Article having cured product of surface treatment agent containing fluoropolyether group-containing polymer on surface

Abstract

Fluoropolyether Group-Containing Polymer Having Silanol Group and / or Hydrolyzable Silyl Group and / or Moiety Thereof (Hydrolysis), which is Capable of Forming Cured Coating Film Excellent in Water - and Oil-Repellency, Abrasion Resistance, and Droplet Sliding Properties To provide an article surface-treated with a surface treatment agent containing a condensate.SOLUTION: Fluoropolyether Group-Containing Polymer and / or Portion Thereof (Hydrolysis) An article having on its surface a cured product of a surface treatment agent comprising a condensate, wherein the fluoropolyether group-containing polymer is a polymer having three silanol groups or hydrolyzable silyl groups bonded to a hydrocarbon group having a linear siloxane bond at one terminal in the molecule.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an article having, on its surface, a cured product of a surface treatment agent containing a fluoropolyether group-containing polymer, and more particularly to an article having, on its surface, a cured product of a surface treatment agent containing a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, in which a silanol group (a hydroxyl group bonded to a silicon atom) or a hydrolyzable silyl group has been introduced, via a linking group, at one end of the molecule having a fluoropolyether group in the main chain. [Background technology]

[0002] In general, fluoropolyether group-containing compounds have very low surface free energy and therefore possess water- and oil-repellent properties, chemical resistance, lubricity, release properties, and stain resistance. Utilizing 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 substrates, and while they can be applied to the surface of a substrate, it has been difficult to make the coating adhere to it.

[0003] Silane coupling agents are well known as agents for bonding organic compounds to the surfaces of substrates such as glass and cloth, and 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) in one molecule. This hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating. This coating is durable and strong because the hydrolyzable silyl group chemically and physically bonds with the surface of various substrates.

[0004] Therefore, compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced at the ends of fluoropolyether group-containing compounds, which can form coatings that easily adhere to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, etc. on the substrate surfaces (Patent Documents 1 to 4).

[0005] Furthermore, it has been disclosed that substrates containing cured coatings such as lenses and anti-reflection films that have been surface-treated with a composition containing a fluoropolyether group-containing polymer in which a siloxane bond has been introduced as a linking group between the fluorooxyalkylene group-containing polymer residue (Rf) in the main chain of the fluoropolyether group-containing compound and the terminal hydrolyzable silyl group have excellent water repellency and good abrasion resistance against cloth and paper (Patent Documents 5 and 6).

[0006] However, substrates containing cured coatings used in certain applications, such as lenses such as eyeglass lenses and anti-reflective coatings, are required to have good water and oil repellency and abrasion resistance to cloth and paper, as well as good droplet removal properties, i.e., the ability to allow droplets to slide off.

[0007] The receding contact angle is one indicator of the ability of a droplet to slide off. The receding contact angle represents the contact angle at the final state where the end point does not move when the liquid is reduced from the equilibrium state. A low receding contact angle indicates that the droplet has a strong adhesive force to the substrate, making it difficult for the droplet to move. On the other hand, a high receding contact angle indicates that the adhesive force between the droplet and the substrate is weaker, indicating a high ability of the droplet to slide off.

[0008] In light of the above issues, it became necessary to develop an article that combines water and oil repellency, abrasion resistance, and droplet sliding properties (receding contact angle). [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-072272 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-157856 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-136833 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-199906 [Patent Document 5] Patent No. 6531833 [Patent Document 6] International Publication No. 2023 / 199768 Summary of the Invention [Problem to be solved by the invention]

[0010] Therefore, an object of the present invention is to provide an article having, on its surface, a cured product of a surface treatment agent containing a fluoropolyether group-containing polymer having silanol groups and / or hydrolyzable silyl groups and / or a partial (hydrolyzed) condensate thereof, which is capable of forming a cured coating that has excellent water and oil repellency, abrasion resistance, and liquid droplet sliding properties. [Means for solving the problem]

[0011] As a result of intensive research conducted by the present inventors to achieve the above-mentioned object, they discovered that a surface treatment agent containing a fluoropolyether group-containing polymer having, at one end of the molecule, three silanol groups or hydrolyzable silyl groups bonded to a hydrocarbon group having a linear siloxane bond and / or a partial (hydrolyzed) condensate thereof can form a cured coating that is excellent in water and oil repellency, abrasion resistance, and droplet sliding properties, which led to the completion of the present invention.

[0012] That is, by having a hydrocarbon group with a linear siloxane bond and three terminal silanol groups or hydrolyzable silyl groups at one end of the fluoropolyether group, which is the main chain, the linear siloxane bonds in the hydrocarbon group are concentrated in close positions within the molecule, and there are many contact points with the substrate, which further improves abrasion resistance, especially abrasion resistance against cloth and paper. Furthermore, because of the single-end structure, the fluoropolyether groups are oriented on the side opposite the contact points with the substrate, which also improves droplet sliding properties, leading to the present invention.

[0013] That is, the present invention provides the following articles. [1] An article having, on its surface, a cured product of a surface treatment agent containing a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, The fluoropolyether group-containing polymer is a polymer having, at one end of the molecule, three silanol groups or hydrolyzable silyl groups bonded to a hydrocarbon group having a linear siloxane bond. [2] The article according to [1], wherein the linear siloxane bond has 1 to 8 siloxane units. [3] The article according to [1] or [2], wherein the hydrocarbon group having a linear siloxane bond is a group represented by the following formula (1): [ka] (In the formula, G is a methyl group, an ethyl group, or a phenyl group, M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, b is a number from 3 to 4, and c is a number from 1 to 8.) [4] The article according to any one of [1] to [3], wherein the fluoropolyether group is a group represented by the following formula (2): [ka] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is a number from 1 to 6, p, q, r, s, t, u, and v are each a number from 0 to 450, and are numbers that satisfy the relationship p+q+r+s+t+u+v=10 to 450, and each repeating unit shown in parentheses with p, q, r, s, t, u, and v is linear or branched, and the arrangement order thereof is arbitrary.) [5] The article according to any one of [1] to [4], wherein the fluoropolyether group-containing polymer is represented by the following formula (3): [ka] (wherein RF is a fluorine atom or a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and optionally containing an oxygen atom, and Rf is a group represented by the following formula (2): [ka] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is a number from 1 to 6, p, q, r, s, t, u, and v are each a number from 0 to 450, and are numbers that satisfy the relationship p+q+r+s+t+u+v=10 to 450, and each repeating unit shown in parentheses with p, q, r, s, t, u, and v is linear or branched, and the arrangement order thereof is arbitrary.) wherein G is a methyl group, an ethyl group, or a phenyl group; M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms; 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; a is a number from 2 to 3; b is a number from 3 to 4; and c is a number from 1 to 8. [6] The article according to [5], wherein in formula (3), X is any 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. [7] The article according to [5] or [6], wherein in formula (3), G is a methyl group or a phenyl group. [8] The article according to any one of [5] to [7], wherein in formula (3), c is a number from 1 to 3. [9] The article according to any one of [5] to [8], wherein in formula (3), M is a linear or branched divalent hydrocarbon group having 1 to 3 carbon atoms.

[10] The article according to any one of [5] to [9], wherein the fluoropolyether group-containing polymer represented by formula (3) is any one of the polymers represented by the following formulas: [ka] (In the formula, RF represents a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom; p1 represents a number from 5 to 440; q1 represents a number from 5 to 250; p1+q1 represents a number that satisfies the range of 20 to 450; and the order of the repeating units shown in parentheses to which p1 and q1 are added is arbitrary.)

[11] The article according to any one of [1] to

[10] , wherein the surface treatment agent further contains a fluoropolyether group-containing polymer represented by the following formula (4) and / or a partial (hydrolyzed) condensate thereof: [ka] (In the formula, V is a monovalent hydrocarbon group or a hydrogen atom, RF is a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, and Rf is a group represented by the following formula (2): [ka] (wherein W is a fluoroalkylene group containing one or more hydrogen atoms, d is a number from 1 to 6, p, q, r, s, t, u, and v are each a number from 0 to 450, p+q+r+s+t+u+v is a number that satisfies the condition of 10 to 450, and each repeating unit shown in parentheses with p, q, r, s, t, u, and v is linear or branched, and the order of the repeating units is arbitrary), G is a methyl group, ethyl group, or phenyl group, M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, R is independently an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, a is a number from 2 to 3, b is a number from 3 to 4, and c is a number from 1 to 8.)

[12] The article according to any one of [1] to

[11] , wherein the surface treatment agent further contains a fluoropolyether group-containing polymer represented by the following formula (5): [ka] (In the formula, R F at both ends is independently a fluorine atom, or a monovalent fluorine-containing hydrocarbon group having a terminal CF — or CF H — and optionally containing an oxygen atom, and R f′ is a group represented by the following formula (2)′ [ka] (In the formula, p, q, r, and s are each a number from 0 to 450, p+q+r+s is a number that satisfies the range of 10 to 450, and p+q is a number that satisfies the range of 20 to 450, and the order of the repeating units shown in parentheses with p, q, r, and s is arbitrary.)

[13] The article according to any one of [1] to

[12] , wherein the surface treatment agent is for spray coating or vacuum deposition.

[14] The article according to any one of [1] to

[13] , wherein the article is a glass substrate, a film substrate, or a plastic substrate.

[15] The article according to

[14] , wherein the article is a resin product having a plasma-treated SiO2 surface.

[16] The article according to

[14] , wherein the article is a spectacle lens. [Effects of the Invention]

[0014] The article of the present invention having the cured product of the surface treatment agent on its surface is excellent in the water and oil repellency, abrasion resistance, and liquid droplet sliding property. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will be described in detail below.

[0016] The article of the present invention has on its surface a cured product of a surface treatment agent containing a fluoropolyether group-containing polymer and / or its partial (hydrolyzed) condensate, and the fluoropolyether group-containing polymer has, at one end of the molecule, three silanol groups or hydrolyzable silyl groups bonded to a hydrocarbon group having a linear siloxane bond. Hereinafter, the fluoropolyether group-containing polymer will also be referred to as "fluoropolyether group-containing polymer (A)." In this specification, a silanol group refers to a group having a silicon atom and at least one hydroxy group bonded to the silicon atom.

[0017] In the present invention, the number average molecular weight (Mn) of the fluoropolyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group and / or its partial (hydrolyzed) condensate, or the surface treatment agent can be determined by gel permeation chromatography (GPC) or 19 It can be calculated from the characteristic peak intensity ratio in F-NMR analysis. Fluorine-based solvents can be used as developing solvents for GPC.

[0018] In the present invention, the "partial (hydrolyzed) condensate" of the fluoropolyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group is obtained by partially condensing the hydroxyl groups of the fluoropolyether group-containing polymer (A) having a silanol group, or the hydroxyl groups of the fluoropolyether group-containing polymer (A) having a hydrolyzable silyl group obtained by partially hydrolyzing the hydrolyzable groups in advance by a known method.

[0019] In the hydrocarbon group having a linear siloxane bond of the fluoropolyether group-containing polymer (A), the linear siloxane bond preferably has 1 to 8 siloxane units, more preferably 1 to 3 siloxane units.

[0020] In the fluoropolyether group-containing polymer (A), the hydrocarbon group having a linear siloxane bond preferably has a linear siloxane bond in the middle of the hydrocarbon group, and more preferably is a hydrocarbon group represented by the following formula (1): [ka] (In the formula, G is a methyl group, an ethyl group, or a phenyl group, M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, b is a number from 3 to 4, and c is a number from 1 to 8.)

[0021] In formula (1), c, which represents the number of linked siloxane units, is a number from 1 to 8, and preferably a number from 1 to 3. If c exceeds 8, the distance from the polyfluoroether group in the main chain to the terminal silanol group or hydrolyzable silyl group increases, which may make curing difficult, and the fluorine content in the polymer decreases, which may prevent sufficient water repellency from being obtained.

[0022] In formula (1), G is a methyl group, an ethyl group, or a phenyl group, preferably a methyl group or a phenyl group, and more preferably a methyl group.

[0023] In formula (1), M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), and a butylene group (tetramethylene group, methylpropylene group).

[0024] Preferred examples of M include the following groups. [ka]

[0025] Specific examples of the hydrocarbon group represented by formula (1) include the following: [ka]

[0026] In the fluoropolyether group-containing polymer (A), the fluoropolyether group is preferably a group represented by the following formula (2). [ka] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is a number from 1 to 6. p, q, r, s, t, u, and v are each a number from 0 to 450. p+q+r+s+t+u+v is a number that satisfies the range of 10 to 450. Each of these units may be linear or branched. The repeating units shown in parentheses with p, q, r, s, t, u, and v may be arranged in any order.)

[0027] Throughout this specification, the phrase "the order of the repeating units may be arbitrary" means that the repeating units may be bonded alternately, randomly, or in blocks.

[0028] In formula (2), W is a fluoroalkylene group containing one or more hydrogen atoms, such as -CF2-, -C2F4-, -C3F6-, -C4F8-, -CF 10 -, -C6F 12 -, etc., in which one or two fluorine atoms have been substituted with hydrogen atoms.

[0029] In formula (2), d is independently a number of 1 to 6 for each unit, preferably a number of 1 to 3, and more preferably 1 or 2.

[0030] In formula (2), p, q, r, s, t, u, and v are each a number from 0 to 450. Preferably, p is a number from 5 to 440, q is a number from 5 to 250, r is a number from 0 to 180, s is a number from 0 to 100, t is a number from 0 to 100, u is a number from 0 to 100, and v is a number from 0 to 100. p+q+r+s+t+u+v is a number that satisfies the range of 10 to 450, preferably a number that satisfies the range of 20 to 200. When p+q+r+s+t+u+v is smaller than the upper limit, adhesion and curability are good, and when it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited. Each unit may be linear or branched. Furthermore, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be arranged in any order.

[0031] The fluoropolyether group is a polymer having a number average molecular weight of preferably 1,000 to 50,000, more preferably 2,000 to 20,000, where the number average molecular weight (Mn) can be calculated by the above-mentioned means.

[0032] Specific examples of the fluoropolyether group include the following: [ka] [ka] (In the formula, p', q', r', s', t', and u' each represent a number of 1 or greater, the upper limit of which is the same as the upper limit of p, q, r, s, t, and u above, and the sum of p', q', r', s', t', and u' is a number of 20 to 450. r2' and r3' each represent a number of 1 or greater, and the sum of r2' and r3' is a number of 35 to 180. The order of the repeating units shown in parentheses followed by p', q', r', s', t', and u' is arbitrary.)

[0033] The fluoropolyether group-containing polymer (A) is preferably represented by the following formula (3). [ka] (In the formula, RF is a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom; Rf is a divalent fluoropolyether group represented by the formula (2) above; G is a methyl group, ethyl group, or phenyl group; M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms; 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; a is a number from 2 to 3; b is a number from 3 to 4; and c is a number from 1 to 8.)

[0034] In formula (3), RF is a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom. The monovalent fluorine-containing hydrocarbon group preferably has 1 to 3 carbon atoms, and examples include CF3O-, CF3CF2O, CF2H-, CF2HCF2-, and CF3CF2CF2O-.

[0035] In formula (3), Rf is a divalent fluoropolyether group represented by formula (2) above, and for specific examples and preferred ranges thereof, see the above explanation of formula (2).

[0036] In formula (3), G, M, b, and c are the same as those in formula (1), and the explanation of specific examples, preferable ranges, etc. is referred to the explanation of formula (1).

[0037] In formula (3), R is 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, with a methyl group or an ethyl group being preferred.

[0038] In formula (3), a is 2 or 3, and is preferably 3 from the viewpoints of reactivity and adhesion to the substrate.

[0039] Examples of the fluoropolyether group-containing polymer represented by formula (3) include those represented by the following formula:

[0040] [ka] (In the formula, RF represents a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom; p1 represents a number from 5 to 440; q1 represents a number from 5 to 250; p1+q1 represents a number that satisfies the range of 20 to 450; and the order of the repeating units shown in parentheses to which p1 and q1 are added is arbitrary.)

[0041] Examples of methods for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3) include the following methods. A fluoropolyether polymer having alkenyl groups is dissolved in a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having SiH groups and silanol groups or hydrolyzable silyl groups (halogenated silyl groups, alkoxysilyl groups, etc.) and a linear siloxane bond is mixed with the resulting mixture. The resulting mixture is aged in the presence of a hydrosilylation catalyst, such as a 2-ethylhexanol solution of chloroplatinic acid, and in the presence of an acid catalyst, such as acetic acid, at a temperature of preferably 40 to 120°C, more preferably 60 to 100°C, and even more preferably about 80°C, for preferably 1 to 96 hours, more preferably 30 to 50 hours, and even more preferably about 40 hours. When an organosilicon compound having SiH groups and silanol groups or hydrolyzable silyl groups and a linear siloxane bond is used, the substituent (halogen atom) on the silyl group may be subsequently converted to another hydrolyzable group, such as an alkoxy group, e.g., a methoxy group.

[0042] Here, in the production of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3), an example of a fluoropolyether group-containing polymer having an alkenyl group is a fluoropolyether group-containing polymer represented by the following formula (3A): [ka] (In the formula, RF and Rf are the same as in formula (3), and b' is a number of 1 to 2.)

[0043] Examples of the fluoropolyether group-containing polymer having an alkenyl group represented by formula (3A) include the following. [ka] (In the formula, RF is CFO or CFCFO, p1 is a number from 5 to 440, q1 is a number from 5 to 250, p1+q1 is a number that satisfies 20 to 450, and the order of the repeating units shown in parentheses to which p1 and q1 are added is arbitrary.)

[0044] In the production of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3), when the fluoropolyether group-containing polymer having an alkenyl group is reacted with an organosilicon compound having a SiH group, a silanol group or a hydrolyzable silyl group, and a linear siloxane bond, the amount of the organosilicon compound used is preferably 1 to 30 equivalents, more preferably 8 to 24 equivalents, and even more preferably about 16 equivalents of SiH groups in the organosilicon compound relative to 1 equivalent of the olefin moiety (alkenyl group) in the fluoropolyether group-containing polymer.

[0045] In addition, when an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group and a linear siloxane bond in the molecule is used, and the organosilicon compound has a halogen atom as the hydrolyzable silyl group, the substituent (halogen atom) on the silyl group may be subsequently converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group. Examples of reagents that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, and butanol. The amount of this reagent used is preferably 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, per 100 parts by mass of the addition reaction product of a fluoropolyether group-containing polymer having an alkenyl group and an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group (such as a halogenated silyl group or an alkoxysilyl group) and a linear siloxane bond in the molecule.

[0046] In the production of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by formula (3), examples of the solvent include fluorine-based solvents. Examples of fluorine-based solvents include hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series) such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, and perfluorosolvents (manufactured by 3M, trade name: Fluorinert series) composed of fully fluorinated compounds. The amount of the solvent used can be preferably 10 to 300 parts by mass, more preferably 30 to 150 parts by mass, and even more preferably about 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having an alkenyl group.

[0047] In producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3), examples of the hydrosilylation reaction catalyst include platinum group metal catalysts such as platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., tetrakis(triphenylphosphine)palladium, chlorotris(triphenylphosphine)rhodium, etc. Preferred are platinum compounds such as vinylsiloxane coordination compounds. The amount of the hydrosilylation reaction catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (mass), relative to the mass of the fluoropolyether group-containing polymer having alkenyl and alkynyl groups at the molecular chain terminals.

[0048] For example, as a fluoropolyether group-containing polymer having an alkenyl group, a compound represented by the following formula: [ka] (p1 / q1=0.96, p1+q1=47) is used, and 1,1,3,3-tetramethyldisiloxane is used as the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, the compound represented by the following formula is obtained. [ka] (p1 / q1=0.96, p1+q1=47)

[0049] In the present invention, the surface treatment agent comprises a fluoropolyether group-containing polymer (A) and / or a partial (hydrolyzed) condensate thereof. The surface treatment agent may contain the above-mentioned fluoropolyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group as the main component, and may also contain unreacted raw materials or reaction intermediates prior to the introduction of terminal silanol groups or terminal hydrolyzable silyl groups into the fluoropolyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group. Furthermore, the surface treatment agent may also contain a partial (hydrolyzed) condensate obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer (A) or the hydroxyl groups obtained by partially hydrolyzing the terminal hydrolyzable silyl groups of the fluoropolyether group-containing polymer (A) in advance by a known method.

[0050] The surface treatment agent may contain, in addition to the main component, a fluoropolyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, a fluoropolyether group-containing polymer (B) represented by the following formula (4) and / or a partial (hydrolyzed) condensate thereof: [ka] (In the formula, V is a hydrogen atom or a monovalent hydrocarbon group, and RF, Rf, G, M, R, X, a, b, and d are the same as in formula (3).)

[0051] In formula (4), V is a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group is linear or branched and preferably has 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0052] In formula (4), RF represents a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom. For specific examples, preferred ranges, etc., see the above explanation for formula (3).

[0053] In formula (4), Rf is a divalent fluoropolyether group represented by formula (2) above, and for specific examples and preferred ranges thereof, please refer to the above explanations of formula (2) and formula (3) containing it.

[0054] In formula (4), G is a methyl group, ethyl group, or phenyl group, M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, 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, a is a number from 2 to 3, b is a number from 3 to 4, and c is a number from 1 to 8. For specific examples, preferred ranges, etc., see the explanation above for formula (3).

[0055] Examples of the fluoropolyether group-containing polymer (B) represented by formula (4) include the following. [ka] (In the formula, RF represents a fluorine atom or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom; p1 represents a number from 0 to 450; q1 represents a number from 0 to 450; p1+q1 represents a number satisfying the condition of 10 to 450; and the order of the repeating units shown in parentheses to which p1 and q1 are added is arbitrary.)

[0056] When blending the fluoropolyether group-containing polymer (B) represented by formula (4) and / or its partial (hydrolyzed) condensate, the amount used is not particularly limited, but is preferably 50% by mass or less, more preferably 0.1 to 50% by mass, and even more preferably 10 to 40% by mass, based on the mass of the fluoropolyether group-containing polymer (A) and / or its partial hydrolyzed condensate. The fluoropolyether group-containing polymer (B) represented by formula (4) has a lower viscosity and better handleability than the fluoropolyether group-containing polymer (A). Therefore, from the perspective of scale-up production, it is preferable to include the fluoropolyether group-containing polymer (B) represented by formula (4) to an extent that does not impair the effects of the present invention. If the content in the surface treatment agent is too high, problems with adhesion may occur.

[0057] The surface treatment agent may contain, in addition to the main component, a fluoropolyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, a fluoropolyether group-containing polymer (C) represented by the following formula (5): [ka] (In the formula, R F at both ends is independently a fluorine atom, or a monovalent fluorine-containing hydrocarbon group having a terminal CF — or CF H — and optionally containing an oxygen atom, and R f′ is a group represented by the following formula (2)′ [ka] (In the formula, p, q, r, and s are each a number from 0 to 450, p+q+r+s is a number that satisfies the range of 10 to 450, and p+q is a number that satisfies the range of 20 to 450, and the order of the repeating units shown in parentheses with p, q, r, and s is arbitrary.)

[0058] In formula (5), R represents a fluorine atom or a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and optionally containing an oxygen atom, and is the same as R in formula (3). For specific examples, preferred ranges, etc., see the above explanation of formula (3).

[0059] In formula (5), Rf' is a divalent fluoropolyether group represented by formula (2)', and in formula (2)', p, q, r, and s are each a number of 0 to 450. Preferably, p is a number of 5 to 440, q is a number of 5 to 250, r is a number of 0 to 180, and s is a number of 0 to 100. p+q+r+s is a number that satisfies the range of 10 to 450, and preferably a number that satisfies the range of 20 to 200. p+q is a number that satisfies the range of 20 to 450, and preferably a number that satisfies the range of 20 to 200.

[0060] Examples of the fluoropolyether group-containing polymer (C) represented by formula (5) include those shown below. [ka] (In the formula, p', q', r', s' and their sum are the same as p, q, r, and s in formula (2)'. The order of the repeating units shown in parentheses with p, q, r, and s is arbitrary.)

[0061] The amount of the non-functional polymer represented by formula (5) used when blended is not particularly limited, but is preferably 50 mass % or less, more preferably 0.1 to 50 mass %, and even more preferably 10 to 40 mass %, based on the mass of the fluoropolyether group-containing polymer (A) and / or its partial hydrolysis condensate. By blending the fluoropolyether group-containing polymer (C) represented by formula (5), it can be expected that the properties derived from the fluoropolyether group, such as water and oil repellency, can be improved, but if the amount exceeds the above range, problems with adhesion may occur.

[0062] In the surface treatment agent used in the present invention, the number average molecular weight of the composition containing the fluoropolyether group-containing polymer (A) and / or its partial (hydrolyzed) condensate, or the fluoropolyether group-containing polymer (A) together with the fluoropolyether group-containing polymer (B) and / or its partial (hydrolyzed) condensate, and / or the fluoropolyether group-containing polymer (C) is preferably 1,000 to 50,000, more preferably 2,000 to 20,000, even more preferably 2,500 to 10,000, and particularly preferably 3,000 to 8,000.

[0063] If necessary, the surface treatment agent may contain 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.). Of these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly preferred. The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is usually 5 parts by mass or less, preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer (A) and / or its partial (hydrolysis) condensate.

[0064] The surface treatment agent may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, tridecafluorooctane, hexafluoropropene trimer, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptenyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, hexafluoroisopropyl methyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are desirable in terms of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, tridecafluorooctane, and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether are particularly preferred.

[0065] The above-mentioned solvents may be mixed in two or more kinds, and it is preferable to dissolve the fluoropolyether group-containing polymer (A) and its partial (hydrolyzed) condensate uniformly. The optimum concentration of the fluoropolyether group-containing polymer (A) and its partial (hydrolyzed) condensate dissolved in the solvent varies depending on the treatment method, and may be an amount that is easy to measure. In the case of direct coating, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the solvent, the fluoropolyether group-containing polymer (A) and its partial (hydrolyzed) condensate. In the case of vapor deposition treatment, it is preferably 1 to 100 parts by mass, more preferably 3 to 30 parts by mass, per 100 parts by mass of the solvent, the fluoropolyether group-containing polymer (A) and its partial (hydrolyzed) condensate.

[0066] The method for producing the surface treatment agent used in the present invention is not particularly limited, and examples include a method in which the polymer components are added to a container, then diluted with a dilution solvent, and thoroughly mixed using a stirrer or shaker, or a method in which the individual polymer components are diluted and mixed to a predetermined concentration, and then the diluted solutions are further mixed together (using a stirrer or shaker for this mixing). Here, the polymer component is essentially a fluoropolyether group-containing polymer (A) having a silanol group or a hydrolyzable silyl group and / or its partial (hydrolyzed) condensate, and further a fluoropolyether group-containing polymer (B) represented by formula (4) and / or its partial (hydrolyzed) condensate, or a fluoropolyether group-containing polymer (C) represented by formula (5) may also be used as a polymer component.

[0067] The article of the present invention is manufactured by surface treatment with the above-described surface treatment agent. The manufacturing method of the article of the present invention is not particularly limited, but may include, for example, a step of applying the surface treatment agent to the substrate of the article and a step of curing the surface treatment agent.

[0068] In the step of applying the surface treatment agent to the substrate of an article, the surface treatment agent can be applied to the substrate by a known method such as brush coating, dipping, spraying, or vapor deposition. Spray coating and vacuum deposition are preferred modes. The heating method during the vapor deposition treatment may be either a resistance heating method or an electron beam heating method, and is not particularly limited.

[0069] In the step of curing the surface treatment agent, the curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), the curing temperature is preferably 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, particularly 1 to 18 hours. When applied by vapor deposition, the temperature is preferably in the range of 20 to 200°C. Curing may also be carried out under humid conditions. The thickness of the cured coating is selected appropriately depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. For example, in the case of spray coating, diluting the coating in a fluorine-based solvent containing added water and then hydrolyzing, i.e., generating Si—OH groups, before spray coating allows for rapid curing after coating.

[0070] The substrate of the article is not particularly limited and may be made of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, and quartz. Glass substrates, film substrates, and plastic substrates are preferred embodiments. The surface treatment agent used in the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO2-treated glass or film, or as a surface treatment agent for resin products having a plasma-treated SiO2 surface.

[0071] Examples of articles that can be treated with the surface treatment agent include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, and other optical articles. The surface treatment agent used in the present invention can prevent fingerprints and sebum from adhering to the articles and further impart scratch resistance, and is therefore particularly useful as a water- and oil-repellent layer for lenses, touch panel displays, anti-reflection films, and the like.

[0072] Furthermore, by using the surface treatment agent for use in the present invention to treat the surface of an article, it functions as an anti-fouling coating for sanitary products such as bathtubs and washbasins, an anti-fouling coating for window glass or tempered glass for automobiles, trains, aircraft, etc., and headlamp covers, a water- and oil-repellent coating for exterior wall building materials, an anti-grease stain coating for kitchen building materials, an anti-fouling and anti-poster / anti-graffiti coating for telephone booths, an anti-fingerprint coating for artworks, and an anti-fingerprint coating for compact discs, DVDs, etc. Furthermore, the fluoropolyether group-containing polymer (A) and / or its partial (hydrolyzed) condensate contained in the surface treatment agent also functions as a mold release agent for molds, a paint additive, a resin modifier, a flowability or dispersibility modifier for inorganic fillers, and a lubricity improver for tapes, films, etc.

[0073] In particular, the cured film obtained from the surface treatment agent used in the present invention can be endowed with excellent water and oil repellency, droplet sliding property and abrasion resistance. [Example]

[0074] The present invention will be described in more detail below with reference to synthesis examples, working examples, and comparative examples, but the present invention is not limited to these examples. In the following general formula, the repeating units indicated in parentheses with p1 and q1 are bonded randomly.

[0075] [Synthesis Example 1] With reference to Japanese Patent No. 6524955, a compound represented by the following formula (A) was prepared. [ka] (p1 / q1=0.96, p1+q1=47)

[0076] 10 g of a compound represented by formula (A), 10 g of 1,3-bis(trifluoromethyl)benzene, [ka] and 5.8 × 10 toluene solution of a chloroplatinic acid / vinylsiloxane complex. -3 g (1.8×10 as Pt alone) -8 The mixture was stirred at 80°C for 24 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 9 g of a liquid product. 1 It was confirmed by 1 H-NMR to be the following compound (C). [ka] (p1 / q1=0.96, p1+q1=47)

[0077] [Synthesis Example 2] 10 g of the compound represented by the formula (A), 10 g of 1,3-bis(trifluoromethyl)benzene, [ka] and 5.8 × 10 toluene solution of a chloroplatinic acid / vinylsiloxane complex. -3 g (1.8×10 as Pt alone) -8 The mixture was stirred at 80°C for 24 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 9 g of a liquid product. 1 It was confirmed by 1 H-NMR to be the following compound (E). [ka] (p1 / q1=0.96, p1+q1=47) [Synthesis Example 3] With reference to Japanese Patent No. 6524955, a compound represented by the following formula (F) was prepared. [ka] (p1 / q1=0.96, p1+q1=68)

[0078] 10 g of the compound represented by formula (F), 10 g of 1,3-bis(trifluoromethyl)benzene, 2.7 g of the compound represented by formula (B), and 4.9 × 10 toluene solution of chloroplatinic acid / vinylsiloxane complex -3 g (1.4×10 as Pt alone) -8 The mixture was stirred at 80°C for 24 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 9 g of a liquid product. 1 It was confirmed by 1 H-NMR to be the following compound (G). [ka] (p1 / q1=0.96, p1+q1=68)

[0079] [Synthesis Example 4] 10 g of the compound represented by the formula (A), 10 g of 1,3-bis(trifluoromethyl)benzene, [ka] and 5.8 × 10 toluene solution of chloroplatinic acid / vinylsiloxane complex. -3 g (1.8×10 as Pt alone) -8 The mixture was stirred at 80°C for 24 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 9 g of a liquid product. 1It was confirmed by 1 H-NMR that the compound was a mixture of two compounds represented by the following formula (I) (hereinafter also referred to as compound (I)). [ka] (p1 / q1=0.96, p1+q1=47)

[0080] [Synthesis Example 5] With reference to Japanese Patent No. 6531833, a compound represented by the following formula (J) was prepared. [ka] (p1 / q1=0.96, p1+q1=47)

[0081] [Synthesis Example 6] With reference to WO 2023 / 199768, compounds represented by the following formulae (K) and (L) were prepared. [ka] (Equation (K): p1 / q1=0.96, p1+q1=47 Equation (L): p1 / q1=0.96, p1+q1=68)

[0082] [Synthesis Example 7] With reference to Japanese Patent No. 6524955, a compound represented by the following formula (M) was prepared. [ka] (p1 / q1=0.96, p1+q1=47)

[0083] In addition to the compounds of Synthesis Examples 1 to 7, a compound represented by the following formula (N) was prepared. [ka] (p3 / q3=0.89, p3+q3=43)

[0084] The following solvents were used for dilution: Novec 7300 (3M, methyl perfluorohexyl ether) Novec 7200 (3M, ethyl perfluorobutyl ether) Asahiklin AC-6000 (AGC, tridecafluorooctane) Hexafluoropropene trimer (Fujifilm Wako Pure Chemical Industries, Ltd.) Opteon SF10 (Mitsui-Chemours Fluoroproducts, methyl perfluoroheptenyl ether) Hexafluoroisopropyl methyl ether (Tokyo Chemical Industry Co., Ltd.)

[0085] [Examples 1 to 6, Comparative Examples 1 to 4] The compounds obtained in the above synthesis examples were diluted with the solvents shown in Table 1 so that the compounds were 20 mass % to prepare surface treatment agents.

[0086] [Table 1]

[0087] Preparation of surface treatment agent and formation of hardened coating The surface treatment agents prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were used to measure the rate of rise in water contact angle immediately after the formation of a cured coating. Each surface treatment agent was vacuum-deposited (treatment conditions: pressure: 3.0 × 10 -2 The sample was removed from the apparatus and cured for 12 hours in an atmosphere of 25°C and 50% humidity to form a cured coating with a thickness of 10 nm.

[0088] Water and oil repellency evaluation [Measurement of initial water contact angle] The contact angle (water repellency) of the cured coating on the lens prepared as described above was measured with a contact angle meter, Drop Master (Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The results (initial water contact angle) are shown in Table 2.

[0089] Dynamic contact angle evaluation [Measurement of receding water contact angle] The dynamic contact angle of the cured coating on the lenses prepared above with water was measured using a contact angle meter, Drop Master (Kyowa Interface Science Co., Ltd.), by the expansion / contraction method (droplet: 5 μL, liquid speed: 0.5 μL / s, temperature: 25°C, relative humidity: 40%). The results (receding water contact angle) are shown in Table 2.

[0090] Durability evaluation [Measurement of paper abrasion resistance] The lenses with the cured coating formed thereon were rubbed using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.) under the following conditions, and the contact angle (water repellency) of the cured coating with water was measured in the same manner as above to evaluate paper abrasion resistance. The test environmental conditions were 25°C and 40% humidity. The results (water contact angle after abrasion) are shown in Table 2. Lenses with a reduction in water contact angle after abrasion of less than 3° compared to the initial water contact angle were deemed to have excellent abrasion resistance. Paper: Dasper (Ozu Sangyo Co., Ltd.) Contact area: 1cm 2 Travel distance (one way): 40 mm Traveling speed: 4,800mm / min Load: 1kg / 1cm 2 Number of wear cycles: 30,000

[0091] [Table 2]

[0092] [Examples 7 to 11, Comparative Examples 5 to 7] The compounds obtained in the above synthesis examples were diluted with the solvents in the combinations of compounds and solvents shown in Table 3 so that the compounds were 0.1 mass % to prepare surface treatment agents.

[0093] [Table 3]

[0094] Preparation of surface treatment agent and formation of hardened coating Cured coatings were prepared using the surface treatment agents prepared in Examples 7 to 11 and Comparative Examples 5 to 7. The coating was sprayed onto the surface of chemically strengthened glass (Corning Gorilla V) that had been plasma-treated and cleaned using a spray coating device (T&K Corporation, NST-51). The coating was then cured for 12 hours in an atmosphere of 25°C and 50% relative humidity to form a cured coating with a film thickness of 10 nm, and a test specimen was obtained.

[0095] Water and oil repellency evaluation [Measurement of initial water contact angle] The cured coating on the glass was measured for water contact angle (water repellency) using a contact angle meter, Drop Master (Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The results (initial water contact angle) are shown in Table 4.

[0096] Dynamic contact angle evaluation [Measurement of receding water contact angle] The cured coating on the glass was measured for its dynamic contact angle with water using a Drop Master contact angle meter (Kyowa Interface Science Co., Ltd.) according to the method (expansion / contraction method) described in ISO 19043 part 6 (droplet: 5 μL, liquid velocity: 0.5 μL / s, temperature: 25°C, relative humidity: 40%). The results (receding water contact angle) are shown in Table 4.

[0097] Durability evaluation [Measurement of paper abrasion resistance] The glass with the cured coating formed thereon was rubbed using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.) under the following conditions, and the contact angle (water repellency) of the cured coating with water was measured in the same manner as above to evaluate paper abrasion resistance. The test environmental conditions were 25°C and 40% humidity. The results (water contact angle after abrasion) are shown in Table 4. A sample with a decrease in water contact angle after abrasion of less than 3° compared to the initial water contact angle was considered to have excellent abrasion resistance. Paper: Dasper (Ozu Sangyo Co., Ltd.) Contact area: 1cm 2 Travel distance (one way): 40 mm Traveling speed: 4,800mm / min Load: 1kg / 1cm 2 Number of wear cycles: 20,000

[0098] [Table 4]

[0099] The above results confirmed that Comparative Examples 1 to 5 had receding water contact angles significantly below 105°, indicating poor water sliding properties. Furthermore, Comparative Examples 3 and 6 showed a decrease in water contact angle after abrasion of 5° or more compared to the initial water contact angle, indicating reduced paper abrasion. Comparative Examples 4 and 7 had good water sliding properties, and the water contact angle after abrasion did not decrease significantly, but tended to be worse than the Examples. On the other hand, Examples 1 to 11 used compounds (C), (E), (G), and (I), which are fluoropolyether group-containing polymers containing three hydrolyzable silyl groups and three linear siloxane bonds. Articles obtained using compositions containing these compounds as surface treatment agents exhibited high receding water contact angles and good paper abrasion resistance.

Claims

1. An article having, on its surface, a cured product of a surface treatment agent containing a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, The fluoropolyether group-containing polymer is a polymer having, at one end of the molecule, three silanol groups or hydrolyzable silyl groups bonded to a hydrocarbon group having a linear siloxane bond.

2. 2. The article of claim 1, wherein the linear siloxane linkages have from 1 to 8 siloxane units.

3. 2. The article according to claim 1, wherein the hydrocarbon group having a linear siloxane bond is a group represented by the following formula (1): 【Chemistry 1】 (In the formula, G is a methyl group, an ethyl group, or a phenyl group, M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, b is a number from 3 to 4, and c is a number from 1 to 8.)

4. 2. The article according to claim 1, wherein the fluoropolyether group is a group represented by the following formula (2): 【Chemistry 2】 (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms; d is a number from 1 to 6; p, q, r, s, t, u, and v are each a number from 0 to 450, and satisfy the relationship p+q+r+s+t+u+v=10 to 450; and each repeating unit shown in parentheses with p, q, r, s, t, u, and v is linear or branched, and may be arranged in any order.)

5. 5. The article according to claim 4, wherein the fluoropolyether group-containing polymer is represented by the following formula (3): 【Transformation 3】 (wherein RF is a fluorine atom or a CF ３ - or CF ２ H- and a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, and Rf is represented by the following formula (2): 【Chemistry 4】 (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms; d is a number from 1 to 6; p, q, r, s, t, u, and v are each a number from 0 to 450, and satisfy the relationship p+q+r+s+t+u+v=10 to 450; and each repeating unit shown in parentheses with p, q, r, s, t, u, and v is linear or branched, and may be arranged in any order.) wherein G is a methyl group, an ethyl group, or a phenyl group; M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms; 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; a is a number from 2 to 3; b is a number from 3 to 4; and c is a number from 1 to 8.

6. 6. The article according to claim 5, wherein in formula (3), X is any 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.

7. The article according to claim 5, wherein in formula (3), G is a methyl group or a phenyl group.

8. The article according to claim 5, wherein in formula (3), c is a number from 1 to 3.

9. 6. The article according to claim 5, wherein in formula (3), M is a linear or branched divalent hydrocarbon group having 1 to 3 carbon atoms.

10. 6. The article according to claim 5, wherein the fluoropolyether group-containing polymer represented by formula (3) is any one of the polymers represented by the following formulas: 【Transformation 5】 (wherein RF is a fluorine atom or a CF ３ - or CF ２ H- and a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, p1 is a number from 5 to 440, q1 is a number from 5 to 250, p1+q1 is a number which satisfies the range of 20 to 450, and the order of the repeating units shown in parentheses to which p1 and q1 are added is arbitrary.

11. The article according to any one of claims 1 to 10, wherein the surface treatment agent further comprises a fluoropolyether group-containing polymer represented by the following formula (4) and / or a partial (hydrolyzed) condensate thereof: 【Transformation 6】 (wherein V is a monovalent hydrocarbon group or a hydrogen atom, RF is a fluorine atom or a CF ３ - or CF ２ H- and a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, and Rf is represented by the following formula (2): 【Transformation 7】 (wherein W is a fluoroalkylene group containing one or more hydrogen atoms; d is a number from 1 to 6; p, q, r, s, t, u, and v are each a number from 0 to 450; p+q+r+s+t+u+v is a number that satisfies the relationship of 10 to 450; and each repeating unit shown in parentheses with p, q, r, s, t, u, and v is linear or branched, and the arrangement of the repeating units is arbitrary), G is a methyl group, ethyl group, or phenyl group, M is a linear or branched divalent hydrocarbon group having 1 to 9 carbon atoms, R is independently an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, a is a number from 2 to 3, b is a number from 3 to 4, and c is a number from 1 to 8.)

12. The article according to any one of claims 1 to 10, wherein the surface treatment agent further comprises a fluoropolyether group-containing polymer represented by the following formula (5): 【Transformation 8】 (wherein RF at both ends is independently a fluorine atom, or ３ - or CF ２ Rf' is a monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom, and Rf' is a group represented by the following formula (2)' 【Chemistry 9】 (In the formula, p, q, r, and s each represent a number from 0 to 450, p+q+r+s represents a number from 10 to 450, and p+q represents a number from 20 to 450, and the order of the repeating units shown in parentheses with p, q, r, and s is arbitrary.)

13. The article according to any one of claims 1 to 10, wherein the surface treatment agent is for spray coating or vacuum deposition.

14. The article according to any one of claims 1 to 10, which is a glass substrate, a film substrate, or a plastic substrate.

15. The article may comprise a plasma-treated SiO ２ The article according to claim 14, which is a resin product having a surface.

16. 15. The article of claim 14, wherein the article is an eyeglass lens.

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