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

Abstract

A surface treatment agent comprising a fluoropolyether group-containing polymer having at least one group represented by formula (1) at at least one terminal in the molecule and / or a partial (hydrolytic) condensate thereof can form a cured film having excellent water and oil repellency, sliding properties, and chucking properties. # imgabs0 # (In the formula, Y is a divalent organic group including an ortho, meta or p-phenylene group, R is a C1-4 alkyl group or phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and a is 2 or 3. ).

Description

Technical Field

[0001] The present invention relates to a fluoropolyether group-containing polymer, and more specifically, to a fluoropolyether group-containing polymer having a connecting portion containing at least one phenylene group in the molecule and a silanol group (a hydroxyl group bonded to a silicon atom) or a hydrolyzable silyl group linked to the connecting portion at the end of the molecular chain, capable of forming a film having excellent water- and oil-repellency and abrasion resistance, a surface treatment agent containing the polymer and / or a partial (hydrolysis) condensate thereof, and an article surface-treated with the surface treatment agent. Background Art

[0002] Generally, the compound containing fluoropolyether group has water and oil repellency, chemical resistance, lubricity, demoulding property, antifouling property etc. because its surface free energy is very small.Utilize its property, industrially widely utilize as water and oil repellent antifouling agent of paper, fiber etc., lubricant of magnetic recording medium, oil repellent of precision equipment, demoulding agent, cosmetic material, protective film etc.But this property means non-adhesiveness, non-adhesiveness for other base materials simultaneously, even can be coated on base material surface, also be difficult to make its film close.

[0003] On the other hand, silane coupling agents are well known as substances that combine the surface of substrates such as glass and cloth with organic compounds, and have been widely used as coating agents for various substrate surfaces. Silane coupling agents have an organic functional group and a reactive silyl group (generally, a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction due to moisture in the air to form a film. The film is chemically and physically combined with the surface of various substrates through the hydrolyzable silyl group, thereby forming a durable and firm film.

[0004] Therefore, a composition is disclosed, which uses a fluoropolyether group-containing polymer having a hydrolyzable silyl group introduced at the end of a fluoropolyether group-containing compound, thereby being easily adhered to the surface of a substrate and being able to form a film having water and oil repellency, chemical resistance, lubricity, mold release, antifouling properties, etc. on the surface of the substrate (Patent Documents 1 to 4: Japanese Patent Publication No. 2012-072272, Japanese Patent Publication No. 2012-157856, Japanese Patent Publication No. 2013-136833, Japanese Patent Publication No. 2015-199906).

[0005] Although the substrates containing cured films such as lenses and antireflection films that have been surface-treated with a composition containing a fluoropolyether group-containing polymer into which a hydrolyzable silyl group has been introduced have excellent water and oil repellency, when the substrate is fixed for processing, the sliding property is affected and it becomes difficult to fix (poor clamping property). As a result, the substrate is misaligned during processing, resulting in the problem that it cannot be processed into a desired shape.

[0006] It is difficult to produce a substrate having a cured film having both water- and oil-repellency and gripping properties and sliding properties using a fluoropolyether group-containing polymer obtained by introducing a hydrolyzable silyl group into a fluoropolyether group-containing compound.

[0007] In addition, as prior arts related to the present invention, the following documents can be cited together with the above-mentioned documents.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2012-072272

[0011] Patent Document 2: Japanese Patent Application Publication No. 2012-157856

[0012] Patent Document 3: Japanese Patent Application Publication No. 2013-136833

[0013] Patent Document 4: Japanese Patent Application Publication No. 2015-199906

[0014] Patent Document 5: Japanese Patent Application Publication No. 2003-238577 Summary of the invention

[0015] Problems to be solved by the invention

[0016] The present invention has been completed in view of the above-mentioned actual situation, and its purpose is to provide a polymer containing a fluoropolyether group having a silanol group and / or a hydrolyzable silyl group, which can form a cured film with water- and oil-repellency, excellent wear resistance and excellent clamping properties, a surface treatment agent containing the polymer and / or its partial (hydrolysis) condensate, and an article surface-treated with the surface treatment agent.

[0017] Means for solving problems

[0018] The present inventors have conducted intensive studies to achieve the above-mentioned purpose, and as a result, have found that, by using a fluoropolyether group-containing polymer having at least one connecting portion containing a phenylene group and a silanol group (a hydroxyl group bonded to a silicon atom) or a hydrolyzable silyl group connected to the connecting portion, at least one end of the molecule, represented by the formula (1) described later, in the above-mentioned fluoropolyether group-containing polymer, a surface treatment agent containing the polymer and / or its partial (hydrolysis) condensate can form a cured film having excellent water- and oil-repellency, sliding properties, and clamping properties, thereby completing the present invention.

[0019] Therefore, the present invention provides the following fluoropolyether group-containing polymer, surface treatment agent and article.

[0020] [1] A fluoropolyether group-containing polymer having at least one group represented by the following formula (1) at at least one terminal in the molecule.

[0021] [Chemistry 1]

[0022]

[0023] (In the formula, Y is a divalent organic group containing o-, m- or p-phenylene, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and a is 2 or 3.)

[0024] [2] The fluoropolyether group-containing polymer according to [1], wherein in the formula (1), Y is a group represented by the following formula (5).

[0025] [Chemistry 2]

[0026]

[0027] (wherein, g is an integer of 0 to 20, h is an integer of 1 to 3, i1, j1, k1 are integers of 1 to 10, i2, j2, k2 are integers of 0 to 5, k3 is an integer of 1 to 10, and the repeating units may be randomly bonded, (CH2) g When there are multiple (CH2) units, the repetition numbers of the multiple (CH2) units may be the same or different.

[0028] [3] The fluoropolyether group-containing polymer according to [1] or [2], wherein in the formula (1), Y is selected from groups represented by the following formulae.

[0029] [Chemistry 3]

[0030]

[0031] [Chemistry 4]

[0032]

[0033] [Chemistry 5]

[0034]

[0035] (In the formula, the bonding end on the right side is bonded to the silicon atom of formula (1).)

[0036] [4] The fluoropolyether group-containing polymer according to any one of [1] to [3], wherein in the formula (1), X is 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 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, or a halogen atom.

[0037] [5] The fluoropolyether group-containing polymer according to any one of [1] to [4], wherein the fluoropolyether group-containing polymer is represented by the following formula (2).

[0038] [Chemistry 6]

[0039] D-Rf-A (2)

[0040] [wherein, Rf is a divalent polymer residue containing a fluorooxyalkylene group represented by the following formula (3),

[0041] [Chemistry 7]

[0042]

[0043] (W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 450, and p+q+r+s+t+u+v=20 to 450. These units may be linear or branched. In addition, the repeating units shown in the parentheses with p, q, r, s, t, u, and v may be randomly bonded. The number average molecular weight of the polymer residue is 1,000 to 20,000.)

[0044] D is a fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3-, CF2H- or CH2F- and optionally containing an oxygen atom, or A, wherein A is a group represented by the following formula (4),

[0045] [Chemistry 8]

[0046]

[0047] (In the formula, U is a single bond or a 2-4 valent organic group, Z is independently a single bond or a carbon atom, a silicon atom, a nitrogen atom, or a 3-9 valent organic group, Y' is independently an aliphatic divalent hydrocarbon group having 1 to 8 carbon atoms or Y, at least one Y' in the molecule is Y, Y, R, X, and a are the same as above, b is an integer of 1 to 8, and c is an integer of 1 to 3.)]

[0048] [6] The fluoropolyether group-containing polymer according to [5], wherein in the formula (4), Z is a single bond, or a carbon atom, a silicon atom, a nitrogen atom, a linear, branched or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, a trivalent isocyanurate group or a trivalent group containing a triazine ring.

[0049] [7] The fluoropolyether group-containing polymer according to [5] or [6], wherein in the formula (4), U is a single bond, a carbonyl group, an acylamino group, a group represented by the following formula, or a divalent to tetravalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from the group consisting of an oxygen atom, a sulfur atom, a hydroxyl group, a polyether group, a diorganosilylene group, a linear divalent organopolysiloxane residue having 2 to 100 silicon atoms, a silylene group, a silylene group, a secondary amino group, a tertiary amino group, an ether group, a carbonyl group, an acylamino group, and an ester group.

[0050] [Chemistry 9]

[0051]

[0052] (In the formula, B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.)

[0053] [8] The fluoropolyether group-containing polymer according to any one of [5] to [7], wherein the polymer represented by the formula (2) is represented by any one of the following formulas.

[0054] [Chemistry 10]

[0055] D′-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-Y′-Si(OCH3)3

[0056] D′-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2O-Y′-Si(OCH3)3

[0057] D′-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2OCH2-Y′-Si(OCH3)3

[0058] [Chemistry 11]

[0059]

[0060] [Chemistry 12]

[0061]

[0062] [Chemistry 13]

[0063]

[0064] [Chemistry 14]

[0065]

[0066] [Chemical Formula 15]

[0067]

[0068] [Chemical Formula 16]

[0069] (H3CO)3Si-Y′-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-Y′-Si(OCH3)3

[0070] (H3CO)3Si-Y′-OCH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2O-Y′-Si(OCH3)3

[0071] (H3CO)3Si-Y′-CH2OCH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2OCH2-Y′-Si(OCH3)3

[0072] [Chemical Formula 17]

[0073]

[0074] [Chemical Formula 18]

[0075]

[0076] [Chemical Formula 19]

[0077]

[0078] [Chemical Formula 20]

[0079]

[0080] [Chemical Formula 21]

[0081]

[0082] [Chemical Formula 22]

[0083]

[0084] [Chemical Formula 23]

[0085]

[0086] [Chemical Formula 24]

[0087]

[0088] [Chemistry 25]

[0089]

[0090] [Chemistry 26]

[0091]

[0092] [Chemistry 27]

[0093]

[0094] [Chemistry 28]

[0095]

[0096] [Chemistry 29]

[0097]

[0098] [Chemistry 30]

[0099]

[0100] [Chemistry 31]

[0101]

[0102] (In the formula, Y' is the same as above, D' is F, CF3 or CF3CF2, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 20 to 450, r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and r2+r3 is an integer of 20 to 180. The repeating units shown in the parentheses with p1 and q1 may be randomly bonded.)

[0103] [9] A surface treatment agent comprising the fluoropolyether group-containing polymer and / or its partial (hydrolysis) condensate according to any one of [1] to [8] as a main component.

[0104]

[10] An article surface-treated with the surface treatment agent according to [9].

[0105]

[11] The article according to

[10] , which is a lens substrate.

[0106] Effects of the Invention

[0107] The fluoropolyether group-containing polymer of the present invention has a silanol group and / or a hydrolyzable silyl group, and the polymer residue (Rf) containing a fluorooxyalkylene group in the main chain is connected to the silanol group and / or the hydrolyzable silyl group (-SiXa (R) 3-a ) has an o-, m- or p-phenylene group in the linking group (connecting group). The article surface-treated with a surface treatment agent containing the polymer and / or its partial (hydrolysis) condensate has excellent sliding properties in addition to water and oil repellency. In addition, by having an o-, m- or p-phenylene group in the above-mentioned linking group part, the substrate adhesion of the article surface-treated with the above-mentioned surface treatment agent is improved, and the clamping property is excellent, especially for lens substrates, the effect can be further exerted. DETAILED DESCRIPTION

[0108] The fluoropolyether group-containing polymer of the present invention is a fluoropolyether group-containing polymer (or a fluorooxyalkylene group-containing polymer) having at least one, preferably 1 to 12, more preferably 1 to 8 groups represented by the following formula (1) at at least one terminal of the molecule.

[0109] [Chemistry 32]

[0110]

[0111] (In the formula, Y is a divalent organic group containing o-, m- or p-phenylene, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and a is 2 or 3.)

[0112] In the above formula (1), Y is a divalent organic group containing an o-, m- or p-phenylene group, and preferably, an organic group represented by the following formula (5) can be exemplified.

[0113] [Chemistry 33]

[0114]

[0115] (wherein, g is an integer of 0 to 20, h is an integer of 1 to 3, i1, j1, k1 are integers of 1 to 10, i2, j2, k2 are integers of 0 to 5, k3 is an integer of 1 to 10, and the repeating units may be randomly bonded, (CH2) g When there are multiple (CH2) units, the repetition numbers of the multiple (CH2) units may be the same or different.

[0116] In the above formula (5), g is an integer of 0 to 20, preferably an integer of 0 to 8, h is an integer of 1 to 3, preferably 1, i1, j1, k1 are each an integer of 1 to 10, preferably, i1 is an integer of 1 to 3, preferably, j1 is an integer of 1 to 3, preferably, k1 is an integer of 1 to 3, i2, j2, k2 are each an integer of 0 to 5, preferably, i2 is an integer of 0 to 2, preferably, j2 is an integer of 0 to 2, preferably, k2 is an integer of 0 to 2, k3 is an integer of 1 to 10, preferably an integer of 1 to 3, and each repeating unit may be randomly bonded to each other.

[0117] Examples of such Y include the following groups: It is preferred that the right-side bonding end is bonded to the silicon atom of the formula (1).

[0118] [Chemistry 34]

[0119]

[0120] [Chemistry 35]

[0121]

[0122] [Chemistry 36]

[0123]

[0124] In the above formula (1), X is independently a hydroxyl group, or a hydrolyzable group selected from an alkoxy group having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, an alkoxyalkoxy group having 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, an acyloxy group having 2 to 10 carbon atoms such as acetoxy and propionyloxy, an alkenyloxy group having 2 to 10 carbon atoms such as vinyloxy, allyloxy, propenyloxy, isopropenyloxy, and a halogen atom such as chloro, bromo, and iodo.

[0125] In the above formula (1), R is independently an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, or the like, or a phenyl group.

[0126] In the above formula (1), a is 2 or 3, preferably 3.

[0127] In the case where the fluoropolyether group-containing polymer of the present invention has two or more groups represented by the formula (1) in the molecule, the groups represented by the formula (1) may be the same or different.

[0128] The fluoropolyether group-containing polymer of the present invention is preferably a fluoropolyether group-containing polymer represented by the following formula (2).

[0129] [Chemistry 37]

[0130] D-Rf-A (2)

[0131] [wherein, Rf is a divalent fluorooxyalkylene-containing polymer residue represented by the following formula (3),

[0132] [Chemistry 38]

[0133]

[0134] (W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 450, and p+q+r+s+t+u+v=20 to 450. These units may be linear or branched. In addition, the repeating units shown in the parentheses with p, q, r, s, t, u, and v may be randomly bonded. The number average molecular weight of the polymer residue is 1,000 to 20,000.)

[0135] D is a fluorine atom, a monovalent fluorine-containing hydrocarbon group having CF3-, CF2H- or CH2F- at the terminal and optionally containing an oxygen atom, or A, wherein A is a group represented by the following formula (4).

[0136] [Chemistry 39]

[0137]

[0138] (In the formula, U is a single bond or a 2-4 valent organic group, Z is independently a single bond or a carbon atom, a silicon atom, a nitrogen atom, or a 3-9 valent organic group, Y' is independently an aliphatic divalent hydrocarbon group having 1 to 8 carbon atoms or Y, at least one Y' in the molecule is Y, Y, R, X, and a are the same as above, b is an integer of 1 to 8, and c is an integer of 1 to 3.)]

[0139] In the above formula (2), Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following formula (3).

[0140] [Chemistry 40]

[0141]

[0142] In the above formula (3), W is a fluoroalkylene group containing one or more hydrogen atoms, and examples thereof include CF2, C2F4, C3F6, C4F8, C5F 10 、C6F 12 Such as groups in which one or two fluorine atoms in each perfluoroalkylene group are replaced by hydrogen atoms, and the like.

[0143] In the above formula (3), d is independently an integer of 1 to 3, and is preferably 1 or 2, in each unit.

[0144] In addition, p, q, r, s, t, u, and v are each an integer of 0 to 450, preferably, p is an integer of 0 to 440, q is an integer of 0 to 250, r is an integer of 0 to 180, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, and v is an integer of 0 to 100. p+q+r+s+t+u+v is 20 to 450, preferably 20 to 200. If p+q+r+s+t+u+v is less than the upper limit, the adhesion and curing properties are good. If it is greater than the lower limit, the characteristics of the fluoropolyether group can be fully exerted, so it is preferred. Each unit may be linear or branched. In addition, each repeating unit shown in the brackets with p, q, r, s, t, u, and v may be randomly bonded.

[0145] The polymer residue (Rf) containing a fluorooxyalkylene group is a polymer residue having a number average molecular weight of 1,000 to 20,000, preferably 2,000 to 15,000. In the present invention, the number average molecular weight (Mn) can be determined by gel permeation chromatography (GPC) analysis using a fluorinated solvent as an elution solvent. 19 It can be calculated by means of F-NMR etc.

[0146] Specific examples of Rf include the following polymer residues.

[0147] [Chemistry 41]

[0148] ——CF2O(CF2O) p’ CF2——

[0149] ——CF2O(CF2O) p’ (CF2CF2O) q’ CF2——

[0150] ——CF2O(CF2O) p’ (CF2CF2O) q’ (CF2CF2CF2O) r’ CF2——

[0151] ——CF2O(CF2O) p’ (CF2CF2O) q’ (CF2CF2CF2CF2O) s’ CF2——

[0152] ——CF2O(CF2O) p’ (CF2CF2O) q’ (CF2CF2CF2O) 1′ (CF2CF2CF2CF2O) s’ CF2——

[0153] ——CF2O(CF2O) p’ (CF2CF2O) q’ (CF2CF2CF2O) r’ (CF2CF2CF2CF2O) s’ -(CF2CF2CF2CF2CF2O) r (CF2CF2CF2CF2CF2CF2O) u’ CF2——

[0154] ——CF2CF2O(CF2CF2CF2O) r’ CF2CF2——

[0155]

[0156] [Chemistry 42]

[0157]

[0158] ——C2F4O(CF2O) p′ (CF2CF2O) q′ C2F4——

[0159] ——C2F4O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ C2F4——

[0160] (In the formula, p', q', r', s', t', and u' are each an integer greater than or equal to 1, and the upper limit thereof is the same as the upper limit of the above-mentioned p, q, r, s, t, and u, and the total of these p', q', r', s', t', and u' is 20 to 450. r1' is an integer of 20 to 180. r2' and r3' are each an integer of 1 to 100, and the total of r2' and r3' is 20 to 180. In addition, each repeating unit shown in the parentheses with p', q', r', s', t', and u' may be randomly bonded.)

[0161] In the above formula (2), D is a fluorine atom, a monovalent fluorine-containing hydrocarbon group whose terminal is CF3-, CF2H- or CH2F- and which may contain an oxygen atom, or A (a group represented by formula (4) described later). The monovalent fluorine-containing hydrocarbon group whose terminal is CF3-, CF2H- or CH2F- and which may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a fluorine-containing hydrocarbon group whose terminal of the polymer is CF3- or CF2H-.

[0162] Examples of such a monovalent fluorine-containing hydrocarbon group in which D has CF3-, CF2H- or CH2F- at the terminal and which may contain an oxygen atom include the following groups.

[0163] [Chemistry 43]

[0164] CF2H— CF3— C2F5— C3F7— C4F9—

[0165] CH2F- C3F7OCFHCF2OCH2— CF3OCFHCF2OCH2—

[0166] CF3OC3F6OCFHCF2OCH2——

[0167] CF3O— CF3CF2O— CF3CF2CF2O—

[0168] D is preferably a fluorine atom, CF3-, CF3CF2- or A.

[0169] In the above formula (2), A is a group represented by the following formula (4).

[0170] [Chemistry 44]

[0171]

[0172] (In the formula, U is a single bond or a 2-4 valent organic group, Z is independently a single bond or a carbon atom, a silicon atom, a nitrogen atom, or a 3-9 valent organic group, Y' is independently an aliphatic divalent hydrocarbon group having 1 to 8 carbon atoms or Y, at least one Y' in the molecule is Y, Y, R, X, and a are the same as above, b is an integer of 1 to 8, and c is an integer of 1 to 3.)

[0173] In the above formula (4), U is a single bond or a divalent to tetravalent organic group, preferably a single bond, a carbonyl group, an acylamino group, a group represented by the following formula,

[0174] [Chemistry 45]

[0175]

[0176] (In the formula, B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The left-side bonding end is bonded to Rf of formula (2), and the other bonding ends are bonded to Z.)

[0177] Alternatively, it may contain a divalent to tetravalent hydrocarbon group having 1 to 20 carbon atoms which contains one or more atoms or groups selected from oxygen atoms, sulfur atoms, hydroxyl groups, polyether groups, diorganosilylene groups such as dimethylsilylene groups, linear divalent organopolysiloxane residues having 2 to 100 silicon atoms, preferably 2 to 50 silicon atoms, silylene groups, silylene groups, secondary amino groups, tertiary amino groups, ether groups, carbonyl groups, acylamino groups and ester groups.

[0178] Among them, in the above formula, as the monovalent hydrocarbon group having 1 to 20 carbon atoms of B and B', there can be exemplified straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl, branched alkyl groups such as isopropyl, isobutyl, tert-butyl, neopentyl, and tert-hexyl, cyclic alkyl groups such as cyclopentyl and cyclohexyl, alkenyl groups such as vinyl, allyl, and propenyl, aryl groups such as phenyl and tolyl, and aralkyl groups such as benzyl and phenethyl.

[0179] In addition, as the monovalent polyether group of B, it is preferred to be -(C e1 H 2e1 O) e -CH3 (e1 is an integer of 1 to 6, e is an integer of 1 to 30).

[0180] Examples of the linear divalent organopolysiloxane residue having 2 to 100, preferably 2 to 50, silicon atoms which may be contained in the divalent to tetravalent hydrocarbon group include the following organopolysiloxane residues.

[0181] [Chemistry 46]

[0182]

[0183] (Where R 1 is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, or an aryl group having 6 to 10 carbon atoms such as phenyl, 1 They may be the same or different. n is an integer of 1 to 99, preferably an integer of 1 to 49.

[0184] In addition, examples of the silanylene group and the silanylene group include the following groups.

[0185] [Chemistry 47]

[0186]

[0187] (Where R 1 Same as above, R 1 Can be the same or different, R 2 It is an alkylene group having 1 to 4 carbon atoms such as methylene, ethylene, propylene, and butylene, or an arylene group having 6 to 10 carbon atoms such as phenylene.

[0188] Examples of such U include the following groups. It is preferred that the left bonding end is bonded to Rf and the other bonding ends are bonded to Z.

[0189] [Chemistry 48]

[0190] —(CH2) l1 -S-(CH2)2—

[0191] —(CH2) l1 -O-(CH2)2— —(CH2) l1 -O-

[0192]

[0193] [Chemistry 49]

[0194]

[0195] [Chemistry 50]

[0196]

[0197] [Chemistry 51]

[0198]

[0199] [Chemistry 52]

[0200]

[0201] (wherein, f is independently an integer of 1 to 4, l1 and l2 are integers of 1 to 4, n is an integer of 1 to 99, and e is an integer of 1 to 30.)

[0202] In the above formula (4), Z is independently a single bond or a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to 9-valent organic group, preferably a single bond or a carbon atom, a silicon atom, a nitrogen atom, a linear, branched or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms, a trivalent isocyanurate group or a trivalent triazine ring-containing group. In addition, the organopolysiloxane residue may contain a silanylene structure in which two silicon atoms are bonded via an alkylene group.

[0203] Among them, examples of the linear, branched or cyclic tri- to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms, include organopolysiloxane residues represented by the following formula.

[0204] [Chemistry 53]

[0205]

[0206] [Where R 1 is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, or an aryl group having 6 to 10 carbon atoms such as phenyl, 1 Can be the same or different, R 2R is an alkylene group having 1 to 4 carbon atoms such as methylene, ethylene, propylene, and butylene, or an arylene group having 6 to 10 carbon atoms such as phenylene. 3 Independently for R 1 Or by the following formula (6)

[0207] [Chemistry 54]

[0208]

[0209] (Where R 1 As above, m8 is an integer of 1 to 6, preferably 1, and the left bonding end is bonded to Si. )

[0210] The group represented by R 4 are independently single bonds or are represented by the following formula (7):

[0211] [Chemistry 55]

[0212]

[0213] (Where R 2 , R 3 As above, m9 is an integer of 0 to 6, preferably an integer of 0 to 3, m10 is an integer of 0 to 6, preferably an integer of 0 to 2, and m9+m10≠0. Each repeating unit shown in the brackets may be randomly bonded. The left bonding end is bonded to Si.)

[0214] A group represented by at least one R 3 Formula (6). m1 is an integer of 1 to 9, preferably an integer of 1 to 4, m2 is an integer of 0 to 9, preferably an integer of 0 to 3, m3 is an integer of 2 to 6, preferably an integer of 3 to 5, m4 is an integer of 0 to 8, preferably 0 or 1, m3+m4 is an integer of 3 to 10, preferably an integer of 3 to 5, m5 is 2 or 3, m6 is an integer of 3 to 9, preferably an integer of 3 to 7, m7 is an integer of 0 to 9, preferably an integer of 0 to 3, and each repeating unit shown in the brackets may be randomly bonded. The number of silicon atoms in each organopolysiloxane residue is 3 to 13. ]

[0215] Examples of such Z include the following groups. It is preferred that the left bonding end is bonded to U, and the other bonding ends are bonded to Y.

[0216] [Chemistry 56]

[0217]

[0218] [Chemistry 57]

[0219]

[0220] [Chemistry 58]

[0221]

[0222] [Chemistry 59]

[0223]

[0224] [Chemistry 60]

[0225]

[0226] In the above formula (4), Y' is independently an aliphatic divalent hydrocarbon group having 1 to 8 carbon atoms or Y, and at least one Y' in the molecule is Y.

[0227] Examples of the aliphatic divalent hydrocarbon group having 1 to 8 carbon atoms include alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene and octamethylene, and propylene is preferred.

[0228] Y is the same as Y in the above formula (1). As Y', at least one Y in the molecule may be Y, and preferably all Y' are Y. When a plurality of Ys are included in the above formula (4), these Ys may be the same or different.

[0229] In the above formula (4), R, X and a are the same as those in the above formula (1).

[0230] In the above formula (4), b is an integer of 1 to 8, preferably an integer of 1 to 4, and c is an integer of 1 to 3, preferably 1 or 2.

[0231] Examples of the fluoropolyether group-containing polymer represented by the above formula (2) include the following structures.

[0232] [Chemistry 61]

[0233] D′-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-Y′-Si(OCH3)3

[0234] D′-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2O-Y′-Si(OCH3)3

[0235] D′-CF2O-(CF2O)p1-(C2F4O) q1 -CF2-CH2OCH2-Y′-Si(OCH3)3

[0236] [Chemistry 62]

[0237]

[0238] [Chemistry 63]

[0239]

[0240] [Chemistry 64]

[0241]

[0242] [Chemistry 65]

[0243]

[0244] [Chemistry 66]

[0245]

[0246] [Chemistry 67]

[0247] (H3CO)3Si--Y′--OF2-O--(CF2O) p1 -(C2F4O) q1 --CF2--Y′-Si(OCH3)3

[0248] (H3CO)3Si--Y'-OCH2-CF2--O--(CF2O) p1 --(C2F4O) q1 —CF2--CH2O—Y′--Si(OOH3)3

[0249] (H3CO)3Si--Y′--CH2OCH2-CF2--O--(CF2O) p1 --(C2F4O) q1 —CF2--CH2OCH2--Y′-Si(OCH3)3

[0250] [Chemistry 68]

[0251]

[0252] [Chemistry 69]

[0253]

[0254] [Chemistry 70]

[0255]

[0256] [Chemistry 71]

[0257]

[0258] [Chemistry 72]

[0259]

[0260] [Chemistry 73]

[0261]

[0262] [Chemistry 74]

[0263]

[0264] [Chemistry 75]

[0265]

[0266] [Chemistry 76]

[0267]

[0268] [Chemistry 77]

[0269]

[0270] [Chemistry 78]

[0271]

[0272] [Chemistry 79]

[0273]

[0274] [Chemistry 80]

[0275]

[0276] [Chemistry 81]

[0277]

[0278] [Chemistry 82]

[0279]

[0280] (In the formula, Y' is the same as above, D' is F, CF3 or CF3CF2, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 20 to 450, preferably an integer of 20 to 200, r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and r2+r3 is an integer of 20 to 180. The repeating units shown in the parentheses with p1 and q1 may be randomly bonded.)

[0281] As the fluoropolyether group-containing polymer represented by the above formula (2), the following structures can be specifically mentioned. By changing the combination of Rf, D, and A in the above formula (2), a fluoropolyether group-containing polymer having a plurality of silanol groups and / or hydrolyzable silyl groups can be obtained. In the following formula, D' is F, CF3, or CF3CF2, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 20 to 450, preferably an integer of 20 to 200, r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and r2+r3 is an integer of 20 to 180. The repeating units shown in the parentheses with p1 and q1 may be randomly bonded.

[0282] [Chemistry 83]

[0283]

[0284] [Chemistry 84]

[0285]

[0286] [Chemistry 85]

[0287]

[0288] [Chemistry 86]

[0289]

[0290] [Chemistry 87]

[0291]

[0292] [Chemistry 88]

[0293]

[0294] [Chemistry 89]

[0295]

[0296] [Chemistry 90]

[0297]

[0298] [Chemistry 91]

[0299]

[0300] [Chemistry 92]

[0301]

[0302] [Chemistry 93]

[0303]

[0304] [Chemistry 94]

[0305]

[0306] [Chemistry 95]

[0307]

[0308] [Chemistry 96]

[0309]

[0310] [Chemistry 97]

[0311]

[0312] [Chemistry 98]

[0313]

[0314] [Chemistry 99]

[0315]

[0316] [Chemical 100]

[0317]

[0318] [Chemistry 101]

[0319]

[0320] Examples of a method for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2) include the following methods.

[0321] [Preparation method 1]

[0322] A fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organosilicon compound having, for example, an o-, m- or p-phenylene group, a SiH group and a silanol group or a hydrolyzable silyl group (halosilyl group or alkoxysilyl group) in the molecule, and aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 1 to 72 hours, preferably 10 to 36 hours, more preferably about 12 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex. When an organosilicon compound having a halogen atom in a hydrolyzable silyl group is used as the organosilicon compound having an o-, m- or p-phenylene group, a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, the substituent (halogen atom) on the silyl group may be converted to an alkoxy group such as a methoxy group, which is another hydrolyzable group.

[0323] Among them, in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2), as the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group), a fluoropolyether group-containing polymer represented by the following formula (8) can be exemplified.

[0324] [Chemistry 102]

[0325] D 1 -Rf-A 1 (8)

[0326] [wherein, Rf is the same as above, D 1 A fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3-, CF2H- or CH2F- and which may contain an oxygen atom, or A 1 , A 1 It is a group represented by the following formula (9).

[0327] [Chemistry 103]

[0328]

[0329] (wherein, U, Z, b, and c are the same as above, and g' is an integer of 0 to 8, preferably an integer of 0 to 3.)]

[0330] In the above formula (8), as D 1 The terminal of D is a monovalent fluorine-containing hydrocarbon group which is CF3-, CF2H- or CH2F- and which may contain an oxygen atom, and the same fluorine-containing hydrocarbon group as exemplified in the monovalent fluorine-containing hydrocarbon group which is CF3-, CF2H- or CH2F- and which may contain an oxygen atom can be exemplified. 1 , preferably a fluorine atom, CF3-, CF3CF2- or A 1 .

[0331] Examples of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the above formula (8) include the following polymers.

[0332] [Chemistry 104]

[0333] D'-CF2O-(CF2O) p1 -{C2F4O) q1 -CF2--CH2CH=CH2

[0334] D′-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2O-CH2CH=CH2

[0335] [Chemistry 105]

[0336]

[0337] [Chemistry 106]

[0338]

[0339] [Chemistry 107]

[0340]

[0341] [Chemistry 108]

[0342]

[0343] [Chemistry 109]

[0344] H2C=HCH2C—CF2—O—(CF2O) p1 —(C2F4O) q1 —CF2—CH2CH=CH2

[0345] H2C=HCH2C—OH2C—CF2—O--(CF2O) p1 —(C2F4O) q1 --CF2—CH2O—CH2CH=CH2

[0346] [Chemistry 110]

[0347]

[0348] [Chemistry 111]

[0349]

[0350] [Chemistry 112]

[0351]

[0352] [Chemistry 113]

[0353]

[0354] [Chemistry 114]

[0355]

[0356] [Chemistry 115]

[0357]

[0358] [Chemistry 116]

[0359]

[0360] [Chemistry 117]

[0361]

[0362] [Chemistry 118]

[0363]

[0364] [Chemistry 119]

[0365]

[0366] [Chemistry 120]

[0367]

[0368] [Chemistry 121]

[0369]

[0370] [Chemistry 122]

[0371]

[0372] [Chemistry 123]

[0373]

[0374] (In the formula, D', p1, q1, p1+q1, r1, r2, r3, and r2+r3 are the same as above. The repeating units shown in the parentheses with p1 and q1 may be randomly bonded.)

[0375] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2), examples of the organosilicon compound having an o-, m- or p-phenylene group and having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule include the following compounds.

[0376] [Chemistry 124]

[0377]

[0378] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2), the amount of the organosilicon compound having an o-, m- or p-phenylene group, a SiH group and a silanol group or a hydrolyzable silyl group in the molecule can be used in such a manner that the SiH group in the organosilicon compound becomes 1 to 4 mol, preferably 1 to 2.5 mol, based on 1 mol of the olefin part (alkenyl group) in the fluoropolyether group-containing polymer having an olefin part (alkenyl group).

[0379] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2), an organosilicon compound having an o-, m- or p-phenylene group, an SiH group and a silanol group or a hydrolyzable silyl group in the molecule and not having an o-, m- or p-phenylene group, an SiH group and a silanol group or a hydrolyzable silyl group in the molecule can also be reacted. In this case, the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) preferably has two or more olefin moieties (alkenyl groups).

[0380] Among them, examples of the organic silicon compound that does not have an o-, m- or p-phenylene group in the molecule and has a SiH group and a silanol group or a hydrolyzable silyl group include trimethoxysilane and the like.

[0381] When an organosilicon compound having no o-, m- or p-phenylene group and having a SiH group and a silanol group or a hydrolyzable silyl group is used, the reaction ratio is not particularly limited as long as 1 mol or more of the organosilicon compound having an o-, m- or p-phenylene group and having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule is reacted with respect to 1 mol of the fluoropolyether group-containing polymer having an olefinic moiety (alkenyl group). It is preferred to use the organosilicon compound having an o-, m- or p-phenylene group and having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule and the organosilicon compound having no o-, m- or p-phenylene group and having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule to be 1 to 4 mol, preferably 1 to 2.5 mol, based on 1 mol of the olefinic moiety (alkenyl group) in the fluoropolyether group-containing polymer having an olefinic moiety (alkenyl group).

[0382] In the preparation of the polymer containing a fluoropolyether group having a silanol group or a hydrolyzable silyl group represented by formula (2), as a solvent, for example, a fluorine-based solvent can be cited. As the fluorine-based solvent, 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 and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), perfluoro solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), Asahiklin AC-6000 (manufactured by AGC, tridecafluorooctane) and the like can be cited.

[0383] The amount of the solvent used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group).

[0384] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2), as a hydrosilylation reaction catalyst, for example, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., tetrakis(triphenylphosphine)palladium, tris(triphenylphosphine)rhodium chloride, etc., platinum group metal catalysts such as the like are preferred. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0385] The amount of the hydrosilylation reaction catalyst used is 0.01 to 100 ppm, preferably 0.1 to 50 ppm, in terms of transition metal (mass), based on the mass of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group).

[0386] Furthermore, when an organosilicon compound having a halogen atom in a hydrolyzable silyl group is used as the above-mentioned organosilicon compound having an o-, m- or p-phenylene group, a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, the substituent (halogen atom) on the silyl group can be converted into an alkoxy group, such as a methoxy group, which is another hydrolyzable group. As reagents that can be used when converting the substituent (halogen atom) on the silyl group into another hydrolyzable group, for example, alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, etc., can be listed.

[0387] The amount used is 10 to 200 parts by mass, preferably 40 to 100 parts by mass, based on 100 parts by mass of the addition reaction product of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) and the organosilicon compound having an o-, m- or p-phenylene group, a SiH group and a halosilyl group in the molecule.

[0388] For example, a compound represented by the following formula is used as the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group):

[0389] [Chemistry 125]

[0390] CF3O--(CF2O) p1 —(C2F4O) q1 --CF2—CH2OCH2CH=CH2

[0391] (p1=23.8, q1=21.9)

[0392] As the organic silicon compound having an o-, m- or p-phenylene group and having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, a silane compound represented by the following formula is used:

[0393] [Chemistry 126]

[0394] In this case, a compound represented by the following formula is obtained.

[0395] [Chemistry 127]

[0396]

[0397] As another example, when a compound represented by the following formula is used as a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group),

[0398] [Chemistry 128]

[0399]

[0400] and using as a mixture of equal moles the following organic silicon compounds having o-, m- or p-phenylene groups, SiH groups and silanol groups or hydrolyzable silyl groups in the molecule:

[0401] [Chemistry 129]

[0402]

[0403] In the case of a silane compound represented by and an organic silicon compound having no o-, m- or p-phenylene group in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group, for example, trimethoxysilane, a compound represented by the following formula is obtained.

[0404] [Chemistry 130]

[0405]

[0406] As a method for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2), the following method can also be mentioned.

[0407] [Preparation method 2]

[0408] A fluoropolyether group-containing polymer having a carbonyl group is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having, for example, an o-, m- or p-phenylene group, an amino group and a silanol group or a hydrolyzable silyl group (halosilyl group or alkoxysilyl group) in the molecule is mixed, and the mixture is aged at a temperature of 20 to 100° C., preferably 25 to 50° C., more preferably about 25° C. for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours. When an organosilicon compound having a halogen atom in a hydrolyzable silyl group is used as the organosilicon compound having an o-, m- or p-phenylene group, an amino group and a silanol group or a hydrolyzable silyl group in the molecule, the substituent (halogen atom) on the silyl group may be converted to an alkoxy group such as a methoxy group, which is another hydrolyzable group.

[0409] Among them, in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 2), as the fluoropolyether group-containing polymer having a carbonyl group, a fluoropolyether group-containing polymer represented by the following formula (14) can be exemplified.

[0410] [Chemistry 131]

[0411] D 2 -Rf—A 2 (14)

[0412] [wherein, Rf is the same as above, D 2 A fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3-, CF2H- or CH2F- and which may contain an oxygen atom, or A 2 , A 2 It is a group represented by the following formula (15).

[0413] [Chemistry 132]

[0414]

[0415] (wherein Q is OH, OCH3, OCH2CH3 or F.)]

[0416] In the above formula (14), D 2The terminal of D is CF3-, CF2H- or CH2F- and the monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom can be exemplified by the same groups as those exemplified in the monovalent fluorine-containing hydrocarbon group which is CF3-, CF2H- or CH2F- and may contain an oxygen atom. 2 , preferably a fluorine atom, CF3-, CF3CF2- or A 2 .

[0417] Examples of the fluoropolyether group-containing polymer having a carbonyl group represented by the above formula (14) include the following polymers.

[0418] [Chemistry 133]

[0419]

[0420] [Chemistry 134]

[0421]

[0422] [Chemistry 135]

[0423]

[0424] [Chemistry 136]

[0425]

[0426] (In the formula, D', p1, q1, p1+q1, r1, r2, r3, and r2+r3 are the same as above. The repeating units shown in the parentheses with p1 and q1 may be randomly bonded.)

[0427] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 2), examples of the organic silicon compound having an o-, m- or p-phenylene group, an amino group and a silanol group or a hydrolyzable silyl group in the molecule include p-aminophenyltrimethoxysilane, (4-trimethoxysilylphenyl)methylamine, and the like.

[0428] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 2), the amount of the organosilicon compound having an o-, m- or p-phenylene group, an amino group and a silanol group or a hydrolyzable silyl group in the molecule is such that the amino group in the organosilicon compound is 1 to 4 mol, preferably 1 to 2.5 mol, relative to 1 mol of the carbonyl group in the fluoropolyether group-containing polymer having a carbonyl group.

[0429] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (Preparation Method 2), the same solvent as exemplified in the solvent of the above-mentioned Preparation Method 1 can be used as the solvent.

[0430] The amount of the solvent used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having a carbonyl group.

[0431] Furthermore, when an organosilicon compound having a halogen atom in a hydrolyzable silyl group is used as the organosilicon compound having an o-, m- or p-phenylene group, an amino group and a silanol group or a hydrolyzable silyl group in the above-mentioned molecule, the substituent (halogen atom) on the silyl group can be converted into an alkoxy group, such as a methoxy group, which is another hydrolyzable group. As reagents that can be used when converting the substituent (halogen atom) on the silyl group into another hydrolyzable group, for example, alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, etc., can be listed.

[0432] The amount used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, based on 100 parts by mass of the addition reaction product of the fluoropolyether group-containing polymer having a carbonyl group and the organosilicon compound having o-, m- or p-phenylene groups, amino groups and halosilyl groups in the molecule.

[0433] For example, when a compound represented by the following formula is used as a fluoropolyether group-containing polymer having a carbonyl group,

[0434] [Chemistry 137]

[0435]

[0436] When p-aminophenyltrimethoxysilane is used as the organic silicon compound having an o-, m- or p-phenylene group, an amino group and a silanol group or a hydrolyzable silyl group in the molecule, a compound represented by the following formula is obtained.

[0437] [Chemistry 138]

[0438]

[0439] As a method for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2), the following method can also be mentioned.

[0440] [Preparation method 3]

[0441] A fluoropolyether group-containing polymer having an SiH group is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organic silicon compound having an o-, m- or p-phenylene group, an olefin portion (alkenyl) and a silanol group or a hydrolyzable silyl group (halosilyl group or alkoxysilyl group, etc.) in the molecule, and aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 1 to 72 hours, preferably 10 to 36 hours, more preferably about 12 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex. Furthermore, when an organosilicon compound having a halogen atom in a hydrolyzable silyl group is used as an organosilicon compound having an o-, m- or p-phenylene group, an olefin portion (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule, the substituent (halogen atom) on the silyl group can then be converted into an alkoxy group, such as a methoxy group, which is another hydrolyzable group.

[0442] Among them, in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 3), as the fluoropolyether group-containing polymer having a SiH group, a fluoropolyether group-containing polymer represented by the following formula (16) can be exemplified.

[0443] [Chemistry 139]

[0444] D 3 —Rf—A 3 (16)

[0445] [wherein, Rf is the same as above, D 3 A fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3-, CF2H- or CH2F- and which may contain an oxygen atom, or A 3 , A 3 It is a group represented by the following formula (17).

[0446] [Chemistry 140]

[0447]

[0448] (Wherein, U, Z, b, and c are the same as above.)]

[0449] In the above formula (16), D 3 The terminal of D is CF3-, CF2H- or CH2F- and the monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom can be exemplified by the same groups as those exemplified in the monovalent fluorine-containing hydrocarbon group which is CF3-, CF2H- or CH2F- and may contain an oxygen atom. 3 , preferably a fluorine atom, CF3-, CF3CF2- or A 3 .

[0450] Examples of the fluoropolyether group-containing polymer having a SiH group represented by the above formula (16) include the following polymers.

[0451] [Chemistry 141]

[0452]

[0453] [Chemistry 142]

[0454]

[0455] [Chemistry 143]

[0456]

[0457] [Chemistry 144]

[0458]

[0459] [Chemistry 145]

[0460]

[0461] (In the formula, D', p1, q1, p1+q1, r1, r2, r3, and r2+r3 are the same as above. The repeating units shown in the parentheses with p1 and q1 may be randomly bonded.)

[0462] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 3), examples of the organic silicon compound having an o-, m- or p-phenylene group, an olefin portion (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule include p-phenylene trimethoxysilane, p-phenylene ethyl trimethoxysilane, 2-(4-ethynylphenyl) ethyl trimethoxysilane, and the like.

[0463] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 3), the amount of the organosilicon compound having an o-, m- or p-phenylene group, an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule can be such that the amount of alkenyl group in the organosilicon compound is 1 to 4 mol, preferably 1 to 2.5 mol, per 1 mol of SiH group in the fluoropolyether group-containing polymer having a SiH group.

[0464] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (Preparation Method 3), the same solvent as exemplified in the solvent of the above-mentioned Preparation Method 1 can be used as a solvent.

[0465] The amount of the solvent used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, based on 100 parts by mass of the SiH group-containing fluoropolyether group-containing polymer.

[0466] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (Preparation Method 3), as a hydrosilylation reaction catalyst, the same catalyst as exemplified in the hydrosilylation reaction catalyst of the above-mentioned Preparation Method 1 can be used. A platinum-based compound such as a vinylsiloxane complex is preferred.

[0467] The amount of the hydrosilylation reaction catalyst used is 0.01 to 100 ppm, preferably 0.1 to 50 ppm, in terms of transition metal (mass), based on the mass of the SiH group-containing fluoropolyether group-containing polymer.

[0468] Furthermore, when an organosilicon compound having a halogen atom in a hydrolyzable silyl group is used as the organosilicon compound having an o-, m- or p-phenylene group, an olefin portion (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule, the substituent (halogen atom) on the silyl group can be converted into an alkoxy group such as a methoxy group, which is another hydrolyzable group. As reagents that can be used when converting the substituent (halogen atom) on the silyl group into another hydrolyzable group, for example, alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, etc. can be listed.

[0469] The amount used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, based on 100 parts by mass of the addition reaction product of the fluoropolyether group-containing polymer having a SiH group and an organosilicon compound having an o-, m- or p-phenylene group, an olefin portion (alkenyl group) and a halosilyl group in the molecule.

[0470] For example, when a compound represented by the following formula is used as a fluoropolyether group-containing polymer having an SiH group,

[0471] [Chemistry 146]

[0472]

[0473] When p-phenylyltrimethoxysilane is used as the organosilicon compound having an o-, m- or p-phenylene group, an olefin portion (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule, a compound represented by the following formula is obtained.

[0474] [Chemistry 147]

[0475]

[0476] In addition, for example, when using a compound represented by the following formula

[0477] [Chemistry 148]

[0478] CF3O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2OCH2CH2CH2-Si(OCH3)3

[0479] (p1=23.8, q1=21.9)

[0480] A compound represented by the following formula obtained by co-hydrolysis and condensation with 1,1,3,3-tetramethyldisiloxane [another name: bis(dimethylsilyl)ether] as a fluoropolyether group-containing polymer having a SiH group,

[0481] [Chemistry 149]

[0482]

[0483] When p-phenylyltrimethoxysilane is used as the organosilicon compound having an o-, m- or p-phenylene group, an olefin portion (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule, a compound represented by the following formula is obtained.

[0484] [Chemistry 150]

[0485]

[0486] As a method for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2), the following method can also be mentioned.

[0487] [Preparation method 4]

[0488] A fluoropolyether group-containing polymer having a hydroxyl group is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organic compound having an o-, m- or p-phenylene group, a halogen group and an olefin moiety (alkenyl group) in the molecule, and aged at 40 to 120° C., preferably 50 to 100° C., more preferably about 60° C. for 1 to 72 hours, preferably 10 to 36 hours, more preferably 10 to 12 hours in the presence of an alkaline agent such as an aqueous sodium hydroxide solution. The obtained polymer is a fluoropolyether group-containing polymer having an o-, m- or p-phenylene group and an olefin moiety (alkenyl group) in the molecule.

[0489] Next, a fluoropolyether group-containing polymer having an o-, m- or p-phenylene group and an olefin moiety (alkenyl group) in a molecule is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organosilicon compound having, for example, a SiH group and a silanol group or a hydrolyzable silyl group (halosilyl group or alkoxysilyl group) in a molecule, and aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 1 to 72 hours, preferably 10 to 36 hours, more preferably about 12 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex. When an organosilicon compound having a halogen atom in a hydrolyzable silyl group is used as the organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group in a molecule, the substituent (halogen atom) on the silyl group may be converted to an alkoxy group or the like, such as a methoxy group, which is another hydrolyzable group.

[0490] Here, in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 4), as the fluoropolyether group-containing polymer having a hydroxyl group, a fluoropolyether group-containing polymer represented by the following formula (18) can be exemplified.

[0491] [Chemistry 151]

[0492] D 4 -Rf-A 4 (18)

[0493] (where Rf is the same as above, D 4 A fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3-, CF2H- or CH2F- and which may contain an oxygen atom, or A 4 , A 4 is a group represented by the following formula (19).

[0494] [Chemistry 152]

[0495] —CH2—OH (19)

[0496] In the above formula (18), D 4 The terminal of D is CF3-, CF2H- or CH2F-F- and may contain an oxygen atom, and the same groups as those exemplified in the monovalent fluorine-containing hydrocarbon group of which the terminal is CF3-, CF2H- or CH2F- and may contain an oxygen atom can be exemplified. 4 , preferably a fluorine atom, CF3-, CF3CF2- or A 4 .

[0497] Examples of the fluoropolyether group-containing polymer having a hydroxyl group represented by the above formula (18) include the following polymers.

[0498] [Chemistry 153]

[0499] D′--CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-OH

[0500] [Chemistry 154]

[0501] HO--CH2--CF2—O--(CF2O) p1 —(C2F4O) q1 —CF2—CH2—OH

[0502] [Chemistry 155]

[0503]

[0504] [Chemistry 156]

[0505]

[0506] (In the formula, D', p1, q1, p1+q1, r1, r2, r3, and r2+r3 are the same as above. The repeating units shown in the parentheses with p1 and q1 may be randomly bonded.)

[0507] In the preparation of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 4), examples of organic compounds having an o-, m- or p-phenylene group, a halogen group and an olefin portion (alkenyl group) in the molecule include 1-(bromomethyl)-3-allylbenzene, 4-vinylbenzyl bromide, and the like.

[0508] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 4), the amount of the organic compound having an o-, m- or p-phenylene group, a halogen group and an olefin moiety (alkenyl group) in the molecule can be used in such a manner that the number of halogen groups in the organic compound becomes 1 to 4 mol, preferably 1 to 2.5 mol, based on 1 mol of hydroxyl groups in the fluoropolyether group-containing polymer having a hydroxyl group.

[0509] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (Preparation Method 4), the same solvent as exemplified in the solvent of the above-mentioned Preparation Method 1 can be used as a solvent.

[0510] The amount of the solvent used is 0 to 300 parts by mass, preferably 30 to 150 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having a hydroxyl group.

[0511] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (Preparation Method 4), the alkaline agent is preferably sodium hydroxide or potassium hydroxide.

[0512] The alkaline agent can be used in an amount of 0.5 to 15 mol, preferably 0.8 to 7 mol, based on 1 mol of the fluoropolyether group-containing polymer having a hydroxyl group.

[0513] By reacting a fluoropolyether group-containing polymer having a hydroxyl group with an organic compound having an o-, m- or p-phenylene group, a halogen group and an olefin moiety (alkenyl group) in the molecule, a fluoropolyether group-containing polymer having an o-, m- or p-phenylene group and an olefin moiety (alkenyl group) in the molecule can be obtained.

[0514] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 4), examples of the fluoropolyether group-containing polymer having an o-, m- or p-phenylene group and an olefin moiety (alkenyl group) in the molecule include the following polymers.

[0515] [Chemistry 157]

[0516]

[0517] [Chemistry 158]

[0518]

[0519] [Chemistry 159]

[0520]

[0521] [Chemistry 160]

[0522]

[0523] (In the formula, D', p1, q1, p1+q1, r1, r2, r3, and r2+r3 are the same as above. The repeating units shown in the parentheses with p1 and q1 may be randomly bonded.)

[0524] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 4), as an organic silicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule to be reacted with the fluoropolyether group-containing polymer having an o-, m- or p-phenylene group and an olefin portion (alkenyl group) in the molecule obtained above, for example, trimethoxysilane can be exemplified.

[0525] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (preparation method 4), the amount of the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule is such that the SiH group in the organosilicon compound is 1 to 4 mol, preferably 1 to 2.5 mol, based on 1 mol of the olefin part (alkenyl group) in the obtained fluoropolyether group-containing polymer having an o-, m- or p-phenylene group and an olefin part (alkenyl group) in the molecule.

[0526] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (Preparation Method 4), as the solvent used for the reaction of the obtained fluoropolyether group-containing polymer having an o-, m- or p-phenylene group and an olefin portion (alkenyl group) in the molecule and the organic silicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, the same solvent as exemplified in the solvent of the above-mentioned Preparation Method 1 can be used.

[0527] The amount of the solvent used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having an o-, m- or p-phenylene group and an olefin moiety (alkenyl group) in the molecule.

[0528] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) (Preparation Method 4), as a hydrosilylation catalyst for the reaction of the obtained fluoropolyether group-containing polymer having an o-, m- or p-phenylene group and an olefin moiety (alkenyl group) in the molecule with the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, the same catalyst as exemplified in the hydrosilylation catalyst of the above-mentioned Preparation Method 1 can be used. A platinum-based compound such as a vinylsiloxane complex is preferred.

[0529] The amount of the hydrosilylation reaction catalyst used is 0.01 to 100 ppm, preferably 0.02 to 50 ppm, in terms of transition metal (mass), relative to the mass of the fluoropolyether group-containing polymer having o-, m- or p-phenylene and an olefin moiety (alkenyl) in the molecule.

[0530] Furthermore, in the case of using an organosilicon compound having a hydrolyzable silyl group with a halogen atom as the above-mentioned organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, the substituent (halogen atom) on the silyl group can be converted into an alkoxy group such as a methoxy group, which is another hydrolyzable group. As reagents that can be used when converting the substituent (halogen atom) on the silyl group into another hydrolyzable group, for example, alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, etc. can be listed.

[0531] The amount used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, based on 100 parts by mass of the addition reaction product of the fluoropolyether group-containing polymer having a SiH group and an organosilicon compound having an o-, m- or p-phenylene group, an olefin portion (alkenyl group) and a halosilyl group in the molecule.

[0532] For example, when a compound represented by the following formula is used as a fluoropolyether group-containing polymer having a hydroxyl group,

[0533] [Chemistry 161]

[0534] CF3O—(CF2O) o1 —(C2F4O) q1 —CF2—CH2—OH

[0535] (p1=23.8,q1=21.9)

[0536] When 1-(bromomethyl)-3-allylbenzene is used as the organic compound having an o-, m- or p-phenylene group, a halogen group and an olefin moiety (alkenyl group) in the molecule, a compound represented by the following formula is obtained.

[0537] [Chemistry 162]

[0538]

[0539] When the compound represented by the above formula is used and trimethoxysilane is used as the organic silicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, a compound represented by the following formula is obtained.

[0540] [Chemistry 163]

[0541]

[0542] The present invention also provides a surface treatment agent containing a fluoropolyether group-containing polymer having at least one group represented by the above formula (1) at at least one terminal in the molecule, in particular, a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2) as a main component. The surface treatment agent may contain the above-mentioned fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group as a main component, and may contain unreacted raw materials and reaction intermediates before the terminal silanol group or the terminal hydrolyzable silyl group of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group is introduced. In addition, the surface treatment agent may contain a partial (hydrolysis) condensate obtained by condensing the hydroxyl group of the fluoropolyether group-containing polymer or the hydroxyl group obtained by partially hydrolyzing the terminal hydrolyzable silyl group of the fluoropolyether group-containing polymer in advance by a known method. It should be noted that in the present invention, the so-called "partial (hydrolysis) condensate" refers to a partial condensate or a partially hydrolyzed condensate.

[0543] The surface treatment agent may contain, in addition to the fluoropolyether group-containing polymer of the present invention as a main component (particularly the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above-mentioned formula (2)), a fluorine-containing compound (non-functional fluoropolyether polymer) represented by the following formula (20) as required.

[0544] D 5 -Rf-D 5 (20)

[0545] (where Rf is the same as above, D 5 are independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group having a terminal CF3-, CF2H- or CH2F- and which may contain an oxygen atom.

[0546] In the above formula (20), Rf can be exemplified by the same groups as those exemplified in the above formula (2), and these Rf may be the same as or different from Rf in the above formula (2).

[0547] In the above formula (20), D 5 is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group having a terminal CF3-, CF2H- or CH2F- and which may contain an oxygen atom. 5 Specifically, CF3-, CF3CF2-, CF3CF2CF2-, C3F7O-CF(CF3)CH2-, C3F7O-CFHCF2OCH2-, CF3O-, CF3CF2O-, CF3CF2CF2O-, etc. can be exemplified. 5 Among them, fluorine atom, CF3-, CF3CF2-, CF3O-, CF3CF2O-, and CF3CF2CF2O- are preferred.

[0548] Examples of the fluorine-containing compound (non-functional fluoropolyether polymer) represented by the formula (20) include the following compounds.

[0549] [Chemistry 164]

[0550]

[0551] (In the formula, p4, q4, and r4 are each independently an integer of 1 to 450, and the total of p4, q4, and r4 is 20 to 450, and r5 and r6 are each an integer of 20 to 450. The repeating units shown in the parentheses with p4, q4, and r6 may be randomly bonded.)

[0552] The content of the fluorine-containing compound (non-functional fluoropolyether polymer) represented by the above formula (20) can be 0 to 100 parts by mass, preferably 0 to 60 parts by mass, and more preferably about 0 to 30 parts by mass, relative to 100 parts by mass of the fluoropolyether group-containing polymer of the present invention and / or its partial (hydrolysis) condensate as the main component.

[0553] 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.

[0554] 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 of the present invention and / or its partial (hydrolysis) condensate.

[0555] The surface treatment agent may contain an appropriate solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluorohexane, perfluoroheptane, perfluorooctane, tridecafluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluorohexyl ether, methyl perfluoroheptenyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferred in terms of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, methyl perfluoroheptenyl ether, and tridecafluorooctane are particularly preferred.

[0556] As for the above-mentioned solvents, two or more thereof may be mixed, and preferably the polymer containing a fluoropolyether group and its partial (hydrolysis) condensate are uniformly dissolved. In addition, the optimal concentration of the polymer containing a fluoropolyether group and its partial (hydrolysis) condensate dissolved in the solvent varies depending on the treatment method, and any amount that can be easily weighed is sufficient. In the case of direct coating, it is preferably 0.01 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total of the solvent and the polymer containing a fluoropolyether group and its partial (hydrolysis) condensate. In the case of vapor deposition treatment, it is preferably 1 to 100 parts by mass, and particularly preferably 3 to 30 parts by mass, relative to 100 parts by mass of the total of the solvent and the polymer containing a fluoropolyether group and its partial (hydrolysis) condensate.

[0557] The surface treatment agent of the present invention can be applied to the substrate by known methods such as brush coating, dipping, spraying, and evaporation. The heating method during the evaporation treatment may be a resistance heating method or an electron beam heating method, and is not particularly limited. 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 carried out at 25 to 200°C, especially 25 to 150°C for 30 minutes to 36 hours, especially 1 to 24 hours. In addition, in the case of applying by evaporation treatment, it is preferably carried out at 20 to 200°C, especially 20 to 100°C for 12 to 72 hours, especially 12 to 36 hours. In addition, it can be cured under humidification. The film thickness of the cured film is appropriately selected according to the type of substrate, usually 0.1 to 100 nm, especially 1 to 20 nm. In addition, for example, when the material is diluted in a fluorine-based solvent to which water has been added in advance and hydrolyzed, that is, Si-OH is generated before spraying, curing after coating is rapid.

[0558] The film thickness can be measured, for example, by means of spectroscopic reflectivity measurement, X-ray reflectivity measurement, spectroscopic ellipsometry, fluorescent X-ray measurement, or the like.

[0559] The substrate processed with the surface treatment agent of the present invention is not particularly limited, and can be various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz. The surface treatment agent of the present invention can give water and oil repellency to the substrate. Especially, it can be suitable as the surface treatment agent of SiO2 processed glass or film and use.

[0560] As articles processed with the surface treatment agent of the present invention, medical equipment such as car navigation, mobile phones, smart phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films and other optical articles can be listed. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the articles, and can further impart anti-scratch properties, so it can be particularly used as a water-repellent and oil-repellent layer of lenses, touch panel displays, anti-reflection films, etc.

[0561] In addition, the surface treatment agent of the present invention can also be used as an antifouling coating for sanitary products such as bathtubs and washstands, an antifouling coating for window glass or tempered glass of automobiles, trains, aircraft, etc., an antifouling coating for headlight covers, etc., a water-repellent and oil-repellent coating for exterior building materials, an anti-oil coating for kitchen building materials, an antifouling and anti-sticker coating for telephone boxes, an anti-graffiti coating, a coating that imparts anti-fingerprint adhesion to artworks, an anti-fingerprint adhesion coating for CDs, DVDs, etc., a release agent or coating additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, and a lubricity enhancer for tapes, films, etc.

[0562] In particular, the surface treatment agent of the present invention can provide a cured film having excellent water and oil repellency, slidability, abrasion resistance, and gripping properties to a lens substrate.

[0563] The clamping property mentioned here refers to the degree to which the substrate to be processed is fixed when the substrate is processed while being fixed with an adhesive tape. For example, the bonding strength (tensile shear bonding strength) between the lens adhesive tape and the lens when the lens is fixed with a lens adhesive tape for lens grinding processing is used as an indicator. The situation where the substrate can be firmly fixed to the extent that the substrate can be processed with good precision through the bonding of the adhesive tape to the substrate is called good clamping property.

[0564] Example

[0565] The following are synthesis examples, embodiments and comparative examples to illustrate the present invention in more detail, but the present invention is not limited to the following examples. The number of repetitions of each fluorooxyalkylene unit in the polymer residue containing fluorooxyalkylene and the number average molecular weight of the polymer residue containing fluorooxyalkylene are respectively 19 The number average value (number average repetition number) and number average molecular weight calculated by F-NMR, the number average molecular weight of the whole compound having the polymer residue containing fluorooxyalkylene is calculated by the sum of the number average molecular weight of the polymer residue containing fluorooxyalkylene and the formula weight of the remainder of the molecular formula. In addition, in the following formula, each repeating unit shown in the bracket with p1 and q1 is randomly bonded. In addition, the film thickness is a value measured by the spectroscopic ellipsometry measurement method using a spectroscopic ellipsometry instrument.

[0566] [Synthesis example 1]

[0567] In a reaction vessel, the following formula (1A)

[0568] [Chemistry 165]

[0569] The compound represented by 100g (2.32×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4227, the number average molecular weight of the compound (overall) was 4305), 1,3-bis(trifluoromethyl)benzene 50 g, p-aminophenyltrimethoxysilane 9.37 g (4.40×10 -2 mol) were mixed and aged at 25°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 101 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (1B).

[0570] [Chemistry 166]

[0571]

[0572] [Synthesis example 2]

[0573] In a reaction vessel, the following formula (2A)

[0574] [Chemistry 167]

[0575] CF3O--(CF2O) p1 -(C2F4O) q1 --CF2--CH2OCH2CH=CH2 (2A)

[0576] (p1=23.8, q1=21.9)

[0577] The compound represented by 100g (2.32×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group is 4227, the number average molecular weight of the compound (overall) is 4317), 1,3-bis(trifluoromethyl)benzene 50g, and the following formula (2B):

[0578] [Chemistry 168]

[0579]

[0580] The organosilicon compound represented was 9.71 g (2.71 × 10 -2 mol) and toluene solution of chloroplatinic acid / vinylsiloxane complex 6.53×10 -2 g (calculated as Pt single substance, containing 2.26×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 102 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (2C).

[0581] [Chemistry 169]

[0582]

[0583] [Synthesis example 3]

[0584] In a reaction container, 100 g (2.32 × 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 50g, by the following formula (3A)

[0585] [Chemistry 170]

[0586]

[0587] The organosilicon compound represented was 11.36 g (2.71 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 6.53×10 -2 g (calculated as Pt single substance, containing 2.26×10 -8 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 103 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (3B).

[0588] [Chemistry 171]

[0589]

[0590] [Synthesis Example 4]

[0591] In a reaction vessel, the following formula (4A)

[0592] [Chemistry 172]

[0593] CF2O--(CF2O) p1 —(C2F4O) q1 —CF2--CH2OH (4A)

[0594] (p1=23.8, q1=21.9)

[0595] The compound represented by 100g (2.34×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4227, the number average molecular weight of the compound (overall) was 4277), 1,3-bis(trifluoromethyl)benzene 50 g, 1-bromomethyl-3-allylbenzene 5.19 g (2.46×10 -2 mol) were mixed. Then 21.0 mL of 1 mol / L sodium hydroxide aqueous solution was added dropwise and aged at 60°C for 11 hours. Then, the solvent and unreacted products were removed under reduced pressure and washed to obtain 100 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (4B).

[0596] [Chemistry 173]

[0597]

[0598] 100 g (2.27 × 10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4227, the number average molecular weight of the compound (overall) was 4405), 1,3-bis(trifluoromethyl)benzene 50 g, trimethoxysilane 3.30 g (2.71×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 6.53×10 -2 g (calculated as Pt single substance, containing 2.26×10 -8 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 101 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (4C).

[0599] [Chemistry 174]

[0600]

[0601] [Synthesis Example 5]

[0602] In a reaction vessel, the following formula (5A)

[0603] [Chemistry 175]

[0604]

[0605] The compound represented by 100g (2.31×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group is 4227, the number average molecular weight of the compound (as a whole) is 4330), 1,3-bis(trifluoromethyl)benzene 100g, and the following formula (5B):

[0606] [Chemistry 176]

[0607]

[0608] The organosilicon compound represented by 10.7 g (2.76 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 6.64×10 -2 g (calculated as Pt single substance, containing 2.30×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 105 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (5C).

[0609] [Chemistry 177]

[0610]

[0611] [Synthesis example 6]

[0612] In a reaction vessel, the following formula (6A)

[0613] [Chemistry 178]

[0614]

[0615] The compound represented by 100g (2.29×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4227, the number average molecular weight of the compound (as a whole) was 4370), 1,3-bis(trifluoromethyl)benzene was 100 g, the organosilicon compound represented by the above formula (2B) was 18.3 g (5.11×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 7.58×10 -2g (calculated as Pt single substance, containing 2.00×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 104 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (6B).

[0616] [Chemistry 179]

[0617]

[0618] [Synthesis Example 7]

[0619] In a reaction vessel, the following formula (7A)

[0620] [Chemistry 180]

[0621]

[0622] The compound represented by 100g (2.19×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4227, the number average molecular weight of the compound (overall) was 4557), 1,3-bis(trifluoromethyl)benzene 50 g, p-phenylenetrimethoxysilane 15.7 g (7.00×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 6.07×10 -2 g (calculated as Pt single substance, containing 2.10×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 102 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (7B).

[0623] [Chemistry 181]

[0624]

[0625] [Synthesis example 8]

[0626] In a reaction vessel, the following formula (8A)

[0627] [Chemistry 182]

[0628]

[0629] The compound represented by 100g (2.24×10 -2mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4227, the number average molecular weight of the compound (as a whole) was 4469), 1,3-bis(trifluoromethyl)benzene 50 g, the organosilicon compound represented by the above formula (3A) 9.38 g (2.24×10 -2 mol), trimethoxysilane 5.37 g (4.40 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 7.28×10 -2 g (based on Pt single substance, containing 2.52×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 102 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (8B).

[0630] [Chemistry 183]

[0631]

[0632] [Synthesis Example 9]

[0633] In a reaction vessel, the following formula (9A)

[0634] [Chemistry 184]

[0635]

[0636] The compound represented by 100g (2.24×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4227, the number average molecular weight of the compound (as a whole) was 4468), 1,3-bis(trifluoromethyl)benzene 50 g, the organosilicon compound represented by the above formula (5B) 19.0 g (4.90×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 5.55×10 -2 g (based on Pt single substance, containing 1.92×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 106 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (9B).

[0637] [Chemistry 185]

[0638]

[0639] [Synthesis Example 10]

[0640] In a reaction vessel, the following formula (10A)

[0641] [Chemistry 186]

[0642]

[0643] The compound represented by 100g (2.17×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4277, the number average molecular weight of the compound (overall) was 4607), 1,3-bis(trifluoromethyl)benzene 50 g, p-phenylenetrimethoxysilane 15.7 g (7.00×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 6.07×10 -2 g (calculated as Pt single substance, containing 2.10×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were removed by vacuum distillation and washed to obtain 102 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (10B).

[0644] [Chemistry 187]

[0645]

[0646] [Synthesis Example 11]

[0647] In a reaction vessel, the following formulas (11A-1) and (11A-2) are placed.

[0648] [Chemistry 188]

[0649]

[0650] The mixture of the compounds represented by 100 g (2.17 × 10 -2 mol, number average molecular weight of the mixture (whole) 4603) (molar ratio in the mixture: (11A-1) 90%, (11A-2) 10%), 1,3-bis(trifluoromethyl)benzene 50 g, p-phenylenetrimethoxysilane 15.5 g (6.90×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 6.07×10 - 2 g (calculated as Pt single substance, containing 2.10×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 100 g of a liquid product. 1 H-NMR, 19F-NMR confirmed that the obtained compound (mixture) had structures represented by the following formulae (11B-1) and (11B-2) (molar ratio in the mixture: (11B-1) 90%, (11B-2) 10%).

[0651] [Chemistry 189]

[0652]

[0653] [Synthesis Example 12]

[0654] In a reaction vessel, the following formula (12A)

[0655] [Chemistry 190]

[0656]

[0657] The compound represented by 100g (2.26×10 -3 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4084, the number average molecular weight of the compound (overall) was 4414), 1,3-bis(trifluoromethyl)benzene 50 g, p-phenylenetrimethoxysilane 16.2 g (7.23×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 6.74×10 -2 g (based on Pt single substance, containing 2.33×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 102 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (12B).

[0658] [Chemistry 191]

[0659]

[0660] [Synthesis Example 13]

[0661] In a reaction vessel, the following formula (13A)

[0662] [Chemistry 192]

[0663]

[0664] The compound represented by 100g (2.36×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4122, the number average molecular weight of the compound (overall) was 4240), 1,3-bis(trifluoromethyl)benzene 50 g, p-aminophenyltrimethoxysilane 13.4 g (6.29×10 -2mol) were mixed and aged at 25°C for 24 hours. Then, the solvent and unreacted products were removed by vacuum distillation and washed to obtain 102 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (13B).

[0665] [Chemistry 193]

[0666]

[0667] [Synthesis Example 14]

[0668] In a reaction vessel, the following formula (14A)

[0669] [Chemistry 194]

[0670]

[0671] The compound represented by 100g (2.11×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4122, the number average molecular weight of the compound (overall) was 4744), 1,3-bis(trifluoromethyl)benzene 50 g, p-phenylenetrimethoxysilane 44.5 g (1.99×10 -1 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 9.02×10 -2 g (based on Pt single substance, containing 3.12×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 107 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (14B).

[0672] [Chemistry 195]

[0673]

[0674] [Synthesis Example 15]

[0675] In a reaction vessel, the above formula (15A)

[0676] [Chemistry 196]

[0677]

[0678] The compound represented by 100g (1.48×10 -2mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 6142, the number average molecular weight of the compound (total) was 6764), Asahiklin AC-6000 (manufactured by AGC Corporation, tridecafluorooctane) 50 g, p-phenylenetrimethoxysilane 21.0 g (9.36×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 4.89×10 -2 g (calculated as Pt single substance, containing 1.51×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 108 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (15B).

[0679] [Chemistry 197]

[0680]

[0681] [Synthesis Example 16]

[0682] In a reaction container, 100 g (2.32 × 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 50 g, trimethoxysilane 3.31 g (2.71×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 8.30×10 -2 g (calculated as Pt single substance, containing 2.87×10 -7 mol) were mixed and aged at 80°C for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 102 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (16A).

[0683] [Chemistry 198]

[0684] CF3O--(CF2O) p1 —{C2F4O) q1 —CF2—CH2OCH2CH2CH2—Si(OCH3)3 (16A)

[0685] (p1=23.8, q1=21.9)

[0686] [Synthesis Example 17]

[0687] In a reaction container, 100 g (2.24 × 10 -2mol), 1,3-bis(trifluoromethyl)benzene 50 g, trimethoxysilane 9.40 g (7.84×10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 8.30×10 -2 g (calculated as Pt single substance, containing 2.87×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 102 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (17A).

[0688] [Chemistry 199]

[0689]

[0690] [Synthesis Example 18]

[0691] In a reaction vessel, the following formula (18A)

[0692] [Chemistry 200]

[0693] H2C=HCH2COH2C-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2OCH2CH=CH2 (18A)

[0694] (p1=23.8, q1=21.0)

[0695] The compound represented by 100g (2.35×10 -2 mol, the number average molecular weight of the polymer residue containing fluorooxyalkylene group was 4122, the number average molecular weight of the compound (overall) was 4264), 1,3-bis(trifluoromethyl)benzene was 100 g, trimethoxysilane was 9.03 g (7.40×10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.70×10 -2 g (calculated as Pt single substance, containing 1.45×10 -7 mol) were mixed and aged at 80°C for 12 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 110 g of a liquid product. 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (18B).

[0696] [Chemistry 201]

[0697] (H3CO)3Si--H2CH2CH2COH2C-CF2O-(CF2O) p1 -(C2F4O)q1 -CF2-CH2OCH2CH2CH2-Si(OCH3)3(18B)

[0698] (p1=23.8,q1=21.0)

[0699] [Example 1]

[0700] The compound obtained in Synthesis Example 1 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0701] [Example 2]

[0702] The compound obtained in Synthesis Example 2 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0703] [Example 3]

[0704] The compound obtained in Synthesis Example 3 was dissolved in Asahiklin AE-3000 (manufactured by AGC Corporation, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0705] [Example 4]

[0706] The compound obtained in Synthesis Example 4 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0707] [Example 5]

[0708] The compound obtained in Synthesis Example 5 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0709] [Example 6]

[0710] The compound obtained in Synthesis Example 6 was dissolved in Asahiklin AE-3000 (manufactured by AGC Corporation, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0711] [Example 7]

[0712] The compound obtained in Synthesis Example 7 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0713] [Example 8]

[0714] The compound obtained in Synthesis Example 8 was dissolved in Opteon SF10 (manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd., methyl perfluoroheptenyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0715] [Example 9]

[0716] The compound obtained in Synthesis Example 9 was dissolved in Opteon SF10 (manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd., methyl perfluoroheptenyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0717] [Example 10]

[0718] The compound obtained in Synthesis Example 10 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0719] [Example 11]

[0720] The compound obtained in Synthesis Example 11 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0721] [Example 12]

[0722] The compound obtained in Synthesis Example 12 was dissolved in Novec 7300 (manufactured by 3M Co., Ltd., methyl perfluorohexyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0723] [Example 13]

[0724] The compound obtained in Synthesis Example 13 was dissolved in Asahiklin AC-6000 (manufactured by AGC Corporation, tridecafluorooctane) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0725] [Example 14]

[0726] The compound obtained in Synthesis Example 14 was dissolved in Asahiklin AC-6000 (manufactured by AGC Corporation, tridecafluorooctane) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0727] [Example 15]

[0728] The compound obtained in Synthesis Example 15 was dissolved in Asahiklin AC-6000 (manufactured by AGC Corporation, tridecafluorooctane) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0729] [Comparative Example 1]

[0730] The compound obtained in Synthesis Example 16 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0731] [Comparative Example 2]

[0732] The compound obtained in Synthesis Example 17 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0733] [Comparative Example 3]

[0734] The compound obtained in Synthesis Example 18 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass, thereby preparing a surface treatment agent.

[0735] Preparation of surface treatment agent and formation of cured film

[0736] As described in the above examples and comparative examples, surface treatment agents were prepared. For an AR treated plastic lens (size: 80 mmφ) having a SiO2 layer on the outermost surface, each surface treatment agent was vacuum deposited (treatment conditions: pressure: 2.0×10 -2 Pa, heating temperature: 700° C.), and cured for 12 hours in an atmosphere of 25° C. and a relative humidity of 50% to form a cured film with a film thickness of 10 nm.

[0737] Evaluation of water and oil repellency

[0738] [Determination of initial water repellency]

[0739] The contact angle (water repellency) of the cured film on the lens formed with the cured film was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The results (initial water contact angle) are shown in Table 1.

[0740] Evaluation of sliding properties

[0741] [Determination of dynamic friction coefficient]

[0742] The dynamic friction coefficient of the lens on which the cured film was formed was measured with respect to Vencot (manufactured by Asahi Kasei Corporation) under the following conditions using a surface property tester 14FW (manufactured by Shinto Scientific Co., Ltd.).

[0743] Contact area: 10mm×30mm

[0744] Load: 100gf

[0745] The results of the dynamic friction coefficient are shown in Table 1 using the following A to C.

[0746] A: Dynamic friction coefficient is less than 0.04

[0747] B: Dynamic friction coefficient is greater than 0.04 and less than 0.08

[0748] C: Dynamic friction coefficient is 0.08 or more

[0749] Evaluation of cloth abrasion resistance

[0750] The contact angle (water repellency) of the cured film formed on the lens produced above after rubbing under the following conditions was measured in the same manner as above using a friction tester (manufactured by Shinto Scientific Co., Ltd.) to evaluate the cloth abrasion resistance. The test environment conditions were 25° C. and a relative humidity of 40%.

[0751] [Determination of cloth abrasion resistance]

[0752] Cloth: Vencot (manufactured by Asahi Kasei Co., Ltd.)

[0753] Contact area: 1cm 2

[0754] Moving distance (one way): 40mm

[0755] Moving speed: 4800mm / min

[0756] Load: 1kg / 1cm 2

[0757] Wear times: 30,000 times

[0758] The results of cloth abrasion resistance are shown in Table 1 using the following A to C.

[0759] A: Water contact angle decreases from 0 to 2° from the initial stage

[0760] B: Water contact angle decreases by 3 to 5 degrees from the initial stage

[0761] C: Water contact angle decreases by more than 6° from the initial

[0762] Evaluation of clamping properties

[0763] A lens adhesive tape (manufactured by 3M: LEAP III 1695M) was attached to the lens formed with the cured film, and the tensile shear bonding strength was measured. Specifically, the lens formed with the cured film and the lens adhesive tape attached to the lens were stretched in such a way that shear stress acted on the bonding surface, and the maximum strength when the bonding portion was broken was measured.

[0764] [Tensile shear bond strength measurement]

[0765] Bonding area: 2.7cm 2

[0766] Stretching speed: 50mm / min

[0767] The results of the clamping properties (tensile shear adhesive strength) are shown in Table 1 using the following A to C.

[0768] A: Tensile shear bonding strength is more than 50N

[0769] B: Tensile shear bond strength is greater than 30N and less than 50N

[0770] C: Tensile shear bonding strength is less than 30N

[0771] [Table 1]

[0772]

[0773] From the above results, in Comparative Examples 1 and 2, the dynamic friction coefficient is low (evaluation A), the cloth wear resistance is low (evaluation C, B), and the clamping property is also low (evaluation C). In Comparative Example 3, the clamping property is high (evaluation A) due to the presence of functional groups at both ends, but the dynamic friction coefficient is high (evaluation C). On the other hand, in Examples 1 to 15, since the dynamic friction coefficient is low (evaluation A, B), it is easy to slide and the cloth wear resistance is good (evaluation A, B). In addition, by introducing a phenylene group into the linking group of the polymer residue containing a fluorooxyalkylene group in the main chain and the silanol group and / or the hydrolyzable silyl group as shown in formula (1), it becomes a result that the clamping property is improved (evaluation A, B).

Claims

1. A fluoropolyether group-containing polymer having at least one group represented by the following formula (1) at at least one terminal of the molecule, [Chemistry 1] In the formula, Y is a divalent organic group including o-, m- or p-phenylene, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and a is 2 or 3.

2. The fluoropolyether group-containing polymer according to claim 1, wherein In the formula (1), Y is a group represented by the following formula (5), [Chemistry 2] In the formula, g is an integer of 0 to 20, h is an integer of 1 to 3, i1, j1, k1 are integers of 1 to 10, i2, j2, k2 are integers of 0 to 5, k3 is an integer of 1 to 10, and the repeating units may be randomly bonded to each other, (CH2) g When the (CH2) units exist in a plurality of groups, the repetition numbers of the plurality of groups may be the same as or different from each other.

3. The fluoropolyether group-containing polymer according to claim 1, wherein In the formula (1), Y is selected from the group represented by the following formula: [Chemistry 3] [Chemistry 4] [Chemistry 5] In the formula, the bonding end on the right side is bonded to the silicon atom of formula (1).

4. The fluoropolyether group-containing polymer according to claim 1, wherein In the formula (1), X is 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 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, or a halogen atom.

5. The fluoropolyether group-containing polymer according to claim 1, wherein The polymer containing a fluoropolyether group is represented by the following formula (2): [Chemistry 6] D-Rf-A (2) In the formula, Rf is a divalent polymer residue containing a fluorooxyalkylene group represented by the following formula (3): [Chemistry 7] In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 450, and p+q+r+s+t+u+v=20 to 450. Each of these units may be linear or branched. In addition, each repeating unit shown in the parentheses with p, q, r, s, t, u, and v may be randomly bonded. The number average molecular weight of the polymer residue is 1,000 to 20,000. D is a fluorine atom, a monovalent fluorine-containing hydrocarbon group having a terminal CF3-, CF2H- or CH2F- and optionally containing an oxygen atom, or A, wherein A is a group represented by the following formula (4), [Chemistry 8] In the formula, U is a single bond or a 2-4 valent organic group, Z is independently a single bond or a carbon atom, a silicon atom, a nitrogen atom, or a 3-9 valent organic group, Y' is independently an aliphatic divalent hydrocarbon group having 1 to 8 carbon atoms or Y, at least one Y' in the molecule is Y, Y, R, X, and a are the same as above, b is an integer of 1 to 8, and c is an integer of 1 to 3.

6. The fluoropolyether group-containing polymer according to claim 5, wherein In the formula (4), Z is a single bond, or a carbon atom, a silicon atom, a nitrogen atom, a linear, branched or cyclic tri- to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, a trivalent isocyanurate group or a trivalent triazine ring-containing group.

7. The fluoropolyether group-containing polymer according to claim 5, wherein In the formula (4), U is a single bond, a carbonyl group, an acylamino group, a group represented by the following formula, or a divalent to tetravalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from the group consisting of an oxygen atom, a sulfur atom, a hydroxyl group, a polyether group, a diorganosilylene group, a linear divalent organopolysiloxane residue having 2 to 100 silicon atoms, a silylene group, a silylene group, a secondary amino group, a tertiary amino group, an ether group, a carbonyl group, an acylamino group, and an ester group. [Chemistry 9] In the formula, B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

8. The fluoropolyether group-containing polymer according to claim 5, wherein The polymer represented by the formula (2) is represented by any of the following formulae, [Chemistry 10] D′-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-Y′-Si(OCH3)3 D′-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2O-Y′-Si(OCH3)3 D′-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2OCH2-Y′-Si(OCH3)3 [Chemistry 11] [Chemistry 12] [Chemistry 13] [Chemistry 14] [Chemistry 15] [Chemistry 16] (H3CO)3Si-Y′-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-Y′-Si(OCH3)3 (H3CO)3Si-Y′-OCH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2O-Y′-Si(OCH3)3 (H3CO)3Si-Y′-CH2OCH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2OCH2-Y′-Si(OCH3)3 [Chemistry 17] [Chemistry 18] [Chemistry 19] [Chemistry 20] [Chemistry 21] [Chemistry 22] [Chemistry 23] [Chemistry 24] [Chemistry 25] [Chemistry 26] [Chemistry 27] [Chemistry 28] [Chemistry 29] [Chemistry 30] [Chemistry 31] In the formula, Y' is the same as above, D' is F, CF3 or CF3CF2, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 20 to 450, r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, r2+r3 is an integer of 20 to 180, and the repeating units shown in the brackets with p1 and q1 can be randomly bonded.

9. A surface treatment agent comprising the fluoropolyether group-containing polymer according to any one of claims 1 to 8 and / or a partial (hydrolysis) condensate thereof as a main component.

10. An article surface-treated with the surface treating agent according to claim 9. The article according to claim 10 , which is a lens substrate.

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