Fluoropolyether group-containing polymer composition, coating agent, article, and method for modifying surface of article

Abstract

This fluoropolyether group-containing polymer composition contains, at a specific ratio, (I) a polymer having a fluorooxyalkyl group at one terminal and having, at the other terminal, two or more reactive functional groups (hydroxyl group-containing silyl groups or hydrolyzable silyl groups), and / or a partial (hydrolyzed) condensate of the polymer, and (II) a polymer having a fluorooxyalkylene group in the molecule and having reactive functional groups (hydroxyl group-containing silyl groups or hydrolyzable silyl groups) bound to both terminals of the fluorooxyalkylene group via a linkage group not having a polar group, and / or a partial (hydrolyzed) condensate of the polymer. A coating agent containing the fluoropolyether group-containing polymer composition can form a cured coating film that has excellent water repellency and oil repellency and abrasion durability against nonwoven fabric and steel wool.

Description

Fluoropolyether group-containing polymer composition, coating agent and article, and method for modifying the surface of an article

[0001] The present invention relates to a composition containing a fluoropolyether group-containing polymer (a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule), and more particularly to a fluoropolyether group-containing polymer composition capable of forming a cured coating that is excellent in water and oil repellency and abrasion resistance (particularly abrasion resistance to steel wool and nonwoven fabrics), a coating agent containing the composition, an article having a layer made of a cured product of the coating agent, and a method for modifying the surface of an article, which includes the steps of applying the coating agent and curing it to form a layer.

[0002] In recent years, the use of touch panels for screens, including mobile phone displays, has accelerated. However, touch panels have exposed screens, which are often in direct contact with fingers or cheeks, making them susceptible to dirt such as sebum. Therefore, there is an increasing demand every year for technologies that make the display surface less susceptible to fingerprints and easier to clean, in order to improve appearance and visibility. The development of materials that can meet these demands is highly desirable. However, while conventional water- and oil-repellent layers are highly water- and oil-repellent and offer excellent wipeability, they suffer from the problem of deterioration of their anti-fouling properties during use.

[0003] In general, fluoropolyether group-containing compounds have very low surface free energy and therefore have water and oil repellency, chemical resistance, lubricity, release properties, antifouling properties, etc. Utilizing these properties, they are widely used industrially as water and oil repellent and antifouling agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, etc. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and even if they can be applied to the surface of a substrate, it has been difficult to adhere the coating to it.

[0004] On the other hand, silane coupling agents are well known as agents for bonding organic compounds to the surface 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. The hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating. The hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, or the like, resulting in a durable, strong coating.

[0005] Thus, compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, which can form coatings that adhere easily to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, and the like on the substrate surfaces (Patent Documents 1 to 6: JP-T-2008-534696A, JP-T-2008-537557A, JP-A-2012-072272A, JP-A-2012-157856A, JP-A-2013-136833A, and JP-A-2015-199906A).

[0006] A cured coating (thin antifouling coating layer) on the surface of a glass substrate or the like that is surface-treated with a composition containing a fluoropolyether group-containing polymer in which a hydrolyzable silyl group has been introduced into the fluoropolyether group-containing compound has excellent abrasion resistance against steel wool and high slipperiness. For the thin antifouling coating layer on the surface of a touch panel display, in addition to its ability to prevent staining, the usability (good slipperiness and smooth feel) when using the touch panel has also been considered important. A low coefficient of friction correlates with a good usability (Patent Document 6: JP 2015-199906 A).

[0007] However, it has been found that high abrasion resistance may not be achieved depending on the type of abrasion material.

[0008] Japanese Patent Publication No. 2008-534696 Japanese Patent Publication No. 2008-537557 Japanese Patent Publication No. 2012-072272 Japanese Patent Publication No. 2012-157856 Japanese Patent Publication No. 2013-136833 Japanese Patent Publication No. 2015-199906

[0009] The present invention has been made in view of the above circumstances, and aims to provide a fluoropolyether group-containing polymer composition capable of forming a cured coating that is excellent in water and oil repellency and abrasion resistance against various scrubbing materials (particularly abrasion resistance against steel wool and nonwoven fabrics); a coating agent containing the composition; an article having a layer made of a cured product of the coating agent; and a method for modifying the surface of an article, which includes the steps of applying and curing the coating agent to form a layer.

[0010] As a result of intensive research to achieve the above object, the present inventors have found that, in the above fluoropolyether group-containing polymer composition, by using a combination of fluoropolyether group-containing polymers and / or partial (hydrolyzed) condensates thereof of specific two components (components (I) and (II)) described below in a specific ratio, a coating agent containing a fluoropolyether group-containing polymer composition using the fluoropolyether group-containing polymers and / or partial (hydrolyzed) condensates thereof in combination can form a cured coating that is excellent in water and oil repellency and abrasion resistance to steel wool and nonwoven fabric, and have completed the present invention.

[0011]

[0010] Accordingly, the present invention provides the following fluoropolyether group-containing polymer composition, coating agent, article, and method for surface modification of an article: [1] (I) A fluoropolyether group-containing polymer composition represented by the following formula (1): [wherein A is a fluorine atom or a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and optionally containing an oxygen atom; Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d-(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 200, the sum of p, q, r, s, t, and u is an integer of 1 to 250, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses followed by p, q, r, s, t, and u may be randomly bonded), Y is independently a single bond, or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, a is independently 2 or 3 for each unit bonded to the silicon atom, W is a hydrogen atom or -OV, and V is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (1a): [In the formula, T is a single bond or a divalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, k is an integer from 0 to 20, and E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent hydroxyl-containing silyl group-containing or hydrolyzable silyl group-containing group represented by the following formula (1b): (wherein Y, R, X, and a are the same as above)) and / or a partial (hydrolyzed) condensate thereof, and (II) a fluoropolyether group-containing polymer represented by the following formula (2): (wherein Rf is the same as above, and D is independently a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at a terminal and having no polar group), and / or a partial (hydrolyzed) condensate thereof, wherein the content of component (I) in the total of component (I) and component (II) is 16 mass % or more and less than 55 mass %. [2] A fluoropolyether group-containing polymer composition comprising a fluoropolyether group-containing polymer represented by the following formula (2a): (wherein R and X are the same as above, M is a divalent to hexavalent hydrocarbon group which may have a silicon atom and / or a siloxane bond, m is an integer of 1 to 5, and n is an integer of 1 to 3 for each unit bonded to a silicon atom). [3] The fluoropolyether group-containing polymer composition according to [1], which is represented by the following formula: (wherein p', q', r', s', t' and u' each represent an integer of 1 to 200, the sum of p', q', r', s', t' and u' is 10 to 250, and each of these units is linear. Furthermore, each of the repeating units shown in parentheses followed by p', q', r', s', t' and u' may be bonded randomly. d' is independently an integer of 0 to 5 for each unit, and each of these units is linear.) The fluoropolyether group-containing polymer composition according to [1] or [2], wherein [4] The fluoropolyether group-containing polymer composition according to any one of [1] to [3], wherein in the formula (1a), T is a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a silalkylene bond, a silarylene bond, and a diorganosilylene group, a divalent siloxane bond, a silalkylene group, or a diorganosilylene group. [5] The fluoropolyether group-containing polymer composition according to any one of [1] to [4], wherein in the formula (1) or (1b), X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group. [6] The fluoropolyether group-containing polymer composition according to any one of [1] to [5], wherein the fluoropolyether group-containing polymer represented by the formula (1) is selected from polymers represented by the following formulas: (Wherein, A and Rf are the same as above.) [7] The fluoropolyether group-containing polymer composition according to any one of [1] to [6], wherein the fluoropolyether group-containing polymer represented by the formula (2) above is selected from polymers represented by the following formulas: (wherein p" and q" are each an integer of 1 to 199, and the sum of p" and q" is 10 to 200.) [8] A coating agent comprising the fluoropolyether group-containing polymer composition according to any one of [1] to [7]. [9] An article having a layer consisting of a cured product of the coating agent according to [8].

[10] The article according to [9], wherein the steel wool abrasion durability number and nonwoven fabric abrasion durability number on the surface are 7,500 or more and 20,000 or more, respectively, under the test conditions described below. [Steel wool abrasion durability test conditions] Evaluation of steel wool abrasion durability using a reciprocating abrasion tester Abrading material: Steel wool #0000 (Bonstar) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocations per minute Test environment conditions: 25°C, relative humidity 50% The water contact angle of the friction-wear portion is measured every 2,500 reciprocating friction cycles, and the number of reciprocating friction cycles at which a water contact angle of 100 degrees or more is defined as the steel wool abrasion durability number. [Nonwoven fabric abrasion durability test conditions] Evaluation of nonwoven fabric abrasion durability using a reciprocating abrasion tester Abrasion material: Bemcot (M-3II, manufactured by Ozu Sangyo) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocations per minute Test environment conditions: 25°C, relative humidity 50% The water contact angle of the friction and wear part is measured every 5,000 reciprocating friction cycles, and the number of reciprocating friction cycles at which the water contact angle is maintained at 100 degrees or more is defined as the nonwoven fabric abrasion durability cycle.

[11] A method for modifying the surface of an article, comprising the steps of applying a coating agent containing the fluoropolyether group-containing polymer composition according to any one of [1] to [7] to the entire or part of the surface of the article by a dry or wet method, and curing the coating agent to form a layer.

[0012] The fluoropolyether group-containing polymer composition of the present invention can provide a cured coating that has excellent water and oil repellency and high abrasion resistance against various scrubbing materials (particularly steel wool and nonwoven fabrics). As a result, an article (e.g., a portable electronic device terminal, etc.) having a layer made of a cured product of a coating agent containing the composition of the present invention has water and oil repellency and high abrasion resistance (particularly abrasion resistance against steel wool and nonwoven fabrics).

[0013] In the present invention, the term "partial (hydrolyzed) condensate" refers to a partial condensate or a partial hydrolyzed condensate.

[0014] The fluoropolyether group-containing polymer composition of the present invention comprises fluoropolyether group-containing polymers of two specific components (components (I) and (II)) and / or their partial (hydrolyzed) condensates in specific proportions. Regarding each component, component (I) is a polymer and / or its partial (hydrolyzed) condensate having a fluorooxyalkyl group at one end and two or more reactive functional groups (hydroxyl group-containing silyl groups or hydrolyzable silyl groups) at the other end, and component (II) is a polymer and / or its partial (hydrolyzed) condensate having a fluorooxyalkylene group in the molecule and reactive functional groups (hydroxyl group-containing silyl groups or hydrolyzable silyl groups) bonded to both ends of the fluorooxyalkylene group via linking groups that do not have polar groups.

[0015] [Component (I)] In the fluoropolyether group-containing polymer composition of the present invention, component (I) is a fluoropolyether group-containing polymer represented by the following formula (1) and / or a partial (hydrolyzed) condensate thereof. [wherein A is a fluorine atom or a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and optionally containing an oxygen atom; Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u-C d F 2d -(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 200, the sum of p, q, r, s, t, and u is an integer of 1 to 250, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses followed by p, q, r, s, t, and u may be randomly bonded), Y is independently a single bond, or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, a is independently 2 or 3 for each unit bonded to the silicon atom, W is a hydrogen atom or -OV, and V is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (1a): [In the formula, T is a single bond or a divalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, k is an integer from 0 to 20, and E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent hydroxyl-containing silyl group-containing or hydrolyzable silyl group-containing group represented by the following formula (1b): (wherein Y, R, X, and a are the same as above.)

[0016] The fluoropolyether group-containing polymer represented by the above formula (1) will now be described.

[0017] In the above formula (1), A is a fluorine atom or a monovalent fluorine-containing hydrocarbon group which has a terminal CF3- or CF2H- and which may contain an oxygen atom. The monovalent fluorine-containing hydrocarbon group which has a terminal CF3- or CF2H- and which may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably one which ends in a polymer at a terminal CF3- or CF2H-.

[0018] Examples of such monovalent fluorine-containing hydrocarbon groups in which the terminal of A is CF3- or CF2H- and which may contain an oxygen atom include the following groups. A is preferably a fluorine atom.

[0019] In the above formula (1), Rf is represented by the following formula: where d is independently an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0 or 1 for each unit. p, q, r, s, t, and u are each independently an integer of 0 to 200, preferably an integer of 0 to 150, more preferably an integer of 0 to 100, and even more preferably an integer of 0 to 60, and the sum of p, q, r, s, t, and u is an integer of 1 to 250, preferably an integer of 3 to 200, more preferably an integer of 7 to 140, and even more preferably an integer of 10 to 70. Each of these units may be linear or branched. Furthermore, the repeating units shown in parentheses with p, q, r, s, t, and u may be randomly bonded.

[0020] The divalent fluoropolyether group Rf can be specifically represented by the following structure. (In the formula, p', q', r', s', t', and u' each represent an integer of 1 to 200, and the sum of p', q', r', s', t', and u' is 10 to 250. Each of these units may be linear or branched, but is preferably linear. Furthermore, each of the repeating units shown in parentheses followed by p', q', r', s', t', and u' may be bonded randomly. d' is independently an integer of 0 to 5 for each unit. Each of these units may be linear or branched, but is preferably linear.)

[0021] As Rf, the following can be preferably used. (In the formula, p" and q" are each an integer of 1 to 199, and the sum of p" and q" is an integer of 10 to 200, and the arrangement of the repeating units (CFCFO) and (CFO) in the formula is random.)

[0022] In the above formula (1), Y is a single bond or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond. The divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms and containing a fluorine atom, alkylene groups containing an arylene group having 6 to 8 carbon atoms (alkylene-arylene groups), divalent groups in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms.

[0023] Specific examples of Y other than a single bond include the following: In the following structure, it is preferable that the left bond is bonded to a carbon atom and the right bond is bonded to a silicon atom.

[0024] In the above formula (1), R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, with a methyl group and an ethyl group being preferred.

[0025] In the above formula (1), X is independently a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group for 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 propionoxy; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups, such as chlorine, bromine, and iodo. Among these, methoxy, ethoxy, isopropenoxy, and chlorine are preferred for X.

[0026] In the above formula (1), a is independently 2 or 3 for each unit bonded to a silicon atom, and is preferably 3 from the viewpoints of reactivity and adhesion to a substrate.

[0027] In the above formula (1), W is a hydrogen atom or —OV, and V is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (1a):

[0028] Here, examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for V include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenylethyl groups, with alkyl groups having 1 to 3 carbon atoms and phenyl groups being preferred.

[0029] In the above formula (1a), T represents a single bond or a divalent group, and is preferably a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a silalkylene bond (e.g., a silethylene bond or a silpropylene bond), a silarylene bond (e.g., a silphenylene bond), and a diorganosilylene group (e.g., a dialkylsilylene group such as a dimethylsilylene group, or a dialkoxysilylene group such as a dimethoxysilylene group), or a divalent siloxane bond, silalkylene group, or diorganosilylene group; specific examples of T other than a single bond include those shown below. In the following structure, it is preferable that the right bond is bonded to L or E.

[0030] In the above formula (1a), L independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms, such as an alkylene group, for example, a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group), and each (LO) unit may have a single carbon atom or a mixture of carbon atoms.

[0031] In the above formula (1a), k is an integer of 0 to 20, preferably an integer of 0 to 10, more preferably an integer of 0 to 6. When (LO) is present, k is preferably 1 or more, particularly preferably 2 or more.

[0032] In the above formula (1a), E 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; a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a phenyl group; or a monovalent hydroxyl-containing silyl group-containing or hydrolyzable silyl group-containing group represented by the following formula (1b): (In the formula, Y, R, X, and a are the same as above.)

[0033] In the above formula (1b), Y, R, X, and a are the same as those described above, and examples thereof include the same as those exemplified for Y, R, X, and a in the above formula (1).

[0034] Examples of the monovalent group represented by the above formula (1a) include the groups shown below.

[0035] Examples of the fluoropolyether group-containing polymer represented by the above formula (1) include the following. (In the formula, A and Rf are the same as above.)

[0036] The component (I) may be a single fluoropolyether group-containing polymer represented by the formula (1) or a combination of two or more fluoropolyether group-containing polymers. The component (I) may further contain a partial (hydrolyzed) condensate obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer represented by the formula (1) or the hydroxyl groups obtained by partially hydrolyzing the terminal hydrolyzable groups of the fluoropolyether group-containing polymer in advance by a known method.

[0037] The number average molecular weight of the fluoropolyether group-containing polymer represented by the above formula (1) and / or its partial (hydrolyzed) condensate is preferably 1,000 to 10,000, more preferably 2,000 to 8,000, and particularly preferably 3,000 to 6,000. If the number average molecular weight is less than 1,000, the surface coverage of the resulting coating agent will be poor and good water and oil repellency may not be obtained, while if it exceeds 10,000, the surface adhesion of the resulting coating agent will be poor and good abrasion resistance may not be obtained. The number average molecular weight is 19 The number average molecular weight (or number average degree of polymerization) can be calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether group-containing polymer based on F-NMR analysis, or can be determined as the number average molecular weight (or number average degree of polymerization) converted into polymethyl methacrylate resin by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent, but is preferably 19 It is calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether group-containing polymer based on F-NMR analysis (the same applies hereinafter).

[0038] [Component (II)] In the fluoropolyether group-containing polymer composition of the present invention, component (II) is a fluoropolyether group-containing polymer represented by the following formula (2) and / or a partial (hydrolyzed) condensate thereof. (In the formula, Rf is the same as above, and D independently represents a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at a terminal and having no polar group.)

[0039] The fluoropolyether group-containing polymer represented by the above formula (2) has a structure in which a fluorooxyalkylene group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group that does not have a polar group, and there are at least one hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group at each end, for a total of two or more in the molecule, and there are no polar groups, specifically, carbonyl groups, —NH— groups, amide groups, hydroxyl groups, etc., in the molecule other than the hydrolyzable silyl groups or hydroxyl group-containing silyl groups, resulting in a simpler bonding mode.

[0040] In the above formula (2), Rf is the same as above, and examples thereof include the same as those exemplified for Rf in the above formula (1).

[0041] In the above formula (2), D independently represents a monovalent group having a hydroxyl-containing silyl group or a hydrolyzable silyl group at a terminal and no polar group, and is preferably a monovalent group consisting of a hydroxyl-containing silyl group or a hydrolyzable silyl group at a terminal and a linking group that links the silyl group with an O group (an ether-bonded oxygen atom) and has no polar group (such as a carbonyl group, an —NH— group, an amide group, or a hydroxyl group), and as such D, a group represented by the following formula (2a) is preferred: (In the formula, R and X are the same as above, M is a divalent to hexavalent hydrocarbon group which may have a silicon atom and / or a siloxane bond, m is an integer of 1 to 5, and n is an integer of 1 to 3 for each unit bonded to a silicon atom.)

[0042] That is, the fluoropolyether group-containing polymer represented by the above formula (2) is preferably represented by the following formula (3). (In the formula, Rf, R, and X are the same as above, M is independently a divalent to hexavalent hydrocarbon group, which may have a silicon atom and / or a siloxane bond, m is independently an integer of 1 to 5, and n is independently an integer of 1 to 3 for each unit bonded to a silicon atom.)

[0043] In the formula (3), Rf, R, and X are the same as those described above, and examples thereof include the same Rf, R, and X as those exemplified in the formula (1).

[0044] In the above formula (3), M independently represents a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent hydrocarbon group, which may contain a silicon atom and / or a siloxane bond, and by not containing a polar group in the molecule, a coating film with excellent water and oil repellency can be provided.

[0045] Specific examples of M include alkylene groups having 3 to 10 carbon atoms, such as propylene, butylene, and hexamethylene; alkylene groups having 2 to 10 carbon atoms, including arylene groups having 6 to 8 carbon atoms, such as phenylene (for example, alkylene-arylene groups having 8 to 16 carbon atoms); divalent groups in which alkylene groups having 2 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure; and alkylene groups having 2 to 10 carbon atoms bonded to a bond of a linear, branched, or cyclic divalent to hexavalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms. Examples of such groups include divalent to hexavalent groups to which an alkylene group is bonded, preferably an alkylene group having 3 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms that includes a phenylene group, a divalent group in which alkylene groups having 2 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, and a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, and more preferably an alkylene group having 3 to 6 carbon atoms.

[0046] Examples of the linear, branched or cyclic divalent to hexavalent organopolysiloxane residue having 2 to 10, preferably 2 to 5, silicon atoms include the following: (In the formula, R 1 is the same as above. x is an integer of 1 to 9, preferably an integer of 1 to 4, y1 is an integer of 2 to 6, preferably an integer of 2 to 4, y2 is an integer of 0 to 8, preferably 0 or 1, y1+y2 is an integer of 3 to 10, preferably an integer of 3 to 5, and z is 2 or 3.

[0047] Examples of M include groups represented by the following formulas. (In the formula, x is the same as above. v is an integer of 3 to 10, preferably an integer of 3 to 6. v0 is an integer of 2 to 10, preferably an integer of 3 to 6. v1 is an integer of 2 to 6, preferably an integer of 2 to 4. v2 is independently an integer of 2 to 10, preferably an integer of 3 to 6.)

[0048] Specific examples of M include the following groups.

[0049] In the above formula (3), m is independently an integer of 1 to 5. If it is less than 1, adhesion to the substrate decreases, and if it is 6 or more, the terminal alkoxy value becomes too high and adversely affects performance, so it is preferably an integer of 1 to 3, and particularly preferably 1. In the above formula (3), n is independently an integer of 1 to 3 for each unit bonded to a silicon atom, and is preferably 3 from the viewpoints of reactivity and adhesion to the substrate.

[0050] Examples of the fluoropolyether group-containing polymer represented by the above formula (2) include the following. (In the formula, p" and q" are each an integer of 1 to 199, and the sum of p" and q" is 10 to 200.)

[0051] The component (II) may be a single fluoropolyether group-containing polymer represented by the above formula (2), or a combination of two or more fluoropolyether group-containing polymers. It may further contain a partial (hydrolyzed) condensate obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer represented by the above formula (2) or the hydroxyl groups obtained by partially hydrolyzing the terminal hydrolyzable groups of the fluoropolyether group-containing polymer in advance by a known method.

[0052] The number average molecular weight of the fluoropolyether group-containing polymer represented by the above formula (2) and / or its partial (hydrolyzed) condensate is preferably 1,000 to 10,000, more preferably 3,000 to 8,000, and particularly preferably 4,000 to 8,000. If the number average molecular weight is less than 1,000, the surface coverage of the resulting coating agent will be poor and good water and oil repellency may not be obtained, whereas if it exceeds 10,000, the surface adhesion of the resulting coating agent will be poor and good abrasion resistance may not be obtained.

[0053] In the fluoropolyether group-containing polymer composition of the present invention, the content of component (I) relative to the total of components (I) and (II) is 16% by mass or more but less than 55% by mass, preferably 16 to 50% by mass, and more preferably 16 to 40% by mass, and the content of component (II) relative to the total of components (I) and (II) is more than 45% by mass but not more than 84% by mass, preferably 50 to 84% by mass, and more preferably 60 to 84% by mass. When the content of component (I) is less than 16% by mass (the content of component (II) exceeds 84% ​​by mass), high steel wool abrasion resistance due to the polymer mobility of component (I) cannot be obtained, and when the content of component (I) is 55% by mass or more (the content of component (II) is 45% by mass or less), high nonwoven fabric abrasion resistance due to the substrate adhesion of component (II) cannot be obtained.

[0054] Furthermore, the number average molecular weight of component (II) is preferably 0.6 to 1.6 times, and more preferably 0.7 to 1.4 times, the number average molecular weight of component (I).

[0055] In addition to the above-mentioned components (I) and (II), the fluoropolyether group-containing polymer composition of the present invention may contain optional components such as hydrocarbon oils, silicone oils, fluoropolyether oils, silane coupling agents, surfactants, etc., within the scope of the present invention.

[0056] Furthermore, the present invention provides a coating agent comprising the above-mentioned fluoropolyether group-containing polymer composition.

[0057] If necessary, the coating agent of the present invention 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 desirable. The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is typically 0.01 to 5 parts by mass, and particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer composition.

[0058] The coating agent of the present invention may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (e.g., perfluoroheptane, perfluorooctane), fluorine-modified aromatic hydrocarbon solvents (e.g., 1,3-bis(trifluoromethyl)benzene), fluorine-modified ether solvents (e.g., methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran)), fluorine-modified alkylamine solvents (e.g., perfluorotributylamine, perfluorotripentylamine), hydrocarbon solvents (e.g., petroleum benzine, toluene, xylene), and ketone solvents (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone). Among these, fluorine-modified solvents are desirable in terms of solubility, wettability, and the like, and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are particularly preferred.

[0059] Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate). The optimal concentration of the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) dissolved in the solvent varies depending on the treatment method, and may be an amount that is easy to weigh. In the case of direct coating, the concentration is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate). In the case of vapor deposition treatment, the concentration is preferably 1 to 100 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate).

[0060] The coating agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition. The heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferably 25 to 200°C, particularly 25 to 80°C, for 30 minutes to 36 hours, particularly 1 to 24 hours. When applied by vapor deposition, it is desirable to apply the coating agent at a temperature range of 20 to 200°C, particularly 25 to 80°C, for 30 minutes to 36 hours, particularly 30 minutes to 24 hours. Furthermore, curing may be performed under humid conditions. For spray coating, for example, diluting the coating agent in a fluorine-based solvent to which moisture has been added and then hydrolyzing it, i.e., generating Si—OH groups, before spray coating can result in rapid curing after application.

[0061] The thickness of the cured coating is determined appropriately depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. The thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, X-ray fluorescence measurement, etc.

[0062] The substrate to be treated with the coating agent of the present invention is not particularly limited and may be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. The coating agent of the present invention can impart water and oil repellency and abrasion resistance (resistance to steel wool abrasion) to the substrate, and can also form a cured coating that maintains high abrasion resistance even after surface cleaning. In particular, it can be used preferably as a coating agent for SiO2-treated glass or film.

[0063] Examples of articles that can be treated with the coating agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio equipment, game consoles, 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 coating agent of the present invention can also be used to treat the housings of mobile phones, smartphones, PCs, and the like. The coating agent of the present invention can prevent fingerprints and sebum from adhering to the above-mentioned articles and further impart scratch resistance (abrasion resistance), making it particularly useful as a water- and oil-repellent layer for the housings of mobile phones, smartphones, PCs, and the like.

[0064] The coating agent of the present invention is also useful 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, and aircraft, and for headlamp covers; a water- and oil-repellent coating for exterior wall building materials; an oil-stain-resistant coating for kitchen building materials; an anti-fouling and anti-posting / anti-graffiti coating for telephone booths; a coating for imparting fingerprint resistance to artworks; and an anti-fingerprint coating for compact discs, DVDs, etc. It is also useful as an anti-fouling coating for building materials, particularly flooring and wall materials. The fluoropolyether group-containing polymer composition of the present invention can also be suitably used as a mold release agent or paint additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, and a water- and oil-repellent agent for tapes, films, etc.

[0065] According to the present invention, the surface of an article can be modified by applying a coating agent containing the fluoropolyether group-containing polymer composition of the present invention to the entire surface or a part of the surface of the article by a dry method (vapor deposition treatment) or a wet method (brushing, dipping, spraying, etc.) and curing it to form a layer.

[0066] An article having a layer made of the cured product of the coating agent of the present invention has excellent abrasion resistance against various rubbing materials. In an article having a layer made of the cured product of the coating agent composition of the present invention, the abrasion resistance when rubbed with steel wool is preferably 7,500 times or more, more preferably 10,000 times or more, under the test conditions described below. If the abrasion resistance when rubbed with steel wool is less than 7,500 times, the water repellency of the cured coating film is likely to decrease and scratches are likely to occur. In the present invention, the abrasion resistance when rubbed with steel wool can be increased to the above value or more by setting the content of component (I) in the total of components (I) and (II) to 16% by mass or more but less than 55% by mass. [Steel wool abrasion durability test conditions] Evaluation of steel wool abrasion durability using a reciprocating abrasion tester Rubbing material: steel wool #0000 (Bonstar) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocations per minute Test environment conditions: 25°C, relative humidity 50% The water contact angle of the friction-wear portion was measured every 2,500 reciprocating friction cycles, and the number of reciprocating friction cycles at which the water contact angle was maintained at 100 degrees or more was defined as the steel wool abrasion durability cycle.

[0067] Furthermore, in an article having a layer made of a cured product of the coating composition of the present invention, the abrasion durability when rubbed with a nonwoven fabric is preferably 20,000 times or more, and more preferably 30,000 times or more, under the test conditions described below. If the abrasion durability when rubbed with a nonwoven fabric is less than 20,000 times, the water repellency of the cured coating film is likely to decrease and scratches are likely to occur. In the present invention, an abrasion durability when rubbed with a nonwoven fabric of the above value or more can be achieved by setting the content of component (I) to 16% by mass or more and less than 55% by mass of the total of components (I) and (II). [Nonwoven Fabric Abrasion Durability Test Conditions] Evaluation of nonwoven fabric abrasion durability using a reciprocating abrasion tester Abrasion material: Bemcot (M-3II, manufactured by Ozu Sangyo) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocations per minute Test environment conditions: 25°C, relative humidity 50% The water contact angle of the friction-wear part was measured every 5,000 reciprocating friction cycles, and the number of reciprocating friction cycles at which the water contact angle was maintained at 100 degrees or more was defined as the nonwoven fabric abrasion durability cycle.

[0068] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. 19 It is a value calculated from the characteristic peak intensity ratio of the terminal structure and the main chain structure of the fluoropolyether group-containing polymer based on F-NMR analysis, and the number of repetitions of each fluorooxyalkylene unit in the fluorooxyalkylene group-containing polymer residue is 19 The film thickness is a number average value calculated from F-NMR. In the formula below, the repeating units shown in parentheses with p1 and q1 are randomly bonded. Furthermore, the film thickness is a value measured by spectroscopic ellipsometry using a spectroscopic ellipsometer. The test environment conditions were 25°C and 50% relative humidity.

[0069] [Examples 1 to 42, Comparative Examples 1 to 19] Preparation of Coating Agents and Formation of Cured Coatings Fluoropolyether group-containing polymers having structures represented by the following formulas (A), (B), (C), (D), and (E) as component (I) and fluoropolyether group-containing polymers having structures represented by the following formulas (F), (G), (H), and (I) as component (II) were mixed in the proportions shown in Tables 1, 2, and 3 to obtain fluoropolyether group-containing polymer compositions. The polymer composition was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a coating agent. A chemically strengthened glass substrate with SiO2 (10 nm thick) was placed in a resistance heating vacuum deposition apparatus (VTR-350M, manufactured by ULVAC Kiko), and 6 μL of the following surface treatment agent was dropped onto the resistance heating section, followed by decompression. When the pressure inside the container reached 3 × 10 -3Once the pressure was reduced to 100 Pa or less, resistance heating was initiated. The power input to the resistance heating was adjusted so that the maximum evaporation rate measured by a quartz crystal oscillator film thickness meter installed approximately 20 cm away from the resistance heating unit was 1.0 nm / sec. Resistance heating was continued for 100 seconds after the evaporation rate measured by the quartz crystal oscillator film thickness meter decreased to 0.1 nm / sec. The device was allowed to cool for 5 minutes, after which it was opened to the atmosphere to obtain a substrate coated with a fluoropolyether group-containing polymer. The glass substrate coated with the fluoropolyether group-containing polymer was left to cure for 30 minutes in an environment of 80°C and 80% relative humidity, yielding a glass substrate having a cured coating of the fluoropolyether group-containing polymer with a thickness of 13 to 15 nm. The film thickness of the water- and oil-repellent surface layer was calculated using a calibration curve by quantifying the fluorescent X-ray intensity derived from elemental fluorine using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, product name: Fluorescent X-ray analyzer Primini).

[0070] [Component (I)] A fluoropolyether group-containing polymer having a structure represented by the following formula (A) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (B) (number average molecular weight: 5,900) A fluoropolyether group-containing polymer having a structure represented by the following formula (C) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (D) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (E) (number average molecular weight: 5,900)

[0071] [Component (II)] A fluoropolyether group-containing polymer having a structure represented by the following formula (F) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (G) (number average molecular weight: 4,300) A fluoropolyether group-containing polymer having a structure represented by the following formula (H) (number average molecular weight: 5,900) A fluoropolyether group-containing polymer having a structure represented by the following formula (I) (number average molecular weight: 5,900)

[0072]

[0073]

[0074]

[0075] [Evaluation of Initial Water Repellency] For the glass on which the cured coating prepared above was formed, the contact angle (water repellency) of the cured coating with water was measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 50%). The results (water contact angle) are shown in Tables 4, 5, and 6. A water contact angle of 111° or more was rated as good. The Example, Comparative Examples 2, 4, 6, 8, and 10, which contained a high proportion of component (I), Comparative Examples 11 to 15, which used component (I) alone, and Comparative Example 18, which used component (II) alone, all exhibited high water contact angles of 111° or more, indicating good water repellency.

[0076] [Abrasion Resistance Evaluation] Evaluation of Steel Wool Abrasion Durability The glass having the cured coating formed thereon was tested using a reciprocating abrasion tester (Type 40, manufactured by Shinto Scientific Co., Ltd.) under the following conditions: Abrasion material: Steel wool #0000 (Bonstar) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocations per minute Total number of reciprocating friction: 15,000 The water contact angle of the friction wear portion was measured using the same method as above every 2,500 reciprocating friction cycles. The number of reciprocating friction cycles at which a water contact angle of 100° or more was maintained was defined as the steel wool abrasion durability cycle. A steel wool abrasion durability cycle of 10,000 or more was evaluated as ◎ (excellent), 7,500 to less than 10,000 was evaluated as ○ (good), 5,000 to less than 7,500 was evaluated as △ (passable), and less than 5,000 was evaluated as × (unacceptable). The evaluation results are shown in Tables 4, 5, and 6.

[0077] Evaluation of Nonwoven Fabric Abrasion Durability The glass having the cured coating formed thereon prepared as described above was tested using a reciprocating abrasion tester (Type 40, manufactured by Shinto Scientific) under the following conditions. Abrasion material: Bemcot (M-3II, manufactured by Ozu Sangyo Co., Ltd.) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocations per minute Total number of reciprocating friction: 40,000 times The water contact angle of the friction wear portion was measured using the same method as above every 5,000 reciprocating friction times. The number of reciprocating friction times at which a water contact angle of 100° or more was maintained was taken as the nonwoven fabric abrasion durability count. A nonwoven fabric abrasion durability count of 30,000 times or more was evaluated as ◎ (excellent), 20,000 times or more but less than 30,000 times was evaluated as ○ (good), 10,000 times or more but less than 20,000 times was evaluated as △ (passable), and less than 10,000 times was evaluated as × (unacceptable). The evaluation results are shown in Tables 4, 5, and 6.

[0078]

[0079]

[0080]

[0081] The cured coatings of the Examples, in which the fluoropolyether group-containing polymer of component (I) and the fluoropolyether group-containing polymer of component (II) were used in specific ratios, exhibited good water repellency and excellent steel wool abrasion resistance and nonwoven fabric abrasion resistance. In contrast, the cured coatings of Comparative Examples 1 to 10, in which the ratio of the fluoropolyether group-containing polymer of component (I) to the fluoropolyether group-containing polymer of component (II) was outside the range of the Examples, Comparative Examples 11 to 15, in which the fluoropolyether group-containing polymer of component (I) was used alone, and Comparative Examples 16 to 19, in which the fluoropolyether group-containing polymer of component (II) was used alone, were all inferior in water repellency, steel wool abrasion resistance, or nonwoven fabric abrasion resistance.

Claims

1. (I) The following formula (1) [wherein A is a fluorine atom or a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and optionally containing an oxygen atom; Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d -(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 200, the sum of p, q, r, s, t, and u is an integer of 1 to 250, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses followed by p, q, r, s, t, and u may be randomly bonded), Y is independently a single bond, or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, a is independently 2 or 3 for each unit bonded to the silicon atom, W is a hydrogen atom or -OV, and V is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (1a): [In the formula, T is a single bond or a divalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, k is an integer from 0 to 20, and E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent hydroxyl-containing silyl group-containing or hydrolyzable silyl group-containing group represented by the following formula (1b): (wherein Y, R, X, and a are the same as above)) and / or a partial (hydrolyzed) condensate thereof, and (II) a fluoropolyether group-containing polymer represented by the following formula (2): (wherein Rf is the same as defined above, and D independently represents a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at a terminal and having no polar group), and / or a partial (hydrolyzed) condensate thereof, wherein the content of component (I) in the total of component (I) and component (II) is 16 mass % or more but less than 55 mass %.

2. In formula (2), D is the following formula (2a): (wherein R and X are the same as defined above, M is a divalent to hexavalent hydrocarbon group which may have a silicon atom and / or a siloxane bond, m is an integer of 1 to 5, and n is an integer of 1 to 3 for each unit bonded to a silicon atom).

3. In formulas (1) and (2), Rf is the following formula: (wherein p', q', r', s', t' and u' each represent an integer of 1 to 200, the sum of p', q', r', s', t' and u' is 10 to 250, and each of these units is linear. Furthermore, each of the repeating units shown in parentheses followed by p', q', r', s', t' and u' may be bonded randomly. d' is independently an integer of 0 to 5 for each unit, and each of these units is linear.) 4. The fluoropolyether group-containing polymer composition according to claim 1, wherein in the above formula (1a), T is a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of silicon atoms, siloxane bonds, silalkylene bonds, silarylene bonds, and diorganosilylene groups, a divalent siloxane bond, a silalkylene group, or a diorganosilylene group.

5. The fluoropolyether group-containing polymer composition according to claim 1, wherein in the above formulas (1) and (1b), X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.

6. The fluoropolyether group-containing polymer composition according to claim 1, wherein the fluoropolyether group-containing polymer represented by the formula (1) is selected from polymers represented by the following formulas: (In the formula, A and Rf are the same as above.) 7. The fluoropolyether group-containing polymer composition according to claim 1, wherein the fluoropolyether group-containing polymer represented by the formula (2) is selected from polymers represented by the following formulas: (In the formula, p" and q" are each an integer of 1 to 199, and the sum of p" and q" is 10 to 200.) 8. A coating agent comprising the fluoropolyether group-containing polymer composition according to any one of claims 1 to 7.

9. An article having a layer made of the cured product of the coating agent according to claim 8.

10. The article according to claim 9, wherein the steel wool abrasion durability number of times and the nonwoven fabric abrasion durability number of times on the surface are 7,500 or more and 20,000 or more, respectively, under the test conditions described below. [Steel wool abrasion durability test conditions] Evaluation of steel wool abrasion durability using a reciprocating abrasion tester: Abrading material: Steel wool #0000 (Bonstar) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocations per minute Test environment conditions: 25°C, relative humidity 50% The water contact angle of the friction-wear area was measured every 2,500 reciprocating friction cycles, and the number of reciprocating friction cycles at which a water contact angle of 100 degrees or more was maintained was defined as the steel wool abrasion durability number. [Nonwoven Fabric Abrasion Durability Test Conditions] Evaluation of nonwoven fabric abrasion durability using a reciprocating abrasion tester Abrasion material: Bemcot (M-3II, manufactured by Ozu Sangyo) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocations per minute Test environment conditions: 25°C, relative humidity 50% The water contact angle of the friction-wear part was measured every 5,000 reciprocating friction cycles, and the number of reciprocating friction cycles at which the water contact angle was maintained at 100 degrees or more was defined as the nonwoven fabric abrasion durability cycle.

11. A method for modifying the surface of an article, comprising the steps of applying a coating agent containing the fluoropolyether group-containing polymer composition according to any one of claims 1 to 7 to the entire surface or a part of the surface of the article by a dry method or a wet method, and curing the coating agent to form a layer.

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