times, it is excellent, within 5 times, it is good, within 20 times, it is acceptable, and more than 20 times is unacceptable.

[0049] [9] The article for use in water-using areas according to [7] or [8], wherein the wear durability of the surface of the cured layer is 10,000 times or more under the test conditions described below,

[0050] [Wear durability test conditions]

[0051] - Evaluation of the durability of the cured product layer provided on the SUS304 substrate by wet cloth abrasion using a reciprocating abrasion tester

[0052] Base material of the item: SUS304

[0053] Abrasive: BEMCOT (M-3II, manufactured by Ozu Sangyo Co., Ltd.) moistened with pure water

[0054] Load: 1kgf

[0055] Reciprocating distance: 40mm

[0056] Reciprocating speed: 60 times / min

[0057] Test environment conditions: 25°C, humidity 50% RH

[0058] The water contact angle of the friction-worn portion was measured every 2500 friction reciprocating cycles, and the number of friction reciprocating cycles at which the water contact angle remained at or above 100° was defined as the wear endurance number.

[0059]

[10] A method for modifying the surface of an article for use in a water-containing area, comprising the steps of applying a fluorine-containing coating agent according to any one of [1] to [6] to the entire surface or a portion of the article by a dry method or a wet method, and curing the coating agent to form a layer consisting 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 contained in the fluorine-containing coating agent.

[0060] Effects of the Invention

[0061] The fluorine-containing coating agent used in articles for use in water-use areas according to the present invention has a fluorine-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group and / or a partial (hydrolyzed) condensate thereof having a molar mass of 2500 Da or more in the fluorine-containing polymer, and a fluorine content of 50% or less (excluding trifluoromethyl groups present in the branched chains of the fluorine-containing polymer) in the polymer. This allows the polymer to be uniformly dissolved (diluted) and applied (wet coating) in an organic solvent that does not contain fluorine atoms in its molecule (excluding fluorine-containing organic solvents), and provides a cured film exhibiting excellent antifouling properties and high wear durability. Furthermore, articles for use in water-use areas, such as residential appliances, having a layer composed of a cured product of a fluorine-containing polymer or the like produced using the fluorine-containing coating agent of the present invention exhibit excellent antifouling properties and high wear durability. DETAILED DESCRIPTION

[0062] [Fluorine-containing coating]

[0063] The fluorine-containing coating agent of the present invention for use in articles for use in water-using areas is characterized in that it comprises a composition in which a specific fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group and / or a partial (hydrolyzed) condensate thereof is uniformly dissolved in an organic solvent having no fluorine atoms in the molecule (a non-fluorine-containing organic solvent), the molar mass of the fluoropolyether group in the polymer being 2500 Da or more, and the fluorine content of the polymer (excluding trifluoromethyl groups present in the branched chains of the fluoropolyether groups) being 50% by mass or less.

[0064] It should be noted that, in the present invention, the so-called "partial (hydrolysis) condensate" refers to a partial condensate or a partially hydrolyzed condensate. In addition, in the present invention, 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 obtained as the number average molecular weight (or number average degree of polymerization) of the polymethyl methacrylate resin analyzed by gel permeation chromatography (GPC) using a fluorine-based solvent as a developing solvent. Preferably, it is obtained by 1 H-NMR analysis and 19 The characteristic peak intensity ratio of the terminal structure and the main chain structure of the fluoropolyether group-containing polymer analyzed by F-NMR was calculated (the same applies hereinafter).

[0065] The present invention is described in detail below.

[0066] In the fluorine-containing coating agent used in the article for use in water-using areas of the present invention, the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group preferably comprises a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the following formula (1) and / or a partial (hydrolysis) condensate thereof. It is particularly preferred that all of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group comprises a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the formula (1) and / or a partial (hydrolysis) condensate thereof. Specifically, the fluorine-containing coating agent may comprise 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 above formula (1), or a partial hydrolysis condensate obtained by condensing the hydroxyl groups of the terminal hydrolyzable silyl groups of the fluoropolyether group-containing polymer obtained by partially hydrolyzing the hydrolyzable groups in advance by a known method.

[0067] [Chemistry 4]

[0068] A 1 —Rf—D (1)

[0069] [wherein, Rf is a divalent fluoropolyether group having a molar mass of 2500 Da or more, A 1 is a fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and optionally containing an oxygen atom, or D, wherein D is independently a monovalent group represented by the following formula (2).

[0070] [Chemistry 5]

[0071]

[0072] (In the formula, 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 trivalent to octavalent group, α is independently an integer from 1 to 7, Y is independently a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and a is independently 2 or 3 for each bonded silicon atom. However, at least one of G, Q, Z, and Y is not a single bond.)]

[0073] The fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the following formula (1) will be described.

[0074] [Chemistry 6]

[0075] A 1 —Rf-D (1)

[0076] In the above formula (1), Rf is a divalent fluoropolyether group having a molar mass of 2500 Da or more, preferably a fluoropolyether group containing -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u (WO) v -C d F 2d - is a group having a divalent polyfluorooxyalkylene structure (a fluoropolyether structure composed of repeating fluorooxyalkylene units).

[0077] In each unit, d is independently an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0 or 1. p, q, r, s, t, u, and v are each independently an integer of 0 to 150, preferably an integer of 0 to 100, and more preferably an integer of 0 to 60. 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, and more preferably an integer of 8 to 70, and is an integer such that the molar mass of Rf is 2500 Da or greater. If the sum of p, q, r, s, t, u, and v is less than the upper limit, adhesion and curing properties are excellent. If it is greater than the lower limit, the characteristics of the fluoropolyether group can be fully utilized, which is preferred. These units may be linear or branched. Furthermore, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.

[0078] W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms, and examples thereof include CF2 unit, C2F4 unit, C3F6 unit, C4F8 unit, C5F 10 Unit, C6F 12 A group in which one or two fluorine atoms in each perfluoroalkylene group such as a unit are replaced by hydrogen atoms.

[0079] The divalent fluoropolyether group as Rf can be specifically represented by the following structure.

[0080] [Chemistry 7]

[0081]

[0082] (In the formula, p', q', q2', r', and s' are each an integer of 1 to 150, r2' and r3' are each an integer of 1 or greater, the total of r2' and r3' is an integer of 2 to 150, the total of p', q', q2', r', r2', r3', and s' is each an integer of 8 to 250, and the molar mass of Rf is an integer of 2500 Da or greater. In addition, the repeating units shown in parentheses with p', q', r', and s' may be randomly bonded.)

[0083] In the above formula (1), A 1 It is a fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and which may contain an oxygen atom, or D (i.e., a monovalent group represented by formula (2) described later). As the monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and which may contain an oxygen atom, preferably a fluoroalkyl group or a fluorooxyalkyl group having 1 to 7 carbon atoms can be listed, and it is particularly preferred that the polymer has a fluoroalkyl group having 1 to 4 carbon atoms or a fluorooxyalkyl group having 4 to 7 carbon atoms and the terminal CF3- or CF2H-.

[0084] As such A 1 The terminal of the monovalent fluorine-containing hydrocarbon group is CF3- or CF2H-, and may contain an oxygen atom. Examples of the monovalent fluorine-containing hydrocarbon group include the following groups.

[0085] [Chemistry 8]

[0086]

[0087] As A 1 , preferably a fluorine atom or D.

[0088] In the above formula (1), D is independently a monovalent group represented by the following formula (2).

[0089] [Chemistry 9]

[0090]

[0091] In the above formula (2), G is a single bond or a trivalent organic group. Examples of the trivalent organic group include the following groups. In the following structure, it is preferred that the left end is bonded to Rf and the other end is bonded to Q.

[0092] [Chemistry 10]

[0093]

[0094] In the above formula (2), Q is independently a single bond, an oxygen atom or a divalent organic group. As Q other than a single bond or an oxygen atom, preferably an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms, preferably 2 to 15 carbon atoms, 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 a bond which may contain one or more bonds selected from the group consisting of 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 triazine bond, a diorganosilylene bond (e.g., a dialkylsilylene bond such as a dimethylsilylene bond), a silarylene bond (e.g., a silphenylene bond) and a silalkylene bond (e.g., a silylene bond). Preferably, the unsubstituted or fluorine-substituted divalent hydrocarbon group having 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, which may contain the above bonds.

[0095] Among these, examples of the silanylene bond and the silanylene bond include the following bonds.

[0096] [Chemistry 11]

[0097]

[0098] (Where R 1 is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, or an aryl group having 6 to 10 carbon atoms, such as phenyl, 1 Can be the same or different. 2 It is an alkylene group having 1 to 4 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), or an arylene group having 6 to 10 carbon atoms, such as phenylene.

[0099] Examples of Q other than such a single bond and oxygen atom include the following groups: In the following structure, it is preferred that the left-side bonding end is bonded to Rf and the right-side bonding end is bonded to Z.

[0100] [Chemistry 12]

[0101]

[0102] (Wherein, t is an integer from 2 to 4.)

[0103] In the above formula (2), Z is independently a single bond or a trivalent to octavalent group, preferably a single bond, or a trivalent to octavalent, preferably a trivalent or tetravalent, group selected from silicon atoms, nitrogen atoms, and trivalent to octavalent organopolysiloxane residues having a siloxane bond, preferably linear, branched, or cyclic organopolysiloxane residues having 3 to 13 silicon atoms, more preferably 3 to 5 silicon atoms. Furthermore, a silalkylene structure such as a silylethylene structure in which two silicon atoms are bonded via an alkylene group such as an ethylene group (i.e., the silalkylene bond exemplified in the above Q) may be included.

[0104] Examples of the trivalent to octavalent organopolysiloxane residue having a siloxane bond include linear, cyclic, and branched organopolysiloxane residues shown below.

[0105] [Chemistry 13]

[0106]

[0107] [Where R 1 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 the repeating units shown in the brackets enclosed by g2 and h1 can be randomly combined. R 3 R 1 Or by the following formula (6)

[0108] [Chemistry 14]

[0109]

[0110] (Where R 1 As above, h2 is an integer of 1 to 6, preferably 1, and the left end is bonded to Si.

[0111] The group represented by R 4 is a single bond or is represented by the following formula (7)

[0112] [Chemistry 15]

[0113]

[0114] (Where R 2 、R 3 As described 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 brackets enclosed by j1 and j2 may be randomly bonded, and the left end of the bond is bonded to Si.)

[0115] However, the total R 3 Medium, 1 to 6 Rs 3 It is a group represented by formula (6) and has 3 to 13 silicon atoms.]

[0116] Examples of Z other than such a single bond include the following groups: In the following structure, it is preferred that the left-side bonding end is bonded to Q, and the other bonding ends are bonded to Y.

[0117] [Chemistry 16]

[0118]

[0119] [Chemistry 17]

[0120]

[0121] [Chemistry 18]

[0122]

[0123] [Chemistry 19]

[0124]

[0125] In the above formula (2), Y is independently a single bond or a divalent hydrocarbon group which may have one or more kinds selected from a fluorine atom, a silicon atom, and a siloxane bond. The divalent hydrocarbon group which may have one or more kinds selected from a fluorine atom, a silicon atom, and a siloxane bond is a group selected from an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms 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 bonded to each other 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 the bonding end of a divalent organopolysiloxane residue which is linear and has 2 to 10 silicon atoms or branched or cyclic and has 3 to 10 silicon atoms.

[0126] Specific examples of Y other than a single bond include the following groups: In the following structure, it is preferred that the left-side bonding end is bonded to Z and the right-side bonding end is bonded to a silicon atom.

[0127] [Chemistry 20]

[0128]

[0129] In the above formula (2), at least one of G, Q, Z and Y is not a single bond.

[0130] In the above formula (2), R is independently an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, or a phenyl group, and methyl and ethyl are preferred.

[0131] In the above formula (2), X is independently a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group of X include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups having 2 to 10 carbon atoms, such as acetoxy and propionyloxy; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy, allyloxy, propenyloxy, and isopropenyloxy; and halogen groups, such as chloro, bromo, and iodo. Among these, methoxy, ethoxy, isopropenyloxy, and chloro are preferred as X.

[0132] In the above formula (2), a is 2 or 3 per bonded silicon atom, and is preferably 3 from the viewpoint of reactivity and adhesion to the substrate.

[0133] In the above formula (2), α representing 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.

[0134] In the above formula (2), m is 1 or 2.

[0135] Examples of the group represented by the above formula (2) (ie, D in the formula (1)) include the following groups.

[0136] [Chemistry 21]

[0137]

[0138] [Chemistry 22]

[0139]

[0140] Examples of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the above formula (1) include the following polymers.

[0141] [Chemistry 23]

[0142]

[0143] [Chemistry 24]

[0144]

[0145] (where A 1 , Rf are the same as above.)

[0146] The molar mass of the fluoropolyether group (Rf) in the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the above formula (1) is 2500 Da or more, preferably 3000 Da or more (i.e., the number average molecular weight of the fluoropolyether group (Rf) is 2500 or more, preferably 3000 or more). If the molar mass of the fluoropolyether group (Rf) is less than 2500 Da (the number average molecular weight is less than 2500), a cured film having excellent antifouling properties and abrasion durability cannot be obtained. The upper limit of the molar mass (number average molecular weight) of the fluoropolyether group (Rf) is generally 10000 Da, preferably about 6000 Da (i.e., the upper limit of the number average molecular weight of the fluoropolyether group (Rf) is 10000, preferably about 6000).

[0147] In addition, the fluorine content in the polymer containing fluoropolyether group with hydrolyzable silyl or hydroxysilyl represented by above-mentioned formula (1) (however, not including the trifluoromethyl atom present in the branch chain of fluoropolyether group) is 50 mass % or less, preferably 45 mass % or less. When the above-mentioned fluorine content (however, not including the trifluoromethyl atom present in the branch chain of fluoropolyether group) exceeds 50 mass %, it cannot be uniformly dissolved in an organic solvent (non-fluorine organic solvent) that does not have fluorine atoms in the molecule, and therefore a uniform cured film cannot be formed. Furthermore, the lower limit of the above-mentioned fluorine content (however, not including the trifluoromethyl atom present in the branch chain of fluoropolyether group) can usually be set to 35 mass %, preferably to about 38 mass %.

[0148] In the present invention, the "fluorine content (excluding trifluoromethyl groups present in the branched chains of the fluoropolyether group)" means the content (mass %) of fluorine atoms in the entire molecular formula of the polymer containing a fluoropolyether group having a hydrolyzable silyl group or a hydroxysilyl group as shown in the above formula (1). However, in the case where the repeating unit (fluorooxyalkylene unit) constituting the fluoropolyether group Rf in the above formula (1) has a branched chain, it means the content (mass %) of fluorine atoms in the molecular formula excluding (deleting) the trifluoromethyl group (CF3) contained in the branched chain from the entire molecule. Such a fluorine content can be obtained, for example, by 1 H-NMR analysis and 19The content of F atoms in the fluoropolyether group-containing polymer is determined by calculating the ratio of the intensity of the characteristic peaks of the terminal structure and the main chain structure of the fluoropolyether group-containing polymer as determined by F-NMR analysis, and calculating the value (theoretical value) of the F atom content in the elemental analysis of the molecular formula based on the number of repetitions of each repeating unit (fluorooxyalkylene unit) constituting the fluoropolyether group Rf in the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group represented by the above formula (1). Alternatively, when the repeating unit (fluorooxyalkylene unit) has a branched chain, the molecular formula is assumed to exclude (delete) the trifluoromethyl group (CF3) contained in the branched chain, and calculating the value (theoretical value) of the F atom content in the elemental analysis of the molecular formula excluding the portion contributed by the trifluoromethyl group (CF3).

[0149] Examples of methods for preparing such a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group represented by formula (1) include methods disclosed in Japanese Patent Application Publication No. 2022-19577 (Patent Document 10), Japanese Patent Application Publication No. 2014-214194 (Patent Document 11), and International Publication No. 2021 / 065537 (Patent Document 12).

[0150] 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 a hydroxysilyl group and / or a partial (hydrolyzed) condensate thereof is uniformly dissolved in an organic solvent having no fluorine atoms in the molecule, and preferably consists of this composition.

[0151] Examples of the organic solvent having no fluorine atoms in its molecule include one or more organic solvents selected from the group consisting of 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. Two or more of these organic solvents may be mixed, and preferably, an organic solvent that uniformly dissolves the fluoropolyether group-containing polymer and / or its partial (hydrolyzed) condensate is preferred.

[0152] The term "uniformly dissolved" means that when the fluoropolyether group-containing polymer and / or its partial (hydrolysis) condensate is mixed with an organic solvent having no fluorine atoms in its molecule, the mixed solution is transparent without any turbidity or precipitation.

[0153] In the fluorine-containing coating agent of the present invention, the optimal concentration of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group and / or its partial (hydrolysis) condensate dissolved in the organic solvent varies depending on the treatment method, and any amount that can be easily weighed may be sufficient. In the case of direct coating, the optimal concentration is preferably 0.01 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total of the organic solvent and the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group and / or its partial (hydrolysis) condensate. In the case of vapor deposition, the optimal concentration is preferably 1 to 80 parts by mass, particularly preferably 3 to 30 parts by mass, relative to 100 parts by mass of the total of the organic solvent and the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group and / or its partial (hydrolysis) condensate.

[0154] Furthermore, in the fluorinated 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, an organic solvent having fluorine atoms in the molecule (fluorinated organic solvent) may be further added as needed, within the range that does not impair the effects of the present invention. Examples of such organic solvents having fluorine atoms (fluorinated organic solvents) include fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorinated aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorinated ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), and fluorinated alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.).

[0155] When an organic solvent having no fluorine atoms in its molecule and an organic solvent having fluorine atoms are used in combination, the ratio of the organic solvent having no fluorine atoms in its molecule to the total organic solvent in the fluorine-containing coating agent is preferably 40% by mass or more and less than 100% by mass, particularly preferably 60 to 99% by mass.

[0156] The fluorine-containing coating agent of the present invention may, if necessary, be added with a hydrolysis-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.). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly preferred.

[0157] The amount of the hydrolysis 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 hydroxysilyl group and / or its partial (hydrolysis) condensate.

[0158] Furthermore, the fluorine-containing coating agent of the present invention may contain any additives as long as they do not hinder the effects of the present invention. Specifically, examples include rust inhibitors, surfactants, antioxidants, antistatic agents, antibacterial agents, silane coupling agents, and primer components. Most of these additives are uniformly soluble in organic solvents that do not contain fluorine atoms in their molecules.

[0159] [thing]

[0160] The article of the present invention is characterized in that it is an article for use in water-containing areas having a layer (also referred to as a cured product layer or cured film layer) composed of a cured product 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 above-mentioned fluorine-containing coating agent. Specifically, it is preferably an article for use in water-containing areas having a substrate and a cured product layer (cured film layer) of 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 formed on the surface of the substrate.

[0161] The surface of the article of the present invention preferably has the following initial water contact angle, antifouling properties, and abrasion durability.

[0162] That is, in the article of the present invention, the initial water contact angle (initial contact angle) of the article's surface (immediately after the cured film is formed) is preferably 105° or greater, more preferably 110° or greater. When the water contact angle is above the above lower limit, sufficient initial antifouling properties can be ensured. The water contact angle of the article's surface is measured using a method in accordance with JIS R3257.

[0163] In articles having a layer composed of a cured product of the fluorinated coating agent of the present invention, the surface antifouling properties of the article are preferably good or better, more preferably excellent, under the test conditions described below. If the test result is unacceptable, the antifouling properties of the cured film are insufficient, and scale from water adhering to the surface of the article is difficult to remove.

[0164] [Antifouling test conditions]

[0165] - Removability of scale from tap water on the surface of the above-mentioned cured layer provided on a SUS304 (preferably SUS304BA finish) substrate

[0166] 0.2 mL of tap water was dropped onto the surface of the cured layer, and the layer was dried for 24 hours at 25°C and 50% RH to form a scale derived from tap water on the surface of the cured layer. BEMCOT (M-3II, manufactured by Ozu Sangyo Co., Ltd.) moistened with pure water was used to measure the scale with a 200 g / cm 2Rub with pressure to remove the scale, visually check the surface, and if the scale can be removed within 3 times, it is excellent, within 5 times, it is good, within 20 times, it is acceptable, and more than 20 times is unacceptable.

[0167] And then, in the article of the present invention, the wear durability (friction durability number) of the surface of the preferred article is more than 10,000 times under the test conditions of the following record, more preferably more than 15,000 times, further preferably more than 20,000 times.If the wear durability (friction durability number) is less than 10,000 times, then by cleaning etc., the cured film easily deteriorates and does not maintain water and oil repellency and antifouling property for a long time.

[0168] [Wear durability test conditions]

[0169] - Evaluation of the durability of SUS304 substrate surface after wet cloth abrasion using a reciprocating wear tester

[0170] Base material of the article: SUS304 (preferably SUS304BA finishing)

[0171] Abrasive: BEMCOT (M-3II, manufactured by Ozu Sangyo Co., Ltd.) moistened with pure water

[0172] Load: 1kgf

[0173] Reciprocating distance: 40mm

[0174] Reciprocating speed: 60 times / min

[0175] Test environment conditions: 25°C, humidity 50% RH

[0176] The water contact angle of the friction-worn portion was measured every 2500 friction reciprocating cycles, and the number of friction reciprocating cycles at which the water contact angle remained at or above 100° was defined as the wear endurance number.

[0177] Furthermore, in the present invention, by setting the molar mass of the fluoropolyether group (Rf) in the above-mentioned fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxyl group-containing silyl group contained in the fluorine-containing coating agent to 2500 Da or more (number average molecular weight of 2500 or more) and setting the fluorine content of the polymer (excluding trifluoromethyl groups present in the branched chains of the fluoropolyether group) to 50% by mass or less, it is possible to achieve good or better antifouling properties on the surface of the article and achieve abrasion durability of the above-mentioned value (friction durability of 10,000 times) or more.

[0178] [Surface Modification Method of Article / Method of Manufacturing Article]

[0179] The surface modification method of an article of the present invention (or the manufacturing method of an article of the present invention) is characterized by comprising the steps of applying the above-mentioned fluorinated coating agent of the present invention to the entire or a portion of the surface of the article by a dry method or a wet method, and curing the coating agent to form a layer (also referred to as a cured product layer or a cured film layer) composed of a cured product 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 fluorinated coating agent.

[0180] The fluorine-containing coating agent used in the article for use in the water part of the present invention can be imparted (coated) to the substrate by a known method such as brush coating, dipping, spraying, and vapor deposition. The heating method during the vapor deposition treatment may be a resistance heating method or an electron beam heating method, and is not particularly limited. In addition, the curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferably performed at 25 to 200°C, especially 25 to 80°C for 30 minutes to 36 hours, especially 1 to 24 hours. In the case of imparting by vapor deposition, it is preferably performed 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. In addition, it can be cured under humidification. For example, in spraying, it is diluted and hydrolyzed in a fluorine-based solvent to which water has been added in advance, that is, Si-OH is generated and then sprayed, and the curing after coating is fast.

[0181] The thickness of the cured film is appropriately selected depending on the type of substrate and is generally 0.1 to 100 nm, particularly 1 to 20 nm. The film thickness can be measured, for example, by spectroscopic reflectivity measurement, X-ray reflectivity measurement, spectroscopic ellipsometry, or fluorescent X-ray measurement.

[0182] The base material of the article of the fluorine-containing coating agent used in the article of water position purposes of the present invention is not particularly limited, can be the base material of various materials such as paper, cloth, metal and oxide thereof, glass, plastics, pottery, quartz.Fluorine-containing coating agent of the present invention can give water and oil repellency, antifouling property, wear durability (wet cloth abrasion resistance) to above-mentioned base material.Especially, as the base layer of this coating usefulness, can preferably use through SiO The base material of processing.

[0183] According to the present invention, the fluorine-containing coating agent of the present invention is applied and cured to form a layer on the entire or a portion of the surface of an article used in water-using areas using a dry method (evaporation treatment) or a wet method (brush coating, dipping, spraying, etc.), thereby modifying the surface of the article with respect to water and oil repellency, stain resistance and wear durability (wet cloth abrasion resistance).

[0184] Therefore, the surface modification method of the article (the manufacturing method of the article) of the present invention can be used for surface modification of articles that come into intermittent contact with tap water or rainwater, in particular, antifouling coatings for sanitary products such as bathtubs, washbasins, and toilets, antifouling coatings for window glass or tempered glass of automobiles, trains, aircraft, etc., antifouling coatings for headlight covers, etc., antifouling coatings for exterior building materials, antifouling coatings for kitchen building materials, etc.

[0185] Example

[0186] The present invention is described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. 1 H-NMR analysis and 19 The fluorine content is calculated based on the ratio of the characteristic peak intensity of the terminal structure and the main chain structure of the polymer containing fluoropolyether group by F-NMR analysis. 1 H-NMR analysis and 19 The fluorine atom content (mass %, theoretical value) in elemental analysis of the molecular formula was calculated based on the number of repetitions of the repeating units (fluorooxyalkylene) constituting the fluoropolyether group. However, if the repeating units (fluorooxyalkylene) have a branched chain, the fluorine atom content (mass %, theoretical value) in elemental analysis of the molecular formula is calculated by subtracting the contribution of the trifluoromethyl group (CF3) from the repeating units (fluorooxyalkylene units) containing the branched chain. Furthermore, the film thickness is a value measured by spectroscopic ellipsometry using a spectroscopic ellipsometer.

[0187] [Example 1]

[0188] The compound (A) shown in the following formula was dissolved in hexane in a manner to form a concentration of 0.1% by mass to prepare a coating agent. Visual observation showed that the compound (A) was transparent and uniformly dissolved in hexane. The coating agent was sprayed on a stainless steel plate (SUS304BA) with a surface finish of BA (Bright Annealing), and after being placed for 30 minutes at 80°C and a humidity of 80% RH, it was kept for more than 12 hours at 25°C and a humidity of 50% RH to cure, thereby forming a cured film layer (film thickness 15nm) of a polymer containing a fluoropolyether group.

[0189] [Chemistry 25]

[0190]

[0191] [Evaluation of initial contact angle]

[0192] The water contact angle of the surface of the cured film layer was measured under the following conditions in accordance with JIS R3257. The results are shown in Table 1.

[0193] Measuring device: DM-701 (manufactured by Kyowa Interface Science Co., Ltd.)

[0194] Measuring method: Liquid adaptation method

[0195] Water drop volume: 2μL

[0196] Contact angle analysis method: θ / 2 method

[0197] Temperature: 25℃

[0198] Humidity: 50% RH

[0199] [Evaluation of Antifouling Properties]

[0200] - Removability of scale from tap water on the surface of the cured film layer

[0201] 0.2 mL of tap water was dropped onto the surface of the SUS304 (BA finishing) substrate (i.e., the surface of the cured film layer) on which a cured film was formed, and the film was dried for 24 hours under an environment of 25°C and 50% RH. Scale from tap water was formed on the surface of the cured film layer. BEMCOT (M-3II, manufactured by Ozu Sangyo Co., Ltd.) moistened with pure water was used to measure the scale with a 200 g / cm 2 The scale was removed by rubbing with a pressure of 100° and visually inspecting the surface. Removal within three rubbing cycles was rated as excellent (◎), within five rubbing cycles was rated as good (○), within 20 rubbing cycles was rated as acceptable (△), and more than 20 rubbing cycles was rated as unacceptable (×). The results are shown in Table 1.

[0202] [Evaluation of wear durability]

[0203] - Evaluation of the durability of the cured film layer surface by wet cloth wear using a reciprocating wear tester

[0204] Base material of the article: SUS304 (BA finishing)

[0205] Abrasive: BEMCOT (M-3II, manufactured by Ozu Sangyo Co., Ltd.) moistened with pure water

[0206] Load: 1kgf

[0207] Reciprocating distance: 40mm

[0208] Reciprocating speed: 60 times / min

[0209] Test environment conditions: 25°C, humidity 50% RH

[0210] The water contact angle of the friction-worn portion was measured every 2500 friction reciprocating cycles, and the number of friction reciprocating cycles at which the water contact angle remained at or above 100° was defined as the wear endurance number.

[0211] [Example 2]

[0212] A cured film layer (15 nm thick) was formed and evaluated in the same manner as in Example 1, except that the coating agent was prepared by dissolving the compound (B) represented by the following formula in isopropyl acetate to a concentration of 0.1% by mass. Furthermore, visual observation revealed that the compound (B) dissolved transparently and uniformly in isopropyl acetate. The evaluation results of the initial contact angle, antifouling properties, and abrasion durability are shown in Table 1.

[0213] [Chemistry 26]

[0214]

[0215] [Example 3]

[0216] A cured film layer (15 nm thick) was formed and evaluated in the same manner as in Example 1, except that the compound (C) represented by the following formula was dissolved in isopropyl alcohol to a concentration of 0.1% by mass. Furthermore, visual observation revealed that the compound (C) dissolved transparently and uniformly in isopropyl alcohol. The evaluation results of the initial contact angle, antifouling properties, and abrasion durability are shown in Table 1.

[0217] [Chemistry 27]

[0218]

[0219] [Comparative Example 1]

[0220] A cured film layer (15 nm thick) was formed and evaluated in the same manner as in Example 1, except that the compound (D) represented by the following formula was dissolved in isopropyl alcohol at a concentration of 0.1% by mass. Furthermore, visual observation revealed that the compound (D) dissolved transparently and uniformly in isopropyl alcohol. The evaluation results of the initial contact angle, antifouling properties, and abrasion durability are shown in Table 1.

[0221] [Chemistry 28]

[0222]

[0223] [Comparative Example 2]

[0224] A coating agent was prepared by mixing the compound (E) represented by the following formula with methyl ethyl ketone to a concentration of 0.1 mass %. The mixed solution of the compound (E) and methyl ethyl ketone was turbid. The formation and evaluation of a cured film by spray coating could not be performed.

[0225] [Chemistry 29]

[0226]

[0227] [Comparative Example 3]

[0228] A coating agent was prepared by mixing the compound (F) represented by the following formula with methyl ethyl ketone to a concentration of 0.1% by mass. The mixed solution of the compound (F) and methyl ethyl ketone was turbid. The formation and evaluation of a cured film by spray coating could not be performed.

[0229] [Chemistry 30]

[0230]

[0231] [Comparative Example 4]

[0232] A cured film layer (15 nm thick) was formed and evaluated in the same manner as in Example 1, except that the coating agent was prepared by dissolving the compound (G) represented by the following formula in methyl ethyl ketone to a concentration of 0.1% by mass. Furthermore, visual observation showed that the compound (G) dissolved transparently and uniformly in methyl ethyl ketone. The evaluation results of the initial contact angle, antifouling properties, and abrasion durability are shown in Table 1.

[0233] [Chemistry 31]

[0234]

[0235] [Table 1]

[0236]

[0237] *: Fluorine content in the compound (polymer) (excluding trifluoromethyl groups in branched chains)

[0238] From the above results, a cured film formed using a fluorine-containing coating agent in which a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group and / or a partial (hydrolyzed) condensate thereof, wherein the molar mass of the fluoropolyether group is 2500 Da or more and the fluorine content of the polymer (excluding trifluoromethyl groups present in the branch chains of the fluoropolyether group) is 50% by mass or less, is uniformly dissolved in an organic solvent having no fluorine atoms in the molecule, exhibits excellent antifouling properties and abrasion durability.

Claims

1. A fluorine-containing coating agent comprising a composition in which a fluoropolyether group-containing polymer having a hydrolyzable silyl group or a 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 2500 Da or more and the fluorine content of the polymer is 50% by mass or less, excluding trifluoromethyl groups present in branched chains of the fluoropolyether group, and the composition is used for articles intended for use in water-using areas.

2. The fluorine-containing coating agent according to claim 1, wherein The fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group is represented by the following formula (1): [Chemistry 1] A 1 -Rf-D (1) Wherein, Rf is a divalent fluoropolyether group with a molar mass of 2500Da or more, A 1 is a fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and optionally containing an oxygen atom, or D, D being independently a monovalent group represented by the following formula (2), [Chemistry 2] In the formula, 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 trivalent to octavalent group, α is independently an integer from 1 to 7, Y is independently a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and a is independently 2 or 3 for each bonded silicon atom. However, at least one of G, Q, Z and Y is not a single bond.

3. The fluorine-containing coating agent according to claim 2, wherein Rf of the formula (1) is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u (WO) v -C d F 2d -, wherein W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, d is independently an integer of 0 to 5 in each unit, p, q, r, s, t, u and v are each independently an integer of 0 to 150, the sum of p, q, r, s, t, u and v is an integer of 8 to 250 and an integer such that the molar mass of Rf is 2500 Da or more, each of these units may be linear or branched, and the repeating units represented by p, q, r, s, t, u and v may be randomly bonded.

4. The fluorine-containing coating agent according to claim 2, wherein In the formula (2), G is a single bond or a trivalent group represented by the following formula; 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; Z is a single bond or a trivalent to octavalent group selected from a silicon atom, a nitrogen atom, and a trivalent to octavalent organopolysiloxane residue having a siloxane bond; [Chemistry 3] In the formula, the left-side binding end is bound to Rf, and the other binding ends are bound to Q.

5. The fluorine-containing coating agent according to claim 2, wherein In the formula (2), X is independently selected from 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 claim 1 , wherein The organic solvent having no fluorine atom 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.

7. An article for use in areas where water is used, comprising a layer composed of a cured product of the fluoropolyether group-containing polymer having a hydrolyzable silyl group or a hydroxysilyl group and / or its partial (hydrolyzed) condensate contained in the fluorine-containing coating agent according to any one of claims 1 to 6.

8. The article for use in water-using areas according to claim 7, wherein The antifouling property of the surface of the cured product layer is good or better under the test conditions described below, [Antifouling test conditions] - Removability of scale from tap water on the surface of the cured layer provided on the SUS304 substrate 0.2 mL of tap water was dropped onto the surface of the cured layer and dried for 24 hours under an environment of 25°C and 50% RH to form a scale derived from tap water on the surface of the cured layer. BEMCOT (M-3II, manufactured by Ozu Sangyo Co., Ltd.) moistened with pure water was used to measure the scale with a 200 g / cm 2 Rub with pressure to remove the scale, visually check the surface, and if the scale can be removed within 3 times, it is excellent, within 5 times, it is good, within 20 times, it is acceptable, and more than 20 times is unacceptable.

9. The article for use in water-using areas according to claim 7, wherein The wear durability of the surface of the cured product layer is 10,000 times or more under the test conditions described below. [Wear durability test conditions] - Evaluation of the durability of the cured product layer provided on the SUS304 substrate by wet cloth abrasion using a reciprocating abrasion tester Base material of the article: SUS304 Abrasive: BEMCOT (M-3II, manufactured by Ozu Sangyo Co., Ltd.) moistened with pure water Load: 1kgf Reciprocating distance: 40mm Reciprocating speed: 60 times / min Test environment conditions: 25°C, humidity 50% RH The water contact angle of the friction-worn portion was measured every 2500 friction reciprocating cycles, and the number of friction reciprocating cycles at which the water contact angle remained at or above 100° was defined as the wear endurance number.

10. A method for modifying the surface of an article for use in water-using areas, comprising the steps of applying the fluorine-containing coating agent according to any one of claims 1 to 6 to the entire surface or a portion of the surface of the article by a dry method or a wet method, and curing the coating agent to form a layer composed 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 contained in the fluorine-containing coating agent.

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