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

Abstract

In the present invention, as a result of using a fluoropolyether group-containing polymer represented by formula (1), this surface treatment agent, which includes the polymer and / or a partial (hydrolysis) condensate thereof, can form a cured coating film having excellent water repellency and oil repellency, dry anti-eraser wear resistance, and wet eraser wear resistance. (In the formula, Rf represents a monovalent or divalent fluoropolyether group; B represents a single bond or a divalent organic group containing no fluorine atom; E independently represents a monovalent group having a urethane bond and a polyether chain; U represents a single bond or a divalent organic group; Z represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group; Y represents a divalent hydrocarbon group that optionally has at least one selected from among an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond; R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; X represents a hydroxyl group or a hydrolyzable group; n is independently 1 to 3 for each silicon atom to be bonded; m is 1 to 7; 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 that is excellent in water and oil repellency and abrasion resistance, particularly in abrasion resistance against dry and wet erasers; 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] Cured coatings of displays, lenses, anti-reflective coatings, etc. 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 dry erasers, but do not perform sufficiently in terms of abrasion resistance against wet (ethanol) erasers, and there has been a demand for a material that can achieve both dry and wet eraser 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 aims to provide a fluoropolyether group-containing polymer capable of forming a cured coating film that is excellent in water and oil repellency and abrasion resistance, particularly in abrasion resistance against dry and wet erasers; a surface treatment agent containing the polymer and / or a partial (hydrolyzed) condensate thereof; and an article that has been 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 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 that is excellent in water and oil repellency and dry eraser abrasion resistance, and also in wet 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): (wherein Rf is a monovalent or divalent fluoropolyether group, B is independently a single bond or a divalent organic group not containing fluorine atoms, E is independently a monovalent group having a urethane bond and a polyether chain, U is independently a single bond or a divalent organic group, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a tri- to octavalent organic group, Y is independently a divalent hydrocarbon group optionally having 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, and α is 1 or 2. [2] A fluoropolyether group-containing polymer according to [1], wherein α in 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] A fluoropolyether group-containing polymer according to any one of [1] to [3], wherein in the formula (1), E is a group represented by the following general formula (4): -O-CONH-W'(-(LO)k -R’) z(4) (In the formula, W' is a single bond, or a divalent or trivalent group which is X' or a combination of X' and an oxygen atom; X' is a divalent or trivalent group containing a urethane bond, urea bond, silicon atom, siloxane bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a silalkylene structure or a silarylene structure; L is independently an alkylene group having 1 to 4 carbon atoms; k is an integer of 1 to 20; R' is an alkyl group or phenyl group having 1 to 4 carbon atoms; and z is 1 or 2.) [5] [1] to [4], wherein Y is a fluoropolyether group-containing polymer selected from the group consisting of alkylene groups having 1 to 10 carbon atoms which may contain oxygen atoms or sulfur atoms, alkylene groups having 1 to 10 carbon atoms which contain an arylene group having 6 to 8 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. [6] In the formula (1), B is a single bond, or a divalent group containing no fluorine atom, 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, 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, and a carbonyl group, and the fluoropolyether group-containing polymer according to any one of [1] to [5], 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] In the formula (1), U is a single bond, or 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. [1] - [6] The fluoropolyether group-containing polymer according to any one of [1] to [6]. [8] The fluoropolyether group-containing polymer according to any one of [1] to [7], wherein in formula (1), Z is selected from the group consisting of a single bond, a carbon atom, a silicon atom, a nitrogen atom, -CH=, and a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, having a valence of 3 to 6. [9] The fluoropolyether group-containing polymer according to any one of [1] to [8], wherein in 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 the fluoropolyether group-containing polymer represented by formula (1) is represented by any one of the following formulas: (In the formula, p1, q1, r1, and s1 each represent an integer of 1 to 200, with the proviso that the sum of p1, q1, r1, and s1 in each formula is 3 to 200. The units shown in parentheses following p1, q1, r1, and s1 may be randomly bonded. k is an integer of 1 to 20.)

[11] A surface treatment agent comprising a fluoropolyether group-containing polymer having two or more hydroxyl group-containing silyl groups or hydrolyzable silyl groups and / or a partial (hydrolyzed) condensate thereof, wherein the fluoropolyether group-containing polymer has a monovalent or divalent fluoropolyether group and the hydroxyl group-containing silyl group or hydrolyzable silyl group bonded via a linking group, and the linking group has a tertiary carbon atom to which a urethane bond and a monovalent group having a polyether chain are bonded.

[12] A surface treatment agent comprising the fluoropolyether group-containing polymer and / or its partial (hydrolysis) condensate according to any one of [1] to

[10] .

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

[11] or

[12] .

[0013] The fluoropolyether group-containing polymer of the present invention has a monovalent group having a urethane bond and a polyether chain on a tertiary carbon atom in the molecule, and the polyether chain (polyether group) improves lubricity, and the urethane bonds have the property of attracting each other. 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, dry eraser abrasion resistance, and wet eraser abrasion resistance.

[0014] The fluoropolyether group-containing polymer of the present invention is represented by the following general formula (1), and has a monovalent or divalent fluoropolyether group and a reactive functional group in the molecule, and also has a monovalent group having a urethane bond and a polyether chain on a tertiary carbon atom. (In the formula, Rf is a monovalent or divalent fluoropolyether group; B is independently a single bond or a divalent organic group not containing fluorine atoms; E is independently a monovalent group having a urethane bond and a polyether chain; U is independently a single bond or a divalent organic group; Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, 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 to which it is bonded; m is independently an integer of 1 to 7; and α is 1 or 2.)

[0015] The fluoropolyether group-containing polymer of the present invention 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, it has a monovalent group having a urethane bond and a polyether chain on a tertiary carbon atom in the molecule.The polyether chain (polyether group) improves lubricity, and the urethane bonds have the property of attracting each other, so that a cured coating film having excellent water and oil repellency, dry eraser abrasion resistance, and wet 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). Note that a cured coating formed using a fluoropolyether group-containing polymer having such a monovalent or divalent fluoropolyether group will also exhibit a certain level of oil repellency if it exhibits good water repellency.

[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 terminated with a —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, 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, and a carbonyl 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. The divalent organic group does not contain a fluorine atom.

[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 8 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, 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 8, 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 a urethane bond and a polyether chain, and can be represented by the following general formula (4): -O-CONH-W'(-(LO) k -R') z (4)

[0027] In the above formula (4), W' is a single bond, or a divalent or trivalent group which is X' or a combination of X' and an oxygen atom, and X' is a divalent or trivalent group containing a urethane bond, urea bond, silicon atom, siloxane bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a silalkylene structure or a silarylene structure, and 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, ethyl group, propyl group, or butyl group, or a phenyl group, and may have a hydroxyl group or an alkoxy group such as a methoxy 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), etc.

[0028] Examples of such W′ include the following groups: In the following structure, the bond on the left side is bonded to the nitrogen atom, and the other bond is bonded to L. (wherein e is the same as above.)

[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. The carbon number may be a single group or a mixture of groups. In the above formula (4), k is an integer of 1 to 20, preferably an integer of 2 to 10. 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), z is 1 or 2, preferably 1.

[0030] Examples of such E include the following groups. (wherein e and k are the same as above.)

[0031] In the above formula (1), U is independently 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 arylene groups having 6 to 8 carbon atoms (e.g., alkylene-arylene groups 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, and the divalent organic group may contain an oxygen atom or a sulfur atom. Note that when Z is a single bond, U 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 8 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 U include the following groups in addition to a single bond: In the following structure, the left bond is bonded to a carbon atom, and the right bond is bonded to Z. (In the formula, f is an integer of 2 to 8, 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), Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, and the trivalent to octavalent organic group is preferably -CH=, a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 3 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, and a trivalent to hexavalent organopolysiloxane residue. Furthermore, the organopolysiloxane residue preferably contains 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).

[0035] 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.

[0036] Examples of such Z include the following, in addition to a single bond: In the following structure, it is preferred that the bond on the left side is bonded to U, and the other bond is bonded to Y.

[0037] 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.

[0038] 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 8 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).

[0039] Examples of such Y include the following groups: In the following structure, 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 8, 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.)

[0040] 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.

[0041] 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.

[0042] In the above formula (1), α is 1 or 2. Furthermore, n is independently an integer of 1 to 3, preferably 3, for each silicon atom to which it is bonded, and m is independently an integer of 1 to 7, preferably 1 or 3.

[0043] Examples of the structure of the fluoropolyether group-containing polymer represented by the above formula (1) include the following structures: By changing the combination of Rf, B, E, U, Z, Y, R, X, and n in the above formula (1), several types of fluoropolyether group-containing polymers can be obtained.

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051] (In the formula, k is the same as above. p1, q1, r1, and s1 each represent an integer of 1 to 200, provided that the total of p1, q1, r1, and s1 in each formula is 3 to 200. The units shown in parentheses with p1, q1, r1, and s1 may be bonded randomly.)

[0052] Examples of methods for preparing the fluoropolyether group-containing polymer 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 a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties, an organosilicon compound having a 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.

[0053] Here, in preparing the fluoropolyether group-containing polymer represented by formula (1), the fluoropolyether group-containing polymer having a monovalent group having a urethane bond and a polyether chain at one or both ends of the molecular chain and two or more olefin moieties can be exemplified by the fluoropolyether group-containing polymer represented by the following general formula (5): (In the formula, Rf, B, E, U, Z, m, and α 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.)

[0054] 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.

[0055] The fluoropolyether group-containing polymer represented by the formula (5) can be prepared, for example, by the following method: (wherein Rf, B, U, Z, Y', m, and α are the same as above), 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.

[0056] Examples of the fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, represented by the above formula (6), include the following.

[0057] (In the formula, p1, q1, r1, s1, and the sum of p1, q1, r1, and s1 in each formula are the same as above. In addition, each repeating unit shown in parentheses with p1, q1, r1, and s1 may be bonded randomly.)

[0058] Examples of the isocyanate group-containing polyether group-introducing agent to be reacted with the fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals represented by the above formula (6) include the following compounds.

[0059] (wherein e and k are the same as above.)

[0060] 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 hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, as represented by formula (6).

[0061] Examples of catalysts used in the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both 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 a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, represented by the above formula (6).

[0062] A solvent may be used in the method for preparing the fluoropolyether group-containing polymer represented by formula (5). 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 two or more olefin moieties at one or both molecular chain terminals, as represented by formula (6).

[0063] 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).

[0064] Examples of the fluoropolyether group-containing polymer represented by the above formula (5) include the following.

[0065]

[0066] (In the formula, k, p1, q1, r1, s1, and the sum of p1, q1, r1, and s1 in each formula are the same as above. In addition, each repeating unit shown in parentheses with p1, q1, r1, and s1 may be bonded randomly.)

[0067] In preparing the fluoropolyether group-containing polymer 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.

[0068] 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. 3 Examples 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.

[0069] 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.

[0070] In preparing the fluoropolyether group-containing polymer represented by formula (1), 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 4 equivalents, per equivalent of the olefin moiety of the fluoropolyether group-containing polymer having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties.

[0071] In preparing the fluoropolyether group-containing polymer represented by formula (1), 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 the hydrosilylation reaction 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 a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties.

[0072] In preparing the fluoropolyether group-containing polymer represented by formula (1), examples of the solvent include fluorine-based solvents, such as 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 a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties.

[0073] 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 a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties with a SiH group-containing halogenated (organic) silicon compound.

[0074] 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 (1).

[0075] As an alternative method for preparing the fluoropolyether group-containing polymer 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 a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more SiH groups, an organosilicon compound having an olefin moiety and a hydroxyl group or a hydrolyzable group in the molecule, 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. The organosilicon compound having an olefin moiety and a hydroxyl group or a hydrolyzable group in the molecule may be two different compounds, and in this case, the compound can be produced by adding them in stages.

[0076] Here, in another method for preparing the fluoropolyether group-containing polymer represented by formula (1), the fluoropolyether group-containing polymer having a monovalent group having a urethane bond and a polyether chain at one or both ends of the molecular chain and two or more SiH groups can be exemplified by the fluoropolyether group-containing polymer represented by the following general formula (11) or (12): (Wherein, Rf, B, E, U, m, and α are the same as above. Z 1 is a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 3 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, and having a valence of 3 to 6, provided that H is bonded to a silicon atom. (wherein Rf, B, E, U, Z, m, and α are the same as above, and Y 2 are independently divalent hydrocarbon groups having a silicon atom, provided that H is bonded to the silicon atom.

[0077] In the above formula (11), Z 1is a linear or branched or cyclic trivalent to hexavalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 3 to 8 silicon atoms, and having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms. The organopolysiloxane residue contains 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).

[0078] 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.

[0079] Such a Z 1 Examples of such a bond include those shown below. In the following structure, it is preferred that the bond on the left side is bonded to U, and the other bond is bonded to Y.

[0080] In the above formula (12), Y 2 is a divalent hydrocarbon group having a silicon atom and preferably having 1 to 18 carbon atoms. Specifically, the divalent hydrocarbon group is a group selected from the group consisting of a divalent group in which an alkylene group having 1 to 10 carbon atoms, which may contain an oxygen atom, is bonded to 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, which may contain an oxygen atom, 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.

[0081] Such a Y 2 Examples of such groups include the following: In the following structure, the left bond is bonded to Z, and the right bond is bonded to H. (In the formula, a, e, and f are the same as above.)

[0082] The fluoropolyether group-containing polymer represented by the formula (11) can be prepared, for example, by the following method: (wherein Rf, B, and α are the same as above, and U' is independently a single bond or a divalent organic group), 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, to prepare a fluoropolyether group-containing polymer having a monovalent group having a urethane bond and a polyether chain and two olefin moieties at one or both molecular chain terminals. Next, the resulting fluoropolyether group-containing polymer having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two olefin moieties is mixed with an organosilicon compound having no hydrolyzable groups in the molecule and having three or more SiH groups, and 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.

[0083] In the above formula (13), U' 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 8 carbon atoms, 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 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, and the divalent organic group may contain an oxygen atom or a sulfur atom.

[0084] Examples of U' include the following groups in addition to a single bond: In the following structure, the bond on the left is bonded to the carbon atom to which a hydroxyl group is bonded, and the bond on the right is bonded to the carbon atom of the olefin moiety. (wherein f, a, and e are the same as above, b″ is 0, 1, or 2, and c′ is an integer of 1 to 8.)

[0085] Examples of the fluoropolyether group-containing polymer having a hydroxyl group and two olefin moieties at one or both molecular chain terminals, represented by the above formula (13), include the following. (In the formula, p1, q1, 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.)

[0086] Examples of the isocyanate group-containing polyether group-introducing agent to be reacted with the fluoropolyether group-containing polymer having a hydroxyl group and two olefin moieties at one molecular chain terminal or both molecular chain terminals, represented by the above formula (13), include the above-mentioned isocyanate group-containing polyether group-introducing agents, and the following compounds are preferred: (wherein k is the same as above.)

[0087] 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 hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and two olefin moieties at one or both molecular chain terminals, as represented by formula (13).

[0088] Examples of catalysts used in the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and two olefin moieties at one or both molecular chain terminals, represented by the above formula (13), 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 a hydroxyl group and two olefin moieties at one or both molecular chain terminals, represented by the formula (13).

[0089] A solvent may be used in the reaction between the fluoropolyether group-containing polymer having a hydroxyl group and two olefin moieties at one or both molecular chain terminals, represented by the above formula (13), and the isocyanate group-containing polyether group-introducing agent. While the use of a solvent is not essential, examples of the solvent that can be used include the same fluorine-based solvents and organic solvents as exemplified in the above preparation method, and the blending amount 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 two olefin moieties at one or both molecular chain terminals, represented by the formula (13).

[0090] 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 a fluoropolyether group-containing polymer represented by the following general formula (14), which has a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two olefin moieties: (In the formula, Rf, B, E, U′, and α are the same as above.)

[0091] Examples of the fluoropolyether group-containing polymer represented by the above formula (14) having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two olefin moieties include the following: (In the formula, k, p1, q1, 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.)

[0092] Examples of organosilicon compounds having no hydrolyzable groups in the molecule and three or more SiH groups to be reacted with the fluoropolyether group-containing polymer represented by formula (14) above, which has a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two olefin moieties, include the following:

[0093] The amount of the organosilicon compound having no hydrolyzable groups in the molecule and three or more SiH groups used is 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 represented by formula (14) having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two olefin moieties.

[0094] Examples of the hydrosilylation catalyst used in the reaction of a fluoropolyether group-containing polymer having a monovalent group containing a urethane bond and a polyether chain at one or both molecular chain terminals and two olefin moieties, represented by the above formula (14), with an organosilicon compound having no hydrolyzable groups in the molecule and three or more SiH groups, include the same hydrosilylation catalysts as exemplified in the above preparation method, and the blending amount 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 a monovalent group containing a urethane bond and a polyether chain at one or both molecular chain terminals and two olefin moieties, represented by the formula (14).

[0095] Examples of solvents used in the reaction of a fluoropolyether group-containing polymer having a monovalent group containing a urethane bond and a polyether chain at one or both molecular chain terminals and two olefin moieties, represented by the above formula (14), with an organosilicon compound having no hydrolyzable groups in the molecule and three or more SiH groups, include the same fluorine-based solvents as 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 a fluoropolyether group-containing polymer having a monovalent group containing a urethane bond and a polyether chain at one or both molecular chain terminals and two olefin moieties, represented by the formula (14).

[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, 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.)

[0098] Next, as a method for preparing the fluoropolyether group-containing polymer represented by the above formula (12), for example, the following method can be mentioned: (wherein Rf, B, U, Z, m, and α are the same as above. Y 1are independently a single bond or a divalent hydrocarbon group which may have an oxygen atom.) A fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, represented by the formula (I), 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, to prepare a fluoropolyether group-containing polymer having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals, and two or more olefin moieties. Next, the resulting fluoropolyether group-containing polymer having a monovalent group containing a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties is mixed with an organosilicon compound having no hydrolyzable groups in the molecule and two SiH groups, and 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.

[0099] In the above formula (15), Y 1 are preferably divalent hydrocarbon groups having 1 to 10 carbon atoms, each of which may independently have a single bond or an oxygen atom. Examples of divalent hydrocarbon groups include those shown below. In the following structure, the bond on the left is bonded to Z, and the bond on the right is bonded to a carbon atom. (Wherein, a" is 1 or 2.)

[0100] Examples of the fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, represented by the above formula (15), include the following. (In the formulae, 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 to which p1 and q1 are added may be bonded randomly.)

[0101] Examples of the isocyanate group-containing polyether group-introducing agent to be reacted with the fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, represented by the above formula (15), include the above-mentioned isocyanate group-containing polyether group-introducing agents, and the following compounds are preferred: (wherein k is the same as above.)

[0102] 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 hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, as represented by formula (15).

[0103] Examples of catalysts used in the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, represented by the above formula (15), 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 a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, represented by the formula (15).

[0104] A solvent may be used in the reaction between the fluoropolyether group-containing polymer having a hydroxyl group and two or more olefin moieties at one or both molecular chain terminals, represented by the above formula (15), and the isocyanate group-containing polyether group-introducing agent. While the use of a solvent is not essential, examples of the solvent that can be used include the same fluorine-based solvents and organic solvents as exemplified in the above preparation method, and the blending amount 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 two or more olefin moieties at one or both molecular chain terminals, represented by the formula (15).

[0105] 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 a fluoropolyether group-containing polymer represented by the following general formula (16), which has a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties: (In the formula, Rf, B, E, U, Z, Y 1 , m, and α are the same as above.)

[0106] Examples of the fluoropolyether group-containing polymer represented by the above formula (16) having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties 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.)

[0107] Examples of organosilicon compounds having no hydrolyzable groups in the molecule and two SiH groups, which are to be reacted with the fluoropolyether group-containing polymer represented by formula (16) above and having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties, include the following: (wherein e and f are the same as above.)

[0108] The amount of the organosilicon compound having no hydrolyzable groups in the molecule and two 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 in the fluoropolyether group-containing polymer having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more olefin moieties, as represented by formula (16).

[0109] Examples of the hydrosilylation catalyst used in the reaction between the fluoropolyether group-containing polymer represented by formula (16) above, which has a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals, and two or more olefin moieties, and an organosilicon compound having no hydrolyzable groups in the molecule and two SiH groups, include the same hydrosilylation catalysts as exemplified in the above preparation method, and the blending amount can be 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 represented by formula (16), which has a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals, and two or more olefin moieties.

[0110] Examples of the solvent used in the reaction of the fluoropolyether group-containing polymer represented by the above formula (16), which has a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals, and two or more olefin moieties, with the organosilicon compound having no hydrolyzable groups in the molecule and two SiH groups, include the same fluorine-based solvents as 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 represented by the formula (16), which has a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals, and two or more olefin moieties.

[0111] 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 (12).

[0112] Examples of the fluoropolyether group-containing polymer represented by the above formula (12) include the following.

[0113]

[0114] (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.)

[0115] In another method for preparing the fluoropolyether group-containing polymer represented by formula (1), the organosilicon compound having an olefin moiety and a hydroxyl group or a hydrolyzable group in the molecule, which is to be reacted with the fluoropolyether group-containing polymer having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain ends and two or more SiH groups, is preferably a compound represented by the following general formula (17): (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.)

[0116] In the above formula (17), 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.

[0117] 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. Among these, vinyltrimethoxysilane and allyltrimethoxysilane are preferred.

[0118] In another method for preparing the fluoropolyether group-containing polymer 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, relative to 1 equivalent of SiH groups in the fluoropolyether group-containing polymer having a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more SiH groups.

[0119] Examples of the hydrosilylation catalyst used in this alternative method for preparing the fluoropolyether group-containing polymer represented by formula (1) include the same hydrosilylation catalysts as exemplified in the above preparation method, and the amount of the catalyst to be blended 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 a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more SiH groups.

[0120] Examples of the solvent used in the alternative method for preparing the fluoropolyether group-containing polymer represented by formula (1) include the same fluorine-based solvents as 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 a monovalent group having a urethane bond and a polyether chain at one or both molecular chain terminals and two or more SiH groups.

[0121] 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 (1).

[0122] The present invention also provides a surface treatment agent comprising the fluoropolyether group-containing polymer and / or its partial (hydrolysis) condensate, which has two or more hydroxyl-containing silyl groups or hydrolyzable silyl groups, characterized in that the fluoropolyether group-containing polymer is characterized in that the fluoropolyether group-containing polymer is monovalent or divalent fluoropolyether group and the hydroxyl-containing silyl group or hydrolyzable silyl group are bonded via a linking group, and the linking group has a tertiary carbon atom to which the monovalent group having urethane bond and polyether chain is bonded.Preferably, the fluoropolyether group-containing polymer is the fluoropolyether group-containing polymer represented by the above formula (1).

[0123] That is, the present invention provides a surface treatment agent containing a fluoropolyether group-containing polymer represented by the above formula (1) and / or its partial (hydrolyzed) condensate.The surface treatment agent only needs to contain the fluoropolyether group-containing polymer represented by the above formula (1) and / or its partial (hydrolyzed) condensate as the main component, and may also contain unreacted raw materials, reaction intermediates, etc. before the introduction of terminal hydroxyl groups or hydrolyzable groups into the fluoropolyether group-containing polymer represented by the above formula (1).In addition, in the present invention, the "partial (hydrolyzed) condensate" refers to a partial condensate or partial hydrolyzed condensate, and is obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer represented by the above formula (1) or the hydroxyl groups obtained by partially hydrolyzing the terminal hydrolyzable groups of the fluoropolyether group-containing polymer in advance by a known method.

[0124] If necessary, the surface treatment agent may contain a hydrolysis condensation catalyst, such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra n-butyl titanate, tetra n-propyl titanate, etc.), an organozirconium 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 represented by the above formula (1) and / or its partial (hydrolysis) condensate.

[0125] 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.

[0126] The above-mentioned solvent may be a mixture of two or more kinds, and it is preferable to dissolve the fluoropolyether group-containing polymer 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 may be an amount that is easy to measure, but in the case of direct coating, it is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer, and in the case of vapor deposition treatment, it is preferably 1 to 100 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer.

[0127] 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 humid conditions. Furthermore, 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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. In the following examples, p1, q1, and the molar amount in the formula are 19 F-NMR, 1 This is a value calculated from the results of analysis such as H-NMR.

[0133] Synthesis Example 1 A reaction vessel was charged with a compound represented by the following formula (1-A): 120 g (2.84 × 10 -2 mol), 120 g of 1,3-bis(trifluoromethyl)benzene, 21.5 g (0.113 mol) of a compound represented by the formula (I), 0.6 g (1.06 × 10-3 After mixing the above 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, yielding 125 g of a compound represented by the following formula (1-C).

[0134] Into a reaction vessel, 100 g (2.30 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 11.2 g of trimethoxysilane (9.18 × 10 -2 mol), and 8.51 × 10 chloroplatinic acid / vinylsiloxane complex in toluene -2 g (2.23 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 101 g of a liquid product.

[0135] The resulting compound is 1 H-NMR confirmed that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (1-D).

[0136] Synthesis Example 2 A reaction vessel was charged with a compound represented by the following formula (2-A): 60 g (1.41 × 10 -2 mol), 60 g of 1,3-bis(trifluoromethyl)benzene, 18.1 g (5.62 × 10) of a compound represented by the formula -2 mol), titanium tetra-2-ethylhexoxide 0.3 g (5.31 × 10 -4 After mixing the above 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, yielding 58 g of a compound represented by the following formula (2-C).

[0137] Into a reaction vessel, 50 g (1.10 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 5.39 g of trimethoxysilane (4.41 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.09 × 10 -2 g (1.07 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.

[0138] The resulting compound is 1 It was confirmed by H-NMR that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (2-D).

[0139] Synthesis Example 3 A reaction vessel was charged with a compound represented by the following formula (3-A): 60 g (1.32 × 10 -2 mol), 60 g of 1,3-bis(trifluoromethyl)benzene, 17.0 g (5.28 × 10 -2 mol), titanium tetra-2-ethylhexoxide 0.3 g (5.31 × 10 -4 After mixing the above 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, yielding 62 g of a compound represented by the following formula (3-C).

[0140] Into a reaction vessel, 50 g (1.06 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 5.16 g of trimethoxysilane (4.41 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.92 × 10 -2 g (1.03 x 10 as Pt alone) -6The 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.

[0141] The resulting compound is 1 It was confirmed by H-NMR that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (3-D).

[0142] Synthesis Example 4 A reaction vessel was charged with a compound represented by the following formula (4-A): 120 g (2.84 × 10 -2 mol), 120 g of 1,3-bis(trifluoromethyl)benzene, 46.5 g (0.114 mol) of a compound represented by the formula (I), 0.6 g (1.06 × 10 -4 After mixing the above 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 128 g of a compound represented by the following formula (4-C).

[0143] Into a reaction vessel, 100 g (2.19 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 10.7 g of trimethoxysilane (8.74 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 8.10 × 10 -2 g (2.12 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 102 g of a liquid product.

[0144] The resulting compound is 1 It was confirmed by H-NMR that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (4-D).

[0145] Synthesis Example 5 A reaction vessel was charged with a compound represented by the following formula (5-A): 60 g (1.42 × 10 -2 mol), 60 g of 1,3-bis(trifluoromethyl)benzene, 34.9 g (5.68 × 10 -2 mol), titanium tetra-2-ethylhexoxide 0.3 g (5.31 × 10 -4 After mixing the above 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 68 g of a compound represented by the following formula (5-C).

[0146] Into a reaction vessel, 50 g (1.05 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 5.11 g of trimethoxysilane (4.18 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.88 × 10 -2 g (1.02 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 49 g of a liquid product.

[0147] The resulting compound is 1 H-NMR confirmed that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (5-D).

[0148] Synthesis Example 6 A reaction vessel was charged with a compound represented by the following formula (6-A): 60 g (9.60 × 10 -3 mol), 60 g of 1,3-bis(trifluoromethyl)benzene, 15.7 g (3.84 × 10 -2 mol), titanium tetra-2-ethylhexoxide 0.3 g (5.31 × 10 -4After 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 60 g of a compound represented by the following formula (6-C).

[0149] Into a reaction vessel, 50 g (7.51 × 10) of the compound represented by formula (6-C) obtained above was added. -3 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 3.66 g of trimethoxysilane (3.00 × 10 -2 mol), and 2.78 × 10 chloroplatinic acid / vinylsiloxane complex in toluene -2 g (7.29 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 50 g of a liquid product.

[0150] The resulting compound is 1 It was confirmed by H-NMR that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (6-D).

[0151] Synthesis Example 7 A reaction vessel was charged with a compound represented by the following formula (7-A): 60 g (1.50 × 10 -2 mol), 60 g of 1,3-bis(trifluoromethyl)benzene, 33.3 g (0.120 mol) of a compound represented by the formula (I), 0.3 g (5.31 × 10 -4 After mixing the above 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, yielding 64 g of a compound represented by the following formula (7-C).

[0152] Into a reaction vessel, 50 g (1.10 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 10.7 g of trimethoxysilane (8.78 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.07 × 10 -2 g (1.07 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 23 g of a liquid product.

[0153] The resulting compound is 1 It was confirmed by H-NMR that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (7-D).

[0154] Synthesis Example 8 A reaction vessel was charged with a compound represented by the following formula (8-A): 120 g (2.84 × 10 -2 mol), 120 g of 1,3-bis(trifluoromethyl)benzene, 41.5 g (0.114 mol) of a compound represented by the formula (I), 0.6 g (1.06 × 10 -4 After mixing the above 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 119 g of a compound represented by the following formula (8-C).

[0155] Into a reaction vessel, 100 g (2.24 × 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, and 8.31 × 10 toluene solution of a chloroplatinic acid / vinylsiloxane complex. -2 g (2.18 x 10 as Pt alone) -6mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 103 g of a compound represented by the following formula (8-E).

[0156] Into a reaction vessel, 50 g (9.95 × 10 -3 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 27.7 g (0.119 mol) of octenyltrimethoxysilane, and 3.69 × 10 toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (9.66 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 62 g of a liquid product.

[0157] The resulting compound is 1 H-NMR confirmed that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (8-F):

[0158] Synthesis Example 9 A reaction vessel was charged with a compound represented by the following formula (9-A): 120 g (2.86 × 10 -2 mol), 120 g of 1,3-bis(trifluoromethyl)benzene, 26.7 g (0.114 mol) of a compound represented by the formula (I), 0.6 g (1.06 × 10 -4 After mixing the above 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, yielding 121 g of a compound represented by the following formula (9-C).

[0159] Into a reaction vessel, 100 g (2.26 × 10 -2mol), 100 g of 1,3-bis(trifluoromethyl)benzene, 49.6 g (0.370 mol) of 1,1,3,3-tetramethyldisiloxane, and 8.56 × 10 toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (2.24 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 102 g of a compound represented by the following formula (9-D).

[0160] Into a reaction vessel, 50 g (1.07 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 6.97 g of allyltrimethoxysilane (4.30 × 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 52 g of a liquid product.

[0161] The resulting compound is 1 It was confirmed by H-NMR that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (9-E).

[0162] Synthesis Example 10 A reaction vessel was charged with a compound represented by the following formula (10-A): 60 g (1.42 × 10 -2 mol), 60 g of 1,3-bis(trifluoromethyl)benzene, 25.7 g (5.66 × 10) of a compound represented by -2 mol), titanium tetra-2-ethylhexoxide 0.3 g (5.31 × 10 -4After mixing the above 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, yielding 64 g of a compound represented by the following formula (10-C).

[0163] Into a reaction vessel, 50 g (1.08 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 5.25 g of trimethoxysilane (4.30 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.99 × 10 -2 g (1.05 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.

[0164] The resulting compound is 1 H-NMR confirmed that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (10-D).

[0165] Synthesis Example 11 A reaction vessel was charged with a compound represented by the following formula (11-A): 60 g (1.42 × 10 -2 mol), 60 g of 1,3-bis(trifluoromethyl)benzene, 18.3 g (5.70 × 10) of a compound represented by the formula -2 mol), titanium tetra-2-ethylhexoxide 0.3 g (5.31 × 10 -4 After mixing the above 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 57 g of a compound represented by the following formula (11-C).

[0166] Into a reaction vessel, 50 g (1.10 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 7.24 g of triethoxysilane (4.41 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.09 × 10 -2 g (1.07 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.

[0167] The resulting compound is 1 It was confirmed by H-NMR that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (11-D).

[0168] Synthesis Example 12 A reaction vessel was charged with a compound represented by the following formula (12-A): 60 g (1.42 × 10 -2 mol), 60 g of 1,3-bis(trifluoromethyl)benzene, 25.8 g (5.70 × 10) of a compound represented by -2 mol), titanium tetra-2-ethylhexoxide 0.3 g (5.31 × 10 -4 After mixing the above 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 55 g of a compound represented by the following formula (12-C).

[0169] Into a reaction vessel, 50 g (1.07 × 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 5.23 g of trimethoxysilane (4.29 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.97 × 10 -2 g (1.04 x 10 as Pt alone) -6mol) 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.

[0170] The resulting compound is 1 H-NMR confirmed that the polymer was a fluoropolyether group-containing polymer having the structure represented by the following formula (12-D).

[0171] Example 1 The compound represented by formula (1-D) obtained in Synthesis Example 1 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0172] Example 2 The compound represented by formula (2-D) obtained in Synthesis Example 2 was dissolved in Opteon SF10 (manufactured by Mitsui-Chemours Fluoroproducts, Inc., methyl perfluoroheptenyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0173] Example 3 The compound represented by formula (4-D) obtained in Synthesis Example 4 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0174] Example 4 The compound represented by formula (5-D) obtained in Synthesis Example 5 was dissolved in Asahiklin AC-6000 (manufactured by AGC, tridecafluorooctane) to a concentration of 20 mass % to prepare a surface treatment agent.

[0175] Example 5 The compound represented by formula (6-D) obtained in Synthesis Example 6 was dissolved in Novec 7300 (manufactured by 3M, methyl perfluorohexyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0176] Example 6 The compound represented by formula (8-F) obtained in Synthesis Example 8 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0177] Example 7 The compound represented by formula (10-D) obtained in Synthesis Example 10 was dissolved in Asahiklin AE-3000 (manufactured by AGC, tetrafluoroethyl trifluoroethyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0178] Example 8 The compound represented by formula (11-D) obtained in Synthesis Example 11 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0179] Example 9 The compound represented by formula (12-D) obtained in Synthesis Example 12 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0180] [Comparative Example 1] A compound represented by the following formula (Y) The compound represented by the formula (I) was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0181] [Comparative Example 2] A compound represented by the following formula (Z) The compound represented by the formula (I) was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0182] 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.

[0183] Evaluation of Water Repellency [Evaluation of Initial Water Repellency] For the glass on which the cured coating prepared above was formed, the contact angle (water repellency) of the cured coating with water was measured using a 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.

[0184] [Evaluation of Abrasion Resistance] The glass having the cured coating formed thereon prepared as described above 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 described above to evaluate abrasion resistance. The test environmental conditions were 25°C and a relative humidity of 40%. The results (water contact angle after abrasion) are shown in Table 1. Dry eraser abrasion resistance Eraser: Rubber Eraser (manufactured by Minoan Co., Ltd.) Contact area: 6 mmφ Travel distance (one way): 60 mm Travel speed: 3,600 mm / min Load: 1 kgf / 1 cm 2 Number of abrasions: 5,000 times Wet eraser abrasion resistance Eraser: Rubber Eraser (manufactured by Minoan Co., Ltd.) Contact area: 6 mmφ Travel distance (one way): 20 mm Travel speed: 1,600 mm / min Load: 1 kgf / 1 cm 2 Ethanol discharge amount: 0.3 ml / min Number of wears: 10,000 times

[0185] The surface treatment agents of Examples 1 to 9 exhibited improved wettability due to the presence of polyether groups in the molecules of the compounds used, resulting in high dry eraser abrasion durability. Furthermore, the presence of urethane bonds in the molecules confirmed high wet eraser abrasion durability. The surface treatment agent of Comparative Example 1 did not have either polyether groups or urethane bonds in the molecules of the compounds used, resulting in low dry and wet eraser abrasion durability. The surface treatment agent of Comparative Example 2 exhibited high dry eraser abrasion durability but low wet eraser abrasion durability. As described above, the surface treatment agents of the Examples were able to achieve high levels of both dry eraser abrasion durability and wet eraser abrasion durability.

[0186]

[0187] Example 10 The compound represented by formula (1-D) obtained in Synthesis Example 1 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 0.1 mass % to prepare a surface treatment agent.

[0188] Example 11 The compound represented by formula (2-D) obtained in Synthesis Example 2 was dissolved in Opteon SF10 (manufactured by Mitsui-Chemours Fluoroproducts, Inc., methyl perfluoroheptenyl ether) to a concentration of 0.1 mass % to prepare a surface treatment agent.

[0189] Example 12 The compound represented by formula (4-D) obtained in Synthesis Example 4 was dissolved in Novec 7300 (manufactured by 3M, methyl perfluorohexyl ether) to a concentration of 0.1 mass % to prepare a surface treatment agent.

[0190] Example 13 The compound represented by formula (6-D) obtained in Synthesis Example 6 was dissolved in Asahiklin AC-6000 (manufactured by AGC, tridecafluorooctane) to a concentration of 0.1 mass % to prepare a surface treatment agent.

[0191] Comparative Example 3 The compound (Y) was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0192] Comparative Example 4 The compound (Z) was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0193] 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.

[0194] Evaluation of Water Repellency [Evaluation of Initial Water Repellency] For the glass on which the cured coating prepared above was formed, the contact angle (water repellency) of the cured coating with water was measured using a 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.

[0195] [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 abrasion) are shown in Table 2. Dry eraser abrasion resistance Eraser: Rubber Eraser (manufactured by Minoan Co., Ltd.) Contact area: 6 mmφ Travel distance (one way): 60 mm Travel speed: 3,600 mm / min Load: 1 kgf / 1 cm 2 Number of abrasions: 5,000 times Wet eraser abrasion resistance Eraser: Rubber Eraser (manufactured by Minoan Co., Ltd.) Contact area: 6 mmφ Travel distance (one way): 20 mm Travel speed: 1,600 mm / min Load: 1 kgf / 1 cm 2 Ethanol discharge amount: 0.3 ml / min Number of wears: 10,000 times

[0196] The surface treatment agents of Examples 10 to 13 showed high dry eraser abrasion resistance and wet eraser abrasion resistance, similar to when vapor-deposited coated. The surface treatment agent of Comparative Example 3 showed low eraser abrasion resistance and steel wool abrasion resistance, and the surface treatment agent of Comparative Example 4 showed high dry eraser abrasion resistance but low wet eraser abrasion resistance. 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 dry eraser abrasion resistance and wet eraser abrasion resistance.

[0197]

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 a urethane bond and a polyether chain, U is independently a single bond or a divalent organic group, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, Y is independently a divalent hydrocarbon group which may have at least one selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, 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, and α is 1 or 2.) A fluoropolyether group-containing polymer represented by the 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 -CF3 group at the terminal, 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, v are each an integer of 0 to 200, and the sum of p, q, r, s, t, u, v is 3 to 200. These units may be linear or branched. Also, each repeating unit shown in the parentheses with p, q, r, s, t, u, 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, v are each an integer of 0 to 200, and the sum of p, q, r, s, t, u, v is 3 to 200, and each of these units may be linear or branched. Further, each repeating unit shown in the parentheses with p, q, r, s, t, u, v may be randomly bonded.) 4. The fluoropolyether group-containing polymer according to claim 1, wherein in the formula (1), E is a group represented by the following general formula (4). -O-CONH-W'(-(LO) k -R') z (4) (In the formula, W' is a single bond, or a divalent or trivalent group which is X' or a combination of X' and an oxygen atom, X' is a divalent or trivalent group containing a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a urethane bond, a urea bond, a silicon atom, a siloxane bond, a silaalkylene structure or a silarylene structure, L is independently an alkylene group having 1 to 4 carbon atoms, k is an integer of 1 to 20, R' is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and z is 1 or 2.) 5. 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 containing 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 silaalkylene structure or a silaarylene 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. The fluoropolyether group-containing polymer according to claim 1.

6. In the formula (1), B is a divalent group selected from the group consisting of a single bond, an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms containing 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 silaalkylene structure or a silaarylene 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, and a carbonyl 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 and does not contain a fluorine atom. The fluoropolyether group-containing polymer according to claim 1.

7. In the formula (1), U is a group selected from the group consisting of a single bond, 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 containing 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 silaalkylene structure or a silaarylene 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. The fluoropolyether group-containing polymer according to claim 1.

8. The fluoropolyether group-containing polymer according to claim 1, wherein in the formula (1), Z is selected from the group consisting of a single bond, a carbon atom, a silicon atom, a nitrogen atom, -CH=, and a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent to hexavalent organopolysiloxane residue having 3 to 10 silicon atoms.

9. The fluoropolyether group-containing polymer according to claim 1, 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 represented by the formula (1) is the fluoropolyether group-containing polymer according to claim 1, which is represented by any of the following formulas. (In the formula, p1, q1, r1, and s1 are each an integer of 1 to 200, provided that the sum of p1, q1, r1, and s1 in each formula is 3 to 200. Each unit shown in the parentheses with p1, q1, r1, and s1 may be randomly bonded. k is an integer of 1 to 20.) 11. A surface treatment agent containing a fluoropolyether group-containing polymer having two or more hydroxyl group-containing silyl groups or hydrolyzable silyl groups and / or a partial (hydrolyzed) condensate thereof, wherein the fluoropolyether group-containing polymer has a monovalent or divalent fluoropolyether group and the hydroxyl group-containing silyl group or hydrolyzable silyl group are bonded via a linking group, and the linking group has a tertiary carbon atom to which a monovalent group having a urethane bond and a polyether chain is bonded. A surface treatment agent containing a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof.

12. A surface treatment agent containing the fluoropolyether group-containing polymer according to any one of claims 1 to 10 and / or a partial (hydrolyzed) condensate thereof.

13. An article surface-treated with the surface treatment agent according to claim 12.

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