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

Abstract

To provide a fluoropolyether group-containing polymer capable of forming a cured film having excellent water and oil repellency and abrasion resistance.SOLUTION: There is provided a fluoropolyether group-containing polymer of the following formula (1). (Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, B is a divalent organic group, V is C, Si, N or a tri- to octavalent organic group, E is a monovalent group having an oxyalkylene group, R' is H, OH, an alkyl group, a phenyl group, an alkoxy group or a halogen atom, U is a single bond or a divalent organic group, Z is a single bond, C, Si, N, or a tri- to octavalent organic group, Y is O, S, Si, or a divalent hydrocarbon group which may have a siloxane bond, R is an alkyl group or a phenyl group, X is a hydroxy group or a hydrolyzable group, n is 1 to 3, m is 1 to 7, α is 1 or 2, β is 1 to 6, γ is 0 or 1, δ is 1 or 2.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluorooxyalkylene group-containing polymer residue in the molecule), and more particularly to a fluoropolyether group-containing polymer that forms a coating excellent in water and oil repellency and abrasion resistance, 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. [Background technology]

[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 possess properties such as water and oil repellency, chemical resistance, lubricity, mold release properties, and stain resistance. These properties have led to a wide range of industrial applications, including water, oil, and stain repellency agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, mold release agents, cosmetics, and protective films. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and while they can be applied to the surface of a substrate, it has been difficult to form a coating that adheres to it.

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

[0005] Therefore, 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, etc. on the substrate surfaces (Patent Documents 1 to 6: JP-A Nos. 2008-534696, 2008-537557, JP-A Nos. 2012-072272, 2012-157856, 2013-136833, and 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 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 has been introduced into a fluoropolyether group-containing compound (Patent Document 7: International Publication No. 2017 / 212850).

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

[0009] [Patent Document 1] Special Publication No. 2008-534696 [Patent Document 2] Special Publication No. 2008-537557 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-072272 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-157856 [Patent Document 5] Japanese Patent Application Laid-Open No. 2013-136833 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-199906 [Patent Document 7] International Publication No. 2017 / 212850 Summary of the Invention [Problem to be solved by the invention]

[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 having excellent water and oil repellency and abrasion resistance, a surface treatment agent containing the polymer and / or a partial (hydrolyzed) condensate thereof, and an article surface-treated with the surface treatment agent. [Means for solving the problem]

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

[0012] Therefore, the present invention provides the following fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluorooxyalkylene group-containing polymer residue in the molecule), surface treatment agent, and article. [1] The following general formula (1) [ka] (In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue; B is independently a divalent organic group; V is independently a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group; E is independently a monovalent group having an oxyalkylene group; R' is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen group; 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 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; α is 1 or 2; β is independently an integer of 1 to 6; γ is independently 0 or 1; δ is independently 1 or 2; and the sum of β, γ, and δ is independently an integer of 2 to 7 for each V to which it is bonded. The fluoropolyether group-containing polymer has a hydroxyl group or a hydrolyzable group and a polyether group, and is represented by the formula: [2] The fluoropolyether group-containing polymer according to [1], wherein α in the formula (1) is 1 and Rf is a group represented by the following general formula (2): [ka] (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, and p, q, r, s, t, u, and v are each integers of 0 to 200, such that p+q+r+s+t+u+v=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] The fluoropolyether group-containing polymer according to [1], wherein α in the formula (1) is 2 and Rf is a group represented by the following general formula (3): [ka] (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, such that p+q+r+s+t+u+v=3 to 200, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.) [4] The fluoropolyether group-containing polymer according to any one of [1] to [3], wherein in the formula (1), B is a divalent group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a diorganosilylene group, a silalkylene structure or a silarylene structure, a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl group, and an amide group, and which may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group. [5] The fluoropolyether group-containing polymer according to any one of [1] to [4], wherein in the formula (1), V is a carbon atom, a silicon atom, a nitrogen atom, a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent isocyanuric group, or a trivalent triazine ring-containing group. [6] The fluoropolyether group-containing polymer according to any one of [1] to [5], wherein in the formula (1), Y is a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom or a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are mutually bonded via a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms. [7] The fluoropolyether group-containing polymer according to any one of [1] to [6], wherein 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 and a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are mutually bonded via a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms. [8] The fluoropolyether group-containing polymer according to any one of [1] to [7], wherein in the formula (1), Z is any one 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, and having a valence of 3 to 6. [9] The fluoropolyether group-containing polymer according to any one of [1] to [8], wherein in the formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.

[10] The fluoropolyether group-containing polymer according to any one of [1] to [9], wherein the fluoropolyether group-containing polymer represented by formula (1) is represented by any one of the following formulas: [ka] [ka] [ka] [ka] [ka]

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[11] A surface treatment agent comprising a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group and / or a partial (hydrolyzed) condensate thereof.

[12] The surface treatment agent according to

[11] , wherein the polyether group in the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group is a group containing a monovalent oxyalkylene group located at a branched portion of the molecular chain.

[13] The surface treatment agent according to

[11] or

[12] , wherein the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group is the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group according to any one of [1] to

[10] .

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

[11] to

[13] . [Effects of the Invention]

[0013] The fluoropolyether group-containing polymer of the present invention, which has a hydroxyl group or a hydrolyzable group and a polyether group, has improved substrate adhesion and wettability due to the presence of polyether groups in the molecule in a predetermined structure, and as a result, articles surface-treated with a surface treatment agent containing the polymer and / or its partial (hydrolyzed) condensate exhibit excellent water and oil repellency, eraser abrasion resistance, and steel wool abrasion resistance. DETAILED DESCRIPTION OF THE INVENTION

[0014] As used herein, the term "about (numeric value)" refers to a numerical value (approximate number) that is rounded off. When the last digit of the displayed numerical value is not "0," the last digit is rounded off to the nearest whole number, thereby encompassing the range of the displayed numerical value. For example, "about 3 equivalents" refers to 2.5 equivalents or more and 3.4 equivalents or less, and "about 0.02 equivalents" refers to 0.015 equivalents or more and 0.024 equivalents or less. Furthermore, when the last digit of the displayed numerical value is "0," the last digit is rounded off to the nearest whole number, thereby encompassing the range of the displayed numerical value. For example, "about 80°C" refers to 75°C or more and 84°C or less. Furthermore, in the present invention, the term "partial (hydrolyzed) condensate" refers to a partial condensate or a partial hydrolyzed condensate.

[0015] The fluoropolyether group-containing polymer of the present invention, which has a fluoropolyether group (a monovalent or divalent fluorooxyalkylene group-containing polymer residue) and a reactive functional group in the molecule and also has a polyether group, is a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the following general formula (1): [ka] (In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue; B is independently a divalent organic group; V is independently a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group; E is independently a monovalent group having an oxyalkylene group; R' is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen group; 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 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; α is 1 or 2; β is independently an integer of 1 to 6; γ is independently 0 or 1; δ is independently 1 or 2; and the sum of β, γ, and δ is independently an integer of 2 to 7 for each V to which it is bonded.

[0016] The fluoropolyether group-containing polymer of the present invention, which has a hydroxyl group or a hydrolyzable group and a polyether group, has a structure in which a fluorooxyalkyl group or a fluorooxyalkylene group (i.e., a monovalent or divalent fluorooxyalkylene group-containing polymer residue) and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group, and has a polyether group in the molecule. Furthermore, the long molecular chain between the fluorooxyalkylene group-containing polymer residue and the polyether group improves substrate adhesion and wettability, and is characterized by excellent water and oil repellency, eraser abrasion resistance, and steel wool abrasion resistance.

[0017] In the above formula (1), Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and when α is 1 (i.e., when Rf is a monovalent fluorooxyalkylene group-containing polymer residue), 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 fluorooxyalkylene group-containing polymer residue), it is preferably a divalent fluoropolyether group represented by the following general formula (3).

[0018] [ka] [ka] (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, and p, q, r, s, t, u, and v are each integers of 0 to 200, such that p+q+r+s+t+u+v=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.)

[0019] In the above formula (2), A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group terminated with a -CF3 group, and is preferably a fluorine atom.

[0020] 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 Units, 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.

[0021] In the above formulas (2) and (3), d is an integer of 1 to 3, preferably 1 or 2, independently for each unit. Furthermore, p, q, r, s, t, u, and v are each integers of 0 to 200, preferably p is an integer of 0 to 100, particularly 5 to 100, q is an integer of 0 to 100, particularly 5 to 100, r is an integer of 0 to 100, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, and v is an integer of 0 to 100, and p+q+r+s+t+u+v is 3 to 200, preferably 10 to 100, and p+q is preferably 10 to 105, particularly 15 to 60, and it is preferable that r=s=t=u=v=0. If p+q+r+s+t+u+v is smaller than the upper limit, adhesion and curability are good, and if it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable.

[0022] 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.

[0023] Specific examples of Rf include the following: [ka] [ka] [ka] [ka] (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 sum 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 sum 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.)

[0024] In the above formula (1), B is independently a divalent organic group, which is a linking group connecting the Rf group and the V group. The divalent organic group is a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a diorganosilylene group, a silalkylene structure, or a silarylene structure, a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl group, and an amide group, and the divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group. When B is a divalent organic group, flexibility can be imparted between the Rf group and the branched group V having a polyether group, and the mobility of the molecule is increased, resulting in good abrasion resistance.

[0025] Here, the group bonded to a silicon atom in a diorganosilylene group, a silalkylene structure, a silarylene structure, or an organopolysiloxane residue is preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group. Furthermore, the alkylene group in the silalkylene structure is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group).

[0026] 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 V. [ka] [ka] [ka] [ka] (In the formula, f is an integer of 2 to 4, a, a', and b are each an integer of 1 to 4, c is an integer of 1 to 10, and e is an integer of 1 to 9.)

[0027] In the formula (1), each V is independently a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, and is preferably a carbon atom, a silicon atom, a nitrogen atom, a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 5 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 5 silicon atoms, a trivalent isocyanuric group, or a trivalent triazine ring-containing group. Furthermore, the organopolysiloxane residue preferably contains a silalkylene structure in which two silicon atoms are bonded by an alkylene group, i.e., Si-(CH2) x It may contain —Si (where x is an integer of 2 to 6).

[0028] The organopolysiloxane residue may have 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.

[0029] Examples of such V include the following: [ka] [ka] [ka] [ka]

[0030] In the above formula (1), E is independently a monovalent group having an oxyalkylene group, -W'(-(LO) k -R”) f’ It can be expressed as: Here, W' is a single bond, an oxygen atom, X', or a divalent or trivalent group that is a combination of X' and an oxygen atom, and X' is a nitrogen atom, a silicon atom, a divalent or trivalent group containing a divalent hydrocarbon group having 1 to 20 carbon atoms that may have a siloxane bond, a silalkylene bond, or a silarylene bond, or an amide group, 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 a hydrolyzable group. Furthermore, the alkylene group in the silalkylene bond is preferably an alkylene group having 1 to 6 carbon atoms, particularly an alkylene group having 2 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group). L is independently an alkylene group having 1 to 4 carbon atoms, such as a methylene group, ethylene group, propylene group, or butylene group, and the carbon atoms may be a single group or a mixture. k is an integer of 1 to 20, and preferably an integer of 1 to 10. R" is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, and of these, a methyl group is preferred. f' is 1 or 2.

[0031] Examples of such E include the following groups. [ka] [ka] [ka] [ka] (wherein k is the same as above.)

[0032] In the above formula (1), R' independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, or a halogen group such as fluorine, chlorine, bromine, or iodine.

[0033] In the above formula (1), U is independently a single bond or a divalent organic group, and is a linking group connecting the V group and the Z group. The divalent organic group is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups 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, and the divalent organic group may contain an oxygen atom or a sulfur atom.

[0034] 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. The alkylene group in the silalkylene structure is preferably an alkylene group having 1 to 6 carbon atoms, particularly an alkylene group having 2 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group).

[0035] Examples of such U include the following groups in addition to a single bond: In the following structure, the left bond is bonded to V, and the right bond is bonded to Z. [ka] [ka] [ka] (In the formula, f1 is an integer of 1 to 4, 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.)

[0036] In the formula (1), Z is independently 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 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms. The organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded via an alkylene group, i.e., Si-(CH2) x It may contain —Si (where x is an integer of 2 to 6).

[0037] 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.

[0038] Examples of such Z include the following groups in addition to a single bond. [ka] [ka] [ka]

[0039] In the above formula (1), Y is a divalent hydrocarbon group, preferably having 1 to 20 carbon atoms, more preferably 2 to 20 carbon atoms, which may independently contain at least one bond selected from the group consisting of an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond, and which serves as a linking group connecting the Z group (or the V group) and the Si group. Specifically, the divalent hydrocarbon group is preferably a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups containing an arylene group having 6 to 8 carbon atoms, which may contain an oxygen atom or a sulfur atom, divalent groups in which alkylene groups are mutually bonded 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.

[0040] 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. The alkylene group in the silalkylene structure is preferably an alkylene group having 1 to 6 carbon atoms, particularly an alkylene group having 2 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group).

[0041] Examples of such Y include the following groups: In the following structure, the left bond is bonded to Z (or V), and the right bond is bonded to Si. [ka] [ka] [ka] [ka] (In the formula, f1 is an integer of 1 to 4, a and b are each an integer of 1 to 4, b' and c are each an integer of 1 to 10, and e is an integer of 1 to 9.)

[0042] In the above formula (1), R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, with a methyl group being preferred. Furthermore, 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.

[0043] In the above formula (1), α is 1 or 2, β is independently an integer of 1 to 6, preferably 1 or 2, γ is independently 0 or 1, preferably 0, and δ is independently 1 or 2, preferably 1. The sum of β, γ, and δ is a number that is independently an integer of 2 to 7 (i.e., the valence of V - 1) for each V bonded thereto. Furthermore, n is an integer of 1 to 3, preferably 3, independently for each silicon atom to which it is bonded; m is an integer of 1 to 7, preferably 1 or 3, independently.

[0044] As a method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the above formula (1), when α is 1 (i.e., Rf is a monovalent fluorooxyalkylene group-containing polymer residue) or when α is 2 (i.e., Rf is a divalent fluorooxyalkylene group-containing polymer residue), the following method can be mentioned, for example. A fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals is dissolved in a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having SiH groups and hydroxyl or hydrolyzable terminal groups (e.g., halogen atoms or alkoxy groups) in the molecule, such as trichlorosilane or trialkoxysilane, is mixed in. The resulting mixture is aged in the presence of a hydrosilylation catalyst, such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at 40 to 120°C, preferably 60 to 100°C, and more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours. When a SiH group-containing halogenated (organic)silicon compound such as trichlorosilane is used as the organosilicon compound having SiH groups and hydroxyl or hydrolyzable terminal groups 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. Furthermore, two different types of organosilicon compounds having a SiH group and a hydroxyl group or a hydrolyzable terminal group in the molecule can also be used. In this case, compounds having different Y moieties in formula (1) can be produced by adding them in a stepwise manner.

[0045] Here, in preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), an example of the fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals is the fluoropolyether group-containing polymer represented by the following general formula (4): [ka] (In the formula, Rf, B, V, R', E, U, Z, α, β, γ, δ, and m are the same as above, and Y' independently represents a single bond or a divalent hydrocarbon group which may have at least one bond selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond.)

[0046] In the above formula (4), 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 the group consisting of an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond. The divalent hydrocarbon group is preferably selected from the group consisting of an alkylene group having 1 to 8 carbon atoms, which may contain an oxygen atom or a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which an alkylene group 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 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.

[0047] Examples of the fluoropolyether group-containing polymer represented by the above formula (4) include the following. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, k is the same as above. p1, q1, and r1 each represent an integer of 1 or more, the upper limit of which is the same as the upper limit of p, q, and r above, and the total of p1, q1, and r1 in each formula is 3 to 200. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.)

[0048] A method for producing the fluoropolyether group-containing polymer represented by formula (4) is, for example, to use a fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals, and a polyether group-introducing agent, and aging the polymer in the presence of a base, if necessary using an additive or solvent that improves reactivity, at a temperature of 0 to 90°C, preferably 50 to 80°C, more preferably about 60°C, for 1 to 48 hours, preferably 10 to 40 hours, more preferably about 24 hours.

[0049] Here, specific examples of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) include those shown below. [ka] [ka] [ka] [ka] (In the formula, p1, q1, r1, and the sum of p1 and q1 are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.)

[0050] Examples of polyether group-introducing agents that can be used in preparing the fluoropolyether group-containing polymer represented by formula (4) include polyether halides, and specific examples include 2-bromoethyl methyl ether, ethylene glycol 2-bromoethyl methyl ether, diethylene glycol 2-bromoethyl methyl ether, and triethylene glycol 2-bromoethyl methyl ether. The amount of polyether group-introducing agent used is 1 to 15 equivalents, more preferably 3 to 9 equivalents, and even more preferably about 6 equivalents, per equivalent of reactive terminal group of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals.

[0051] Examples of the base used in preparing the fluoropolyether group-containing polymer represented by formula (4) include amines and alkali metal bases, and specific examples of amines include triethylamine, diisopropylethylamine, pyridine, DBU, imidazole, etc. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, potassium t-butoxide, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide. The amount of base used is 1 to 15 equivalents, more preferably 3 to 9 equivalents, and even more preferably about 6 equivalents, per equivalent of the reactive terminal group of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals.

[0052] In preparing the fluoropolyether group-containing polymer represented by formula (4), the reaction between the fluoropolyether group-containing polymer having at least one hydroxyl group or amino group and at least one olefin moiety at one or both molecular chain terminals and the polyether group-introducing agent may involve the use of additives such as tetrabutylammonium halide or alkali metal halides to improve reactivity. Specific examples of additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, and crown ether. These additives improve reactivity by catalytic halogen exchange with the olefin-introducing agent in the reaction system, and crown ethers improve reactivity by coordinating with the metal. The amount of the additive used is 0.005 to 0.1 equivalents, more preferably 0.01 to 0.05 equivalents, and even more preferably about 0.02 equivalents, relative to 1 equivalent of the reactive terminal group of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals.

[0053] In preparing the fluoropolyether group-containing polymer represented by formula (4), a solvent may be used to react a fluoropolyether group-containing polymer having at least one hydroxyl group or amino group and at least one olefin moiety at one or both molecular chain terminals with a polyether group-introducing agent. While a solvent is not necessarily required, examples of suitable solvents include fluorine-containing 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 perfluorosolvents composed of fully fluorinated compounds (manufactured by 3M, product name: Fluorinert series). Furthermore, organic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, and THF can be used. 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 about 50 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals.

[0054] In another method (Production Method 2) for producing the fluoropolyether group-containing polymer represented by formula (4), for example, a fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals and an organosilicon compound having two or more SiH groups in the molecule are used, and a dehydrogenation reaction is carried out in the presence of a dehydrogenation catalyst, if necessary using a solvent, at a temperature of 0 to 60°C, preferably 15 to 35°C, more preferably about 25°C, for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour, to obtain a fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin moieties at one or both molecular chain terminals. Next, the fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin moieties at one or both molecular chain terminals and a polyether compound having an olefin moiety in the molecule (for example, a polyalkylene oxide compound capped with an alkenyloxy group at one molecular chain terminal) are dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and aged in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, and more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours.

[0055] Here, the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals, which is used in the preparation (production method 2) of the fluoropolyether group-containing polymer represented by formula (4), can be exemplified by the same as the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals exemplified above.

[0056] As the organosilicon compound having two or more SiH groups in the molecule used in the preparation (production method 2) of the fluoropolyether group-containing polymer represented by formula (4), compounds represented by the following general formulas (5) to (7) are preferred. [ka] (In the formula, R 1 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 R 1 may be the same or different. 2is an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4, 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. g is an integer of 1 to 9, preferably 1 to 4, i is 2 or 3, j is an integer of 0 to 7, preferably 0 or 1, and i+j is an integer of 2 to 9. In formula (7), the repeating units shown in parentheses may be bonded randomly.

[0057] Examples of such organosilicon compounds having two or more SiH groups in the molecule include the compounds shown below. [ka]

[0058] In the preparation (Production Method 2) of the fluoropolyether group-containing polymer represented by formula (4), the amount of the organosilicon compound having two or more SiH groups in the molecule is preferably 5 to 30 equivalents, more preferably 7 to 20 equivalents, and even more preferably about 8 to 12 equivalents, per equivalent of the reactive terminal group of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals.

[0059] The dehydrogenation catalyst used in the preparation (Production Method 2) of the fluoropolyether group-containing polymer represented by formula (4) can be, for example, a platinum group metal catalyst such as rhodium, palladium, or ruthenium, or a boron catalyst. Specific examples include platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium, and boron catalysts such as tris(pentafluorophenyl)borane. The amount of the dehydrogenation catalyst used is 0.0005 to 0.01 equivalent, more preferably 0.001 to 0.007 equivalent, per equivalent of the reactive terminal group of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals.

[0060] In the preparation (production method 2) of the fluoropolyether group-containing polymer represented by formula (4), examples of the polyether compound having an olefin moiety in the molecule to be reacted with the obtained fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin moieties at one or both molecular chain terminals include polyalkylene oxide compounds capped at one molecular chain terminal with an alkenyloxy group, such as polyethylene oxide shown below, in which one molecular chain terminal is capped with an allyloxy group and the other terminal is capped with a methoxy group. [ka] (wherein k is the same as above.)

[0061] Specific examples of polyether compounds having an olefin moiety in the molecule, such as polyalkylene oxide compounds having one molecular chain end blocked with an alkenyloxy group, include UNIOX MA-200, UNIOX MA-300, UNIOX MA-350S, and UNIOX MA-500 manufactured by NOF Corporation. The amount of the polyether compound having an olefin moiety in the molecule is 1 to 10 equivalents, more preferably 2 to 5 equivalents, and even more preferably about 3 equivalents, per equivalent of the SiH group of the fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin moieties at one or both molecular chain terminals.

[0062] In the preparation (production method 2) of the fluoropolyether group-containing polymer represented by formula (4), when a fluoropolyether group-containing polymer having at least one SiH group and at least one olefin moiety at one or both molecular chain terminals is reacted with a polyether compound having an olefin moiety in the molecule, examples of the hydrosilylation reaction catalyst include 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 are preferred. Platinum compounds such as vinylsiloxane coordination compounds are also preferred. The amount of the hydrosilylation reaction catalyst used is 0.1 to 100 ppm, more preferably 0.5 to 50 ppm, calculated as transition metal (by mass) relative to the mass of the fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin moieties at one or both molecular chain terminals.

[0063] In the preparation (Production Method 2) of the fluoropolyether group-containing polymer represented by formula (4), the solvent used is preferably a fluorine-based solvent. Examples of the fluorine-based solvent include hydrofluoroether (HFE) solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name: Novec series), and perfluorosolvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series). When a solvent is used, the amount used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals, or the fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin moieties at one or both molecular chain terminals.

[0064] Furthermore, as another method (Production Method 3) for producing the fluoropolyether group-containing polymer represented by formula (4), for example, a fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals and an organosilicon compound having SiH groups and polyether groups in the molecule are subjected to a dehydrogenation reaction in the presence of a dehydrogenation catalyst, if necessary using a solvent, at a temperature of 0 to 60°C, preferably 15 to 35°C, more preferably about 25°C, for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.

[0065] Here, the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals, which is used in the preparation (Production Method 3) of the fluoropolyether group-containing polymer represented by formula (4), can be exemplified by the same as the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals exemplified above.

[0066] Examples of organosilicon compounds having SiH groups and polyether groups in the molecule, which are used in the preparation (Production Method 3) of the fluoropolyether group-containing polymer represented by formula (4), include the following. [ka] (wherein k is the same as above.)

[0067] In the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 3), the amount of the organosilicon compound having a SiH group and a polyether group in the molecule is 1 to 5 equivalents, more preferably 1 to 3 equivalents, per equivalent of the hydroxyl group of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals.

[0068] Examples of the dehydrogenation catalyst used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 3) include the same dehydrogenation catalysts as exemplified in the above (Production Method 2), and the amount to be added is 0.0005 to 0.01 equivalent, more preferably 0.001 to 0.007 equivalent, per equivalent of hydroxyl groups in the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals.

[0069] Examples of the solvent used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 3) include the same solvents as those exemplified in the above (Production Method 2), and the amount used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin moieties at one or both molecular chain terminals.

[0070] Furthermore, as another method (Production Method 4) for producing the fluoropolyether group-containing polymer represented by formula (4), a fluoropolyether group-containing polymer having two or more olefin moieties at one or both molecular chain terminals is used as a raw material. For example, the fluoropolyether group-containing polymer having three olefin moieties at one or both molecular chain terminals is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having SiH groups and polyether groups in the molecule is first added to, for example, one or both molecular chain terminals. The mixture is mixed with a fluoropolyether group-containing polymer having three olefin moieties in an amount of 1 / 3 equivalent of the reactive terminal group (olefin moiety) of the fluoropolyether group-containing polymer, and 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, and more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours, to react some of the olefin moieties of the fluoropolyether group-containing polymer with the SiH groups of the SiH group-containing organosilicon compound.

[0071] Here, specific examples of the fluoropolyether group-containing polymer having two or more olefin moieties at one or both molecular chain terminals used in the preparation (production method 4) of the fluoropolyether group-containing polymer represented by formula (4) include those shown below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, p1, q1, r1, and the sum of p1 and q1 are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.)

[0072] Examples of organosilicon compounds having SiH groups and polyether groups in the molecule used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 4) include the following. [ka] (wherein k is the same as above.)

[0073] The amount of organosilicon compound having SiH groups and polyether groups in the molecule used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 4) is, relative to the n equivalents of olefin moieties in the fluoropolyether group-containing polymer having two or more olefin moieties at one or both molecular chain terminals, 1 equivalent can be used when n=2, and 1 / n to 2 / n equivalents can be used when n<2.

[0074] Examples of the hydrosilylation catalyst used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 4) include the same hydrosilylation catalysts as exemplified in the above (Production Method 2), and the amount used is an amount equivalent to 0.1 to 100 ppm, more preferably 0.5 to 50 ppm, in terms of transition metal (by mass), relative to the mass of the fluoropolyether group-containing polymer having two or more olefin moieties at one or both molecular chain terminals.

[0075] Examples of the solvent used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 4) include the same solvents as those exemplified in the above (Production Method 2), and the amount used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having two or more olefin moieties at one or both ends of the molecular chain.

[0076] Furthermore, as an alternative method (Production Method 5) for producing the fluoropolyether group-containing polymer represented by formula (4), for example, a fluoropolyether group-containing polymer having an acid halide or the like at one or both molecular chain terminals is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and aged using an organic nitrogen compound having a polyether group and an olefin moiety in the molecule in the presence of a base, and if necessary, using a solvent, at a temperature of 0 to 90°C, preferably 60 to 90°C, for 1 to 48 hours, preferably 10 to 40 hours, and more preferably 15 to 24 hours.

[0077] Here, the fluoropolyether group-containing polymer having an acid halide or the like at one or both ends of the molecular chain used in the preparation (Production Method 5) of the fluoropolyether group-containing polymer represented by formula (4) may use, as the group at one end of the molecular chain, not only the above-mentioned acid halide but also an acid anhydride, an ester, a carboxylic acid, an amide, a sulfonic acid ester, etc. Specific examples of fluoropolyether group-containing polymers having these groups at one or both molecular chain terminals include the following. [ka] [ka] [ka] [ka] (In the formula, p1, q1, r1, and the sum of p1 and q1 are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.)

[0078] Examples of organic nitrogen compounds having a polyether group and an olefin moiety in the molecule used in the preparation (Production Method 5) of the fluoropolyether group-containing polymer represented by formula (4) include the following. [ka] [ka] (wherein k is the same as above.)

[0079] The amount of the organic nitrogen compound having a polyether group and an olefin moiety in the molecule used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 5) is 1 to 15 equivalents, more preferably 2 to 6 equivalents, and even more preferably about 4 equivalents per equivalent of the reactive terminal group of the fluoropolyether group-containing polymer having an acid halide or the like at one or both molecular chain terminals.

[0080] Examples of the base used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 5) include amines and alkali metal bases, and specific examples of amines include triethylamine, diisopropylethylamine, pyridine, DBU, imidazole, etc. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, potassium t-butoxide, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide. The amount of base used is 1 to 15 equivalents, more preferably 2 to 6 equivalents, and even more preferably about 4 equivalents, per equivalent of the reactive terminal group of the fluoropolyether group-containing polymer having an acid halide or the like at one or both molecular chain terminals.

[0081] A solvent may be used in the preparation of the fluoropolyether group-containing polymer represented by formula (4) (Production Method 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 like 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene, hydrofluoroether (HFE) solvents like 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, organic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, and THF can be used. 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 an acid halide or the like at one or both molecular chain terminals.

[0082] In preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), the organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable terminal group in the molecule is preferably a compound represented by the following general formulas (8) to (11). [ka] (In the formula, R, X, n, R 1 , R 2 , e, j are the same as above. R 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 (11), the repeating units shown in parentheses may be bonded randomly.

[0083] where R 3 Examples of the divalent hydrocarbon group having 2 to 8 carbon atoms, preferably 2 to 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.

[0084] Examples of such organosilicon compounds having a SiH group and a hydroxyl group or a hydrolyzable terminal group in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, as well as the following silane or siloxane compounds, and (partial) hydrolysates thereof. [ka] [ka]

[0085] In preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), when a fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals is reacted with an organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable terminal group in the molecule, the amount of the organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable terminal group in the molecule can be 1 to 4 equivalents, more preferably 1.5 to 4 equivalents, per equivalent of the olefin moiety in the fluoropolyether group-containing polymer.

[0086] 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 terminal 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. 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 about 65 parts by mass, per 100 parts by mass of an addition reaction product of a fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals with a SiH group-containing halogenated (organic) silicon compound.

[0087] In preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), examples of the solvent include fluorine-based solvents. Examples of fluorine-based solvents include hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series) such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, and perfluorosolvents (manufactured by 3M, trade name: Fluorinert series) composed of fully fluorinated compounds. The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals.

[0088] In preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group 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., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferred are platinum compounds such as vinylsiloxane coordination compounds. The amount of the hydrosilylation reaction catalyst used is 0.1 to 100 ppm, more preferably 1 to 50 ppm, calculated as transition metal (by mass) relative to the mass of the fluoropolyether group-containing polymer having one or more polyether groups and one or more olefin moieties at one or both molecular chain terminals.

[0089] As an alternative method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by the above formula (1), when α is 1 (i.e., Rf is a monovalent fluorooxyalkylene group-containing polymer residue) or when α is 2 (i.e., Rf is a divalent fluorooxyalkylene group-containing polymer residue), the following method can be mentioned. Using a fluoropolyether group-containing polymer having two or more SiH groups at one or both molecular chain ends as a raw material, for example, a fluoropolyether group-containing polymer having three SiH groups at one or both molecular chain ends is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and then a polyether compound having an olefin moiety in the molecule (for example, a polyalkylene oxide compound capped with an alkenyloxy group at one molecular chain end) is first added to the reactive terminal group (SiH group) of the fluoropolyether group-containing polymer having three SiH groups at one or both molecular chain ends. ) are mixed so that the amount is 1 / 3 equivalent to 1 equivalent of the fluoropolyether group-containing polymer, and in order to react some of the SiH groups of the fluoropolyether group-containing polymer with the olefin moieties of the polyether compound having an olefin moiety in the molecule, the mixture is aged in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, and more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours, to obtain a fluoropolyether group-containing polymer having an SiH group and a polyether group at one or both molecular chain terminals. Next, the fluoropolyether group-containing polymer having SiH groups and polyether groups at one or both molecular chain terminals and an organosilicon compound having an olefin moiety and a hydroxyl or hydrolyzable terminal group in the molecule are dissolved in a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and aged in the presence of a hydrosilylation catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex at 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours. The organosilicon compound having an olefin moiety and a hydroxyl or hydrolyzable terminal group in the molecule can also be two different compounds, and in this case, compounds with different Y moieties in formula (1) can be produced by stepwise addition.

[0090] Here, in another method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), examples of the fluoropolyether group-containing polymer having two or more SiH groups at one or both ends of the molecular chain include the following. [ka] [ka] (In the formula, p1, q1, r1, and the sum of p1 and q1 are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.)

[0091] In another method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), examples of the polyether compound having an olefin moiety in the molecule include polyalkylene oxide compounds having one molecular chain end blocked with an alkenyloxy group, such as polyethylene oxide shown below, in which one molecular chain end is blocked with an allyloxy group and the other end is blocked with a methoxy group. [ka] (wherein k is the same as above.)

[0092] Specific examples of polyether compounds having an olefin moiety in the molecule, such as polyalkylene oxide compounds having one molecular chain end blocked with an alkenyloxy group, include UNIOX MA-200, UNIOX MA-300, UNIOX MA-350S, and UNIOX MA-500 manufactured by NOF Corporation. In another method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), the amount of polyether compound having an olefin moiety in the molecule can be 1 equivalent when n=2 relative to the n equivalents of reactive terminal groups (SiH groups) of the fluoropolyether group-containing polymer having two or more SiH groups at one or both molecular chain terminals, and 1 / n to 2 / n equivalents when n<2.

[0093] In another method for preparing the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), the organosilicon compound having an olefin moiety and a hydroxyl group or a hydrolyzable terminal group in the molecule, which is to be reacted with the obtained fluoropolyether group-containing polymer having an SiH group and a polyether group at one or both molecular chain terminals, is preferably a compound represented by the following general formula (12): [ka] (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.)

[0094] In the above formula (12), Y" is a single bond or a divalent hydrocarbon group preferably 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 alkylene groups having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom, alkylene groups containing an arylene group having 6 to 8 carbon atoms, divalent groups in which an alkylene group 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 single bond or a linear alkylene group having 1 to 6 carbon atoms.

[0095] Examples of such organosilicon compounds having an olefin moiety and a hydroxyl group or a hydrolyzable terminal 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. [ka]

[0096] In another method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), the amount of the organosilicon compound having an olefin moiety and a hydroxyl group or a hydrolyzable terminal group in the molecule is used in an amount of 1 to 4 equivalents, more preferably 1.5 to 2.5 equivalents, and even more preferably about 2 equivalents, per equivalent of the unreacted SiH groups in the reactive terminal groups of the fluoropolyether group-containing polymer having two or more SiH groups at one or both molecular chain terminals (i.e., the SiH groups of the fluoropolyether group-containing polymer having an SiH group and a polyether group at one or both molecular chain terminals, which is the reaction product of a fluoropolyether group-containing polymer having two or more SiH groups at one or both molecular chain terminals and a polyether compound having an olefin moiety in the molecule).

[0097] Examples of the hydrosilylation catalyst used in this alternative method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group, represented by formula (1), include the same hydrosilylation catalysts as exemplified in the above preparation method. The amount of the catalyst to be added 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 two or more SiH groups at one or both molecular chain terminals, or the fluoropolyether group-containing polymer having an SiH group and a polyether group at one or both molecular chain terminals, which is the reaction product of a fluoropolyether group-containing polymer having two or more SiH groups at one or both molecular chain terminals with a polyether compound having an olefin moiety in the molecule.

[0098] As a solvent used in another method for preparing a fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by formula (1), the same solvents as those exemplified in the above preparation method can be exemplified, and the blending amount is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, per 100 parts by mass of a fluoropolyether group-containing polymer having two or more SiH groups at one or both molecular chain ends, or a fluoropolyether group-containing polymer having an SiH group and a polyether group at one or both molecular chain ends, which is a reaction product of a fluoropolyether group-containing polymer having two or more SiH groups at one or both molecular chain ends and a polyether compound having an olefin moiety in the molecule.

[0099] Examples of the structure of the fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by the above formula (1) include the following structures: By changing the combination of Rf, B, V, E, R', U, Z, Y, R, X, α, β, γ, δ, m, and n in the above formula (1), several types of fluoropolyether group-containing polymers having a hydroxyl group or a hydrolyzable group and a polyether group can be obtained.

[0100] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

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[0101] For example, a fluoropolyether group-containing polymer having two olefin moieties at one end of the molecular chain may be a polymer represented by the following formula: [ka] (In the formula, p1, q1, and the sum of p1 and q1 are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.) When a compound represented by the formula (I) is used and trimethoxysilane is used as the organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable terminal group in the molecule, a compound represented by the formula (I) is obtained. [ka] (In the formula, p1, q1, and the sum of p1 and q1 are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.)

[0102] For example, a fluorooxyalkylene group-containing polymer having two olefin moieties at each end of the molecular chain may be a polymer represented by the following formula: [ka] (In the formula, p1, q1, and the sum of p1 and q1 are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.) When a compound represented by the formula (I) is used and trimethoxysilane is used as the organosilicon compound having a SiH group and a hydroxyl group or a hydrolyzable terminal group in the molecule, a compound represented by the formula (I) is obtained. [ka] (In the formula, p1, q1, and the sum of p1 and q1 are the same as above. In addition, each repeating unit shown in parentheses with p1 and q1 may be bonded randomly.)

[0103] The present invention further provides a surface treatment agent containing, as a base, a fluoropolyether group-containing polymer having hydroxyl groups or hydrolyzable groups and polyether groups, preferably a polymer in which the polyether group in the polymer is a monovalent oxyalkylene group-containing polymer residue located at a molecular chain branch, particularly a fluoropolyether group-containing polymer having hydroxyl groups or hydrolyzable groups and polyether groups represented by the above formula (1). The surface treatment agent may contain, as a base, a fluoropolyether group-containing polymer having hydroxyl groups or hydrolyzable groups and polyether groups, and may also contain unreacted raw materials or reaction intermediates prior to the introduction of terminal hydroxyl groups or hydrolyzable groups into the fluoropolyether group-containing polymer having hydroxyl groups or hydrolyzable groups and polyether groups. Furthermore, the surface treatment agent may contain a partial (hydrolyzed) condensate obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer or the hydroxyl groups obtained by partially hydrolyzing the terminal hydrolyzable groups of the fluoropolyether group-containing polymer in advance by a known method.

[0104] If necessary, the surface treatment agent may contain a hydrolysis condensation catalyst, such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Of these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. The amount of the hydrolysis condensation catalyst added is a catalytic amount, which is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer and / or its partial (hydrolysis) condensate.

[0105] 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, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptenyl ether, tetrafluoroethyl trifluoroethyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are desirable in terms of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether, tridecafluorooctane, and tetrafluoroethyl trifluoroethyl ether are particularly preferred.

[0106] The above solvents may be a mixture of two or more kinds, and it is preferable to dissolve the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate uniformly. The optimal concentration of the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate dissolved in the solvent varies depending on the treatment method, and may be an amount that is easy to measure. In the case of direct coating, the amount is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of the solvent and the fluoropolyether group-containing polymer (and its partial (hydrolyzed) condensate). In the case of vapor deposition treatment, the amount is preferably 1 to 100 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the solvent and the fluoropolyether group-containing polymer (and its partial (hydrolyzed) condensate).

[0107] 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. In the case of vapor deposition, it is preferably 20 to 200°C for 1 to 24 hours. Curing may also be performed under humidified conditions. The thickness of the cured coating film is determined appropriately depending on the type of substrate, but is typically 0.1 to 100 nm, particularly 1 to 20 nm. For spray coating, for example, diluting the coating in a fluorine-based solvent containing added water and then hydrolyzing it, i.e., generating Si—OH groups, before spray coating can result in rapid curing after coating.

[0108] 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 SiO2-treated glass or film.

[0109] Examples of articles that can be treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio equipment, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, and other optical articles. The surface treatment agent 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.

[0110] 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, etc.; 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.; an anti-fingerprint 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. [Example]

[0111] 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, the molar amount of a compound is a value calculated by dividing the measured mass of the target compound by the molecular weight of the polymer calculated from the values ​​of p1 and q1 obtained by analysis.

[0112] [Synthesis Example 1] In a reaction vessel, the following formula (A) [ka] 100g (2.4 × 10-2 mol), diethylene glycol 2-bromoethyl methyl ether 33 g (1.4 × 10 -1 mol), tetrabutylammonium iodide 0.17 g (4.8 × 10 -4 mol), followed by mixing 7.8 g (1.4 × 10 -1 After adding 200 mol of fluorine compound, the mixture was heated at 60°C for 24 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (B): [ka] 89 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0113] In a reaction vessel, the compound of the following formula (B) obtained above was added. [ka] 50g (1.1 x 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 5.4 g of trimethoxysilane (4.4 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.2 × 10 -2 g (1.1×10 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.

[0114] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (C): [ka]

[0115] [Synthesis Example 2] In a reaction vessel, the following formula (D) [ka] 50g (1.2 x 10 -2 mol), triethylene glycol 2-bromoethyl methyl ether 19.4 g (7.2 × 10 -2 mol), tetrabutylammonium iodide 0.09 g (2.4 × 10 -4 mol), followed by mixing 4.0 g (7.2 × 10 -2 After adding 200 mol of fluorine compound, the mixture was heated at 60°C for 24 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (E): [ka] 47 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0116] In a reaction vessel, the compound of the following formula (E) obtained above was added. [ka] 25g (5.7 x 10 -3 mol), 1,3-bis(trifluoromethyl)benzene 13 g, trimethoxysilane 2.8 g (2.3 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.2 × 10 -2 g (5.6×10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 47 g of a liquid product.

[0117] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (F): [ka]

[0118] [Synthesis Example 3] A reaction vessel was charged with 50 g of 1,3-bis(trifluoromethyl)benzene and 0.014 g (2.6 × 10 -5 mol), the following formula (A) [ka] 50g (1.3 x 10 -2 mol) and the following formula (G) [ka] 25g (1.3 x 10 -1 After slowly adding dropwise fluorine compound (mol), the mixture was heated at 25°C for 1 hour. Water was then added dropwise, and the lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was again recovered, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (H): [ka] Thus, 46 g of a fluoropolyether group-containing polymer represented by the formula:

[0119] In a reaction vessel, the compound of the following formula (H) obtained above was added. [ka] 20g (4.5 x 10 -3 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, [ka] 2.8 g (1.4 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.0 × 10 -2 g (5.1×10 as Pt alone) -7mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. After that, acetone was added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (J): [ka] 21 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0120] In a reaction vessel, the compound of the following formula (J) obtained above was added. [ka] 20g (4.3 x 10 -3 mol), 1,3-bis(trifluoromethyl)benzene 10 g, trimethoxysilane 2.1 g (1.7 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.9 × 10 -2 g (4.9 × 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 19 g of a liquid product.

[0121] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (K): [ka]

[0122] [Synthesis Example 4] A reaction vessel was charged with 50 g of 1,3-bis(trifluoromethyl)benzene and 0.014 g (2.6 × 10 -5 mol), the following formula (A) [ka] 50g (1.3 x 10 -2 mol) and the following formula (L) [ka] 10g (2.6 x 10 -2 After slowly adding dropwise fluorine compound (mol), the mixture was heated at 25°C for 1 hour. Water was then added dropwise, and the lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was again recovered, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (J): [ka] This compound corresponds to the intermediate of Synthesis Example 3.

[0123] Using 20 g (4.3 × 10-3 mol) of the fluoropolyether group-containing polymer represented by formula (J) obtained above, 19 g of a liquid product having a structure represented by formula (K) was obtained in the same manner as in Synthesis Example 3.

[0124] [Synthesis Example 5] In a reaction vessel, the following formula (M) [ka] 25g (1.2 × 10 -2 mol), diethylene glycol 2-bromoethyl methyl ether 17 g (7.4 × 10 -2 mol), tetrabutylammonium iodide 0.09 g (2.4 × 10 -4 mol), followed by mixing 4.1 g (7.4 × 10 -2 After adding 200 mol of fluorine compound, the mixture was heated at 60°C for 24 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound represented by the following formula (N): [ka] 21 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0125] In a reaction vessel, the compound of the following formula (N) obtained above was added. [ka] 20g (9.2 x 10 -3 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, 4.5 g of trimethoxysilane (3.7 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.7 × 10 -2 g (9.5×10 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 21 g of a liquid product.

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

[0127] [Synthesis Example 6] In a reaction vessel, the following formula (P) [ka] 50g (9.5 x 10 -3 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 5.1 g (9.5 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.2 × 10 -2 g (1.1×10 as Pt alone) -6mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (R [ka] 48 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0128] In a reaction vessel, the compound of the following formula (R) obtained above was added. [ka] 40 g (7.1 × 10 -3 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, 3.4 g of trimethoxysilane (2.8 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.2 × 10 -2 g (8.2 × 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 41 g of a liquid product.

[0129] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (S): [ka]

[0130] [Synthesis Example 7] In a reaction vessel, the following formula (T) [ka] 50g (7.7 x 10 -3 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 5.1 g (7.7 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.4 × 10 -2 g (8.7 × 10 as Pt alone) -7 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Dibutyl ether was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (V): [ka] 45 g of a fluoropolyether group-containing polymer represented by the formula:

[0131] In a reaction vessel, the compound of the following formula (V) obtained above was added. [ka] 30 g (4.3 × 10 -3 mol), 30 g of 1,3-bis(trifluoromethyl)benzene, 2.6 g of vinyltrimethoxysilane (1.7 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.9 × 10 -2 g (4.8×10 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 29 g of a liquid product.

[0132] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (W): [ka]

[0133] [Synthesis Example 8] In a reaction vessel, the following formula (X) [ka] 50g (1.1 x 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 4.8 g (1.1 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.8 × 10 -2 g (1.2 × 10 as Pt alone) -6 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Dibutyl ether was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (Z): [ka] 47 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0134] In a reaction vessel, the compound of the following formula (Z) obtained above was added. [ka] 40 g (8.3 × 10 -3 mol), 40 g of 1,3-bis(trifluoromethyl)benzene, 7.7 g of octenyltrimethoxysilane (3.3 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.7 × 10 -2 g (9.5×10 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 41 g of a liquid product.

[0135] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AA): [ka]

[0136] [Synthesis Example 9] In a reaction vessel, the following formula (AB) [ka] 50g (1.1 x 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 8.7 g (2.2 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.9 × 10 -2 g (1.3 × 10 as Pt alone) -6 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (AD): [ka] 53 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0137] In a reaction vessel, the compound of the following formula (AD) obtained above was added: [ka] 50g (9.9 x 10 -3 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, 2.4 g of trimethoxysilane (2.8 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.4 × 10 -2 g (1.1×10 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 H-NMR confirmed that the structure was represented by the following formula (AE): [ka]

[0139] [Synthesis Example 10] In a reaction vessel, the following formula (AF) [ka] 50g (1.2 x 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 3.3 g (1.2 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.3 × 10 -2 g (1.4×10 as Pt alone) -6 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (AH): [ka] 51 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0140] In a reaction vessel, the compound of the following formula (AH) obtained above was added. [ka] 40 g (8.7 × 10 -3 mol), 40 g of 1,3-bis(trifluoromethyl)benzene, [ka] 10 g (3.5 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.9 × 10 -2 g (1.0×10 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 41 g of a liquid product.

[0141] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AI): [ka]

[0142] [Synthesis Example 11] In a reaction vessel, the following formula (AJ) [ka] 100g (4.3 x 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] Polyethersilane 14g (4.3 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.6 × 10 -1 g (2.1×10 as Pt alone) -6 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (AK): [ka] Thus, 104 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0143] In a reaction vessel, the compound of the following formula (AK) obtained above was added. [ka] 50g (1.9 x 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 4.6 g of trimethoxysilane (3.7 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.2 × 10 -2 g (1.1×10 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.

[0144] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AL): [ka]

[0145] [Synthesis Example 12] In a reaction vessel, the following formula (AM) [ka] 50g (1.0 × 10 -2 mol), diethylene glycol 2-bromoethyl methyl ether 14 g (6.2 × 10 -2 mol), tetrabutylammonium iodide 0.08 g (2.1 × 10 -4 mol), followed by mixing 3.4 g (6.2 × 10 -2 After adding 200 mol of fluorine compound, the mixture was heated at 60°C for 24 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound of the following formula (AN): [ka] 48 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0146] In a reaction vessel, the compound of the following formula (AN) obtained above was added. [ka] 40 g (8.0 × 10 -3 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, 2.0 g of trimethoxysilane (1.6 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.1 × 10 -2 g (7.9 × 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 40 g of a liquid product.

[0147] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AO): [ka]

[0148] [Synthesis Example 13] In a reaction vessel, the following formula (AP) [ka] 100g (2.4 × 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 8.1 g (2.4 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.0 × 10 -2 g (1.0×10 as Pt alone) -6mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (AQ): [ka] 96 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0149] In a reaction vessel, the compound of the following formula (AQ) obtained above was added [ka] 50g (1.1 x 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 3.4 g of trimethoxysilane (4.4 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.9 × 10 -2 g (4.8×10 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 49 g of a liquid product.

[0150] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AR): [ka]

[0151] [Synthesis Example 14] In a reaction vessel, the following formula (B) [ka] 50g (1.1 x 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 2.6 g of trimethoxysilane (2.1 × 10 -2mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.2 × 10 -2 g (1.1×10 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.

[0152] The resulting compound is 1 H-NMR confirmed that the compound was a mixture of structures represented by the following formulas (C) and (AS), with a mixture ratio of (C):(AS) = 96:4. [ka] [ka]

[0153] [Synthesis Example 15] In a reaction vessel, the following formula (AT) [ka] 50g (7.7 x 10 -3 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 3.0 g (7.7 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.7 × 10 -2 g (1.2 × 10 as Pt alone) -6 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (AU): [ka] 49 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0154] In a reaction vessel, the compound of the following formula (AU) obtained above was added. [ka] 40 g (5.8 × 10 -3 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, 1.4 g of trimethoxysilane (1.2 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.3 × 10 -2 g (8.5 × 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 39 g of a liquid product.

[0155] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AV): [ka]

[0156] [Synthesis Example 16] In a reaction vessel, the following formula (AW) [ka] 50g (1.2 x 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 3.1 g (1.2 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.1 × 10 -2 g (1.3 × 10 as Pt alone) -6mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (AX): [ka] 48 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0157] In a reaction vessel, the compound of the following formula (AX) obtained above was added. [ka] 40 g (8.7 × 10 -3 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, 4.3 g of trimethoxysilane (3.5 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.9 × 10 -2 g (1.0×10 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 40 g of a liquid product.

[0158] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AY): [ka]

[0159] [Synthesis Example 17] In a reaction vessel, the following formula (AZ) [ka] 50g (9.5 x 10 -3 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 3.2 g (9.5 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.8 × 10 -2 g (1.5×10 as Pt alone) -6 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (BA): [ka] 51 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0160] In a reaction vessel, the compound of the following formula (BA) obtained above was added. [ka] 50g (8.9 x 10 -3 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 2.2 g of trimethoxysilane (1.7 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.4 × 10 -2 g (1.4×10 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.

[0161] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (BB): [ka]

[0162] [Synthesis Example 18] In a reaction vessel, the following formula (BC) [ka] 30 g (7.0 × 10 -3 mol), 30 g of 1,3-bis(trifluoromethyl)benzene, [ka] 2.8 g (7.0 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.3 × 10 -2 g (1.1×10 as Pt alone) -6 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (BD): [ka] Thus, 29 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0163] In a reaction vessel, the compound of the following formula (BD) obtained above was added. [ka] 25g (5.3 x 10 -3 mol), 13 g of 1,3-bis(trifluoromethyl)benzene, 1.3 g of trimethoxysilane (1.0 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.0 × 10 -2 g (7.7 × 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 24 g of a liquid product.

[0164] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (BE): [ka]

[0165] [Synthesis Example 19] In a reaction vessel, the following formula (BF) [ka] 20g (5.2 x 10 -3 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, [ka] 3.7 g (5.2 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.0 × 10 -2 g (5.1×10 as Pt alone) -7 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (BH): [ka] Thus, 17 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0166] In a reaction vessel, the compound of the following formula (BH) obtained above was added. [ka] 15g (3.3 x 10 -3 mol), 8 g of 1,3-bis(trifluoromethyl)benzene, 0.81 g of trimethoxysilane (6.6 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.3 × 10 -2 g (3.3 × 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 15 g of a liquid product.

[0167] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (BI): [ka]

[0168] [Synthesis Example 20] In a reaction vessel, the following formula (BJ) [ka] 100g (2.4 × 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] Polyethersilane 14g (2.4 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 9.0 × 10 -2 g (2.3 × 10 as Pt alone) -6 mol) were mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure. Acetone was then added, and the fluorine compound was washed by a separation operation. The fluorine compound layer, which was the lower layer after washing, was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (BL): [ka] Thus, 106 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0169] In a reaction vessel, the compound of the following formula (BL) obtained above was added. [ka] 100g (2.1 x 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 14 g (4.2 × 10) of a silane compound having a trimethoxysilyl group represented by -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 7.9 × 10 -2 g (2.0×10 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 105 g of a liquid product.

[0170] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (BN): [ka]

[0171] [Synthesis Example 21] In a reaction vessel, the following formula (BO) [ka] 50g (1.1 x 10 -2 mol), diethylene glycol 2-bromoethyl methyl ether 15 g (6.5 × 10 -2 mol), tetrabutylammonium iodide 0.08 g (2.2 × 10 -4 mol), followed by mixing 3.6 g (6.5 × 10 -2 After adding 200 mol of fluorine compound, the mixture was heated at 60°C for 24 hours. After heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound of the following formula (BP): [ka] 48 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0172] In a reaction vessel, the compound of the following formula (BP) obtained above was added. [ka] 45g (9.5 x 10 -3 mol), 23 g of 1,3-bis(trifluoromethyl)benzene, [ka] 5.6 g (1.9 × 10) of a silane compound having a trimethoxysilyl group represented by -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.6 × 10 -2 g (9.2 × 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 45 g of a liquid product.

[0173] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (BR): [ka]

[0174] [Synthesis Example 22] In a reaction vessel, the following formula (BS) [ka] 100g (1.5 x 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 12g (6.0 x 10 -2 mol), triethylamine 6.1 g (6.0 × 10 -2After mixing the above components, the mixture was heated at 90°C for 18 hours. After heating, the mixture was cooled to room temperature, and water was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound of the following formula (BU): [ka] Thus, 101 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0175] In a reaction vessel, the compound of the following formula (BU) obtained above was added. [ka] 80g (1.2 x 10 -2 mol), 40 g of 1,3-bis(trifluoromethyl)benzene, 5.7 g of trimethoxysilane (4.7 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.5 × 10 -2 g (1.2 × 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 79 g of a liquid product.

[0176] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (BV): [ka]

[0177] [Synthesis Example 23] In a reaction vessel, the following formula (BW) [ka] 50g (1.6 x 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, [ka] 13g (6.4 x 10 -2 mol), triethylamine 6.5 g (6.4 × 10 -2 After mixing the above components, the mixture was heated at 60°C for 15 hours. After heating, the mixture was cooled to room temperature, and water was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (BX): [ka] 47 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0178] In a reaction vessel, the compound of the following formula (BX) obtained above was added. [ka] 40 g (1.3 × 10 -2 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, 3.1 g of trimethoxysilane (2.5 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.8 × 10 -2 g (1.2 × 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 41 g of a liquid product.

[0179] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (BY): [ka]

[0180] [Synthesis Example 24] In a reaction vessel, the following formula (BZ) [ka] 100g (2.4 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 30 g (9.6 × 10 -2 mol), triethylamine 6.5 g (9.6 × 10 -2 After mixing the above components, the mixture was heated at 60°C for 15 hours. After heating, the mixture was cooled to room temperature, and water was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound of the following formula (CB): [ka] 96 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0181] In a reaction vessel, the compound of the following formula (CB) obtained above was added. [ka] 50g (1.1 x 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 8.2 g of trimethoxysilane (6.7 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.2 × 10 -2 g (1.1×10 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.

[0182] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (CC): [ka]

[0183] [Synthesis Example 25] In a reaction vessel, a compound of the following formula (CB) obtained in the same manner as in Synthesis Example 24 was added. [ka] 40 g (9.0 × 10 -3 mol), 40 g of 1,3-bis(trifluoromethyl)benzene, [ka] 15 g (5.4 × 10) of a silane compound having a trimethoxysilyl group represented by -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.4 × 10 -2 g (8.7 × 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 44 g of a liquid product.

[0184] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (CE): [ka]

[0185] [Synthesis Example 26] In a reaction vessel, the following formula (CF) [ka] 50g (9.8 x 10 -3 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, [ka] 12g (3.9 x 10 -2 mol), triethylamine 4.0 g (3.9 × 10 -2After mixing the above components, the mixture was heated at 60°C for 15 hours. After heating, the mixture was cooled to room temperature, and water was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound of the following formula (CG): [ka] 51 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0186] In a reaction vessel, the compound of the following formula (CG) obtained above was added. [ka] 50g (9.3 x 10 -3 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 6.8 g of trimethoxysilane (5.5 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.6 × 10 -2 g (9.2 × 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.

[0187] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (CH): [ka]

[0188] [Synthesis Example 27] In a reaction vessel, a compound of the following formula (CI) [ka] 50g (1.4 × 10 -2 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 20g (5.5 x 10 -2 mol), triethylamine 5.6 g (5.5 × 10 -2 After mixing the above components, the mixture was heated at 60°C for 15 hours. After heating, the mixture was cooled to room temperature, and water was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound of the following formula (CK): [ka] 52 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0189] In a reaction vessel, the compound of the following formula (CK) obtained above was added. [ka] 50g (1.3 x 10 -2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, 9.2 g of trimethoxysilane (7.5 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.0 × 10 -2 g (1.3 × 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.

[0190] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (CL): [ka]

[0191] [Synthesis Example 28] In a reaction vessel, the following formula (CM) [ka] 50g (1.2 x 10-2 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, [ka] 9.8 g (4.8 × 10 -2 mol), triethylamine 4.9 g (4.8 × 10 -2 After mixing the above components, the mixture was heated at 80°C for 24 hours. After heating, the mixture was cooled to room temperature, and water was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a fluorine compound of the following formula (CN): [ka] 49 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0192] In a reaction vessel, the compound of the following formula (CN) obtained above was added. [ka] 40 g (9.3 × 10 -3 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, [ka] 7.1 g (1.9 × 10) of a silane compound having a trimethoxysilyl group represented by -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.5 × 10 -2 g (9.0×10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 53 g of a liquid product.

[0193] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (CP): [ka]

[0194] [Synthesis Example 29] In a reaction vessel, the following formula (CQ) [ka] 50g (9.7 x 10 -3 mol), 25 g of 1,3-bis(trifluoromethyl)benzene, [ka] 19g (3.9 x 10 -2 mol), triethylamine 3.9 g (3.9 × 10 -2 After mixing the above components, the mixture was heated at 60°C for 15 hours. After heating, the mixture was cooled to room temperature, and water was added dropwise. The lower fluorine compound layer was recovered by a separation operation and washed with acetone. The lower fluorine compound layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain a compound of the following formula (CS): [ka] 48 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

[0195] In a reaction vessel, the compound of the following formula (CS) obtained above was added. [ka] 40 g (7.2 × 10 -3 mol), 20 g of 1,3-bis(trifluoromethyl)benzene, 4.7 g of triethoxysilane (2.9 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.7 × 10 -2 g (6.9 × 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 41 g of a liquid product.

[0196] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (CT): [ka]

[0197] [Example 1] The final compound obtained in Synthesis Example 1 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0198] [Example 2] The final compound obtained in Synthesis Example 2 was dissolved in Opteon SF10 (manufactured by Mitsui-Chemours Fluoroproducts, methyl perfluoroheptenyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0199] [Example 3] The final compound obtained in Synthesis Example 3 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0200] [Example 4] The final compound obtained in Synthesis Example 6 was dissolved in Asahiklin AC-6000 (manufactured by AGC, tridecafluorooctane) to a concentration of 20 mass % to prepare a surface treatment agent.

[0201] [Example 5] The final compound obtained in Synthesis Example 7 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0202] [Example 6] The final compound obtained in Synthesis Example 10 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0203] [Example 7] The final compound obtained in Synthesis Example 11 was dissolved in Asahiklin AE-3000 (manufactured by AGC, tetrafluoroethyl trifluoroethyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0204] [Example 8] The final compound obtained in Synthesis Example 13 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0205] [Example 9] The final compound obtained in Synthesis Example 14 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0206] [Example 10] The final compound obtained in Synthesis Example 15 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0207] [Example 11] The final compound obtained in Synthesis Example 16 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0208] [Example 12] The final compound obtained in Synthesis Example 18 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0209] [Example 13] The final compound obtained in Synthesis Example 25 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0210] [Example 14] The final compound obtained in Synthesis Example 26 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0211] [Comparative Example 1] The following formula (CU) [ka] The compound represented by the following formula was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0212] Comparative Example 2 The following formula (CV) [ka] The compound represented by the following formula was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0213] Comparative Example 3 The following formula (CW) [ka] The compound represented by the following formula was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0214] Preparation of surface treatment agent and formation of hardened coating 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% humidity (Pa, heating temperature: 700°C) to form a cured coating with a thickness of 10 nm.

[0215] Water and oil repellency evaluation [Evaluation of initial water and oil repellency] The glass on which the cured coating was formed was subjected to measurement of the water contact angle (water repellency) of the cured coating using a contact angle meter, Drop Master (Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., humidity: 40%). The results (initial water contact angle) are shown in Table 1. In the initial stage, both the Example and Comparative Examples showed good water repellency.

[0216] [Wear resistance evaluation] 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 of the cured coating with water (water repellency) was measured in the same manner as above to evaluate abrasion resistance. The test environment conditions were 25°C and 40% humidity. The results (water contact angle after abrasion) are shown in Table 1. Steel wool abrasion resistance Steel wool: Bonster #0000 Contact area: 1cm 2 Travel distance (one way): 40 mm Traveling speed: 4,800mm / min Load: 1kg / 1cm 2 Number of wear cycles: 15,000 Eraser abrasion resistance Eraser: Rubber Eraser (Minoan) Contact area: 6mmφ Travel distance (one way): 60 mm Traveling speed: 3,600mm / min Load: 1kg / 6mmφ Number of wear cycles: 5,000

[0217] The surface treatment agents of Examples 1 to 14 exhibited improved substrate adhesion and wettability due to the presence of polyether groups in the molecules of the compounds used, resulting in high eraser abrasion durability. Furthermore, the long link between the fluorine chain and the terminal adhesive group branch point ensured molecular mobility, confirming high steel wool abrasion durability. The surface treatment agent of Comparative Example 1 exhibited low eraser abrasion durability and steel wool abrasion durability, while the surface treatment agent of Comparative Example 2 exhibited high steel wool abrasion durability but low eraser abrasion durability. Furthermore, the surface treatment agent of Comparative Example 3 exhibited high eraser abrasion durability but low steel wool abrasion durability. As described above, the surface treatment agents of the Examples were able to achieve high levels of both eraser abrasion durability and steel wool abrasion durability.

[0218] [Table 1]

[0219] [Example 15] The compound obtained in Synthesis Example 1 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.

[0220] [Example 16] The compound obtained in Synthesis Example 2 was dissolved in Opteon SF10 (manufactured by Mitsui-Chemours Fluoroproducts, methyl perfluoroheptenyl ether) to a concentration of 0.1 mass % to prepare a surface treatment agent.

[0221] [Example 17] The compound obtained in Synthesis Example 3 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.

[0222] [Example 18] The compound obtained in Synthesis Example 6 was dissolved in Asahiklin AC-6000 (manufactured by AGC, tridecafluorooctane) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0223] [Example 19] The compound obtained in Synthesis Example 10 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.

[0224] [Example 20] The compound obtained in Synthesis Example 16 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.

[0225] [Example 21] The compound obtained in Synthesis Example 25 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.

[0226] [Example 22] The compound obtained in Synthesis Example 26 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.

[0227] Comparative Example 4 The above compound (CU) 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.

[0228] Comparative Example 5 The above compound (CV) 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.

[0229] Comparative Example 6 The above compound (CW) 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.

[0230] Preparation of surface treatment agent and formation of hardened coating Surface treatment agents were prepared as in the above Examples and Comparative Examples. Each surface treatment agent was spray-coated onto glass (Corning Gorilla), cured in an atmosphere at 120°C for 30 minutes, and then cured in an atmosphere at 25°C and 50% humidity for 12 hours to form a cured coating with a thickness of 10 nm.

[0231] Water and oil repellency evaluation [Evaluation of initial water and oil repellency] The cured coating was applied to the glass substrate and the contact angle (water repellency) of the cured coating was measured using a contact angle meter, Drop Master (Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., humidity: 40%). The results (initial water contact angle) are shown in Table 2. In the initial stage, both the Example and Comparative Examples showed good water repellency.

[0232] [Wear resistance evaluation] 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 of the cured coating with water (water repellency) was measured in the same manner as above to evaluate abrasion resistance. The test environment conditions were 25°C and 40% humidity. The results (water contact angle after abrasion) are shown in Table 2. Steel wool abrasion resistance Steel wool: Bonster #0000 Contact area: 1cm 2 Travel distance (one way): 40 mm Traveling speed: 4,800mm / min Load: 1kg / 1cm 2 Number of wear cycles: 10,000 Eraser abrasion resistance Eraser: Rubber Eraser (Minoan) Contact area: 6mmφ Travel distance (one way): 30 mm Traveling speed: 3,600mm / min Load: 1kg / 6mmφ Number of wear cycles: 5,000

[0233] The surface treatment agents of Examples 15 to 22 exhibited high eraser abrasion resistance and high steel wool abrasion resistance, similar to when vapor deposition coating was used. The surface treatment agent of Comparative Example 4 exhibited low eraser abrasion resistance and steel wool abrasion resistance, and the surface treatment agent of Comparative Example 5 exhibited high steel wool abrasion resistance but low eraser abrasion resistance. Furthermore, the surface treatment agent of Comparative Example 6 exhibited high eraser abrasion resistance but low steel wool 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 eraser abrasion resistance and steel wool abrasion resistance.

[0234] [Table 2]

Claims

[Claim 1] The following general formula (1) 【Chemical 1】 (In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue; B is independently a divalent organic group; V is independently a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group; E is independently a monovalent group having an oxyalkylene group; R' is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen group; 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; α is 1 or 2; β is independently an integer of 1 to 6; γ is independently 0 or 1; δ is independently 1 or 2; and the sum of β, γ, and δ is independently an integer of 2 to 7 for each V to which it is bonded. The fluoropolyether group-containing polymer has a hydroxyl group or a hydrolyzable group and a polyether group, and is represented by the formula:

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