Fluoropolyether-group-containing polymer, surface-treating agent, and article

Abstract

Provided is a surface-treating agent comprising a fluoropolyether-group-containing polymer of formula (1) and / or a product of partial (hydrolytic) condensation thereof. The surface-treating agent can form cured films excellent in terms of water and oil repellency, resistance to wear by steel wool, and resistance to wear by rubber erasers. (Rf is a mono- or divalent fluoropolyether group, B is a single bond or a divalent organic group containing no fluorine atom, E is a monovalent group having an oxyalkylene group, T is a single bond or a divalent organic group, U is a single bond, C, Si, N, or a tri- or tetravalent organic group, V is a single bond or a divalent organic group, Z is a single bond or a tri- to octavalent organic group, Y is O, S, Si, or a divalent hydrocarbon group optionally having a siloxane bond, R is an alkyl group or a phenyl group, X is a hydroxyl group or a hydrolyzable group, n is 1-3, m is 1-7, β is 1-3, and α is 1 or 2.)

Description

Fluoropolyether group-containing polymer, surface treatment agent and article

[0001] The present invention relates to a fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluoropolyether group in the molecule), and more particularly to a fluoropolyether group-containing polymer capable of forming a coating having excellent water and oil repellency and abrasion resistance, a surface treatment agent containing the polymer and / or a partial (hydrolyzed) condensate thereof, and an article surface-treated with the surface treatment agent.

[0002] In recent years, the use of touch panels in displays, including smartphones, has accelerated. However, touch panels have exposed screens, which are often directly touched by fingers or cheeks, making them susceptible to sebum and other contaminants. Therefore, there is an increasing demand for technologies that make display surfaces less susceptible to fingerprints and easier to clean, thereby improving appearance and visibility. The development of materials that can meet these demands is highly desirable. Touch panel display surfaces are particularly susceptible to fingerprints, making them ideal for providing a water- and oil-repellent layer. However, while conventional water- and oil-repellent layers offer high water- and oil-repellent properties and excellent wipeability, they suffer from the problem of degradation 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 easily adhere 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-2008-534696, JP-T-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, and JP-A-2015-199906).

[0006] Lenses and cured coatings such as anti-reflective films that have been 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 have excellent slip properties, release properties, and abrasion resistance to steel wool, but do not exhibit sufficient performance, particularly in terms of abrasion resistance to erasers.

[0007] In addition, a composition has been disclosed that can form a coating film that is excellent in slipperiness and releasability and has abrasion resistance against erasers by using a fluoropolyether group-containing polymer in which a polyether group is introduced into a fluoropolyether group-containing compound (Patent Document 7: International Publication No. 2017 / 212850).

[0008] Lenses and cured coatings such as anti-reflective films that have been surface-treated with a composition containing a fluoropolyether group-containing polymer in which a polyether group has been introduced into the fluoropolyether group-containing compound have excellent abrasion resistance against erasers, but do not perform sufficiently in terms of abrasion resistance against steel wool, and there has been a demand for a material that has both eraser and steel wool abrasion resistance.

[0009] Japanese Patent Publication No. 2008-534696 Japanese Patent Publication No. 2008-537557 Japanese Patent Application Laid-Open No. 2012-072272 Japanese Patent Application Laid-Open No. 2012-157856 Japanese Patent Application Laid-Open No. 2013-136833 Japanese Patent Application Laid-Open No. 2015-199906 International Publication No. 2017 / 212850

[0010] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluoropolyether group-containing polymer capable of forming a cured coating film excellent in water and oil repellency, steel wool abrasion resistance, and eraser abrasion resistance, a surface treatment agent containing the polymer and / or a partial (hydrolyzed) condensate thereof, and an article surface-treated with the surface treatment agent.

[0011] As a result of intensive research conducted by the present inventors to achieve the above object, they have found that by using a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, which is represented by the general formula (1) described below, a surface treatment agent containing the polymer and / or a partial (hydrolyzed) condensate thereof can form a cured coating film that is excellent in water and oil repellency, steel wool abrasion resistance, and eraser abrasion resistance, and have thus completed the present invention.

[0012] Therefore, the present invention provides the following fluoropolyether group-containing polymer, surface treatment agent, and article: [1] A fluoropolyether group-containing polymer represented by the following general formula (1): (In the formula, Rf is a monovalent or divalent fluoropolyether group; B is independently a single bond or a divalent organic group not containing a fluorine atom; E is independently a monovalent group having an oxyalkylene group; T is independently a single bond or a divalent organic group; U is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group; V is independently a single bond or a divalent organic group; Z is independently a single bond or a tri- to octavalent organic group; Y is independently a divalent hydrocarbon group which may have at least one bond selected from an oxygen atom, a sulfur 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; n is independently an integer of 1 to 3 for each silicon atom to which it is bonded; m is independently an integer of 1 to 7; β is independently an integer of 1 to 3; and α is 1 or 2.) [2] A fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the following general formula (2): [1] wherein α in the formula (1) is 1 and Rf is a group represented by the following general formula (2): (In the formula, A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group terminally having a —CF3 group, and W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, the total of p, q, r, s, t, u, and v is 3 to 200, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.) [3] A fluoropolyether group-containing polymer according to [1], wherein α in formula (1) is 2 and Rf is a group represented by the following general formula (3): (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 3 for each unit. p, q, r, s, t, u, and v are each an integer of 0 to 200, the total of p, q, r, s, t, u, and v is 3 to 200, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.) [4] The fluoropolyether group-containing polymer according to any one of [1] to [3], wherein Y is a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom or a sulfur atom, an alkylene group having 1 to 10 carbon atoms which contains an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups having 1 to 10 carbon atoms are mutually bonded via a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 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. [5] The fluoropolyether group-containing polymer according to any one of [1] to [4], wherein in the formula (1), B is a single bond, or a divalent group in which alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 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, a carbonyl group, and an amide group, and may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.[6] The fluoropolyether group-containing polymer according to any one of [1] to [5], wherein in the formula (1), T is a single bond, or a divalent group in which alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 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, a carbonyl group, and an amide group, and may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group. [7] The fluoropolyether group-containing polymer according to any one of [1] to [6], wherein in the formula (1), U is selected from the group consisting of a single bond, a carbon atom, a silicon atom, a nitrogen atom, -CH=, and -Si(CH3)=. [8] The fluoropolyether group-containing polymer according to any one of [1] to [7], wherein in the formula (1), Z is a single bond or a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms and having a valence of 3 to 6. [9] The fluoropolyether group-containing polymer according to any one of [1] to [8], wherein in the formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.

[10] The fluoropolyether group-containing polymer according to any one of [1] to [9], wherein in the formula (1), m is an integer of 1 to 3.

[11] The fluoropolyether group-containing polymer according to any one of [1] to

[10] , wherein in the formula (1), β is 2 or 3.

[12] The fluoropolyether group-containing polymer according to any one of [1] to

[11] , wherein the fluoropolyether group-containing polymer represented by formula (1) is represented by any one of the following formulas: (In the formulae, p1, q1, and s1 each represent an integer of 1 to 200, with the proviso that the sum of p1, q1, and s1 in each formula is 3 to 200. r1 and r2 each represent an integer of 3 to 200. The repeating units shown in parentheses following p1, q1, and s1 may be bonded randomly. k is an integer of 1 to 30.)

[13] A surface treatment agent comprising a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group according to any one of [1] to

[12] and / or a partial (hydrolyzed) condensate thereof.

[14] An article surface-treated with the surface treatment agent according to

[13] .

[0013] The fluoropolyether group-containing polymer of the present invention, which has a hydroxyl group or a hydrolyzable group and a polyether group on a secondary carbon, has the polyether group on the secondary carbon in a predetermined structure, which makes the polyether molecules more mobile during abrasion and improves abrasion resistance. As a result, articles surface-treated with a surface treatment agent containing the polymer and / or its partial (hydrolyzed) condensate have excellent water and oil repellency, steel wool abrasion resistance, and eraser abrasion resistance.

[0014] The fluoropolyether group-containing polymer of the present invention has a monovalent or divalent fluoropolyether group and a reactive functional group in the molecule and has a polyether group on a secondary carbon, and is a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the following general formula (1): (In the formula, Rf is a monovalent or divalent fluoropolyether group; B is independently a single bond or a divalent organic group not containing a fluorine atom; E is independently a monovalent group having an oxyalkylene group; T is independently a single bond or a divalent organic group; U is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group; V is independently a single bond or a divalent organic group; Z is independently a single bond or a tri- to octavalent organic group; Y is independently a divalent hydrocarbon group which may have at least one bond selected from an oxygen atom, a sulfur 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; n is independently an integer of 1 to 3 for each silicon atom to which it is bonded; m is independently an integer of 1 to 7; β is independently an integer of 1 to 3; and α is 1 or 2.)

[0015] The fluoropolyether group-containing polymer of the present invention, which has a hydroxyl group or a hydrolyzable group and a polyether group on a secondary carbon, has a structure in which a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group (i.e., a monovalent or divalent fluoropolyether group) is bonded to a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group via a linking group.Furthermore, by having a polyether group on a secondary carbon in a predetermined structure, the polyether molecule becomes easy to move when worn, and the wear resistance is improved, and a cured coating film having excellent water and oil repellency, steel wool abrasion resistance and eraser abrasion resistance can be obtained.

[0016] In the above formula (1), Rf is a monovalent or divalent fluoropolyether group, and when α is 1 (i.e., when Rf is a monovalent fluoropolyether group), it is preferably a monovalent fluoropolyether group represented by the following general formula (2), and when α is 2 (i.e., when Rf is a divalent fluoropolyether group), it is preferably a divalent fluoropolyether group represented by the following general formula (3).

[0017] (In the formula, A represents a fluorine atom, a hydrogen atom, or a fluoroalkyl group having a —CF group at the terminal; W represents a fluoroalkylene group containing one or more hydrogen atoms; d represents an integer of 1 to 3 independently for each unit; p, q, r, s, t, u, and v each represent an integer of 0 to 200; the total of p, q, r, s, t, u, and v is 3 to 200; and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.)

[0018] In the above formula (2), A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group having a terminal —CF 3 group, and is preferably a fluorine atom.

[0019] In the above formulas (2) and (3), W is a fluoroalkylene group containing one or more hydrogen atoms, such as a CF2 unit, a C2F4 unit, a C3F6 unit, a C4F8 unit, or a C5F 10 Unit: C6F 12 Examples include those in which one or two fluorine atoms in each perfluoroalkylene group of the unit etc. are substituted with hydrogen atoms.

[0020] In the above formulas (2) and (3), d is independently an integer of 1 to 3 for each unit, preferably 1 or 2. Furthermore, p, q, r, s, t, u, and v are each an integer of 0 to 200, preferably an integer of 0 to 100, and the sum of p, q, r, s, t, u, and v is 3 to 200, preferably 10 to 100. When the sum of p, q, r, s, t, u, and v is smaller than the upper limit, the resulting cured coating has good adhesion and curability, while when it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable. Furthermore, when r, s, t, u, and v are all 0, p and q are each an integer of 5 to 100, and the sum of p and q is preferably 10 to 105, particularly 15 to 60.

[0021] In the above formulas (2) and (3), each unit may be linear or branched, and each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.

[0022] Specific examples of Rf include the following: (In the formula, p', q', r', s', t', and u' each represent an integer of 1 or more, the upper limit of which is the same as the upper limit of p, q, r, s, t, and u above, and the total of p', q', r', s', t', and u' is 3 to 200. r2' and r3' each represent an integer of 1 or more, and the total of r2' and r3' is 2 to 199. In addition, the repeating units shown in parentheses followed by p', q', r', s', t', and u' may be bonded randomly.)

[0023] In the above formula (1), B independently represents a divalent organic group that does not contain a single bond or a fluorine atom, and the divalent organic group 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 that contain an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms), divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure, or a silarylene structure, and a divalent group in which an alkylene group having 1 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, a carbonyl group, and an amide group, and the divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

[0024] Here, the group bonded to a silicon atom in a diorganosilylene group, a silalkylene structure, a silarylene structure, an organopolysiloxane residue, or the like is preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group. Furthermore, the alkylene group in the silalkylene structure is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group).

[0025] Examples of such B include the following groups: In the following structure, it is preferred that the left bond is bonded to Rf and the right bond is bonded to a carbon atom. (In the formula, f is an integer of 2 to 4, a, a', and b are each an integer of 1 to 4, c is an integer of 1 to 10, and e is an integer of 1 to 9.)

[0026] In the above formula (1), E is independently a monovalent group having an oxyalkylene group, and can be represented by the following general formula (4): -O-Q(-(LO) k -R') g (4)

[0027] In the above formula (4), Q is a single bond, G, or a divalent or trivalent group formed by combining G with an oxygen atom; G is an amide group, or a divalent or trivalent group containing an amide group, a silicon atom, a siloxane bond, a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a silalkylene structure or a silarylene structure; the silicon atom preferably has an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group; and may have a hydroxyl group or a hydrolyzable group. Furthermore, the alkylene group in the silalkylene structure is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group). When Q is a single bond, it is preferable that B or U is other than a single bond; it is particularly preferable that U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group.

[0028] Examples of such Q include the following groups. (In the formula, e is an integer from 1 to 9.)

[0029] In the above formula (4), L is independently an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or a butylene group, with an ethylene group being preferred. These groups may be used alone or in combination. In the above formula (4), k is an integer of 1 to 30, preferably an integer of 1 to 20, and more preferably an integer of 3 to 12. In the above formula (4), 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 being preferred. In the above formula (4), g is 1 or 2, and preferably 1.

[0030] Examples of such E include the following groups. (In the formula, k is the same as above, k1 and k2 are each an integer of 1 or more, and k1+k2 is an integer of 2 to 30. e is an integer of 1 to 9.)

[0031] In the above formula (1), T independently represents a single bond or a divalent organic group, and the divalent organic group 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 including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms), divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure, or a silarylene structure, and a divalent group in which an alkylene group having 1 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, a carbonyl group, and an amide group, and the divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group. When U is a single bond, T is preferably a single bond.

[0032] Here, the group bonded to a silicon atom in a diorganosilylene group, a silalkylene structure, a silarylene structure, an organopolysiloxane residue, or the like is preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group. Furthermore, the alkylene group in the silalkylene structure is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group).

[0033] Examples of such T include the following groups in addition to a single bond: In the following structure, it is preferable that the left bond is bonded to a carbon atom and the right bond is bonded to U. (In the formula, f is an integer of 2 to 4, a, a', and b are each an integer of 1 to 4, c is an integer of 1 to 10, and e is an integer of 1 to 9.)

[0034] In the above formula (1), U independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, and the trivalent or tetravalent organic group is preferably -CH= or -Si(CH3)=.

[0035] Examples of U include the following, in addition to a single bond: In the following structure, it is preferable that the left bond is bonded to T, and the other bond is bonded to V.

[0036] In the above formula (1), V is independently a single bond or a divalent organic group, and the divalent organic group is preferably an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms), and the divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group. Note that when Z is a single bond, V is preferably a single bond.

[0037] Examples of such V include the following groups in addition to a single bond: In the following structure, it is preferable that the left bond is bonded to U and the right bond is bonded to Z. (In the formula, a, a', and b are each an integer of 1 to 4, and c is an integer of 1 to 10.)

[0038] In the above formula (1), Z is independently a single bond or a trivalent to octavalent organic group, and the trivalent to octavalent organic group is preferably a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent to hexavalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms. The organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded via an alkylene group, i.e., Si-(CH2) x It may contain —Si (where x is an integer of 2 to 6).

[0039] The organopolysiloxane residue preferably has an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group.

[0040] Examples of such Z include the following, in addition to a single bond: In the following structure, it is preferable that the bond on the left side is bonded to V, and the other bond is bonded to Y.

[0041] In the above formula (1), Y independently may have at least one bond selected from the group consisting of an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the divalent hydrocarbon group include alkylene groups having 1 to 10 carbon atoms which may contain an oxygen atom or a sulfur atom, alkylene groups having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms), divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure, or a silarylene structure, and divalent groups in which an alkylene group having 1 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.

[0042] Here, the group bonded to a silicon atom in a diorganosilylene group, a silalkylene structure, a silarylene structure, an organopolysiloxane residue, or the like is preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group. Furthermore, the alkylene group in the silalkylene structure is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group).

[0043] Examples of such Y include the following groups: In the following structure, it is preferred that the left bond is bonded to Z and the right bond is bonded to Si. (In the formula, f is an integer of 2 to 4, a and b are each an integer of 1 to 4, b' and c are each an integer of 1 to 10, and e is an integer of 1 to 9.)

[0044] In the above formula (1), R independently represents 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 being preferred.

[0045] In the above formula (1), X is independently a hydroxyl group or a hydrolyzable group, and examples of such X include hydroxyl group, alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, and butoxy group, alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy group and methoxyethoxy group, acyloxy groups having 1 to 10 carbon atoms such as acetoxy group, alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy group, and halogen groups such as chlorine group, bromo group, and iodo group. Of these, methoxy group, ethoxy group, isopropenoxy group, and chlorine group are preferred.

[0046] In the above formula (1), n ​​is independently an integer of 1 to 3, preferably 3, for each silicon atom to which it is bonded. m is independently an integer of 1 to 7, preferably 1 to 3. β is independently an integer of 1 to 3, preferably 2 or 3, and α is 1 or 2.

[0047] Examples of the structure of the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by the above formula (1) include the following structures: By changing the combination of Rf, B, E, T, U, V, Z, Y, R, X, and n in the above formula (1), several types of fluoropolyether group-containing polymers having a hydroxyl group or a hydrolyzable group and a polyether group can be obtained.

[0048] (In the formula, k is the same as above. p1, q1, and s1 each represent an integer of 1 to 200, provided that the sum of p1, q1, and s1 in each formula is 3 to 200. r1 and r2 each represent an integer of 3 to 200. The repeating units shown in parentheses with p1, q1, and s1 may be bonded randomly.)

[0049] Examples of methods for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the above formula (1), when α is 1 (i.e., Rf is a monovalent fluoropolyether group) or when α is 2 (i.e., Rf is a divalent fluoropolyether group) include the following: A fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals, an organosilicon compound having an SiH group and a hydroxyl group or a hydrolyzable group (e.g., a halogen atom or an alkoxy group) in the molecule, such as trichlorosilane or trialkoxysilane, and a solvent, such as a fluorine-containing solvent, such as 1,3-bis(trifluoromethyl)benzene, are mixed, and the mixture is aged in the presence of a hydrosilylation reaction catalyst, such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably 70 to 90°C, for 1 to 72 hours, preferably 20 to 36 hours, more preferably 22 to 30 hours. When a SiH group-containing halogenated (organic) silicon compound such as trichlorosilane is used as the organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable group in the molecule, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group. Furthermore, two different compounds may also be used as the organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable group in the molecule, and in this case, the compound can be produced by adding them in stages.

[0050] Here, in preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), the fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals can be exemplified by the fluoropolyether group-containing polymer represented by the following general formula (5): (In the formula, Rf, B, E, T, U, V, Z, α, β, and m are the same as above, and Y′ independently represents a single bond or a divalent hydrocarbon group which may have at least one bond selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond.)

[0051] In the above formula (5), Y' independently represents a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms which may have at least one bond selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond, and is preferably a divalent hydrocarbon group having 1 to 18 carbon atoms. Specific examples of the divalent hydrocarbon group include alkylene groups having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom, alkylene groups having 1 to 8 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 16 carbon atoms), divalent groups in which an alkylene group having 1 to 10 carbon atoms is bonded to a diorganosilylene group, a silalkylene structure, or a silarylene structure, and divalent groups in which an alkylene group having 1 to 8 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. Y' is preferably a linear alkylene group having 1 to 6 carbon atoms.

[0052] The fluoropolyether group-containing polymer represented by the formula (5) can be prepared, for example, by the following method: (wherein Rf, B, T, U, V, Z, Y', α, β, and m are the same as above), a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal and a polyether group-introducing agent are aged in the presence of a base, if necessary, using an additive or solvent that improves reactivity, at a temperature of 0 to 90°C, preferably 40 to 60°C, and more preferably 50 to 60°C, for 1 to 48 hours, preferably 10 to 40 hours, and more preferably 20 to 30 hours.

[0053] Examples of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal, represented by the above formula (6), include the following. (In the formula, k, p1, q1, r1, s1, and the sum of p1, q1, and s1 in each formula are the same as above. In addition, each repeating unit shown in parentheses with p1, q1, and s1 may be bonded randomly.)

[0054] Examples of polyether group-introducing agents to be reacted with the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal, represented by the above formula (6), include the following compounds. (In the formula, k, k1, and k2 are the same as above, and R″ is an optionally fluorine-substituted alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, such as a phenyl group.)

[0055] The amount of the polyether group-introducing agent used is 1 to 15 equivalents, more preferably 3 to 6 equivalents, per equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (6).

[0056] Examples of the base used in the reaction between the fluoropolyether group-containing polymer having hydroxyl groups and olefin moieties at the molecular chain terminals represented by formula (6) and the polyether group-introducing agent include amines and alkali metal bases. Specific examples of amines include triethylamine, diisopropylethylamine, pyridine, DBU, and imidazole. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, potassium t-butoxide, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide. The amount of base used is 1 to 20 equivalents, more preferably 4 to 8 equivalents, and even more preferably 5 to 7 equivalents, per equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having hydroxyl groups and olefin moieties at the molecular chain terminals represented by formula (6).

[0057] In the reaction between the fluoropolyether group-containing polymer having hydroxyl groups and olefin moieties at the molecular chain terminals represented by formula (6) and the polyether group-introducing agent, additives such as tetrabutylammonium halide and alkali metal halides may be used to improve reactivity. Specific examples of additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, and crown ethers. These additives improve reactivity by catalytically exchanging halogen with the polyether group-introducing agent in the reaction system, and crown ethers improve reactivity by coordinating with the metal. The additive can be used in an amount of 0.005 to 0.1 equivalents, more preferably 0.01 to 0.05 equivalents, and even more preferably 0.015 to 0.03 equivalents, per equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having hydroxyl groups and olefin moieties at the molecular chain terminals represented by formula (6).

[0058] A solvent may be used in the reaction between the fluoropolyether group-containing polymer having hydroxyl groups and olefin moieties at the molecular chain terminals represented by formula (6) and the polyether group-introducing agent. While the use of a solvent is not essential, examples of solvents that can be used include fluorine-based solvents such as fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene, hydrofluoroether (HFE) solvents such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, product name: Novec series), and perfluoro-based solvents composed of fully fluorinated compounds (manufactured by 3M, product name: Fluorinert series). Furthermore, examples of organic solvents that can be used include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, and THF. When a solvent is used, the amount used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (6).

[0059] After the reaction is completed, the aqueous layer and the fluorine-containing solvent layer are separated by a separation operation. The resulting fluorine-containing solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain the fluoropolyether group-containing polymer represented by the above formula (5).

[0060] As an alternative method for preparing the fluoropolyether group-containing polymer represented by the above formula (5), for example, a fluoropolyether group-containing polymer having hydroxyl groups and olefin moieties at the molecular chain terminals represented by the above formula (6) and an organosilicon compound having no hydrolyzable terminal groups in the molecule and two or more SiH groups are subjected to a dehydrogenation reaction in the presence of a dehydrogenation catalyst, if necessary using a solvent, at a temperature of 0 to 60°C, preferably 15 to 35°C, more preferably 20 to 30°C, for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably 1 to 1.5 hours, to obtain a fluoropolyether group-containing polymer having SiH groups and olefin moieties at the molecular chain terminals. Next, the fluoropolyether group-containing polymer having an SiH group and an olefin moiety at the molecular chain terminal and a polyether compound having an olefin moiety in the molecule (for example, a polyalkylene oxide compound having one molecular chain terminal blocked with an alkenyloxy group) are dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and aged in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably 70 to 90°C, for 1 to 72 hours, preferably 20 to 36 hours, more preferably 22 to 30 hours.

[0061] Here, when reacting the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal, represented by formula (6) obtained above, with an organosilicon compound having no hydrolyzable terminal groups in the molecule and two or more SiH groups, the organosilicon compound having no hydrolyzable terminal groups in the molecule and two or more SiH groups is preferably a compound represented by the following formula: (wherein f and e are the same as above.)

[0062] Examples of such organosilicon compounds having no hydrolyzable terminal groups in the molecule and having two or more SiH groups include the compounds shown below.

[0063] When reacting the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal, represented by the above formula (6), with an organosilicon compound having no hydrolyzable terminal groups in the molecule and two or more SiH groups, the amount of the organosilicon compound having no hydrolyzable terminal groups in the molecule and two or more SiH groups can be 7 to 30 equivalents, more preferably 5 to 20 equivalents, and even more preferably 8 to 12 equivalents, per equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal.

[0064] Examples of dehydrogenation catalysts that can be used in the reaction of a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal, represented by the above formula (6), with an organosilicon compound having no hydrolyzable terminal groups in the molecule and two or more SiH groups include platinum group metal catalysts such as rhodium, palladium, and ruthenium, and boron catalysts.Specific examples include platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium, and boron catalysts such as tris(pentafluorophenyl)borane.The amount of dehydrogenation catalyst used is 0.0005 to 0.01 equivalents, more preferably 0.001 to 0.007 equivalents, and even more preferably 0.004 to 0.006 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal, represented by the above formula (6).

[0065] In another method for preparing the fluoropolyether group-containing polymer represented by the formula (5), a solvent may be used. While the use of a solvent is not essential, examples of the solvent that can be used include the same solvents as those exemplified in the method for preparing the fluoropolyether group-containing polymer represented by the formula (5). When a solvent is used, the amount used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the formula (6).

[0066] After reacting the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (6) with an organosilicon compound having no hydrolyzable terminal groups in the molecule and having two or more SiH groups, the aqueous layer and the fluorine-containing solvent layer are separated by a liquid separation operation. The obtained fluorine-containing solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain the fluoropolyether group-containing polymer having a SiH group and an olefin moiety at the molecular chain terminal.

[0067] When the fluoropolyether group-containing polymer having an SiH group and an olefin moiety at the molecular chain terminal obtained above is reacted with a polyether compound having an olefin moiety in the molecule, examples of the polyether compound having an olefin moiety in the molecule include those represented by the following formula: (In the formula, L, R', and k are the same as above, and e' is an integer of 0 to 2.)

[0068] Specific examples include polyalkylene oxide compounds having one molecular chain end blocked with an alkenyloxy group, such as polyethylene oxide shown below, in which one molecular chain end is blocked with an allyloxy group and the other end is blocked with a methoxy group. (wherein k is the same as above.)

[0069] Specific examples of polyether compounds having an olefin moiety in the molecule, such as polyalkylene oxide compounds capped with an alkenyloxy group at one molecular chain terminal, include UNIOX MA-200, UNIOX MA-300, UNIOX MA-350S, and UNIOX MA-500, manufactured by NOF Corp. The amount of the polyether compound having an olefin moiety in the molecule to be used is 1 to 10 equivalents, more preferably 2 to 5 equivalents, and even more preferably 2.5 to 3.5 equivalents, per equivalent of the reactive terminal group (SiH group) of the fluoropolyether group-containing polymer having an SiH group and an olefin moiety at the molecular chain terminal.

[0070] Examples of hydrosilylation catalysts that can be used when reacting the fluoropolyether group-containing polymer having SiH groups and olefin moieties at the molecular chain terminals obtained above with a polyether compound having an olefin moiety in the molecule include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The amount of hydrosilylation catalyst used is 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal (mass), relative to the mass of the fluoropolyether group-containing polymer having SiH groups and olefin moieties at the molecular chain terminals.

[0071] After the reaction is completed, the aqueous layer and the fluorine-containing solvent layer are separated by a separation operation. The resulting fluorine-containing solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain the fluoropolyether group-containing polymer represented by the above formula (5).

[0072] Furthermore, as an alternative method for preparing the fluoropolyether group-containing polymer represented by the above formula (5), for example, a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (6) and an isocyanate group-containing polyether group-introducing agent are aged in the presence of a catalyst, if necessary using a solvent, at a temperature of 0 to 190°C, preferably 40 to 150°C, more preferably 80 to 100°C, for 1 to 48 hours, preferably 10 to 40 hours, more preferably 20 to 30 hours.

[0073] Here, examples of the isocyanate group-containing polyether group-introducing agent to be reacted with the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal, represented by the above formula (6), include the following compounds. (wherein k and e are the same as above.)

[0074] The amount of the isocyanate group-containing polyether group-introducing agent used is 1 to 15 equivalents, more preferably 3 to 6 equivalents, per equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (6).

[0075] Examples of catalysts used in the reaction of the fluoropolyether group-containing polymer having hydroxyl groups and olefin moieties at the molecular chain terminals, represented by the above formula (6), with an isocyanate group-containing polyether group-introducing agent include titanium compounds such as titanium tetra-2-ethylhexoxide, tetra n-butyl titanate, and tetra n-propyl titanate; zirconium compounds such as tetra n-butyl zirconate and tetra n-propyl zirconate; tin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate; bismuth compounds such as bismuth tris(2-ethylhexanoate); and amine catalysts such as diazabicycloundecene. The amount of catalyst used is 0.01 to 100 parts by mass, preferably 0.05 to 20 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having hydroxyl groups and olefin moieties at the molecular chain terminals, represented by the above formula (6).

[0076] In another method for preparing the fluoropolyether group-containing polymer represented by the formula (5), a solvent may be used. While the use of a solvent is not essential, examples of the solvent that can be used include the same solvents as those exemplified in the method for preparing the fluoropolyether group-containing polymer represented by the formula (5). When a solvent is used, the amount used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the formula (6).

[0077] After the reaction is completed, the aqueous layer and the fluorine-containing solvent layer are separated by a separation operation. The resulting fluorine-containing solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain the fluoropolyether group-containing polymer represented by the above formula (5).

[0078] Examples of the fluoropolyether group-containing polymer represented by the above formula (5) include the following. (In the formula, k, p1, q1, r1, s1, and the sum of p1, q1, and s1 in each formula are the same as above. In addition, each repeating unit shown in parentheses with p1, q1, and s1 may be bonded randomly.)

[0079] In preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), the organosilicon compound having a SiH group and a hydrolyzable group in the molecule is preferably a compound represented by the following general formulas (7) to (10): (Wherein, R, X, n, and e are the same as above. R 1 are independently an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 2 is an alkylene group having 2 to 6 carbon atoms or an arylene group having 6 to 8 carbon atoms. 3 is a divalent hydrocarbon group having 2 to 8 carbon atoms, h is 1, j is an integer of 1 to 8, and h+j is an integer of 2 to 9. In formula (10), the repeating units shown in parentheses may be bonded randomly.

[0080] Here, R 1 R is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, and among these, a methyl group is preferred. 1 may be the same or different. 2 R is an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as an ethylene group, a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group), or an arylene group having 6 to 8 carbon atoms, such as a phenylene group, and among these, an ethylene group, a trimethylene group, or a phenylene group is preferred. 3Examples of the divalent hydrocarbon group having 2 to 8 carbon atoms, preferably 2 or 3 carbon atoms, include alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, and octamethylene, arylene groups such as phenylene, and combinations of two or more of these groups (e.g., alkylene-arylene groups), and of these, ethylene and trimethylene are preferred.

[0081] Examples of such organosilicon compounds having a SiH group and a hydroxyl group or a hydrolyzable group in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silane or siloxane compounds, as well as (partial) hydrolysates thereof.

[0082] In the preparation of the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), when the fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals is reacted with an organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable group in the molecule, the amount of the organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable group in the molecule can be 1 to 4 equivalents, more preferably 1.5 to 3 equivalents, per equivalent of the olefin moiety in the fluoropolyether group-containing polymer.

[0083] In preparing the fluoropolyether group-containing polymer represented by formula (1) having a hydroxyl group or a hydrolyzable group and a polyether group, examples of hydrosilylation reaction catalysts include the following: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The hydrosilylation reaction catalyst is used in an amount equivalent to 0.1 to 100 ppm, more preferably 1 to 50 ppm, by mass, in terms of transition metal, relative to the mass of the fluoropolyether group-containing polymer having at least one polyether group and at least one olefin moiety at one or both molecular chain terminals.

[0084] In preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), the solvent may be, for example, a fluorine-based solvent. Examples of the fluorine-based solvent 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 composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series). The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals.

[0085] When a SiH group-containing halogenated (organic) silicon compound such as trichlorosilane is used as the organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable group in the molecule, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, such as an alkoxy group such as a methoxy group. Reagents that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include, for example, alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol. The amount used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 50 to 70 parts by mass, per 100 parts by mass of the addition reaction product of a fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals with a SiH group-containing halogenated (organic) silicon compound.

[0086] After the reaction is completed, the solvent and unreacted materials are distilled off under reduced pressure to obtain the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, as represented by the above formula (1).

[0087] As another method for preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the above formula (1), when α is 1 (i.e., Rf is a monovalent fluoropolyether group) or when α is 2 (i.e., Rf is a divalent fluoropolyether group), for example, the following method can be mentioned. A fluoropolyether group-containing polymer having one or more polyether groups and one or more SiH groups at one or both molecular chain terminals (e.g., a fluoropolyether group-containing polymer having three polyether groups and three SiH groups at one or both molecular chain terminals), an organosilicon compound having an olefin moiety and a hydroxyl or hydrolyzable group in the molecule, and a solvent such as 1,3-bis(trifluoromethyl)benzene are mixed, and the resulting mixture is aged in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex at 40 to 120°C, preferably 60 to 100°C, more preferably 70 to 90°C, for 1 to 72 hours, preferably 20 to 36 hours, more preferably 22 to 30 hours. The organosilicon compound having an olefin moiety and a hydroxyl or hydrolyzable group in the molecule can also be two different compounds, in which case the mixture can be produced by stepwise addition.

[0088] Here, in another method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), an example of a fluoropolyether group-containing polymer having one or more polyether groups and one or more SiH groups at one or both molecular chain terminals is a fluoropolyether group-containing polymer represented by the following general formula (11): (In the formula, Rf, B, E, T, U, V, Z, α, β, and m are the same as above.)

[0089] The fluoropolyether group-containing polymer represented by formula (11) can be prepared, for example, by the following method: A fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals, an organosilicon compound having no hydrolyzable terminal groups in the molecule and two or more SiH groups, and a solvent, for example, a fluorine-containing solvent such as 1,3-bis(trifluoromethyl)benzene, are mixed together, and the mixture is aged in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably 70 to 90°C, for 1 to 72 hours, preferably 20 to 36 hours, more preferably 22 to 30 hours.

[0090] In preparing the fluoropolyether group-containing polymer represented by the above formula (11), examples of the fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals include the following. (In the formula, k, p1, q1, and the sum of p1 and q1 in each formula are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.)

[0091] In preparing the fluoropolyether group-containing polymer represented by the above formula (11), the organosilicon compound having no hydrolyzable terminal groups in the molecule and two or more SiH groups is preferably a compound represented by the following formula: (wherein f and e are the same as above.)

[0092] Examples of such organosilicon compounds having no hydrolyzable terminal groups in the molecule and having two or more SiH groups include the compounds shown below.

[0093] In preparing the fluoropolyether group-containing polymer represented by the above formula (11), the amount of the organosilicon compound having no hydrolyzable terminal groups in the molecule and two or more SiH groups is preferably 7 to 30 equivalents, more preferably 5 to 20 equivalents, and even more preferably 8 to 12 equivalents, per equivalent of the olefin moiety of the fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals.

[0094] In preparing the fluoropolyether group-containing polymer represented by formula (11), examples of hydrosilylation reaction catalysts include the following: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc.; platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The amount of hydrosilylation reaction catalyst used is 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal (by mass), relative to the mass of the fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals.

[0095] In preparing the fluoropolyether group-containing polymer represented by formula (11), the solvent may be, for example, a fluorine-based solvent. Examples of fluorine-based solvents include hydrofluoroether (HFE) solvents 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 (manufactured by 3M, trade name: Novec series), and perfluorosolvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series). The amount of solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having at least one polyether group and at least one olefin moiety at one or both molecular chain terminals.

[0096] After the reaction is completed, the solvent and unreacted materials are distilled off under reduced pressure to obtain the fluoropolyether group-containing polymer represented by the above formula (11).

[0097] Examples of the fluoropolyether group-containing polymer represented by the above formula (11) include the following. (In the formula, k, p1, q1, r1, and the sum of p1 and q1 in each formula are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.)

[0098] In another method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by formula (1), the organosilicon compound having an olefin moiety and a hydroxyl group or a hydrolyzable group in the molecule, which is reacted with a fluoropolyether group-containing polymer having one or more polyether groups and one or more SiH groups at one or both molecular chain terminals, is preferably a compound represented by the following general formula (12): (In the formula, R, X, and n are the same as above. Y″ is a single bond or a divalent hydrocarbon group which may have at least one bond selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond.)

[0099] In the above formula (12), Y" is a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms, which may have at least one bond selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond. Specific examples of the divalent hydrocarbon group include an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 8 carbon atoms, and an alkylene group having 1 to 8 carbon atoms, which may contain an oxygen atom or a sulfur atom (for example, an alkylene arylene group having 7 to 18 carbon atoms). Y" is preferably a single bond or a linear alkylene group having 1 to 6 carbon atoms.

[0100] Examples of such organosilicon compounds having an olefin moiety and a hydroxyl group or a hydrolyzable group in the molecule include vinyltrimethoxysilane, allyltrimethoxysilane, hexenyltrimethoxysilane, octenyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, hexenyltriethoxysilane, octenyltriethoxysilane, vinyltriisopropoxysilane, allyltriisopropoxysilane, vinyltributoxysilane, allyltributoxysilane, vinyltriacetoxysilane, allyltriacetoxysilane, vinyltrichlorosilane, vinyltribromosilane, vinyltriiodosilane, as well as the following silane or siloxane compounds and (partial) hydrolysates thereof.

[0101] In another method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), the amount of the organosilicon compound having an olefin moiety and a hydroxyl group or a hydrolyzable group in the molecule can be 1 to 4 equivalents, more preferably 1.5 to 2.5 equivalents, and even more preferably 1.8 to 2.2 equivalents, per equivalent of SiH groups in the fluoropolyether group-containing polymer having one or more polyether groups and one or more SiH groups at one or both molecular chain terminals.

[0102] Examples of the hydrosilylation catalyst used in this alternative method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by formula (1), include the same hydrosilylation catalysts as exemplified in the above preparation method, and the amount of the catalyst used is 0.1 to 100 ppm, more preferably 0.3 to 50 ppm, in terms of transition metal (by mass), relative to the mass of the fluoropolyether group-containing polymer having one or more polyether groups and one or more SiH groups at one or both molecular chain terminals.

[0103] Examples of the solvent used in the alternative method for preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1) include the same solvents as those exemplified in the above preparation method, and the blending amount is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having one or more polyether groups and one or more SiH groups at one or both molecular chain terminals.

[0104] After the reaction is completed, the solvent and unreacted materials are distilled off under reduced pressure to obtain the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, as represented by the above formula (1).

[0105] The present invention further provides a surface treatment agent containing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the above formula (1), and / or its partial (hydrolysis) condensate.The surface treatment agent only needs to contain the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the above formula (1), and / or its partial (hydrolysis) condensate as the main component, and may also contain unreacted raw materials, reaction intermediates, etc. before the terminal hydroxyl group or hydrolyzable group of the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group is introduced.In addition, in the present invention, "partial (hydrolysis) condensate" refers to a partial condensate or partial hydrolysis condensate, and is obtained by condensing the hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the above formula (1), or the hydroxyl group obtained by partially hydrolyzing the terminal hydrolyzable group of the fluoropolyether group-containing polymer by a known method in advance.

[0106] If necessary, the surface treatment agent may contain a hydrolysis condensation catalyst, such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, tetra n-propyl titanate, etc.), an organic zirconium compound (tetra n-butyl zirconate, tetra n-propyl zirconate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is typically 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by the above formula (1) and / or its partial (hydrolysis) condensate.

[0107] The surface treatment agent may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, tridecafluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, methyl perfluoropentyl ether, methyl perfluorohexyl ether, methyl perfluoroheptenyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), tetrafluoroethyl trifluoroethyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotripropylamine, 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, methyl perfluorohexyl ether, methyl perfluoroheptenyl ether, ethyl perfluorobutyl ether, tridecafluorooctane, and tetrafluoroethyl trifluoroethyl ether are particularly preferred.

[0108] The above-mentioned solvent may be a mixture of two or more kinds, and it is preferable to dissolve the fluoropolyether group-containing polymer having hydroxyl group or hydrolyzable group and polyether group represented by the above formula (1) and its partial (hydrolysis) condensate (hereinafter referred to as fluoropolyether group-containing polymer) uniformly.The optimum concentration of the fluoropolyether group-containing polymer dissolved in the solvent varies depending on the treatment method, and it is sufficient to be an amount that is easy to measure.In the case of direct coating, it is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, relative to the total 100 parts by mass of the solvent and the fluoropolyether group-containing polymer; in the case of vapor deposition treatment, it is preferably 1 to 100 parts by mass, particularly 3 to 30 parts by mass, relative to the total 100 parts by mass of the solvent and the fluoropolyether group-containing polymer.

[0109] The surface treatment 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 150°C, for 30 minutes to 36 hours, particularly 1 to 24 hours. When applied by vapor deposition, it is desirable to use a temperature in the range of 20 to 200°C for 1 to 24 hours. Furthermore, curing may be performed under humidified conditions. For spray coating, for example, diluting the agent in a fluorine-based solvent to which water has been added in advance, hydrolyzing the agent, i.e., generating Si—OH, and then spray coating the agent results in rapid curing after coating.

[0110] 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.

[0111] The substrate to be treated with the surface treatment agent of the present invention is not particularly limited and may be made of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, and quartz. The surface treatment agent of 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 SiO-treated glass or film.

[0112] Examples of articles that can be treated with the surface treatment agent of the present invention include optical articles and electronic components such as 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, and anti-reflection films. The surface treatment agent of 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 touch panel displays, anti-reflection films, and the like.

[0113] The surface treatment 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, 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; a coating for imparting fingerprint resistance to artworks, etc.; a fingerprint-resistant coating for compact discs, DVDs, etc.; a release agent or paint additive for molds; a resin modifier; a flowability modifier or dispersibility modifier for inorganic fillers; and a lubricity improver for tapes, films, etc.

[0114] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. 19 F-NMR, 1 This is a value calculated from the results of analysis such as H-NMR.

[0115] Synthesis Example 1 A reaction vessel was charged with a compound represented by the following formula (A): 100 g (2.35 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 42.0 g (9.41 × 10 -2 mol), tetrabutylammonium iodide 0.174 g (4.71 × 10-4 mol) were mixed. Subsequently, 7.90 g (0.141 mol) of potassium hydroxide was added, and the mixture was heated at 60°C for 24 hours. After the heating was completed, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (C): Thus, 89 g of a fluoropolyether group-containing polymer represented by the formula:

[0116] Into a reaction vessel, 50 g (1.06 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 5.19 g of trimethoxysilane (4.25 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.94 × 10 -2 g (1.03 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 50 g of a liquid product.

[0117] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (D):

[0118] Synthesis Example 2 A reaction vessel was charged with a compound represented by the following formula (E): 100 g (1.51 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 20.3 g (6.34 × 10) of a compound represented by -2 mol), titanium tetra-2-ethylhexoxide 0.447 g (7.92 × 10 -4 After mixing the components (mol), the mixture was heated at 90°C for 24 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (G): Thus, 95 g of a fluoropolyether group-containing polymer represented by the formula:

[0119] Into a reaction vessel, 50 g (7.54 × 10 -3 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 3.68 g of trimethoxysilane (3.01 × 10 -2 mol), and 2.79 × 10 chloroplatinic acid / vinylsiloxane complex in toluene -2 g (7.32 x 10 as Pt alone) -7 The mixture was aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 49 g of a liquid product.

[0120] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (H):

[0121] Synthesis Example 3 A reaction vessel was charged with a compound represented by the following formula (I): 100 g (2.35 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 25.1 g (9.31 × 10 -2 mol), tetrabutylammonium iodide 0.172 g (4.66 × 10 -4 mol) were mixed. Subsequently, 7.86 g (0.140 mol) of potassium hydroxide was added, and the mixture was heated at 60°C for 24 hours. After the heating was completed, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (K): Thus, 93 g of a fluoropolyether group-containing polymer represented by the formula:

[0122] Into a reaction vessel, 50 g (1.11 × 10) of the compound represented by formula (K) obtained above was added. -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 5.44 g of trimethoxysilane (4.45 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.13 × 10 -2g (1.08 x 10 as Pt alone) -6 The mixture was aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 48 g of a liquid product.

[0123] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (L):

[0124] Synthesis Example 4 A reaction vessel was charged with a compound represented by the following formula (M): 100 g (2.33 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 41.6 g (9.32 × 10 -2 mol), tetrabutylammonium iodide 0.172 g (4.66 × 10 -4 mol) were mixed. Subsequently, 7.83 g (0.140 mol) of potassium hydroxide was added, and the mixture was heated at 60°C for 24 hours. After the heating was completed, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound of the following formula (N): Thus, 94 g of a fluoropolyether group-containing polymer represented by the formula:

[0125] Into a reaction vessel, 50 g (1.07 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 7.86 g of trimethoxysilane (6.44 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.98 × 10 -2 g (1.04 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 50 g of a liquid product.

[0126] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (O):

[0127] Synthesis Example 5 A reaction vessel was charged with a compound represented by the following formula (P): 100 g (2.35 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 17.8 g (9.43 × 10 -2 mol), titanium tetra-2-ethylhexoxide 0.666 g (1.18 × 10 -3 After mixing the components (mol), the mixture was heated at 90°C for 24 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound of the following formula (R Thus, 90 g of a fluoropolyether group-containing polymer represented by the formula:

[0128] Into a reaction vessel, 50 g (1.13 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 5.51 g of trimethoxysilane (4.51 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.18 × 10 -2 g (1.10 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 51 g of a liquid product.

[0129] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (S):

[0130] Synthesis Example 6 A reaction vessel was charged with a compound represented by the following formula (T): 100 g (2.11 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 22.8 g (8.43 × 10 -2 mol), tetrabutylammonium iodide 0.156 g (4.22 × 10-4 mol) were mixed. Subsequently, 7.08 g (0.126 mol) of potassium hydroxide was added, and the mixture was heated at 60°C for 24 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (U): Thus, 97 g of a fluoropolyether group-containing polymer represented by the formula:

[0131] Into a reaction vessel, 50 g (1.01 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 7.42 g of trimethoxysilane (6.08 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.76 × 10 -2 g (9.84 x 10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 47 g of a liquid product.

[0132] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (V):

[0133] Synthesis Example 7 A reaction vessel was charged with a compound represented by the following formula (W): 100 g (2.30 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 41.0 g (9.20 × 10 -2 mol), tetrabutylammonium iodide 0.170 g (4.60 × 10 -4 mol) were mixed. Subsequently, 7.72 g (0.138 mol) of potassium hydroxide was added, and the mixture was heated at 60°C for 24 hours. After the heating was completed, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (X): Thus, 94 g of a fluoropolyether group-containing polymer represented by the formula:

[0134] Into a reaction vessel, 50 g (1.06 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 7.76 g of trimethoxysilane (6.36 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.93 × 10 -2 g (1.03 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 50 g of a liquid product.

[0135] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (Y):

[0136] Synthesis Example 8 A reaction vessel was charged with a compound represented by the following formula (A): 100 g (2.35 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 55.1 g (9.41 × 10 -2 mol), titanium tetra-2-ethylhexoxide 0.664 g (1.18 × 10 -3 After mixing the components (mol), the mixture was heated at 90°C for 24 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound of the following formula (AB): Thus, 90 g of a fluoropolyether group-containing polymer represented by the formula:

[0137] Into a reaction vessel, 50 g (1.03 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 14.7 g (4.13 × 10 -2mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.83 × 10 -2 g (1.00 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 52 g of a liquid product.

[0138] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AD):

[0139] Synthesis Example 9 A reaction vessel was charged with a compound represented by the following formula (AE): 100 g (2.44 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 78.4 g (0.195 mol) of a compound represented by the formula (I), 0.360 g (9.75 × 10 -4 mol) were mixed. Subsequently, 16.4 g (0.292 mol) of potassium hydroxide was added, and the mixture was heated at 60°C for 24 hours. After the heating was completed, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound of the following formula (AG): 87 g of a fluoropolyether group-containing polymer represented by the formula:

[0140] Into a reaction vessel, 30 g (6.31 × 10 -3 mol), 15 g of 1,3-bis(trifluoromethyl)benzene, 6.17 g of trimethoxysilane (5.05 × 10 -2 mol), and 2.34 × 10 chloroplatinic acid / vinylsiloxane complex in toluene -2 g (6.13 x 10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 51 g of a liquid product.

[0141] The resulting compound is 1H-NMR confirmed that the compound had a structure represented by the following formula (AH):

[0142] Synthesis Example 10 A reaction vessel was charged with a compound represented by the following formula (C) obtained in the same manner as in Synthesis Example 1. 50 g (1.06 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, and 3.94 × 10 toluene solution of a chloroplatinic acid / vinylsiloxane complex. -2 g (1.03 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 52 g of a liquid product.

[0143] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AJ):

[0144] Into a reaction vessel, 50 g (9.81 × 10 -3 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 27.4 g (0.118 mol) of octenyltrimethoxysilane, and 3.64 × 10 toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (9.52 x 10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 53 g of a liquid product.

[0145] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AK):

[0146] Example 1 The compound obtained in Synthesis Example 1 was dissolved in Opteon SF10 (manufactured by Mitsui-Chemours Fluoroproducts, methyl perfluoroheptenyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0147] Example 2 The compound obtained in Synthesis Example 2 was dissolved in Asahiklin AC-6000 (manufactured by AGC, tridecafluorooctane) to a concentration of 20% by mass to prepare a surface treatment agent.

[0148] Example 3 The compound obtained in Synthesis Example 3 was dissolved in Novec 7300 (manufactured by 3M, methyl perfluorohexyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0149] Example 4 The compound obtained in Synthesis Example 4 was dissolved in AE3000 (manufactured by AGC, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0150] Example 5 The compound obtained in Synthesis Example 6 was dissolved in a mixed solution of Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) / AE3000 in a mass ratio of 50:50 to give a concentration of 20 mass % to prepare a surface treatment agent.

[0151] Example 6 The compound obtained in Synthesis Example 7 was dissolved in a mixed liquid of Novec 7300 / AE3000 in a mass ratio of 50:50 to give a concentration of 20 mass % to prepare a surface treatment agent.

[0152] Example 7 The compound obtained in Synthesis Example 10 was dissolved in Novec 7200 to a concentration of 20% by mass to prepare a surface treatment agent.

[0153] [Comparative Example 1] The following formula (AL) The compound represented by the formula (I) was dissolved in Novec 7200 to a concentration of 20 mass % to prepare a surface treatment agent.

[0154] [Comparative Example 2] The following formula (AM) The compound represented by the formula (I) was dissolved in Novec 7200 to a concentration of 20 mass % to prepare a surface treatment agent.

[0155] [Comparative Example 3] The following formula (AN) The compound represented by the formula (I) was dissolved in Novec 7200 to a concentration of 20 mass % to prepare a surface treatment agent.

[0156] Preparation of Surface Treatment Agents and Formation of Hardened Coatings Surface treatment agents were prepared as in the above Examples and Comparative Examples. Each surface treatment agent was vacuum-deposited (treatment conditions: pressure: 2.0 × 10 -2 The coating was cured for 12 hours in an atmosphere of 25°C and 50% relative humidity (Pa, heating temperature: 700°C) to form a cured coating having a thickness of 10 nm. The coating thickness was measured by spectroscopic ellipsometry using a spectroscopic ellipsometer.

[0157] Evaluation of Water and Oil Repellency [Evaluation of Initial Water and Oil 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 contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The results (initial water contact angle) are shown in Table 1. Initially, both the Examples and Comparative Examples showed good water repellency.

[0158] [Evaluation of Abrasion Resistance] The glass having 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 abrasion resistance. The test environmental conditions were 25°C and a relative humidity of 40%. The results (water contact angle after steel wool abrasion, water contact angle after eraser abrasion) are shown in Table 1. Steel wool abrasion resistance Steel wool: Bonstar #0000 Contact area: 1 cm 2 Travel distance (one way): 40 mm Travel speed: 4,800 mm / min Load: 1 kgf / 1 cm 2 Number of abrasions: 10,000 times Eraser abrasion resistance Eraser: Rubber Eraser (manufactured by Minoan Co., Ltd.) Contact area: 6 mmφ Travel distance (one way): 40 mm Travel speed: 3,600 mm / min Load: 1 kgf / 6 mmφ Number of abrasions: 10,000 times

[0159] The surface treatment agents of Examples 1 to 7, in which the polyether group of the compound used was located on a secondary carbon, ensured molecular mobility of the polyether group, resulting in high eraser abrasion resistance while exhibiting steel wool abrasion resistance. The surface treatment agent of Comparative Example 1 exhibited low eraser abrasion resistance and steel wool abrasion resistance, while the surface treatment agent of Comparative Example 2 exhibited high steel wool abrasion resistance but low eraser abrasion resistance. Furthermore, the surface treatment agent of Comparative Example 3 exhibited poor eraser abrasion resistance compared to the Examples because the polyether group of the compound used was located on a tertiary carbon, restricting molecular movement. As described above, the surface treatment agents of the Examples were able to achieve high levels of both eraser abrasion resistance and steel wool abrasion resistance.

[0160]

[0161] Example 8 The compound obtained in Synthesis Example 1 was dissolved in Opteon SF10 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0162] Example 9 The compound obtained in Synthesis Example 2 was dissolved in AE3000 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0163] Example 10 The compound obtained in Synthesis Example 4 was dissolved in Novec 7200 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0164] Comparative Example 4 The compound (AL) was dissolved in Novec 7300 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0165] Comparative Example 5 The above compound (AM) was dissolved in Novec 7300 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0166] Comparative Example 6 The compound (AN) was dissolved in Novec 7300 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0167] Preparation of Surface Treatment Agents and Formation of Cured Coatings Surface treatment agents were prepared as in the above Examples and Comparative Examples. Each surface treatment agent was spray-coated onto glass (Corning Gorilla) and cured for 30 minutes in an atmosphere at 120°C, followed by curing for 12 hours in an atmosphere at 25°C and 50% relative humidity to form a cured coating with a thickness of 10 nm. The film thickness was measured by spectroscopic ellipsometry using a spectroscopic ellipsometer.

[0168] Evaluation of Water and Oil Repellency [Evaluation of Initial Water and Oil 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 contact angle meter Drop Master (manufactured by 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. Initially, both the Examples and Comparative Examples showed good water repellency.

[0169] [Evaluation of Abrasion Resistance] The glass having 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 abrasion resistance. The test environmental conditions were 25°C and a relative humidity of 40%. The results (water contact angle after steel wool abrasion, water contact angle after eraser abrasion) are shown in Table 2. Steel wool abrasion resistance Steel wool: Bonstar #0000 Contact area: 1 cm 2 Travel distance (one way): 40 mm Travel speed: 4,800 mm / min Load: 1 kgf / 1 cm 2 Number of abrasions: 10,000 times Eraser abrasion resistance Eraser: Rubber Eraser (manufactured by Minoan Co., Ltd.) Contact area: 6 mmφ Travel distance (one way): 40 mm Travel speed: 3,600 mm / min Load: 1 kgf / 6 mmφ Number of abrasions: 10,000 times

[0170] The surface treatment agents of Examples 8 to 10 exhibited high eraser abrasion resistance and high steel wool abrasion resistance, similar to those obtained with vapor deposition coating. The surface treatment agent of Comparative Example 4 exhibited low eraser abrasion resistance and steel wool abrasion resistance, while the surface treatment agent of Comparative Example 5 exhibited high steel wool abrasion resistance but low eraser abrasion resistance. Furthermore, the surface treatment agent of Comparative Example 6 exhibited inferior eraser abrasion resistance compared to the Examples because the polyether group of the compound used was located on a tertiary carbon, restricting molecular motion. As described above, even when the coating method was changed, the surface treatment agents of the Examples were able to achieve high levels of both eraser abrasion resistance and steel wool abrasion resistance.

[0171]

Claims

1. The following general formula (1): (In the formula, Rf is a monovalent or divalent fluoropolyether group, B is independently a single bond or a divalent organic group not containing a fluorine atom, E is independently a monovalent group having an oxyalkylene group, T is independently a single bond or a divalent organic group, U is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, V is independently a single bond or a divalent organic group, Z is independently a single bond or a trivalent to octavalent organic group, Y is independently a divalent hydrocarbon group which may have at least one bond selected from an oxygen atom, a sulfur 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, n is independently an integer of 1 to 3 for each silicon atom bonded thereto, m is independently an integer of 1 to 7, β is independently an integer of 1 to 3, and α is 1 or 2.) The fluoropolyether group-containing polymer has a hydroxyl group or a hydrolyzable group and a polyether group, and is represented by the following formula:

2. The fluoropolyether group-containing polymer according to claim 1, wherein α in the formula (1) is 1, and Rf is a group represented by the following general formula (2): (In the formula, A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group having a terminal -CF3 group, and W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer of 1 to 3 independently for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, the total of p, q, r, s, t, u, and v is 3 to 200, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.) 3. The fluoropolyether group-containing polymer according to claim 1, wherein α in the formula (1) is 2, and Rf is a group represented by the following general formula (3): (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 3 for each unit. p, q, r, s, t, u, and v are each an integer of 0 to 200, the total of p, q, r, s, t, u, and v is 3 to 200, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.) 4. The fluoropolyether group-containing polymer according to claim 1, wherein in the formula (1), Y is a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom or a sulfur atom, an alkylene group having 1 to 10 carbon atoms which contains an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 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.

5. The fluoropolyether group-containing polymer according to claim 1, wherein in the formula (1), B is a single bond, or a divalent group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure or a silarylene structure, a divalent group in which an alkylene group having 1 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, a carbonyl group, and an amide group, and which may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

6. The fluoropolyether group-containing polymer according to claim 1, wherein in the formula (1), T is a single bond, or a divalent group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure or a silarylene structure, a divalent group in which an alkylene group having 1 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, a carbonyl group, and an amide group, and which may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

7. The fluoropolyether group-containing polymer according to claim 1, wherein in said formula (1), U is selected from the group consisting of a single bond, a carbon atom, a silicon atom, a nitrogen atom, -CH=, and -Si(CH3)=.

8. The fluoropolyether group-containing polymer according to claim 1, wherein in said formula (1), Z is a single bond, or a linear organopolysiloxane residue having 2 to 10 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, and having a valence of 3 to 6.

9. The fluoropolyether group-containing polymer according to claim 1, wherein in said formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.

10. The fluoropolyether group-containing polymer according to claim 1, wherein in said formula (1), m is an integer of 1 to 3.

11. The fluoropolyether group-containing polymer according to claim 1, wherein in formula (1), β is 2 or 3.

12. The fluoropolyether group-containing polymer according to claim 1, wherein the fluoropolyether group-containing polymer represented by formula (1) is represented by any one of the following formulas: (In the formula, p1, q1, and s1 are each an integer of 1 to 200, provided that the sum of p1, q1, and s1 in each formula is 3 to 200. r1 and r2 are each an integer of 3 to 200. Each repeating unit shown in parentheses with p1, q1, and s1 may be bonded randomly. k is an integer of 1 to 30.) 13. A surface treatment agent comprising the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group according to any one of claims 1 to 12 and / or a partial (hydrolyzed) condensate thereof.

14. An article whose surface has been treated with the surface treatment agent according to claim 13.

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