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

Abstract

A fluoropolyether group-containing polymer represented by general formula (1) has excellent solubility in at least one non-fluorine organic solvent, and is capable of forming a cured film having excellent water and oil repellency and wear resistance. Rf [Q-CH (V) 2] [alpha] (1) (In the formula, Rf is a monovalent or divalent fluoropolyether group-containing polymer residue, Q is a single bond or a divalent organic group, V is independently a monovalent group having a polyvalent polysiloxane structure and having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable silyl group at a terminal, and [alpha] is 1 or 2).

Description

Technical Field

[0001] The present invention relates to a polymer containing a fluoropolyether group (a compound having a monovalent or divalent polymer residue containing a fluoropolyether group in the molecule), and more particularly, to a polymer containing a fluoropolyether group that forms a cured film excellent in water and oil repellency and abrasion resistance, a surface treatment agent containing the polymer and / or its partial (hydrolytic) condensate, and an article surface-treated with the surface treatment agent. Background Art

[0002] Generally, compounds containing a fluoropolyether group have a very small surface free energy, and thus have water and oil repellency, chemical resistance, lubricity, mold release property, antifouling property, etc. Utilizing these properties, they are widely used industrially as water, oil, and stain repellents for paper, fibers, etc., lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, protective films, etc. However, this property also means non-pressure-sensitive adhesiveness and non-sealing property to other substrates. Even if it can be coated on the substrate surface, it is difficult to make the film adhere closely.

[0003] On the other hand, as a substance that binds the surface of a substrate such as glass or cloth to an organic compound, a silane coupling agent is well known and widely used as a coating agent for various substrate surfaces. A silane coupling agent has an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group undergoes a self-condensation reaction by using moisture in the air, etc., to form a film. This film becomes a durable and firm film by chemically and physically bonding the alkoxysilyl group to the surface of glass, metal, etc.

[0004] In Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-238577), a polymer-modified silane containing a fluoropolyether group having a linear fluoropolyether group is described as a compound having a fluoropolyether group and an alkoxysilyl group. By treating the glass surface with a cured product of a surface treatment agent containing the polymer-modified silane containing a fluoropolyether group, excellent slidability, mold release property, and abrasion resistance can be imparted to the glass surface.

[0005] On the other hand, when the compound containing a fluoropolyether group described in this Patent Document 1 is used as a surface treatment agent, its solubility in non-fluorinated organic solvents is low, so it is diluted with a fluorinated organic solvent. In recent years, due to environmental concerns and concerns about the health of workers, for safe disposal, dedicated exclusion equipment different from general organic solvents is required, so it is inclined to avoid using fluorinated organic solvents, and it is necessary to develop a water and oil repellent treatment agent (surface treatment agent) that can impart excellent properties to the surface of the cured product without using fluorinated organic solvents.

[0006] Prior Art Documents

[0007] Patent Document

[0008] Patent Document 1: Japanese Patent Laid-Open No. 2003-238577 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] The present invention has been completed in view of the above actual situation, and an object thereof is to provide a fluoropolyether group-containing polymer having excellent solubility in at least one non-fluorinated organic solvent, capable of forming a water- and oil-repellent and excellent abrasion-resistant cured film, a surface treatment agent containing the polymer and / or its partial (hydrolytic) condensate, and an article surface-treated with the surface treatment agent.

[0011] Means for Solving the Problems

[0012] The inventors of the present invention conducted intensive studies to solve the above object, and as a result, found that: among the above fluoropolyether group-containing polymers, a fluoropolyether group-containing polymer having a polyvalent polysiloxane structure (a polyvalent polysiloxane structure of trivalent or higher) and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom represented by the following general formula (1), particularly a fluoropolyether group-containing polymer having a polyvalent polysiloxane structure (a polyvalent polysiloxane structure of trivalent or higher) and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom represented by the following general formula (2) has excellent solubility in at least one non-fluorinated organic solvent, and a surface treatment agent containing the polymer and / or its partial (hydrolytic) condensate can form a water- and oil-repellent and excellent abrasion-resistant cured film, thereby completing the present invention.

[0013] Therefore, the present invention provides the following fluoropolyether group-containing polymer.

[0014] [1] A fluoropolyether group-containing polymer represented by the following general formula (1):

[0015] Rf[Q-CH(V)2] α (1)

[0016] (In the formula, Rf is a monovalent or divalent polymer residue containing a fluoropolyether group, Q is a single bond or a divalent organic group, V is independently a monovalent group having a polyvalent polysiloxane structure and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom at the terminal, and α is 1 or 2.).

[0017] [2] The fluoropolyether group-containing polymer according to [1], which is represented by the following general formula (2):

[0018] [Chemical Formula 1]

[0019]

[0020] (In the formula, Rf is a monovalent or divalent polymer residue containing a fluoropolyether group, X is independently a single bond or a divalent heteroatom, Y 1 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom, and a sulfur atom, Z is independently an (m + 1)-valent linking group having a polyvalent polysiloxane structure, Y 2 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom, and a sulfur atom, R 1 is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, L is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each bonded silicon atom, m is independently an integer of 2 to 9, and α is 1 or 2.).

[0021] [3] The fluoropolyether group-containing polymer according to [1] or [2], wherein α in the formula (1) or (2) is 1, and Rf is a monovalent fluoropolyether group represented by the following general formula (3),

[0022] [Chemical formula 2]

[0023]

[0024] (In the formula, A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms. d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, v are each an integer of 0 to 200, and the sum of p, q, r, s, t, u, v is 3 to 200. These units may be linear or branched. In addition, the respective repeating units shown in the parentheses with p, q, r, s, t, u, v may be bonded randomly.).

[0025] [4] The fluoropolyether group-containing polymer according to [1] or [2], wherein α in the formula (1) or (2) is 2, and Rf is a divalent fluoropolyether group represented by the following general formula (4),

[0026] [Chemical formula 3]

[0027]

[0028] (In the formula, W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, v are each an integer of 0 to 200, and the sum of p, q, r, s, t, u, v is 3 to 200. These units may be linear or branched. In addition, the respective repeating units shown in the parentheses with p, q, r, s, t, u, v may be bonded randomly.)

[0029] [5] A fluoropolyether group-containing polymer according to any one of [2] to [4], wherein, in the formula (2), of the two Xs present at one end of the molecular chain when α=1 and of the two (four in the molecule) Xs present at both ends of the molecular chain when α=2, at each end, one X is an oxygen atom and the other X is a single bond.

[0030] [6] The fluoropolyether group-containing polymer according to any one of [2] to [5], wherein in the formula (2), Y 1 They are independently an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms.

[0031] [7] The fluoropolyether group-containing polymer according to any one of [2] to [6], wherein in the formula (2), Z is a linear, branched or cyclic tri- to decavalent organopolysiloxane residue having 3 to 10 silicon atoms.

[0032] [8] The fluoropolyether group-containing polymer according to any one of [2] to [7], wherein in the formula (2), Z is represented by any one of the following formulas:

[0033] [Chemistry 4]

[0034]

[0035] (wherein, * is the same as Y in general formula (2) 1 The bonding end of the bond, ** is the Y in the general formula (2) 2 Bonded end of the bond. R 2 Each of the above is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, a is an integer of 0 to 6, a1 is an integer of 1 to 6, a2 is an integer of 2 to 7, b is an integer of 2 to 9, and c is 1. The repeating units shown in the parentheses with a, a2, and c may be randomly bonded. ).

[0036] [9] The fluoropolyether group-containing polymer according to any one of [2] to [8], wherein in the formula (2), Y 2 They are independently an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms.

[0037]

[10] A fluoropolyether group-containing polymer according to any one of [2] to [9], wherein in the formula (2), L is independently a group selected from 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.

[0038]

[11] The fluoropolyether group-containing polymer according to any one of [2] to

[10] , wherein the polymer represented by the formula (2) is a polymer represented by the following general formula (5) or (6).

[0039] [Chemical formula 5]

[0040]

[0041] [In the formula, d is independently an integer of 1 to 3 in each unit, p", q", r", s" are each an integer of 0 to 200, and the sum of p", q", r", s" in each formula is 3 to 200. In addition, the respective repeating units shown in the parentheses with p", q", r", s" can be bonded randomly. i and j are independently integers of 2 to 10 in each unit, and these units can be linear or branched. G is independently represented by any one of the following formulas.

[0042] [Chemical formula 6]

[0043]

[0044] (In the formula, k is independently an integer of 2 to 8 in each unit.).

[0045]

[12] A surface treatment agent, which contains the fluoropolyether group-containing polymer according to any one of [1] to

[11] and / or its partial (hydrolytic) condensate.

[0046]

[13] The surface treatment agent according to

[12] , which further contains an organic solvent without fluorine atoms.

[0047]

[14] The surface treatment agent according to

[12] or

[13] , wherein the content of the fluoropolyether group-containing polymer and / or its partial (hydrolytic) condensate is 0.005 to 80% by mass.

[0048]

[15] The surface treatment agent according to any one of

[12] to

[14] , wherein the content of the fluoropolyether group-containing polymer and / or its partial (hydrolytic) condensate is 0.005 to 80% by mass, and the balance is an organic solvent without fluorine atoms.

[0049]

[16] An article, which is an article surface-treated with the surface treatment agent according to any one of

[12] to

[15] .

[0050] Effects of the invention

[0051] The novel fluoropolyether group-containing polymer of the present invention has excellent solubility in at least one non-fluorine-based organic solvent, and by treating with a surface treatment agent containing the polymer and / or its partial (hydrolytic) condensate, excellent water and oil repellency and abrasion resistance can be imparted to various articles. Detailed Embodiments

[0052] As used in this specification, the so-called “about (numerical value)” is a rounded numerical value (approximate number). When the lower digit of the numerical value it represents is not “0”, it also includes the numerical range until the lower digit is rounded to become the numerical value it represents. For example, “about 3 equivalents” means 2.5 equivalents or more and 3.4 equivalents or less, and “about 0.02 equivalents” means 0.015 equivalents or more and 0.024 equivalents or less. In addition, when the lower digit of the numerical value it represents is “0”, it includes the numerical range until the lower digit is rounded to become the numerical value it represents. For example, “about 80 ° C” means 75 ° C or more and 84 ° C or less.

[0053] [Fluoropolyether Group-Containing Polymer]

[0054] The fluoropolyether group-containing polymer of the present invention has a fluoropolyether group and a reactive functional group in the molecule and is represented by the following general formula (1). The fluoropolyether group-containing polymer of the present invention may be a single type or a mixture of two or more types.

[0055] Rf[Q-CH(V)2] α (1)

[0056] (In the formula, Rf is a monovalent or divalent polymer residue containing a fluoropolyether group, Q is a single bond or a divalent organic group, V is independently a monovalent group having a polyvalent polysiloxane structure and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom at the end, and α is 1 or 2.)

[0057] In the above formula (1), Rf is a monovalent or divalent polymer residue containing a fluoropolyether group. When α is 1 (that is, when Rf is a monovalent polymer residue containing a fluoropolyether group), it is preferably a monovalent fluoropolyether group represented by the following general formula (3). When α is 2 (that is, when Rf is a divalent polymer residue containing a fluoropolyether group), it is preferably a divalent fluoropolyether group represented by the following general formula (4).

[0058] [Chemical Formula 7]

[0059]

[0060] [Chemical Formula 8]

[0061]

[0062] (In the above formulas, A is a hydrogen atom, a fluorine atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or fluorine-substituted, W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms. d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, v are each an integer of 0 to 200, and the sum of p, q, r, s, t, u, v is 3 to 200. Each of these units may be linear or branched. In addition, the respective repeating units shown in the parentheses with p, q, r, s, t, u, v may be bonded randomly.)

[0063] In the above formula (3), A is a hydrogen atom, a fluorine atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or fluorine-substituted, preferably a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, more preferably a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0064] In the above formula (3), when A is a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, after forming a cured coating film, the fluoropolyether group also has high molecular mobility, and particularly a cured coating film having excellent liquid repellency, antifouling property, and abrasion resistance is obtained.

[0065] In the above formulas (3) and (4), W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, and examples thereof include groups in which one or two fluorine atoms are substituted with hydrogen atoms in each perfluoroalkylene group such as CF2 unit, C2F4 unit, C3F6 unit, C4F8 unit, C5F 10 unit, C6F 12 unit, etc.

[0066] In the above formulas (3) and (4), d is independently an integer of 1 to 3 in each unit, preferably 1 or 2.

[0067] In addition, p, q, r, s, t, u, v are each an integer of 0 to 200. Preferably, p is an integer of 0 to 100, q is an integer of 0 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, v is an integer of 0 to 100, and the sum of p, q, r, s, t, u, v is 3 to 200, preferably 10 to 100. If the sum of p, q, r, s, t, u, v is smaller than the above upper limit value, the adhesion and curability of the obtained cured coating film are good. If it is larger than the above lower limit value, the characteristics of the fluoropolyether group can be fully exhibited, so it is preferred.

[0068] Furthermore, when r, s, t, u, v are all 0, preferably p and q are each an integer of 5 to 100, and the sum of p and q is 10 to 105, particularly preferably 15 to 60.

[0069] In the above formulas (3) and (4), each unit may be linear or branched. Additionally, the respective repeating units shown within the parentheses with p, q, r, s, t, u, and v may be bonded randomly.

[0070] As Rf, specifically, the following groups can be exemplified.

[0071] [Chemical formula 9]

[0072] CF3O(CF2O) p′ CF2-

[0073] CF3O(CF2O) p′ (CF2CF2O) q′ CF2-

[0074] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2-

[0075] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2CF2O) s′ CF2-

[0076] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ CF2-

[0077] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ (CF2CF2CF2CF2CF2O) t′ CF2-

[0078] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ (CF2CF2CF2CF2CF2O) t′ (CF2CF2CF2CF2CF2CF2O) u′ CF2-

[0079] CF3O(CF2CF2O)q′ CF2-

[0080] [Chemical formula 10]

[0081] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2CF2-

[0082]

[0083] CF3CF2CF2O(CF2CF2CF2O) r′ CF2CF2-

[0084]

[0085] [Chemical formula 11]

[0086] -CF2O(CF2O) p′ CF2-

[0087] -CF2O(CF2O) p′ (CF2CF2O) q′ CF2-

[0088] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2-

[0089] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2CF2O) s′ CF2-

[0090] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ CF2-

[0091] -CF2CF2O(CF2CF2CF2O) r′ CF2CF2-

[0092]

[0093] (wherein p’, q’, r’, s’, t’, u’, q1’, r1’, and r2’ are each an integer of 1 or more, and the sum of p’, q’, r’, s’, t’, u’, q1’, r1’, and r2’ in each formula is from 3 to 200. Further, the respective repeating units shown in the parentheses with p’, q’, r’, s’, t’, and u’ may be bonded randomly.)

[0094] As Rf, the following groups are preferred.

[0095] [Chemical Formula 12]

[0096]

[0097] CF3CF2CF2O-(CF2CF2CF2O) r′ -CF2CF2-

[0098]

[0099] CF3O-(CF2O) p′ -(CF2CF2O) q′ -(CF2CF2CF2O) r′ -CF2CF2-

[0100]

[0101] (wherein p’, q’, r’ and their sum in each formula are the same as above, and the respective repeating units shown in the parentheses with p’, q’, r’ may be bonded randomly.)

[0102] The molecular weight of Rf only needs to be such that the number-average molecular weight of this structural part is in the range of 400 to 40,000, preferably 2,000 to 25,000, and there is no particular limitation on its molecular weight distribution (or degree of polymerization distribution). Further, in the present invention, the molecular weight (or degree of polymerization or number of repeating units) can be determined as the number-average molecular weight (or number-average degree of polymerization) in terms of polystyrene obtained by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as the eluent solvent. Preferably, it is the number-average molecular weight (or number-average degree of polymerization) calculated from the characteristic peak intensity ratio of the terminal structure and the main chain structure of the fluoropolyether group-containing polymer based on 1 1H-NMR analysis and 19 19F-NMR analysis (the same applies hereinafter).

[0103] In the above formula (1), Q is a single bond or a divalent organic group, preferably a single bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom, more preferably a single bond. Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom include the following groups.

[0104] [Chemical formula 13]

[0105] *-CH2-**

[0106] *-CH2CH2-**

[0107] *-CH2CH2CH2-**

[0108]

[0109] *-CH2CH2CH2CH2-**

[0110] *-CH2CH2CH2CH2CH2-**

[0111] *-CH2CH2CH2CH2CH2CH2-**

[0112] *-CH2CH2CH2CH2CH2CH2CH2-**

[0113] *-CH2CH2CH2CH2CH2CH2CH2CH2-**

[0114]

[0115] [Chemical formula 14]

[0116]

[0117] [Chemical formula 15]

[0118]

[0119] (In the formula, * is the bonding end bonded to Rf in the above formula (1), and ** is the bonding end bonded to the carbon atom in the above formula (1).)

[0120] In the above formula (1), V is independently a monovalent group having a polyvalent polysiloxane structure and a hydroxyl group bonded to a silicon atom at the terminal (i.e., hydroxysilyl group, silanol group or silyl group containing a hydroxyl group) and / or a hydrolyzable silyl group, preferably a monovalent group having a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom at the terminal and having a polyvalent polysiloxane structure (i.e., a polyvalent polysiloxane structure of trivalent or higher, preferably 3 to 10 valent) connecting these terminal groups to a CH group, more preferably a monovalent organic group having a plurality (specifically 2 to 9, preferably 2 to 7) of hydroxyl groups and / or hydrolyzable silyl groups bonded to a silicon atom introduced at the terminal. As such a V, for example, groups represented by the following general formulas (7a) to (7f) can be cited.

[0121] [Chemical formula 16]

[0122]

[0123] (In the formula, X is independently a single bond or a divalent heteroatom, D and D’ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, R 1 is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, R 2 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, a is an integer of 0 to 6, a1 is an integer of 1 to 6, a2 is an integer of 2 to 7, b is an integer of 2 to 9, c is 1. Each repeating unit shown in the parentheses with a, a2, c may be bonded randomly. L is independently a hydroxyl group or a hydrolyzable group, and n is independently an integer of 1 to 3 for each bonded silicon atom.)

[0124] In the above general formulas (7a) to (7f), X is a single bond or a divalent heteroatom. As the divalent heteroatom, an oxygen atom, a nitrogen atom, a sulfur atom can be cited. Preferably, in formula (1), among the two Vs each present at each terminal of the molecular chain (i.e., at the single terminal of the molecular chain when α = 1 and at both terminals of the molecular chain when α = 2), it is preferred that X in one V is a single bond and X in the other V is a divalent heteroatom, particularly an oxygen atom.

[0125] In the above formulas (7a) to (7f), D and D' are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, which may contain one or more selected from oxygen atoms, nitrogen atoms, silicon atoms, and sulfur atoms. Examples of the divalent hydrocarbon group include alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, and octamethylene; arylene groups such as phenylene; or combinations of two or more of these groups (alkylene-arylene, etc.). As D and D', ethylene, propylene, butylene, hexamethylene, octamethylene, and phenylene are preferred.

[0126] In the above formulas (7a) to (7f), R 1 is an alkyl group such as methyl, ethyl, propyl, or butyl having 1 to 4 carbon atoms, or phenyl, and among them, methyl is preferred.

[0127] L is a hydroxyl group or a hydrolyzable group which may be different from each other. Examples of such L include alkoxy groups having 1 to 10 carbon atoms such as hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, and butoxy; alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy; acyloxy groups having 1 to 10 carbon atoms such as acetoxy; alkenyloxy groups having 2 to 10 carbon atoms such as isopropenyloxy; and halogen groups such as chloro, bromo, and iodo. Among them, methoxy, ethoxy, isopropenyloxy, and chloro are preferred.

[0128] In the above formulas (7a) to (7f), R 2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Specifically, it is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, and butyl, or an aryl group having 6 to 10 carbon atoms such as phenyl. R 2 may be the same or different, and among them, methyl is preferred.

[0129] In the above formulas (7a) to (7f), n is independently an integer of 1 to 3 for each silicon atom to which it is bonded, preferably 2 or 3, and more preferably 3 from the viewpoints of reactivity and adhesion to the substrate. a is an integer of 0 to 6, preferably an integer of 2 to 6; a1 is an integer of 1 to 6, preferably an integer of 2 to 6; a2 is an integer of 2 to 7, preferably an integer of 3 to 7; and b is an integer of 2 to 9, preferably an integer of 3 to 5.

[0130] Specific examples of such V include the groups shown below.

[0131] [Chemical formula 17]

[0132]

[0133] [Chemical formula 18]

[0134]

[0135] In the above formula (1), α is 1 or 2, preferably 1.

[0136] As the polymer containing a fluoropolyether group of the present invention, a polymer represented by the following general formula (2) is more preferable.

[0137] [Chemical formula 19]

[0138]

[0139] (In the formula, Rf, X, R 1 , L, n, α are the same as above, and Y 1 independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, Z independently represents an (m + 1)-valent linking group having a polyvalent polysiloxane structure, and Y 2 independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, and m independently represents an integer of 2 to 9.)

[0140] In the above formula (2), Rf and α are the same as Rf and α in the above formula (1), and the same examples as above can be exemplified. In addition, R 1 , L, and n are the same as R 1 , L, and n in the above formulas (7a) to (7f), and the same examples as above can be exemplified.

[0141] In the above formula (2), X is the same as X in the above formulas (7a) to (7f). Preferably, among the two X's each present at each end of the molecular chain (i.e., at the single end of the molecular chain when α = 1, and at both ends of the molecular chain when α = 2), one X is an oxygen atom and the other X is a single bond.

[0142] In the above formula (2), Y 1 independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom. As Y 1, specifically, it is possible to exemplify an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene, etc., an arylene group having 6 to 20 carbon atoms such as phenylene, and a combination of two or more of these groups (for example, an alkylene group having 2 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms (alkylene-arylene having 8 to 18 carbon atoms), etc.). Among these groups, there is a group in which one or more bonds selected from an amide bond (for example, an unsubstituted amide bond, an N-methyl-substituted amide bond, an N-phenyl-substituted amide bond), a urethane bond, an ether bond, a carbonyl bond, an ester bond, a diorganosilylene (for example, a dialkylsilylene such as dimethylsilylene), a silylarylene bond (for example, a silylphenylene bond), and a silylalkylene bond (for example, a silylethylene bond) are connected or interposed. Preferably, it is an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms, and more preferably a straight-chain alkylene group having 3 to 6 carbon atoms.

[0143] As Y 1 , specific examples thereof include the following groups.

[0144] [Chemical formula 20]

[0145] *-CH2CH2-**

[0146] *-CH2CH2CH2-**

[0147]

[0148] *-CH2CH2CH2CH2-**

[0149] *-CH2CH2CH2CH2CH2-**

[0150] *-CH2CH2CH2CH2CH2CH2-**

[0151] *-CH2CH2CH2CH2CH2CH2CH2-**

[0152] *-CH2CH2CH2CH2CH2CH2CH2CH2-**

[0153]

[0154] [Chemical formula 21]

[0155]

[0156] [Chemical formula 22]

[0157]

[0158] (In the formula, * is the bonding end bonded to X in the above formula (2), and ** is the bonding end bonded to Z in the above formula (2).)

[0159] As Y 1 , more preferably the groups shown below.

[0160] [Chemical formula 23]

[0161] *-CH2CH2-**

[0162] *-CH2CH2CH2-**

[0163]

[0164] *-CH2CH2CH2CH2-**

[0165] *-CH2CH2CH2CH2CH2-**

[0166] *-CH2CH2CH2CH2CH2CH2-**

[0167] (In the formula, * is the bonding end bonded to X in formula (2), and ** is the bonding end bonded to Z in formula (2).)

[0168] In the above formula (2), Z is independently an (m + 1)-valent, i.e., trivalent to decavalent, linking group having a polyvalent polysiloxane structure (i.e., a polysiloxane structure with a valence of 3 or more, preferably 3 to 10), and is preferably a linear, branched or cyclic trivalent to decavalent organopolysiloxane residue having 3 to 10 silicon atoms.

[0169] As specific examples of Z, for example, the following groups can be cited.

[0170] [Chemical formula 24]

[0171]

[0172] (In the formula, R 2 , a, a1, a2, b, c are the same as above, and the respective repeating units shown in the parentheses with a, a2, c can be bonded randomly. * is the bonding end bonded to Y in formula (2) 1 bonding end, and ** is the bonding end bonded to Y in formula (2) 2 bonding end.)

[0173] As Z, the following groups are preferred.

[0174] [Chemical formula 25]

[0175]

[0176] (In the formula, a2 and c are the same as above, and the repeating units shown in the parentheses with a2 and c may be bonded randomly. * is the bonding end bonded to Y in formula (2), and ** is the bonding end bonded to Y in formula (2).) 1 (The bonding end bonded to Y in formula (2), and ** is the bonding end bonded to Y in formula (2).) 2 )

[0177] In the above formula (2), Y 2 independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from oxygen atom, nitrogen atom, silicon atom and sulfur atom. As Y 2 , specifically, examples thereof include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene, etc., arylene groups having 6 to 20 carbon atoms such as phenylene, combinations of two or more of these groups (for example, an alkylene group having 2 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms (an alkylene-arylene group having 8 to 18 carbon atoms), etc.), and groups in which one or more bonds selected from amide bonds (for example, unsubstituted amide bond, N-methyl substituted amide bond, N-phenyl substituted amide bond), urethane bond, ether bond, carbonyl bond, ester bond, diorganosilylene (for example, dialkylsilylene such as dimethylsilylene), silylarylene bond (for example, silylphenylene bond) and silylalkylene bond (for example, silylethylene bond) are connected or intervened, preferably an alkylene group having 2 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms, more preferably a straight-chain alkylene group having 3 to 8 carbon atoms.)

[0178] As specific examples of Y 2 , for example, the following groups can be listed.)

[0179] [Chemical formula 26]

[0180] *-CH2CH2-**

[0181] *-CH2CH2CH2-**

[0182]

[0183] *-CH2CH2CH2CH2-**

[0184] *-CH2CH2CH2CH2CH2-**

[0185] *-CH2CH2CH2CH2CH2CH2-**

[0186] *-CH2CH2CH2CH2CH2CH2CH2-**

[0187] *-CH2CH2CH2CH2CH2CH2CH2CH2-**

[0188]

[0189] [Chemical formula 27]

[0190]

[0191] [Chemical formula 28]

[0192]

[0193] (In the formula, * is the bonding end bonded to Z in the general formula (2), and ** is the bonding end bonded to the silicon atom in the general formula (2).)

[0194] In the above formula (2), m is independently an integer of 2 to 9, preferably an integer of 2 to 7, more preferably an integer of 2 to 5. If m is 10 or more, the number of hydroxyl groups and / or hydrolyzable silyl groups bonded to the silicon atom at the end is too large, which has an adverse effect on water repellency and stain resistance.

[0195] As the polymer containing a fluoropolyether group represented by the above formula (2), a polymer represented by the following general formula (5) or (6) is preferred.

[0196] [Chemical formula 29]

[0197]

[0198] [In the formula, d is independently an integer of 1 to 3 in each unit, p”, q”, r”, s” are each an integer of 0 to 200, preferably an integer of 0 to 100, and the sum of p”, q”, r”, s” in each formula is 3 to 200, preferably 10 to 100. In addition, the respective repeating units shown in the parentheses with p”, q”, r”, s” can be bonded randomly. i and j are each independently an integer of 2 to 10 in each unit. These units can be linear or branched. G is independently represented by any of the following formulas.

[0199] [Chemical formula 30]

[0200]

[0201] (In the formula, k is independently an integer of 2 to 8 in each unit.)]

[0202] As the polymer containing a fluoropolyether group represented by the above formula (2), a polymer represented by the following formula can be specifically exemplified.

[0203] [Chemical formula 31]

[0204]

[0205] [Chemical Formula 32]

[0206]

[0207] [Chemical Formula 33]

[0208]

[0209] [Chemical Formula 34]

[0210]

[0211] [Chemical Formula 35]

[0212]

[0213] [Chemical Formula 36]

[0214]

[0215] [Chemical Formula 37]

[0216]

[0217] [Chemical Formula 38]

[0218]

[0219] [Chemical Formula 39]

[0220]

[0221] [Chemical Formula 40]

[0222]

[0223] [Chemical Formula 41]

[0224]

[0225] (In the formula, p’, q’, r’ and their sums in each formula are the same as above, and the respective repeating units shown in the parentheses with p’, q’, r’ can be bonded randomly.)

[0226] As a method for preparing the fluoropolyether group-containing polymer represented by the above formula (2), for example, the following methods can be cited.

[0227] First, a compound represented by the following general formula (8)

[0228] [Chemical Formula 42]

[0229]

[0230] (In the formula, Rf and α are the same as described above, and M is a leaving monovalent group.) The fluoropolyether group-containing polymer having a carbonyl group at the terminal preferably reacts with an organometallic reagent having an aliphatic unsaturated double bond (olefin moiety) at the terminal and having a β-hydrogen atom (i.e., a hydrogen atom bonded to the carbon atom at the β-position of the metal atom) in the presence of a solvent.

[0231] In the above formula (8), M is a leaving monovalent group, and examples thereof include a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a thiol group, an alkylthio group, an acyl group, and the like.

[0232] Examples of such M include the following groups.

[0233] [Chemical formula 43]

[0234] -H -F -Cl -Br -I -OH -OCH3 -OCH2CH3 -NH2 -SH -SCH3

[0235] As the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (8), specifically, the following polymers can be exemplified.

[0236] [Chemical formula 44]

[0237]

[0238] [Chemical formula 45]

[0239]

[0240] (In the formula, p’, q’, r’ and their total in each formula are the same as described above, and the respective repeating units shown in the parentheses with p’, q’, r’ can be bonded randomly. r3’ and r4’ are each an integer of 1 or more, and the sum of r3’ and r4’ is 2 to 199.)

[0241] As the above organometallic reagent having an aliphatic unsaturated double bond at the terminal and having a β-hydrogen atom, specifically, organolithium reagents, Grignard reagents, organozinc reagents, organoboron reagents, organotin reagents, etc. can be exemplified. Particularly from the viewpoint of ease of handling, Grignard reagents and organozinc reagents are preferably used. As such organometallic reagents, the following reagents can be particularly preferably used.

[0242] [Chemical formula 46]

[0243]

[0244] The amount of the organometallic reagent having an aliphatic unsaturated double bond at the terminal and having a β-hydrogen atom is preferably 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and further preferably about 3 equivalents, relative to 1 equivalent of the reactive terminal group (leavable monovalent group) of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (8).

[0245] For the reaction of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (8) and the organometallic reagent having an aliphatic unsaturated double bond at the terminal and having a β-hydrogen atom, a solvent can be used. There is no particular limitation on the solvent used at this time, but from the aspect that the reaction compounds are fluorine compounds, a fluorine-based solvent is preferably used. Examples of the fluorine-based solvent include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, perfluorinated solvents (such as Asahiklin AC2000 and Asahiklin AC6000) sold by AGC Inc., hydrofluoroether (HFE) solvents (such as NOVEC7100: C4F9OCH3, NOVEC7200: C4F9OC2H5, NOVEC7300: C2F5-CF(OCH3)-CF(CF3)2, etc.) sold by 3M Company, and perfluorinated solvents (such as PF5080, PF5070, PF5060, etc.) also sold by 3M Company. The fluorine-based solvents can be used alone or in combination.

[0246] In addition, as the solvent, an organic solvent other than the above fluorine-based solvents can be used. Examples of the organic solvent include ether solvents such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane. The organic solvents can be used alone or in combination with the fluorine-based solvents.

[0247] Regarding the amount of the solvent used, 10 to 600 parts by mass, preferably 50 to 400 parts by mass, and more preferably 200 to 350 parts by mass can be used relative to 100 parts by mass of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (8).

[0248] As the reaction conditions for the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (8) and the organometallic reagent having an aliphatic unsaturated double bond at the terminal and having a β-hydrogen atom, it can be set at 0 to 80 °C, preferably 45 to 70 °C, and more preferably about 50 °C for 1 to 12 hours, preferably 5 to 7 hours.

[0249] After the reaction was carried out under the above conditions, the reaction was stopped, and the aqueous layer was separated from the fluorinated solvent layer by liquid separation. The obtained fluorinated solvent layer was further washed with an organic solvent, and the solvent was distilled off to obtain a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the following general formula (9).

[0250] [Chemical formula 47]

[0251]

[0252] (In the formula, Rf and α are the same as above, and Y 1’ is independently a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms that may contain one or more selected from oxygen atom, nitrogen atom, silicon atom and sulfur atom.)

[0253] Among them, in the above formula (9), Y 1’ is independently a single bond or a divalent hydrocarbon group having 1 to 18, particularly 2 to 12 carbon atoms that may contain one or more selected from oxygen atom, nitrogen atom, silicon atom and sulfur atom. Specifically, it is a single bond, methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene and other alkylene groups having 1 to 18 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms such as phenylene (for example, an alkylene-arylene group having 7 to 18 carbon atoms), etc. As Y 1’ , a linear alkylene group having 1 to 4 carbon atoms is preferred.

[0254] As such Y 1’ , the following groups can be exemplified, for example.

[0255] [Chemical formula 48]

[0256] *-CH2CH2-**

[0257] *-CH2CH2CH2-**

[0258] *-CH2CH2CH2CH2-**

[0259] *-CH2CH2CH2CH2CH2-**

[0260] *-CH2CH2CH2CH2CH2CH2-**

[0261]

[0262] (In the formula, * is the bonding end bonded to the carbon atom bonded to Rf in formula (9), and ** is the bonding end bonded to the vinyl group in formula (9).)

[0263] As the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (9), the following polymers can be specifically exemplified.

[0264] [Chemical Formula 49]

[0265]

[0266] [Chemical Formula 50]

[0267]

[0268] (In the formula, p', q', r', r3', r4' and their total in each formula are the same as above, and the respective repeating units shown in the parentheses with p', q', r' can be bonded randomly.)

[0269] Next, for the above-obtained fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (9) and the olefin introducing agent, in the presence of a base, if necessary, an additive and a solvent for enhancing reactivity are used, and the mixture is aged at a temperature of 0 to 90 °C, preferably 40 to 60 °C, more preferably about 50 °C for 1 to 48 hours, preferably 10 to 40 hours, more preferably about 24 hours.

[0270] Among them, as the olefin introducing agent that reacts with the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9), for example, halides can be used. Specifically, allyl bromide, allyl chloride, 3-butenyl bromide, etc. can be cited.

[0271] Regarding the usage amount of the olefin introducing agent, 1 to 15 equivalents, more preferably 3 to 6 equivalents, and further preferably about 4 equivalents can be used relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9).

[0272] As the base used in the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9) with the olefin introducing agent, for example, amines, alkali metal-based bases, etc. can be used. Specifically, for amines, triethylamine, diisopropylethylamine, pyridine, DBU, imidazole, etc. can be cited. For alkali metal-based bases, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, potassium tert-butoxide, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, etc. can be cited.

[0273] Regarding the amount of base used, 1 to 20 equivalents, more preferably 4 to 8 equivalents, and still more preferably about 6 equivalents, can be used relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9).

[0274] For the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9) with an olefin introducing agent, tetrabutylammonium halide, alkali metal halide, etc. can be used as additives to improve the reactivity. Specifically, as additives, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, sodium iodide, potassium iodide, cesium iodide, crown ether, etc. can be cited. These additives improve the reactivity by catalytically performing halogen exchange with the olefin introducing agent in the reaction system. In addition, crown ether improves the reactivity by coordinating with the metal.

[0275] Regarding the amount of the additive used, 0.005 to 0.1 equivalent, more preferably 0.01 to 0.05 equivalent, and still more preferably about 0.02 equivalent, can be used relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9).

[0276] For the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9) with an olefin introducing agent, a solvent can be used. Although it is not necessary to use a solvent, as the fluorine-based solvent, fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene, hydrofluoroether (HFE) solvents such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M Company, trade name: Novec series), perfluorinated solvents composed of completely fluorinated compounds (manufactured by 3M Company, trade name: Fluorinert series), etc. can be cited. Further, as the organic solvent, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran (THF), etc. can be used.

[0277] Regarding the amount used when a solvent is used, 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and still more preferably about 50 parts by mass, can be used relative to 100 parts by mass of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9).

[0278] By the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the above formula (9) with an olefin introducing agent, a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain end represented by the following general formula (10) is obtained.

[0279] [Chemical Formula 51]

[0280]

[0281] (In the formula, Rf, Y 1’ , α are the same as above. Multiple Y 1’ may be the same or different.)

[0282] As a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends represented by the formula (10), the polymers shown below can be preferably exemplified.

[0283] [Chemical Formula 52]

[0284]

[0285] [Chemical Formula 53]

[0286]

[0287] (In the formula, p’, q’, r’, r3’, r4’ and their total in each formula are the same as above, and the respective repeating units shown in the parentheses with p’, q’, r’ can be bonded randomly.)

[0288] Next, the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends represented by the above formula (10) is dissolved in a solvent such as a fluorine-based solvent like 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having three or more SiH groups in the molecule such as 2,4,6,8-tetramethylcyclotetrasiloxane is mixed, and it is cured at a temperature of 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 in the presence of a hydrosilylation reaction catalyst such as a toluene solution of chloroplatinic acid / vinylsiloxane complex.

[0289] Among them, as the organosilicon compound having three or more SiH groups in the molecule that reacts with the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends represented by the above formula (10), a compound represented by the following formula is preferred.

[0290] [Chemical Formula 54]

[0291]

[0292] (In the formula, R 2 , a, a1, a2, b, c are the same as above.)

[0293] Examples of such organosilicon compounds having three or more SiH groups in the molecule include 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, methyltris(dimethylsilyloxy)silane, tetrakis(dimethylsilyloxy)silane, 1,1,1,3,5,7,9,11,13,15,17,19,19,19-tetradecamethyl decasiloxane and other compounds.

[0294] When the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends represented by the above formula (10) is subjected to an addition reaction with an organosilicon compound having three or more SiH groups in the molecule, the amount of the organosilicon compound having three or more SiH groups in the molecule used can be 2 to 10 equivalents, more preferably 3 to 6 equivalents, and further preferably about 5 equivalents, relative to 1 equivalent of the reactive end groups (terminal olefin moieties) of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends.

[0295] For the reaction of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends represented by the above formula (10) with an organosilicon compound having three or more SiH groups in the molecule, a fluorine-based solvent is preferably used as the solvent. Examples of the fluorine-based solvent include hydrofluoroether (HFE)-based solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M Company, trade name: Novec series), perfluorinated solvents composed of completely fluorinated compounds (manufactured by 3M Company, trade name: Fluorinert series), and the like.

[0296] Regarding the amount of the solvent used, 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably 100 to 150 parts by mass can be used relative to 100 parts by mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends represented by the above formula (10).

[0297] For the reaction of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends represented by the above formula (10) with an organosilicon compound having three or more SiH groups 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, alkynols, etc., platinum group metal-based catalysts such as tetrakis(triphenylphosphine)palladium, tris(triphenylphosphine)rhodium chloride, etc. Platinum-based compounds such as vinylsiloxane coordination compounds are preferred.

[0298] Regarding the amount of the hydrosilylation reaction catalyst used, in terms of the mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends represented by the above formula (10), it is used in an amount preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of the transition metal conversion (mass).

[0299] By reacting the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends represented by the above formula (10) with an organosilicon compound having three or more SiH groups in the molecule, a fluoropolyether group-containing polymer having two monovalent groups having two or more SiH groups at the molecular chain ends represented by the following general formula (11) is obtained.

[0300] [Chemical formula 55]

[0301]

[0302] (In the formula, Rf, Y 1 are the same as above, and Z' is independently a monovalent group having two or more SiH groups.)

[0303] Among them, in the above formula (11), Z' is a monovalent group having two or more SiH groups, preferably a monovalent group having a linear, branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms. Specific examples of Z' include the following groups.

[0304] [Chemical formula 56]

[0305]

[0306] (In the formula, R 2 are the same as above, and each repeating unit shown in the parentheses with a, a2, and c can be bonded randomly.)

[0307] As the fluoropolyether group-containing polymer having two monovalent groups having two or more SiH groups at the molecular chain ends represented by the formula (11), the following polymers can be preferably exemplified.

[0308] [Chemical formula 57]

[0309]

[0310] [Chemical formula 58]

[0311]

[0312] [In the formula, p', q', r', r3', r4' and their total in each formula are the same as above, and the repeating units shown in the parentheses with p', q', r' can be bonded randomly. Z" is independently represented by any one of the following formulas.

[0313] [Chemical Formula 59]

[0314]

[0315] (In the formula, a2 and c are the same as above, and the repeating units shown in the parentheses with a2 and c can be bonded randomly.)]

[0316] Next, the obtained fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends represented by the formula (11) is dissolved in a solvent such as a fluorine-based solvent like 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group (halosilyl group, alkoxysilyl group, etc.) bonded to a silicon atom, such as 7-octenyltrimethoxysilane and 7-octenyltrichlorosilane, is mixed. In the presence of a hydrosilylation reaction catalyst such as a toluene solution of chloroplatinic acid / vinylsiloxane complex, it is cured at a temperature of 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, thereby obtaining the fluoropolyether group-containing polymer represented by the above formula (2). Further, in the case of using an organosilicon compound having a halogen atom as the hydrolyzable silyl group among the organosilicon compounds having an olefin moiety and a hydrolyzable silyl group in the molecule, then, the substituent (halogen atom) on the silyl group can be converted to another hydrolyzable group such as an alkoxy group such as a methoxy group.

[0317] Among them, as the organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom that reacts with the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends represented by the above formula (11), a compound represented by the following general formula (12) is preferred.

[0318] [Chemical Formula 60]

[0319]

[0320] (In the formula, R 1 , L, n are the same as above, and Y 2’ is a single bond, or a divalent hydrocarbon group having 1 to 18 carbon atoms that may contain one or more selected from oxygen atom, nitrogen atom, silicon atom and sulfur atom.)

[0321] In the above formula (12), Y 2’is a single bond, or a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom. Specifically, examples include a single bond, a methylene group, an ethylene group, a propylene group (trimethylene, methylethylene), a butylene group (tetramethylene, methylpropylene), a hexamethylene group, an octamethylene group, etc., an alkylene group having 1 to 18 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms such as a phenylene group (for example, an alkylene-arylene group having 7 to 18 carbon atoms, etc.). As Y 2’ , it is preferably an alkylene group having 1 to 6 carbon atoms.

[0322] As Y 2’ , for example, the following groups can be cited.

[0323] [Chemical formula 61]

[0324] *-CH2-**

[0325] *-CH2CH2-**

[0326] *-CH2CH2CH2-**

[0327] *-CH2CH2CH2CH2-**

[0328] *-CH2CH2CH2CH2CH2-**

[0329] *-CH2CH2CH2CH2CH2CH2-**

[0330] (In the formula, * is the bonding end bonded to the vinyl group in formula (12), and ** is the bonding end bonded to the silicon atom in formula (12).)

[0331] As such an organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, for example, the following compounds can be cited.

[0332] [Chemical formula 62]

[0333] CH2=CHCH2-Si(OCH3)3

[0334] CH2=CHCH2CH2-Si(OCH3)3

[0335] CH2=CHCH2CH2CH2-Si(OCH3)3

[0336] CH2=CHCH2CH2CH2CH2-Si(OCH3)3

[0337] CH2=CHCH2CH2CH2CH2CH2-Si(OCH3)3

[0338] CH2=CHCH2CH2CH2CH2CH2CH2-Si(OCH3)3

[0339] When the fluoropolyether group-containing polymer having two monovalent groups having two or more SiH groups at the molecular chain end represented by the above formula (11) is subjected to an addition reaction with an organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, the amount of the organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule can be 1 to 5 equivalents, more preferably 1 to 3 equivalents, and further preferably 1.2 to 1.4 equivalents, relative to 1 equivalent of the reactive end group (Si-H site) of the fluoropolyether group-containing polymer having two monovalent groups having two or more SiH groups.

[0340] For the reaction of the fluoropolyether group-containing polymer having two monovalent groups having two or more SiH groups at the molecular chain end represented by the above formula (11) with an organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, a fluorine-based solvent is preferably used as the 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 Company, trade name: Novec series), perfluorinated solvents composed of completely fluorinated compounds (manufactured by 3M Company, trade name: Fluorinert series), etc.

[0341] Regarding the amount of the solvent used, 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and further preferably about 150 parts by mass can be used relative to 100 parts by mass of the fluoropolyether group-containing polymer having two monovalent groups having two or more SiH groups at the molecular chain end represented by the above formula (11).

[0342] For the reaction of the fluoropolyether group-containing polymer having two monovalent groups having two or more SiH groups at the molecular chain end represented by the above formula (11) with an organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom 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, alkynols, etc., platinum group metal-based catalysts such as tetrakis(triphenylphosphine)palladium and tris(triphenylphosphine)rhodium chloride. A platinum-based compound such as a vinylsiloxane coordination compound is preferred.

[0343] Regarding the amount of the hydrosilylation reaction catalyst used, relative to the mass of the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends represented by the above formula (11), it is used in an amount, in terms of the transition metal conversion (mass), preferably of 0.01 to 100 ppm, more preferably of 0.1 to 50 ppm.

[0344] For example, a compound represented by the following formula is used as the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends.

[0345] [Chemical formula 63]

[0346] When 7-octenyltrimethoxysilane is used as the organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, a compound represented by the following formula is obtained.

[0347] [Chemical formula 64]

[0348]

[0349] In addition, for example, a compound represented by the following formula is used as the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends.

[0350] [Chemical formula 65]

[0351] When 7-octenyltrimethoxysilane is used as the organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, a compound represented by the following formula is obtained.

[0352] [Chemical formula 66]

[0353]

[0354] Then, by distilling off the solvent and unreacted substances under reduced pressure, the fluoropolyether group-containing polymer represented by the above formula (2) as the target compound can be obtained.

[0355] In addition, as another method for the preparation method of the fluoropolyether group-containing polymer represented by the above formula (2), for example, the following method can be cited.

[0356] In the reaction of a fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminals represented by the above formula (11) with an organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, instead of the organosilicon compound having an olefin moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, an alcohol having an olefin moiety and a terminal hydroxyl group in the molecule is used.

[0357] The fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminals represented by the above formula (11) obtained above is dissolved in a solvent such as a fluorine-based solvent like 1,3-bis(trifluoromethyl)benzene, and an alcohol having an olefin moiety and a terminal hydroxyl group in the molecule is mixed. In the presence of a hydrosilylation reaction catalyst such as a toluene solution of chloroplatinic acid / vinylsiloxane complex, it is cured at a temperature of 40 to 120 °C, preferably 60 to 100 °C, more preferably about 80 °C for 1 to 24 hours, preferably 1 to 12 hours, more preferably 1 to 4 hours.

[0358] Among them, as the alcohol having an olefin moiety and a terminal hydroxyl group in the molecule that reacts with the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain terminals represented by the above formula (11), a compound represented by the following general formula (13) is preferred.

[0359] [Chemical formula 67]

[0360] H2C=CH—U—OH (13)

[0361] (In the formula, U is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.)

[0362] In the above formula (13), U is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms that may contain one or more selected from oxygen atom, nitrogen atom, silicon atom and sulfur atom, and is preferably an alkylene group having 1 to 6 carbon atoms that may intervene an oxygen atom.

[0363] As such an alcohol having an olefin moiety and a terminal hydroxyl group in the molecule, for example, allyl alcohol, ethylene glycol monoallyl ether, ethylene glycol monovinyl ether, 1,4-butanediol monoallyl ether, 1,4-butanediol monovinyl ether, etc. can be cited.

[0364] When an alcohol having an olefin moiety and a terminal hydroxyl group in the molecule is subjected to an addition reaction with a fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends represented by the above formula (11), the amount of the alcohol having an olefin moiety and a terminal hydroxyl group in the molecule can be 1 to 5 equivalents, more preferably 1 to 3 equivalents, and further preferably 1.0 to 1.7 equivalents, relative to 1 equivalent of the reactive terminal group (Si-H site) of the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups.

[0365] For the reaction of a fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends represented by the above formula (11) with an alcohol having an olefin moiety and a terminal hydroxyl group in the molecule, a fluorine-based solvent is preferably used as the solvent, and as the fluorine-based solvent, fluorine-based solvents similar to the above-exemplified fluorine-based solvents can be cited.

[0366] Regarding the amount of the solvent used, 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably about 150 parts by mass can be used relative to 100 parts by mass of the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends represented by the above formula (11).

[0367] For the reaction of a fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends represented by the above formula (11) with an alcohol having an olefin moiety and a terminal hydroxyl group in the molecule, catalysts similar to the above-exemplified catalysts can be cited as the hydrosilylation reaction catalyst. A platinum-based compound such as a vinylsiloxane coordination compound is preferred.

[0368] Regarding the amount of the hydrosilylation reaction catalyst used, it is used in an amount such that, in terms of the mass of the transition metal conversion (mass), it preferably becomes 0.01 to 100 ppm, and more preferably becomes 0.1 to 50 ppm, relative to the mass of the fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends represented by the above formula (11).

[0369] By the reaction of a fluoropolyether group-containing polymer having two monovalent groups each having two or more SiH groups at the molecular chain ends represented by the above formula (11) with an alcohol having an olefin moiety and a terminal hydroxyl group in the molecule, a fluoropolyether group-containing polymer having four or more OH groups at the molecular chain ends represented by the following general formula (14) is obtained.

[0370] [Chemical formula 68]

[0371]

[0372] (In the formula, Rf, Y1 , Z, U, m, α are the same as described above.)

[0373] As the fluoropolyether group-containing polymer having 4 or more OH groups at the molecular chain terminals represented by the formula (14), the following polymers can be preferably exemplified.

[0374] [Chemical formula 69]

[0375]

[0376] [Chemical formula 70]

[0377]

[0378] [In the formula, U, m, p’, q’, r’, r3’, r4’ and their total in each formula are the same as described above, and each repeating unit shown in the parentheses with p’, q’, r’ can be bonded randomly. Z 1 is independently represented by any one of the following formulas.

[0379] [Chemical formula 71]

[0380]

[0381] (In the formula, ** is the bonding end bonded to the terminal carbon atom in the unit enclosed by m, and * is the bonding end bonded to the remaining carbon atoms.)]

[0382] Next, the above-obtained fluoropolyether group-containing polymer having 4 or more OH groups at the molecular chain terminals represented by the formula (14) and an organosilicon compound having an isocyanate moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, such as 3-(isocyanatopropyl)trimethoxysilane, are dissolved and mixed in a solvent such as a fluorine-based solvent like 1,3-bis(trifluoromethyl)benzene, and cured at a temperature of 20 to 80 °C, preferably 40 to 60 °C, more preferably about 50 °C, in the presence of a Lewis acid catalyst such as tetra(2-ethylhexoxy)titanium for 1 to 24 hours, preferably 1 to 10 hours, more preferably about 3 hours, to obtain the fluoropolyether group-containing polymer represented by the above formula (2). Further, in the case of using an organosilicon compound having a halogen atom as the hydrolyzable silyl group among the organosilicon compounds having an isocyanate moiety and a hydrolyzable silyl group in the molecule, then, the substituent (halogen atom) on the silyl group can be converted to another hydrolyzable group such as an alkoxy group like a methoxy group.

[0383] Among them, as the organosilicon compound having an isocyanate moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom that reacts with a fluoropolyether group-containing polymer having four or more OH groups at the molecular chain end represented by the above formula (14), a compound represented by the following general formula (15) is preferred.

[0384] [Chemical Formula 72]

[0385]

[0386] (In the formula, R 1 , L, and n are the same as above, and U' is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.)

[0387] In the above formula (15), U' is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms.

[0388] Examples of such an organosilicon compound having an isocyanate moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule include 3-(isocyanatopropyl)trimethoxysilane, 3-(isocyanatopropyl)triethoxysilane, and the like.

[0389] When subjecting the fluoropolyether group-containing polymer having four or more OH groups at the molecular chain end represented by the above formula (14) to an addition reaction with an organosilicon compound having an isocyanate moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, the amount of the organosilicon compound having an isocyanate moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule used can be 1 to 5 equivalents, more preferably 1 to 3 equivalents, and further preferably 1 to 2 equivalents, relative to 1 equivalent of the reactive terminal group (OH group) of the fluoropolyether group-containing polymer having four or more OH groups.

[0390] For the reaction between the fluoropolyether group-containing polymer having four or more OH groups at the molecular chain end represented by the above formula (14) and an organosilicon compound having an isocyanate moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, a fluorine-based solvent is preferably used as the solvent. As the fluorine-based solvent, fluorine-based solvents similar to the fluorine-based solvents exemplified above can be cited.

[0391] Regarding the amount of the solvent used, 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and further preferably 100 to 150 parts by mass can be used relative to 100 parts by mass of the fluoropolyether group-containing polymer having four or more OH groups at the molecular chain end represented by the above formula (14).

[0392] Regarding the reaction of a fluoropolyether group-containing polymer having 4 or more OH groups at the molecular chain ends represented by the above formula (14) with an organosilicon compound having an isocyanate moiety and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom in the molecule, examples of the Lewis acid catalyst include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, stannous octoate, etc., titanate or titanium chelate compounds such as titanium tetraisopropoxide, titanium tetra-n-butoxide, tetra(2-ethylhexoxy)titanium [alias: tetra(2-ethylhexyl) orthotitanate], dipropoxybis(acetylacetone)titanium, isopropoxyoctanediol titanium, etc., zirconium acetylacetonate, tributoxymonoacetylacetone zirconium, monobutoxybis(ethyl acetoacetate)acetylacetone zirconium, dibutoxybis(ethyl acetoacetate)zirconium, zirconium acetylacetonate, zirconium chelate compounds, etc. These Lewis acid catalysts can be used alone or in combination of two or more.

[0393] Regarding the amount of the Lewis acid catalyst used, it can be set to 0.01 to 2% by mass, preferably 0.03 to 1% by mass, based on the total mass of the reaction components.

[0394] Then, by distilling off the solvent and unreacted substances under reduced pressure, a fluoropolyether group-containing polymer represented by the above formula (2), which is the target compound, can be obtained.

[0395] [Surface treatment agent]

[0396] The present invention provides a surface treatment agent containing: a fluoropolyether group-containing polymer having a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom represented by the above formula (1), particularly a fluoropolyether group-containing polymer having a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom represented by formula (2). The surface treatment agent may contain a partial (hydrolysis) condensate obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer or the hydroxyl groups formed by partially hydrolyzing the terminal hydrolyzable groups of the fluoropolyether group-containing polymer by a known method in advance. Herein, the so-called "partial (hydrolysis) condensate" refers to a partial condensate or a partial hydrolysis condensate.

[0397] The surface treatment agent of the present invention preferably contains 0.005 to 80% by mass, particularly 0.01 to 75% by mass, of the above-mentioned fluoropolyether group-containing polymer and / or its partial (hydrolysis) condensate.

[0398] In the surface treatment agent, a hydrolysis condensation catalyst may be added as needed, such as an organic tin compound (dimethoxydibutyltin, dibutyltin dilaurate, etc.), an organic titanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), and an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly preferred.

[0399] The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer and / or its partial (hydrolysis) condensate.

[0400] The surface treatment agent can be used as a solvent-free composition, but may contain an appropriate solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, 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), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (pentane, hexane, heptane, isododecane, isononane, etc.), and fluorine-modified ether solvents. The organic solvents include methyl ethyl ketone, isooctane, cyclohexane, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ether organic solvents (ethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetraethylene glycol dimethyl ether, etc.), ester organic solvents (ethyl acetate, propyl acetate, butyl acetate, etc.), alcohol organic solvents (methanol, ethanol, isopropanol, butanol, etc.). Among these, organic solvents not containing fluorine atoms (non-fluorine-based organic solvents) are preferred from the perspective of the environment and concerns about the health of workers. From the perspective of excellent solubility of the fluoropolyether group-containing polymer of the present invention, ether-based organic solvents (ethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetraethylene glycol dimethyl ether, etc.) and alcohol-based organic solvents (methanol, ethanol, isopropyl alcohol, butanol, etc.) are more preferred. Among them, from the perspective of safety, dibutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and tetraethylene glycol dimethyl ether, which are Class 4, Class 2 petroleum and Class 3 petroleum, which are classified as less dangerous substances in the classification of dangerous substances in the Fire Services Act, are further preferred.

[0401] As for the above-mentioned solvent, two or more thereof may be mixed, preferably to uniformly dissolve the fluoropolyether group-containing polymer and its partial (hydrolysis) condensate. In addition, the amount of the above-mentioned solvent used is not particularly limited, as long as it is diluted in any proportion according to the application, for example, it is preferably contained in 25 to 1999900 parts by mass relative to 100 parts by mass of the fluoropolyether group-containing polymer (and its partial (hydrolysis) condensate) of the present invention.

[0402] Furthermore, within the scope that does not impede the effects of the present invention, optional additives can be added to the surface treatment agent of the present invention. Specifically, rust inhibitors, surfactants, antioxidants, antistatic agents, antibacterial agents, silane coupling agents, primer components, etc. can be cited. Most of these additives can be uniformly dissolved in a fluorine-free organic solvent.

[0403] From the aspects of the stability and processability of the surface treatment agent, the surface treatment agent of the present invention preferably contains 0.005 to 80% by mass of the above-mentioned fluorine-containing polyether group-containing polymer and / or its partial (hydrolytic) condensate, and in addition, the balance is a fluorine atom-free organic solvent.

[0404] Known methods such as brush coating, dipping, spraying, evaporation coating treatment, etc. can be used to apply the surface treatment agent of the present invention to a substrate. The heating method during evaporation coating treatment can be either a resistance heating method or an electron beam heating method, and there is no particular limitation. In addition, the curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferably set at 25 to 200 °C, particularly 25 to 80 °C for 30 minutes to 36 hours, particularly 1 to 24 hours. In addition, in the case of applying by evaporation coating treatment, a range of 20 to 200 °C is preferred. In addition, it can be cured under humidification. The film thickness of the cured film is appropriately selected according to the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. In addition, for example, in spraying, if it is diluted, hydrolyzed in a solvent to which water has been previously added, particularly a non-fluorine-based organic solvent, that is, Si-OH is generated and then sprayed, the curing after coating is fast.

[0405] It should be noted that the film thickness can be measured by means such as spectrophotometric reflectance measurement method, X-ray reflectance measurement method, spectroscopic ellipsometry measurement method, fluorescent X-ray measurement method, etc.

[0406] There is no particular limitation on the substrate treated with the surface treatment agent of the present invention, and it can be a substrate of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, quartz, etc. The surface treatment agent of the present invention can impart water and oil repellency, abrasion resistance, chemical resistance, mold release property, low dynamic friction property, and antifouling property to these substrates. In particular, excellent antifouling performance can be imparted without impairing the transparency and texture of various articles, and the substrate can be protected from the intrusion of chemicals, etc., and the antifouling performance can be maintained for a long time. Examples of articles treated with the surface treatment agent of the present invention include optical articles, films, glass, quartz substrates, antireflection films, etc., and are particularly used for touch panels, antireflection-treated articles, glass, tempered glass, sapphire glass, quartz glass, SiO2-treated substrates.

[0407] Examples of articles treated with the surface treatment agent of the present invention include automotive navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, automotive audio systems, game consoles, spectacle lenses, camera lenses, lens filters, sunglasses, medical instruments such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, optical articles such as protective films and antireflection films. The surface treatment agent of the present invention prevents fingerprints and sebum from adhering to the above articles, and can further impart scratch resistance (abrasion resistance), so it can be used particularly as a water and oil repellent layer for touch panel displays, antireflection films, etc.

[0408] In addition, the surface treatment agent of the present invention can also be used as an antifouling coating for various household equipment such as kitchen sinks, washbasins, faucets, mirrors, bathroom interior decorations, bathtubs, etc., an antifouling coating for window glass or tempered glass, headlight covers, etc. of automobiles, trams, aircraft, etc., a water and oil repellent coating for exterior building materials, an oil stain resistant coating for kitchen building materials, an antifouling and anti-sticker / graffiti coating for telephone booths, a coating for imparting fingerprint adhesion prevention to artworks, etc., an antifingerprint adhesion coating for CDs, DVDs, etc., a mold release agent or coating additive, a fluidity modifier or dispersibility modifier for resin modifiers and inorganic fillers, and a lubricity improver for tapes, films, etc.

[0409] Examples

[0410] Synthesis examples, examples and comparative examples are shown below to illustrate the present invention in more detail. The present invention is not limited by the following examples. It should be noted that in the following examples, the respective repeating units shown in parentheses in the fluoropolyether group in the formula may be bonded randomly. Furthermore, the film thickness is a value measured by spectroscopic ellipsometry using a spectroscopic ellipsometer.

[0411] [Synthesis Example 1]

[0412] 272 ml (0.5 M THF solution: 1.4 × 10 -1 mol) of 3-butenylmagnesium bromide was placed in a reaction vessel and stirred. Then, 200 g (4.5 × 10 -2 mol) of the following formula (A)

[0413] [Chemical 73]

[0414]

[0415] After a mixed liquid of the represented compound, 400 g of Asahiklin AC6000, and 200 g of PF5060 was dropped into the reaction vessel, it was heated at 50 °C for 6 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. By liquid separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain 193 g of a polymer containing a fluoropolyether group represented by the following formula (B).

[0416] [Chemical formula 74]

[0417]

[0418] 193 g of a polymer containing a fluoropolyether group represented by the following formula (B).

[0419] In the reaction vessel, 100 g (2.3×10 -2 mol) of the compound represented by the above formula (B), 11 g (9.2×10 -2 mol) of allyl bromide, and 0.17 g (4.6×10 -4 mol) of tetrabutylammonium iodide were mixed. Then, after adding 18 g (1.4×10 -1 mol) of a 30 mass% aqueous sodium hydroxide solution, it was heated at 50 °C for 24 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. By liquid separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain 97 g of a polymer containing a fluoropolyether group represented by the following formula (C).

[0420] [Chemical formula 75]

[0421]

[0422] 97 g of a polymer containing a fluoropolyether group represented by the following formula (C).

[0423] In the reaction vessel, 80 g (1.8×10 -2 mol) of the compound represented by the above formula (C), 120 g of 1,3-bis(trifluoromethyl)benzene, 43 g (1.8×10 -1 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, and 8.0×10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4×10 -7 mol in terms of Pt element) were mixed and cured at 80 °C for 24 hours. Then, by distilling off the solvent and unreacted substances under reduced pressure, a compound represented by the following formula (D) was obtained.

[0424] [Chemical formula 76]

[0425]

[0426] 84 g of the fluoropolyether group-containing polymer represented.

[0427] In a reaction vessel, 80 g (1.6 × 10 -2 mol) of the compound represented by the following formula (D) obtained above, 120 g of 1,3-bis(trifluoromethyl)benzene, 28 g (1.2 × 10 -1 mol) of 7-octenyltrimethoxysilane, and 8.0 × 10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4 × 10 -7 mol in terms of Pt element) were mixed and cured at 80°C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of the fluoropolyether group-containing polymer represented by the following formula (E)

[0428] [Chemical Formula 77]

[0429]

[0430] 84 g of the fluoropolyether group-containing polymer represented.

[0431] [Synthesis Example 2]

[0432] In a reaction vessel, 80 g (1.8 × 10

[0433] [Chemical Formula 78]

[0434]

[0435] mol) of the compound represented by the following formula (C) obtained in the same manner as in Synthesis Example 1, 120 g of 1,3-bis(trifluoromethyl)benzene, 54 g (1.8 × 10 -2 mol) of 2,4,6,8,10-pentamethylcyclopentasiloxane, and 8.0 × 10 -1 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4 × 10 -2 mol in terms of Pt element) were mixed and cured at 80°C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of the fluoropolyether group-containing polymer represented by the following formula (F) -7 mol) of the compound represented by the following formula (C) obtained in the same manner as in Synthesis Example 1, 120 g of 1,3-bis(trifluoromethyl)benzene, 54 g (1.8 × 10

[0436] [Chemical Formula 79]

[0437]

[0438] 84 g of the fluoropolyether group-containing polymer represented.

[0439] In a reaction vessel, 80 g (1.6 × 10 -2 mol), 120 g 1,3-bis(trifluoromethyl)benzene, 40 g 7-octenyltrimethoxysilane (1.7×10 -1 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (G):

[0440] [Chemistry 80]

[0441]

[0442] 84 g of the polymer containing fluoropolyether groups was expressed.

[0443] [Synthesis example 3]

[0444] In a reaction container, the following formula (C) obtained in the same manner as in Synthesis Example 1 was added

[0445] [Chemistry 81]

[0446]

[0447] The compound represented by 80g (1.8×10 -2 mol), 120 g 1,3-bis(trifluoromethyl)benzene, 48 g methyltris(dimethylsiloxy)silane (1.8×10 -1 mol), and a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) 8.0×10 -2 g (calculated as Pt single substance, containing 2.4×10 -7 mol) and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain the following formula (H):

[0448] [Chemistry 82]

[0449]

[0450] 84 g of the polymer containing fluoropolyether groups was expressed.

[0451] In a reaction container, 80 g (1.6 × 10 -2(mol), 120 g of 1,3-bis(trifluoromethyl)benzene, 19 g of 7-octenyltrimethoxysilane (8.2×10 -2 mol), and 8.0×10 -2 g of a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4×10 -7 mol) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a fluoropolyether group-containing polymer represented by the following formula (I)

[0452] [Chemical Formula 83]

[0453]

[0454] .

[0455] [Synthesis Example 4]

[0456] In a reaction vessel, 80 g (1.8×10

[0457] [Chemical Formula 84]

[0458]

[0459] mol) of the compound represented by the following formula (C) obtained in the same manner as in Synthesis Example 1, 120 g of 1,3-bis(trifluoromethyl)benzene, 59 g (1.8×10 -2 mol) of tetrakis(dimethylsilyloxy)silane, and 8.0×10 -1 g of a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4×10 -2 mol) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a fluoropolyether group-containing polymer represented by the following formula (J) -7 .

[0460] [Chemical Formula 85]

[0461]

[0462] .

[0463] In a reaction vessel, 80 g (1.6×10 -2 mol) of the compound represented by formula (J) obtained above, 120 g of 1,3-bis(trifluoromethyl)benzene, 29 g (1.2×10 -1mol), and 8.0×10 -2 g of a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4×10 -7 mol) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a fluoropolyether group-containing polymer represented by the following formula (K)

[0464] [Chemical formula 86]

[0465]

[0466]

[0467] [Synthesis Example 5]

[0468] In a reaction vessel, 80 g (1.8×10

[0469] [Chemical formula 87]

[0470]

[0471] mol) of the compound represented by the following formula (C) obtained in the same manner as in Synthesis Example 1, 120 g of 1,3-bis(trifluoromethyl)benzene, 116 g (1.8×10 -2 mol) of 1,1,1,3,5,7,9,11,13,15,17,19,19,19-tetradecamethyl decasiloxane, and 8.0×10 -1 g of a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4×10 -2 mol) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a fluoropolyether group-containing polymer represented by the following formula (L) -7 mol)

[0472] [Chemical formula 88]

[0473]

[0474]

[0475] In a reaction vessel, 80 g (1.4×10 -2 mol) of the compound represented by the formula (L) obtained above, 120 g of 1,3-bis(trifluoromethyl)benzene, 59 g (2.5×10 -1 mol) of 7-octenyltrimethoxysilane, and 8.0×10​​-2 g (containing 2.4×10 -7 mol) was mixed and aged at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a fluoropolyether group-containing polymer represented by the following formula (M).

[0476] [Chemical Formula 89]

[0477]

[0478]

[0479] [Synthesis Example 6]

[0480] In a reaction vessel, 80 g (1.6×10

[0481] [Chemical Formula 90]

[0482]

[0483] mol) of the compound represented by the following formula (D) obtained in the same manner as in Synthesis Example 1, 120 g of 1,3-bis(trifluoromethyl)benzene, 26 g (1.3×10 -2 mol) of 5-hexenyltrimethoxysilane, and 8.0×10 -1 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4×10 -2 mol in terms of Pt metal) were mixed and aged at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a fluoropolyether group-containing polymer represented by the following formula (N). -7

[0484] [Chemical Formula 91]

[0485]

[0486]

[0487] [Synthesis Example 7]

[0488] In a reaction vessel, 80 g (1.6×10

[0489] [Chemical Formula 92]

[0490]

[0491] mol) of the compound represented by the following formula (D) obtained in the same manner as in Synthesis Example 1, 120 g of 1,3-bis(trifluoromethyl)benzene, 16 g (1.6×10 -2 mol) of ethylene glycol monoallyl ether, -1 ​​​(mol), and 8.0×10 of a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) -2 g (calculated as elemental Pt, containing 2.4×10 -7 mol) were mixed and cured at 80 °C for 2 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a fluoropolyether group-containing polymer represented by the following formula (O).

[0492] [Chemical formula 93]

[0493]

[0494] 84 g of the polymer containing a fluoropolyether group represented by the following formula (O) was obtained.

[0495] In a reaction vessel, 80 g (1.4×10 -2 mol) of the compound represented by the above formula (O), 80 g of 1,3-bis(trifluoromethyl)benzene, 26 g (1.3×10 -1 mol) of 3-(isocyanatopropyl)trimethoxysilane, and 4.8×10 -2 g (8.5×10 -5 mol) of tetra(2-ethylhexoxy)titanium were mixed and cured at 50 °C for 3 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a fluoropolyether group-containing polymer represented by the following formula (P).

[0496] [Chemical formula 94]

[0497]

[0498] 84 g of the polymer containing a fluoropolyether group represented by the following formula (P) was obtained.

[0499] [Synthesis Example 8]

[0500] 600 ml (0.5 M THF solution: 3.0×10 -1 mol) of 3-butenylmagnesium bromide was placed in a reaction vessel and stirred. Then, 200 g (1.0×10 -1 mol) of the following formula (Q)

[0501] [Chemical formula 95]

[0502]

[0503] After the mixed liquid of the represented compound, 400 g of Asahiklin AC6000, and 200 g of PF5060 was dropped into the reaction vessel, it was heated at 50 °C for 6 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. By liquid separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure, thereby obtaining 193 g of a polymer containing a fluoropolyether group represented by the following formula (R).

[0504] [Chemical Formula 96]

[0505]

[0506] In the reaction vessel, 100 g (4.9×10

[0507] mol) of the compound represented by the above formula (R), 24 g (2.0×10 -2 mol) of allyl bromide, and 0.36 g (9.8×10 -1 mol) of tetrabutylammonium iodide were mixed. Then, after adding 39 g (2.9×10 -4 mol) of a 30 mass% aqueous sodium hydroxide solution, it was heated at 50 °C for 24 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. By liquid separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure, thereby obtaining 97 g of a polymer containing a fluoropolyether group represented by the following formula (S). -1 mol) of a 30 mass% aqueous sodium hydroxide solution, it was heated at 50 °C for 24 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. By liquid separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure, thereby obtaining 97 g of a polymer containing a fluoropolyether group represented by the following formula (S).

[0508] [Chemical Formula 97]

[0509]

[0510] 80 g (3.9×10

[0511] mol) of the compound represented by the above formula (S), 120 g of 1,3-bis(trifluoromethyl)benzene, 94 g (3.9×10 -2 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, and 8.0×10 -1 g of a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4×10 -2 g (calculated as Pt element, containing 2.4×10 -7 mol) were mixed in the reaction vessel and cured at 80 °C for 24 hours. Then, by distilling off the solvent and unreacted substances under reduced pressure, a polymer represented by the following formula (T) was obtained.

[0512] [Chemical Formula 98]

[0513]

[0514] 84 g of the fluoropolyether group-containing polymer represented.

[0515] In a reaction vessel, 80 g (3.1×10 -2 mol) of the compound represented by the formula (T) obtained above, 120 g of 1,3-bis(trifluoromethyl)benzene, 56 g (2.4×10 -1 mol) of 7-octenyltrimethoxysilane, and 8.0×10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4×10 -7 mol in terms of Pt element) were mixed and cured at 80°C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain the compound represented by the following formula (U)

[0516] [Chemical formula 99]

[0517]

[0518] 84 g of the fluoropolyether group-containing polymer represented.

[0519] [Synthesis Example 9]

[0520] 182 ml (0.5 M THF solution: 9.1×10 -2 mol) of 3-butenylmagnesium bromide was placed in a reaction vessel and stirred. Subsequently, a mixture of 200 g (3.2×10 -2 mol) of the compound represented by the following formula (V)

[0521] [Chemical formula 100]

[0522]

[0523] 400 g of Asahiklin AC6000, and 200 g of PF5060 was dropped into the reaction vessel, and then heated at 50°C for 6 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. By liquid separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain 193 g of the fluoropolyether group-containing polymer represented by the following formula (W)

[0524] [Chemical formula 101]

[0525]

[0526] 193 g of the fluoropolyether group-containing polymer represented.

[0527] In a reaction vessel, 100 g (1.6×10 -2 mol) of the compound represented by the formula (W) obtained above, 8 g (6.6×10 -2 mol) of allyl bromide, and 0.12 g (3.2×10 -4 mol) of tetrabutylammonium iodide were mixed. Subsequently, after adding 13 g (9.8×10 -2 mol) of a 30 mass% aqueous sodium hydroxide solution, the mixture was heated at 50 °C for 24 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. After the separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain 97 g of a polymer containing a fluoropolyether group represented by the following formula (X)

[0528] [Chemical formula 102]

[0529]

[0530] .

[0531] In a reaction vessel, 80 g (1.3×10 -2 mol) of the compound represented by the formula (X) obtained above, 120 g of 1,3-bis(trifluoromethyl)benzene, 39 g (1.3×10 -1 mol) of 2,4,6,8,10-pentamethylcyclopentasiloxane, and 8.0×10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 2.4×10 -7 mol in terms of Pt element) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a polymer containing a fluoropolyether group represented by the following formula (Y)

[0532] [Chemical formula 103]

[0533]

[0534] .

[0535] In a reaction vessel, 80 g (1.1×10 -2 mol) of the compound represented by the formula (Y) obtained above, 120 g of 1,3-bis(trifluoromethyl)benzene, 26 g (1.1×10 -1 mol) of 7-octenyltrimethoxysilane, and 8.0×10 -2g (2.4 × 10 in terms of elemental Pt, -7 mol) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 84 g of a fluoropolyether group-containing polymer represented by the following formula (Z).

[0536] [Chemical Formula 104]

[0537]

[0538]

[0539] [Synthesis Example 10]

[0540] 132 ml (0.5 M THF solution: 6.6 × 10 -2 mol) of 3-butenylmagnesium bromide was placed in a reaction vessel and stirred. Subsequently, a mixture of 100 g (2.2 × 10 -2 mol) of the compound represented by the following formula (a), 200 g of Asahiklin AC6000, and 100 g of PF5060 was dropped into the reaction vessel, and then heated at 50 °C for 6 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. After performing a liquid separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain 96 g of a fluoropolyether group-containing polymer represented by the following formula (b).

[0541] [Chemical Formula 105]

[0542]

[0543]

[0544] [Chemical Formula 106]

[0545]

[0546]

[0547] In a reaction vessel, 20 g (4.4 × 10 -3 mol) of the compound represented by formula (b) obtained above, 2.2 g (1.8 × 10 -2 mol) of allyl bromide, and 0.03 g (8.1 × 10 -5 mol) of tetrabutylammonium iodide were mixed. Subsequently, 3.5 g (2.6 × 10 -2 ​​​After (xx mol), it was heated at 50 °C for 24 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. After the separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain 19 g of a polymer containing a fluoropolyether group represented by the following formula (c).

[0548] [Chemical formula 107]

[0549]

[0550] 10 g (2.2×10 xx mol) of the compound represented by the above formula (c) obtained above, 15 g of 1,3-bis(trifluoromethyl)benzene, 6.6 g (2.2×10 xx mol) of 2,4,6,8,10-pentamethylcyclopentasiloxane, and 1.0×10 xx g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 3.0×10 xx mol in terms of Pt element) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 11 g of a polymer containing a fluoropolyether group represented by the following formula (d).

[0551] In a reaction vessel, 10 g (1.9×10 xx mol) of the compound represented by the above formula (d) obtained above, 15 g of 1,3-bis(trifluoromethyl)benzene, 4.6 g (2.0×10 xx mol) of 7-octenyltrimethoxysilane, and 1.0×10 xx g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 3.0×10 xx mol in terms of Pt element) were mixed and cured at 80 °C for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain a polymer containing a fluoropolyether group represented by the following formula (e). -3 mol), 15 g of 1,3-bis(trifluoromethyl)benzene, 6.6 g (2.2×10 -2 mol) of 2,4,6,8,10-pentamethylcyclopentasiloxane, and 1.0×10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 3.0×10 -8 mol) of Pt element) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain a polymer containing a fluoropolyether group represented by the following formula (d).

[0552] [Chemical formula 108]

[0553]

[0554] 11 g of a polymer containing a fluoropolyether group represented by the following formula (d).

[0555] In a reaction vessel, 10 g (1.9×10 -3 mol) of the compound represented by the above formula (d) obtained above, 15 g of 1,3-bis(trifluoromethyl)benzene, 4.6 g (2.0×10 -2 mol) of 7-octenyltrimethoxysilane, and 1.0×10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 3.0×10 -8 mol) of Pt element) were mixed and cured at 80 °C for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain a polymer containing a fluoropolyether group represented by the following formula (e).

[0556] [Chemical formula 109]

[0557]

[0558] 12 g of a fluoropolyether group-containing polymer represented.

[0559] [Synthesis Example 11]

[0560] 132 ml (0.5 M THF solution: 6.6×10 -2 mol) of 3-butenylmagnesium bromide was placed in a reaction vessel and stirred. Subsequently, after dropping a mixed solution of 100 g (2.2×10 -2 mol) of the compound represented by the following formula (f)

[0561] [Chemical Formula 110]

[0562]

[0563] 200 g of Asahiklin AC6000, and 100 g of PF5060 into the reaction vessel, it was heated at 50 °C for 6 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. After the separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the remaining solvent was distilled off under reduced pressure, thereby obtaining 96 g of a fluoropolyether group-containing polymer represented by the following formula (g)

[0564] [Chemical Formula 111]

[0565]

[0566] represented.

[0567] In a reaction vessel, 20 g (4.4×10 -3 mol) of the compound represented by the formula (g) obtained above, 2.2 g (1.8×10 -2 mol) of allyl bromide, and 0.03 g (8.1×10 -5 mol) of tetrabutylammonium iodide were mixed. Subsequently, after adding 3.5 g (2.6×10 -2 mol) of a 30 mass% aqueous sodium hydroxide solution, it was heated at 50 °C for 24 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. After the separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the remaining solvent was distilled off under reduced pressure, thereby obtaining 19 g of a fluoropolyether group-containing polymer represented by the following formula (h)

[0568] [Chemical Formula 112]

[0569]

[0570] represented.

[0571] In a reaction vessel, 10 g (2.2×10 -3 mol) of the compound represented by the formula (h) obtained above, 15 g of 1,3-bis(trifluoromethyl)benzene, 6.6 g (2.2×10 -2 mol) of 2,4,6,8,10-pentamethylcyclopentasiloxane, and 1.0×10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 3.0×10 -8 mol in terms of elemental Pt) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 12 g of a fluoropolyether group-containing polymer represented by the following formula (i).

[0572] [Chemical formula 113]

[0573]

[0574] In a reaction vessel, 10 g (1.9×10

[0575] mol) of the compound represented by the formula (i) obtained above, 15 g of 1,3-bis(trifluoromethyl)benzene, 4.6 g (2.0×10 -3 mol) of 7-octenyltrimethoxysilane, and 1.0×10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 3.0×10 -2 mol in terms of elemental Pt) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 12 g of a fluoropolyether group-containing polymer represented by the following formula (j). -8 [Chemical formula 114]

[0576] [Chemical formula 114]

[0577]

[0578] In a reaction vessel, 282 ml (0.5 M THF solution: 1.4×10

[0579] [Synthesis Example 12]

[0580] mol) of 3-butenylmagnesium bromide was placed and stirred. Subsequently, 100 g (2.4×10 -1 mol) of the compound represented by the following formula (k). -2 [Chemical formula 115]

[0581] [Chemical formula 115]

[0582]

[0583] After dropping a mixed liquid of the represented compound, 200 g of Asahiklin AC6000, and 100 g of PF5060 into the reaction vessel, it was heated at 50 °C for 6 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. After the liquid separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure, thereby obtaining 94 g of a polymer containing a fluoropolyether group represented by the following formula (l).

[0584] [Chemical formula 116]

[0585]

[0586]

[0587] In the reaction vessel, 20 g (4.7×10 -3 mol) of the compound represented by the above formula (l), 4.6 g (3.8×10 -2 mol) of allyl bromide, and 0.06 g (1.6×10 -4 mol) of tetrabutylammonium iodide were mixed. Then, 7.5 g (5.6×10 -2 mol) of a 30 mass% aqueous sodium hydroxide solution was added, and it was heated at 50 °C for 24 hours. After the heating was completed, it was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped in. After the liquid separation operation, the fluorine compound layer as the lower layer was recovered and washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure, thereby obtaining 21 g of a polymer containing a fluoropolyether group represented by the following formula (m).

[0588] [Chemical formula 117]

[0589]

[0590]

[0591] In the reaction vessel, 20 g (4.6×10 -3 mol) of the compound represented by the above formula (m), 30 g of 1,3-bis(trifluoromethyl)benzene, 22 g (9.1×10 -2 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, and 4.8×10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 1.4×10 -7 mol in terms of Pt element) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure, thereby obtaining a compound represented by the following formula (n).

[0592] ​​[Chemical Formula 118]

[0593]

[0594] 22 g of the fluoropolyether group-containing polymer represented.

[0595] In a reaction vessel, 20 g (3.8 × 10 -3 mol) of the compound represented by the formula (n) obtained above, 30 g of 1,3-bis(trifluoromethyl)benzene, 14 g (6.0 × 10 -2 mol) of 7-octenyltrimethoxysilane, and 2.0 × 10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 6.0 × 10 -8 mol in terms of Pt element) were mixed and cured at 80°C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 22 g of the fluoropolyether group-containing polymer represented by the following formula (o)

[0596] [Chemical Formula 119]

[0597]

[0598] represented.

[0599] [Synthesis Example 13]

[0600] In a reaction vessel, 20 g (4.6 × 10

[0601] [Chemical Formula 120]

[0602]

[0603] mol) of the compound represented by the following formula (m) obtained in the same manner as in Synthesis Example 12, 30 g of 1,3-bis(trifluoromethyl)benzene, 28 g (9.3 × 10 -3 mol) of 2,4,6,8,10-pentamethylcyclopentasiloxane, and 4.8 × 10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 1.4 × 10 -2 mol in terms of Pt element) were mixed and cured at 80°C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain the following formula (p) -7 represented.

[0604] [Chemical Formula 121]

[0605]

[0606] 22 g of a fluoropolyether group-containing polymer represented

[0607] In a reaction vessel, 20 g (3.6 × 10 -3 mol) of the compound represented by the formula (p) obtained above, 30 g of 1,3-bis(trifluoromethyl)benzene, 18 g (7.7 × 10 -2 mol) of 7-octenyltrimethoxysilane, and 2.0 × 10 -2 g of a toluene solution of a platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) (containing 6.0 × 10 -8 mol) of Pt element) were mixed and cured at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 22 g of a fluoropolyether group-containing polymer represented by the following formula (q).

[0608] [Chemical Formula 122]

[0609]

[0610] 22 g of a fluoropolyether group-containing polymer represented

[0611] Solubility in Dilution Solvent

[0612] [Example 1]

[0613] The compounds prepared in Synthesis Examples 1 to 13 above were diluted in isopropyl alcohol (IPA) to a solid component concentration of 20% by mass to prepare a surface treatment agent, and its solubility was evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 3.

[0614] ○: The appearance was visually observed and found to be transparent.

[0615] ×: The appearance was visually observed and found to be turbid.

[0616] [Example 2]

[0617] Evaluation was carried out in the same manner as in Example 1 except that the dilution solvent was changed to propylene glycol monomethyl ether (PGM). The evaluation results are shown in Tables 4 to 6.

[0618] [Example 3]

[0619] Evaluation was carried out in the same manner as in Example 1 except that the dilution solvent was changed to propylene glycol monomethyl ether acetate (PGMEA). The evaluation results are shown in Tables 7 to 9.

[0620] [Comparative Example 1]

[0621] Evaluation was carried out in the same manner as in Example 1 except that the diluted compounds were changed to the compounds represented by the following formulas (r) and (s), respectively. The evaluation results are shown in Table 10.

[0622] [Chemical Formula 123]

[0623]

[0624] [Chemical Formula 124]

[0625]

[0626] [Comparative Example 2]

[0627] Evaluation was carried out in the same manner as in Example 2, except that the diluted compound was changed to the compounds represented by the above formulas (r) and (s). The evaluation results are shown in Table 11.

[0628] [Comparative Example 3]

[0629] Evaluation was carried out in the same manner as in Example 3, except that the diluted compound was changed to the compounds represented by the above formulas (r) and (s). The evaluation results are shown in Table 12.

[0630] [Table 1]

[0631] Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Compound (E) (G) (I) (K) (M) Dilution Solvent IPA IPA IPA IPA IPA Appearance ○ ○ ○ ○ ○

[0632] [Table 2]

[0633] Example 1-6 Example 1-7 Example 1-8 Example 1-9 Example 1-10 Compound (N) (P) (U) (Z) (e) Dilution Solvent IPA IPA IPA IPA IPA Appearance ○ ○ ○ ○ ○

[0634] [Table 3]

[0635] Example 1-11 Example 1-12 Example 1-13 Compound (j) (o) (q) Dilution Solvent IPA IPA IPA Appearance ○ ○ ○

[0636] [Table 4]

[0637] Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Compound (E) (G) (I) (K) (M) Dilution Solvent PGM PGM PGM PGM PGM Appearance ○ ○ ○ ○ ○

[0638] [Table 5]

[0639] Example 2-6 Example 2-7 Example 2-8 Example 2-9 Example 2-10 Compound (N) (P) (U) (Z) (e) Dilution Solvent PGM PGM PGM PGM PGM Appearance ○ ○ ○ ○ ○

[0640] [Table 6]

[0641] Example 2-11 Example 2-12 Example 2-13 Compound (j) (o) (q) Dilution Solvent PGM PGM PGM Appearance ○ ○ ○

[0642] [Table 7]

[0643] Example 3-1 Example 3-2 Example 3-3 Example 3-4 Example 3-5 Compound (E) (G) (I) (K) (M) Dilution Solvent PGMEA PGMEA PGMEA PGMEA PGMEA Appearance ○ ○ ○ ○ ○

[0644] [Table 8]

[0645] Example 3-6 Example 3-7 Example 3-8 Example 3-9 Example 3-10 Compound (N) (P) (U) (Z) (e) Dilution Solvent PGMEA PGMEA PGMEA PGMEA PGMEA Appearance ○ ○ ○ ○ ○

[0646] [Table 9]

[0647] Example 3-11 Example 3-12 Example 3-13 Compound (j) (o) (q) Dilution Solvent PGMEA PGMEA PGMEA Appearance ○ ○ ○

[0648] [Table 10]

[0649] Comparative Example 1-1 Comparative Example 1-2 Compound (r) (s) Dilution Solvent IPA IPA Appearance × ○

[0650] [Table 11]

[0651] Comparative Example 2-1 Comparative Example 2-2 Compound (r) (s) Dilution Solvent PGM PGM Appearance × ○

[0652] [Table 12]

[0653] Comparative Example 3-1 Comparative Example 3-2 Compound (r) (s) Dilution Solvent PGMEA PGMEA Appearance × ○

[0654] The compounds of Examples 1-1 to 1-13, 2-1 to 2-13, 3-1 to 3-13 and Comparative Examples 1-2, 2-2, 3-2 were all soluble in the organic solvents used. This is considered to be because, by having a polyvalent polysiloxane structure in the molecule, more hydrocarbon groups can be introduced into the molecule, and the carbon content in the molecule increases.

[0655] On the other hand, the compounds of Comparative Examples 1-1, 2-1, 3-1 that do not have a polyvalent polysiloxane structure were not all soluble in the organic solvents used.

[0656] Formation of Curing Coating Film by Spraying

[0657] [Example 4]

[0658] The compounds prepared in Synthesis Examples 1 to 13 above were diluted in propylene glycol monomethyl ether (PGM) to a solid component concentration of 0.1% by mass to prepare a surface treatment agent, and it was sprayed on the surface of chemically strengthened glass (manufactured by Corning Incorporated, Gorilla III) that had been subjected to plasma treatment cleaning using a spraying device (manufactured by T&K Co., Ltd., NST-51). Then, it was cured for 12 hours in an atmosphere of 25°C and a relative humidity of 50% to form a cured coating film with a film thickness of 10 nm, and a test body was obtained.

[0659] [Comparative Example 4]

[0660] Except that the compound represented by the above formula (s) was diluted in propylene glycol monomethyl ether (PGM) to a solid component concentration of 0.1% by mass to prepare a surface treatment agent, a cured coating film (film thickness: about 10 nm) was formed in the same manner as in Example 4, and a test body was obtained.

[0661] Evaluation of Water and Oil Repellency

[0662] [Evaluation of Initial Water and Oil Repellency]

[0663] For the glass formed with a cured coating film prepared as described above, the contact angle (water repellency) of the cured coating film with respect to water was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μL, temperature: 25°C, relative humidity: 40%). The results (initial water contact angle) are shown in Table 13.

[0664] In the initial stage, both the examples and the comparative examples showed good water repellency.

[0665] [Table 13]

[0666]

[0667] [Evaluation of Abrasion Resistance]

[0668] Regarding the test specimens of Example 4-1, 4-2 and Comparative Example 4, using a friction tester (manufactured by Shinto Kagaku Co., Ltd.), the contact angle (water repellency) of the cured coating film with respect to water after 10,000 times of friction under the following conditions was measured in the same manner as above, as an evaluation of abrasion resistance. The test environmental conditions were 25°C and a relative humidity of 40%. The results (water contact angle after abrasion) are shown in Table 14.

[0669] Abrasion Resistance to Steel Wool

[0670] Steel wool: BONSTER#0000

[0671] Contact area: 1 cm 2

[0672] Moving distance (one-way): 40 mm

[0673] Moving speed: 4800 mm / minute

[0674] Load: 1 kgf / 1 cm 2

[0675] [Table 14]

[0676]

[0677] The test specimens of Example 4-1 and 4-2 also maintained a water contact angle of 110° or more after 10,000 times of steel wool abrasion. This is considered to be because, through the polyvalent polysiloxane structure of the compound used, the number of hydroxyl groups and / or hydrolyzable silyl groups bonded to silicon atoms at the single terminal or both terminals in the molecule increases, the adhesion to the substrate improves, and by introducing the polyvalent polysiloxane structure through secondary carbon, the molecular mobility improves.

[0678] On the other hand, the test specimen of Comparative Example 4 had a water contact angle of less than 100° after 10,000 times of steel wool abrasion and did not show durability.

[0679] In addition, for the present invention, when represented from different viewpoints, it is as described in <1> to <6> below.

[0680] <1> The surface treatment agent is a surface treatment agent containing a polymer having a fluoropolyether group and / or a partial (hydrolytic) condensate thereof, and an organic solvent, characterized in that the fluoropolyether group has at least two monovalent groups having a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom via a polyvalent polysiloxane structure at a single terminal or both terminals, and the organic solvent is one or more organic solvents selected from organic solvents containing no fluorine atoms.

[0681] <2> The surface treatment agent according to <1>, wherein the content of the polymer having a fluoropolyether group and / or a partial (hydrolytic) condensate thereof is 0.005 to 80% by mass.

[0682] <3> The surface treatment agent according to <1>, wherein the content of the polymer having a fluoropolyether group and / or a partial (hydrolytic) condensate thereof is 0.005 to 80% by mass, and the balance is an organic solvent containing no fluorine atoms.

[0683] <4> The surface treatment agent according to <1>, characterized in that the organic solvent is an alcohol-based organic solvent.

[0684] <5> The surface treatment agent according to <1>, characterized in that the organic solvent is an ether-based organic solvent.

[0685] <6> An article surface-treated with the surface treatment agent according to any one of <1> to <5>.

[0686] By changing the polymers, organic solvents, and their blending ratios used in the present invention, the balance of each property sometimes changes. In such cases, although some properties become unstable or deteriorate, since the properties required according to the applicable use change, it can be put to practical use according to the use.

Claims

1. A polymer containing a fluoropolyether group, which is represented by the following general formula (1): Rf[Q-CH(V)2] α (1) In the formula, Rf is a monovalent or divalent polymer residue containing a fluoropolyether group, Q is a single bond or a divalent organic group, V is independently a monovalent group having a polyvalent polysiloxane structure and a hydroxyl group and / or a hydrolyzable silyl group bonded to a silicon atom at the terminal, and α is 1 or 2.

2. The polymer containing a fluoropolyether group according to claim 1, which is represented by the following general formula (2): [Chemical formula 1] In the formula, Rf is a monovalent or divalent polymer residue containing a fluoropolyether group, X is independently a single bond or a divalent heteroatom, Y 1 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, Z is independently an (m + 1)-valent linking group having a polyvalent polysiloxane structure, Y 2 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, R 1 is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, L is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each bonded silicon atom, m is independently an integer of 2 to 9, and α is 1 or 2.

3. The polymer containing a fluoropolyether group according to claim 1 or 2, wherein, In the formula (1) or (2), α is 1, and Rf is a monovalent fluoropolyether group represented by the following general formula (3), [Chemical formula 2] wherein A is a hydrogen atom, a fluorine atom, or an unsubstituted or fluorine-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, v are each an integer of 0 to 200, the sum of p, q, r, s, t, u, v is 3 to 200, these units may be linear or branched, and in addition, the respective repeating units shown in the parentheses with p, q, r, s, t, u, v may be bonded randomly.

4. The polymer containing a fluoropolyether group according to claim 1 or 2, wherein, In the formula (1) or (2), α is 2, and Rf is a divalent fluoropolyether group represented by the following general formula (4), [Chemical formula 3] wherein W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, v are each an integer of 0 to 200, the sum of p, q, r, s, t, u, v is 3 to 200, these units may be linear or branched, and in addition, the respective repeating units shown in the parentheses with p, q, r, s, t, u, v may be bonded randomly.

5. The polymer containing a fluoropolyether group according to claim 2, wherein, In the formula (2), among the two Xs present at the single terminal of the molecular chain when α = 1 and the two Xs (four in the molecule) present at each of the two terminals of the molecular chain when α = 2, at each terminal, one X is an oxygen atom and the other X is a single bond.

6. The polymer containing a fluoropolyether group according to claim 2, wherein, In the formula (2), Y 1 is independently an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms.

7. The polymer containing a fluoropolyether group according to claim 2, wherein, In the formula (2), Z is a linear, branched, or cyclic organic polysiloxane residue having 3 to 10 silicon atoms and a valence of 3 to 10.

8. The polymer containing a fluoropolyether group according to claim 2, wherein, In the formula (2), Z is represented by any one of the following formulas, [Chemical formula 4] In the formula, * is the bonding end bonded to Y in the general formula (2). 1 ** is the bonding end bonded to Y in the general formula (2). 2 The bonding end, R 2 Independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, a is an integer of 0 to 6, a1 is an integer of 1 to 6, a2 is an integer of 2 to 7, b is an integer of 2 to 9, c is 1, and the respective repeating units shown in the parentheses with a, a2, and c may be bonded randomly.

9. The polymer containing a fluoropolyether group according to claim 2, wherein, In the formula (2), Y 2 is independently an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms.

10. The polymer containing a fluoropolyether group according to claim 2, wherein, In the formula (2), L is independently a group selected from 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.

11. The polymer containing a fluoropolyether group according to claim 2, wherein, The polymer represented by the formula (2) is a polymer represented by the following general formula (5) or (6), [Chemical formula 5] wherein d is independently an integer of 1 to 3 in each unit, p″, q″, r″, s″ are each an integer of 0 to 200, the sum of p″, q″, r″, s″ in each formula is 3 to 200, and in addition, the respective repeating units shown in the parentheses with p″, q″, r″, s″ may be bonded randomly, i, j are each independently an integer of 2 to 10 in each unit, these units may be linear or branched, and G is independently represented by any one of the following formulas, [Chemical Formula 6] In the formula, k is independently an integer of 2 to 8 in each unit.

12. A surface treatment agent comprising the fluoropolyether group-containing polymer and / or its partial (hydrolytic) condensate according to claim 1 or 2.

13. The surface treatment agent according to claim 12, further comprising an organic solvent free of fluorine atoms.

14. The surface treatment agent according to claim 12, wherein, The content of the fluoropolyether group-containing polymer and / or its partial (hydrolytic) condensate is 0.005 to 80% by mass.

15. The surface treatment agent according to claim 12, wherein, The content of the fluoropolyether group-containing polymer and / or its partial (hydrolytic) condensate is 0.005 to 80% by mass, and the balance is an organic solvent free of fluorine atoms.

16. An article that has been surface-treated with the surface treatment agent according to claim 12.

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