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

Abstract

The surface treatment agent according to the present invention comprises a polymer containing a fluoropolyether group and / or a partial (hydrolysis) condensate thereof, the polymer being a high-molecular-weight polymer in which the number-average molecular weight of a fluorooxyalkylene group-containing polymer residue in the main chain is 6000-30,000. The present invention relates to a silicone resin which has a silanol group or a hydrolyzable silyl group at both ends of a molecular chain, and which has a siloxane structure in a linking group between a fluorooxyalkylene group-containing polymer residue in the main chain and the silanol group or hydrolyzable silyl group at both ends of the molecular chain. Consequently, a cured coating film having excellent water and oil repellency, wear resistance, and sandwiching properties can be formed.

Description

Technical Field

[0001] The present invention relates to a fluoropolyether group-containing polymer (a compound having a divalent fluorooxyalkylene group-containing polymer residue in the molecule), and more specifically, to a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group that can form 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-repellent, chemical resistance, lubricity, demoulding property, antifouling property etc. because its surface free energy is very small.Utilize its property, be widely used in the water- and oil-repellent antifouling agent of paper, fiber etc., the lubricant of magnetic recording medium, oil-proof agent, demoulding agent, cosmetic material, protective film etc. of precision equipment in industry.But, its property also means the non-adhesiveness, non-adhesiveness for other base materials, even can be coated on the base material surface, also be difficult to make its film close.

[0003] On the other hand, as a substance that combines the surface of a substrate such as glass or cloth with an organic compound, silane coupling agents are well known and widely used as coating agents for the surfaces of various substrates. 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 using moisture in the air to form a film. The film is chemically and physically bonded to the surface of various substrates through the hydrolyzable silyl group, thereby forming a durable and firm film.

[0004] Therefore, a composition is disclosed, in which a fluoropolyether group-containing polymer having a hydrolyzable silyl group introduced at one end of a fluoropolyether group-containing compound is used, thereby making it easy to adhere 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 substrates containing cured films such as lenses and antireflection films that have been surface-treated with a composition containing a fluoropolyether group-containing polymer having a hydrolyzable silyl group introduced into the fluoropolyether group-containing compound have excellent sliding properties and mold release properties, when the substrate is fixed for processing, the sliding properties are affected and it becomes difficult to fix (poor clamping properties). As a result, the substrate shifts during processing and cannot be processed into a desired shape.

[0006] Furthermore, by using a fluoropolyether group-containing polymer having hydrolyzable silyl groups introduced into both ends of the fluoropolyether group-containing compound, the above-mentioned substrate fixing problem can be solved, but sufficient performance in terms of wear durability cannot be exhibited.

[0007] In addition, as prior arts related to the present invention, the following documents are listed 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 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 conducted intensive studies to solve the above-mentioned problems and found that, with respect to the above-mentioned fluoropolyether group-containing polymer, by using a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (1) described later, a surface treatment agent containing the polymer and / or its partial (hydrolysis) condensate can form a cured film having excellent water and oil repellency, excellent wear resistance and excellent clamping properties, thereby completing the present invention.

[0019] Therefore, the present invention provides the following fluoropolyether group-containing polymer, surface treatment agent and article. [1]

[0021] A fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group, which is represented by the following general formula (1):

[0022] [Chemistry 1]

[0023]

[0024] In the formula, Rf is a divalent fluorooxyalkylene-containing polymer residue represented by the following general formula (2):

[0025] [Chemistry 2]

[0026]

[0027] In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 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 6,000 to 30,000.

[0028] U is independently a 2-4 valent organic group, Z is independently a 2-6 valent straight-chain organic (poly)siloxane residue having 2-10 silicon atoms or a branched or cyclic 3-10 silicon atoms, Y is independently a divalent organic group, R is independently an alkyl group having 1-4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1-3 for each bonded silicon atom, m is independently an integer of 1-3, and l is independently an integer of 1-5. [2]

[0030] The fluoropolyether group-containing polymer according to [1], wherein in the formula (1), U is a divalent or trivalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an arylene group having 6 to 8 carbon atoms, an oxygen atom, a sulfur atom, a hydroxyl group, a diorganosilylene group, an unsubstituted or substituted secondary amino group, a tertiary amino group, a carbonyl group, an amide group, an ester group, an isocyanuride group and a triazine ring-containing group, or is a tetravalent group having a carbon atom or a silicon atom as a central atom and having a carbon atom or a silicon atom as a central atom and having a carbon atom or a saturated hydrocarbon group having 1 to 20 carbon atoms or an oxygen atom bonded to three or four of the four bonding ends of the central atom. [3]

[0032] The fluoropolyether group-containing polymer according to [1] or [2], wherein in the formula (1), Y is an alkylene group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom and an arylene group having 6 to 8 carbon atoms. [4]

[0034] The fluoropolyether group-containing polymer according to any one of [1] to [3], wherein in the formula (1), X is selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom. [5]

[0036] The fluoropolyether group-containing polymer according to any one of [1] to [4], wherein the polymer represented by formula (1) is represented by any one of the following formulas:

[0037] [Chemistry 3]

[0038]

[0039] [Chemistry 4]

[0040]

[0041] [Chemistry 5]

[0042]

[0043] [Chemistry 6]

[0044]

[0045] [Chemistry 7]

[0046]

[0047] [Chemistry 8]

[0048]

[0049] [Chemistry 9]

[0050]

[0051] [Chemistry 10]

[0052]

[0053] [Chemistry 11]

[0054]

[0055] [Chemistry 12]

[0056]

[0057] [Chemistry 13]

[0058]

[0059] [Chemistry 14]

[0060]

[0061] [Chemistry 15]

[0062]

[0063] [Chemistry 16]

[0064]

[0065] [Chemistry 17]

[0066]

[0067] [Chemistry 18]

[0068]

[0069] [Chemistry 19]

[0070]

[0071] [Chemistry 20]

[0072]

[0073] [Chemistry 21]

[0074]

[0075] [Chemistry 22]

[0076]

[0077] [Chemistry 23]

[0078]

[0079] [Chemistry 24]

[0080]

[0081] [Chemistry 25]

[0082]

[0083] [Chemistry 26]

[0084]

[0085] [Chemistry 27]

[0086]

[0087] [Chemistry 28]

[0088]

[0089] [Chemistry 29]

[0090]

[0091] [Chemistry 30]

[0092]

[0093] [Chemistry 31]

[0094]

[0095] [Chemistry 32]

[0096]

[0097] [Chemistry 33]

[0098]

[0099] [Chemistry 34]

[0100]

[0101] [Chemistry 35]

[0102]

[0103] [Chemistry 36]

[0104]

[0105] [Chemistry 37]

[0106]

[0107] [Chemistry 38]

[0108]

[0109] [Chemistry 39]

[0110]

[0111] [Chemistry 40]

[0112]

[0113] [Chemistry 41]

[0114]

[0115] In the formula, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 50 to 450, r1 is an integer of 35 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, r2+r3 is an integer of 35 to 180, p2 is an integer of 1 to 400, q2 is an integer of 1 to 250, r4 is an integer of 1 to 100, r5 is an integer of 1 to 100, p2+q2+r4+r5 is an integer of 40 to 403, p3 is an integer from 5 to 440, q3 is an integer from 5 to 250, p3+q3 is an integer from 50 to 445, qs1 is an integer from 1 to 85, qs2 is an integer from 1 to 85, qs1+qs2 is an integer from 16 to 86, and each repeating unit shown in the brackets with p1 and q1, p2 and q2, p3 and q3 may be randomly bonded, and the number average molecular weight of the polymer residue containing fluorooxyalkylene is 6000 to 30000. [6]

[0117] A surface treatment agent comprising the fluoropolyether group-containing polymer and / or its partial (hydrolysis) condensate according to any one of [1] to [5] as a main component. [7]

[0119] The surface treatment agent according to [6], further comprising a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (3) and / or a partial (hydrolyzed) condensate thereof,

[0120] [Chemistry 42]

[0121]

[0122] In the formula, A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group, and Rf is a divalent polymer residue containing a fluorooxyalkylene group represented by the following general formula (2),

[0123] [Chemistry 43]

[0124]

[0125] In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 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 6,000 to 30,000.

[0126] U is independently a 2-4 valent organic group, Z is independently a 2-6 valent straight-chain organic (poly)siloxane residue having 2-10 silicon atoms or a branched or cyclic 3-10 silicon atoms, Y is independently a divalent organic group, R is independently an alkyl group having 1-4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1-3 for each bonded silicon atom, m is independently an integer of 1-3, and l is independently an integer of 1-5. [8]

[0128] An article surface-treated with the surface treatment agent according to [6] or [7]. [9]

[0130] The article according to [8] is a lens.

[0131] Effects of the Invention

[0132] The polymer containing a fluoropolyether group of the present invention is a high molecular weight polymer having a polymer residue (Rf) containing a fluorooxyalkylene group as the main chain and a silanol group or a hydrolyzable silyl group (-SiX n (R) 3-n ) and the polymer residue (Rf) containing fluorooxyalkylene in the main chain and the silanol groups or hydrolyzable silyl groups (-SiX n (R) 3-n ) has a siloxane structure (siloxane bond) in the connecting group, thereby improving the substrate adhesion. As a result, the article surface-treated with a surface treatment agent containing the polymer and / or its partial (hydrolyzed) condensate has excellent water and oil repellency, abrasion resistance (especially paper abrasion resistance) and substrate clamping property. In particular, for lens substrates, the effect can be further exerted. DETAILED DESCRIPTION

[0133] In the present invention, the term "partial (hydrolysis) condensate" refers to a partial condensate or a partially hydrolyzed condensate, and the term "organo(poly)siloxane residue" refers to an organosiloxane residue or an organopolysiloxane residue.

[0134] In addition, in this specification, the so-called "about (numerical value)" refers to a numerical value (approximate number) expressed by rounding, and when the last digit of the numerical value expressed by it is not "0", it includes a numerical range in which the next digit is further rounded to become the numerical value it represents. For example, the so-called "about 1.5 equivalents" means more than 1.45 equivalents and less than 1.54 equivalents, and the so-called "about 65 parts by mass" means more than 64.5 parts by mass and less than 65.4 parts by mass. In addition, when the last digit of the numerical value it represents is "0", it includes a numerical range in which the last digit is rounded to become the numerical value it represents. For example, the so-called "about 80°C" means more than 75°C and less than 84°C, and the so-called "about 100 parts by mass" means more than 95 parts by mass and less than 104 parts by mass.

[0135] The fluoropolyether group-containing polymer of the present invention is represented by the following general formula (1), and is a fluoropolyether group-containing polymer having a siloxane bond (Si—O—Si) in the connecting group between the divalent fluorooxyalkylene group-containing polymer residue (Rf) constituting the main chain and the reactive functional groups (silanol group or hydrolyzable silyl group) at both ends of the molecular chain.

[0136] [Chemistry 44]

[0137]

[0138] [wherein, Rf is a divalent fluorooxyalkylene-containing polymer residue represented by the following general formula (2),

[0139] [Chemistry 45]

[0140]

[0141] (W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 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 6,000 to 30,000.)

[0142] U is independently a 2-4 valent organic group, Z is independently a 2-6 valent straight chain or branched or cyclic organo(poly)siloxane residue having 2-10 silicon atoms or 3-10 silicon atoms, Y is independently a divalent organic group, R is independently an alkyl group or phenyl group having 1-4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1-3 for each bonded silicon atom, m is independently an integer of 1-3, and l is independently an integer of 1-5.]

[0143] In the above formula (1), Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the above general formula (2).

[0144] In the above formula (2), W is a fluoroalkylene group containing one or more hydrogen atoms, for example, CF2, C2F4, C3F6, C4F8, C5F 10 、C6F 12 etc., wherein one or two fluorine atoms in each perfluoroalkylene group are substituted with hydrogen atoms.

[0145] In the above formula (2), d is independently an integer of 1 to 3 for each unit, and is preferably 1 or 2.

[0146] In addition, p, q, r, s, t, u, and v are each an integer of 0 to 450, preferably, p is an integer of 5 to 440, q is an integer of 5 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 50 to 200, and p+q is preferably 50 to 450, and particularly preferably 50 to 200. If p+q+r+s+t+u+v is less than the above upper limit, the adhesion and curing properties are good. If it is greater than the above 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 parentheses with p, q, r, s, t, u, and v may be randomly bonded.

[0147] It should be noted that the polymer residue (Rf) containing a fluorooxyalkylene group is a high molecular weight polymer residue having a number average molecular weight of 6,000 to 30,000, preferably 6,000 to 20,000. 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 is calculated by means of F-NMR, etc. When the number average molecular weight of the polymer residue containing a fluorooxyalkylene group is within this range, a low dynamic friction coefficient is obtained on the surface of the cured film despite having hydrolyzable groups at both ends.

[0148] Specifically, as Rf, the following groups can be exemplified.

[0149] [Chemistry 46]

[0150]

[0151] [Chemistry 47]

[0152]

[0153] (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 p, q, r, s, t, and u, and the total of these p', q', r', s', t', and u' is 20 to 450. r2' and r3' are each an integer greater than or equal to 1, and the total of r2' and r3' is 35 to 180. p", q", r2", and r3" are each an integer greater than or equal to 1, and the total of p", q", r2", and r3" is 35 to 450. In addition, each repeating unit shown in the parentheses with p', q', r', s', t', u', p", and q" may be randomly bonded, and the number average molecular weight of the polymer residue is 6,000 to 30,000.)

[0154] In the above formula (1), U is independently a divalent to tetravalent organic group, preferably a divalent to tetravalent unsubstituted or substituted aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, and the divalent to tetravalent unsubstituted or substituted aliphatic saturated hydrocarbon group may contain one or more atoms or groups selected from an arylene group having 6 to 8 carbon atoms, an oxygen atom, a sulfur atom, a silicon atom, a hydroxyl group, a dimethylsilylene or other diorganosilylene group, an imino group, an N-methyl substituted imino group, an N-phenyl substituted imino group or other unsubstituted or substituted secondary amino group, a tertiary amino group, a carbonyl group (ketone structure), an amide group, an ester group, an isocyanurate group, and a triazine ring-containing group.

[0155] U is preferably a divalent or trivalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from the group consisting of an arylene group having 6 to 8 carbon atoms, an oxygen atom, a sulfur atom, a hydroxyl group, a diorganosilylene group, an unsubstituted or substituted secondary amino group, a tertiary amino group, a carbonyl group, an amide group, an ester group, an isocyanuride group, and a triazine ring-containing group, or a tetravalent group having a carbon atom or a silicon atom as a central atom and having an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom, bonded to three or four of the four bonding ends of the central atom.

[0156] 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.

[0157] [Chemistry 48]

[0158]

[0159] [Chemistry 49]

[0160]

[0161] [Chemistry 50]

[0162]

[0163] [Chemistry 51]

[0164]

[0165] [Chemistry 52]

[0166]

[0167] (In the formula, f is independently an integer of 2 to 8, and a and b are independently an integer of 1 to 4.)

[0168] In the above formula (1), Z is independently a linear di- to hexavalent organo(poly)siloxane residue having 2 to 10, preferably 2 to 5, silicon atoms or a branched or cyclic di- to hexavalent organo(poly)siloxane residue having 3 to 10, preferably 3 to 5 silicon atoms, and examples thereof include groups represented by the following formulae.

[0169] [Chemistry 53]

[0170]

[0171] [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 2 R 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. A is a single bond or a group represented by the following general formula (X),

[0172] [Chemistry 54]

[0173]

[0174] (Where R 1 , R 2 As above, g' is an integer of 0 to 6, preferably 0 or 1, g2' is an integer of 0 to 6, preferably 0 or 1, and each repeating unit shown in the brackets may be randomly bonded. The bonding end on the right is bonded to Si. )

[0175] R B For R 1 or a group represented by the following general formula (Y),

[0176] [Chemistry 55]

[0177]

[0178] (Where R 1As above, g3 is an integer of 1 to 6, and the left bonding end is bonded to Si. )

[0179] R B At least one of them is a group represented by formula (Y). g is an integer of 1 to 9, preferably 1 to 4, g2 is an integer of 0 to 9, preferably 0 to 3, h is an integer of 2 to 6, preferably 3 to 5, j is an integer of 0 to 8, preferably 0 or 1, h+j is an integer of 3 to 10, preferably 3 to 5, k is an integer of 1 to 3, and each repeating unit shown in the brackets may be randomly bonded. In each formula, the upper limit of the number of silicon atoms is 10. ]

[0180] Specifically, the following groups are mentioned as Z. It is preferred that the left bonding end is bonded to U, and the other bonding ends are bonded to Y.

[0181] [Chemistry 56]

[0182]

[0183] [Chemistry 57]

[0184]

[0185] [Chemistry 58]

[0186]

[0187] [Chemistry 59]

[0188]

[0189] (In the formula, g is the same as above.)

[0190] In the above formula (1), Y is independently a divalent organic group, preferably an alkylene group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom and an arylene group having 6 to 8 carbon atoms.

[0191] Examples of such Y include the following groups: It is preferred that the left bonding end is bonded to Z and the right bonding end is bonded to a silicon atom.

[0192] [Chemistry 60]

[0193]

[0194] (In the formula, x is an integer of 1 to 20, preferably an integer of 2 to 10, y and z are integers of 1 to 10, preferably an integer of 1 to 5, and y+z is an integer of 2 to 20, preferably an integer of 2 to 10.)

[0195] 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.

[0196] 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.

[0197] n is independently an integer of 1 to 3, preferably 2 or 3, for each bonded silicon atom, m is independently an integer of 1 to 3, and l is independently an integer of 1 to 5, preferably an integer of 1 to 3.

[0198] In addition, in the fluoropolyether group-containing polymer of the present invention, it is preferred that 2 to 48, particularly 2 to 6, silanol groups or hydrolyzable silyl groups are present in one molecule.

[0199] 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 (1) include the following methods.

[0200] A fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both ends of the molecular chain is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and for example, a linear or branched or cyclic di- to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule, an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group (halosilyl group, alkoxysilyl group, etc.) is mixed, and the mixture is aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex. It should be noted that, in the case of an organosilicon compound having a linear or branched or cyclic di- to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms or 3 to 10 silicon atoms in the molecule, and having a SiH group and a silanol group or a hydrolyzable silyl group, when an organosilicon compound having a halogen atom as a hydrolyzable silyl group is used, the substituent (halogen atom) on the silyl group can then be converted into another hydrolyzable group such as an alkoxy group such as a methoxy group.

[0201] Among them, in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), as the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both ends of the molecular chain, a fluoropolyether group-containing polymer represented by the following general formula (4) can be exemplified.

[0202] [Chemistry 61]

[0203]

[0204] (In the formula, Rf and m are the same as above, and U' is independently a single bond or a divalent to tetravalent organic group.)

[0205] In the above formula (4), U' is independently a single bond or a divalent to tetravalent organic group, and the divalent to tetravalent organic group is preferably a divalent to tetravalent aliphatic saturated hydrocarbon group having 1 to 18 carbon atoms and containing one or more atoms or groups selected from an arylene group having 6 to 8 carbon atoms, an oxygen atom, a sulfur atom, a hydroxyl group, a diorganosilylene group such as a dimethylsilylene group, a secondary amino group, a tertiary amino group, a carbonyl group, an amide group, an ester group, an isocyanurate group, a triazine ring-containing group, and a tetravalent group centered on a silicon atom or a carbon atom.

[0206] As U', the following groups can be preferably exemplified: It is preferred that the left bonding end is bonded to Rf, and the other bonding ends are bonded to alkenyl groups.

[0207] [Chemistry 62]

[0208]

[0209] [Chemistry 63]

[0210]

[0211] [Chemistry 64]

[0212]

[0213] [Chemistry 65]

[0214]

[0215] [Chemistry 66]

[0216]

[0217] (In the formula, f is independently an integer of 2 to 8, f' is independently an integer of 0 to 6, and a and b are independently an integer of 1 to 4.)

[0218] Examples of the fluoropolyether group-containing polymer represented by the above formula (4) having an olefin moiety (alkenyl group) at both ends of the molecular chain include the following polymers.

[0219] [Chemistry 67]

[0220] H2C=CHCH2-O-CH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH=CH2

[0221] H2C=CH-O-CH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH=CH2

[0222] H2C=CHCH2CH2-o-CH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-o-CH2CH2CH=CH2

[0223] H2C=CHCH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2CH=CH2

[0224] H2C=CHCH2CH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2CH2CH=CH2

[0225]

[0226] H2C=CHCH2-O-CH2-CF2CF2O-(C3F6O) r1 -CF2CF2-CH2-O-CH2CH=CH2

[0227]

[0228] H2C=CHCH2-O-CH2-CF2CF2CF2OC2F4O-(C4F8OC2F4O) qs1 -CF2CF2CF2CF2O-(C4F8OC2F4O) qs2 -C2F4OCF2CF2CF2-CH2-O-CH2CH=CH2

[0229]

[0230] [Chemistry 68]

[0231]

[0232] [Chemistry 69]

[0233]

[0234] [Chemistry 70]

[0235]

[0236] [Chemistry 71]

[0237]

[0238] [Chemistry 72]

[0239]

[0240] [Chemistry 73]

[0241]

[0242] [Chemistry 74]

[0243]

[0244] [Chemistry 75]

[0245]

[0246] [Chemistry 76]

[0247]

[0248] [Chemistry 77]

[0249]

[0250] [Chemistry 78]

[0251]

[0252] (wherein, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and p1+q1 is an integer of 50 to 450. r1 is an integer of 35 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 35 to 180. p2 is an integer of 1 to 400, q2 is an integer of 1 to 250, r4 is an integer of 1 to 100, r5 is an integer of 1 to 100, and p2+q2+r4+r5 is an integer of 40 to 403. qs1 is an integer of 1 to 85, qs2 is an integer of 1 to 85, qs1+qs2 is an integer of 16 to 86, p3 is an integer of 5 to 440, q3 is an integer of 5 to 250, and p3+q3 is an integer of 50 to 445. The repeating units shown in the brackets with p1 and q1, p2 and q2, and p3 and q3 may be randomly bonded, and the number average molecular weight of the polymer residue containing a fluorooxyalkylene group is 6,000 to 30,000.)

[0253] In the preparation of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), the organic silicon compound having a linear or branched or cyclic di- to hexavalent organic (poly)siloxane residue having 2 to 10 silicon atoms in the molecule, and having a SiH group and a silanol group or a hydrolyzable silyl group is preferably a compound represented by the following general formula (5), (6) or (Z).

[0254] [Chemistry 79]

[0255]

[0256] (In the formula, Y, R, X, n, R 1 , R 2 , R A , g, g2, j, k are the same as above. B’ For R 1 or a group represented by the following general formula (W),

[0257] [Chemistry 80]

[0258]

[0259] (In the formula, Y, R, X, n, R 1 , g3 is the same as above.)

[0260] R B‘ At least one of the groups is a group represented by formula (W). i is an integer of 1 to 5, preferably 2 to 4, and i+j is an integer of 2 to 9, preferably 2 to 4.

[0261] Examples of such organosilicon compounds having a linear or branched or cyclic divalent to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms, 3 to 10 silicon atoms, and having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule include the following organosilicon compounds.

[0262] [Chemistry 81]

[0263]

[0264] [Chemistry 82]

[0265]

[0266] [Chemistry 83]

[0267]

[0268] [Chemistry 84]

[0269]

[0270] [Chemistry 85]

[0271]

[0272] [Chemistry 86]

[0273]

[0274] [Chemistry 87]

[0275]

[0276] [Chemistry 88]

[0277]

[0278] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (1), when the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) at both ends of the molecular chain is reacted with an organosilicon compound having a linear or branched or cyclic di- to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule, a SiH group and a silanol group or a hydrolyzable silyl group, the organosilicon compound can be used in such an amount that the SiH group in the organosilicon compound is 1 to 4 equivalents, more preferably 1 to 2.5 equivalents, and even more preferably about 1.5 equivalents, per 1 equivalent of the olefin moiety (alkenyl group) in the fluoropolyether group-containing polymer.

[0279] It should be noted that, in the case of an organosilicon compound having a linear or branched or cyclic 2-6-valent organo(poly)siloxane residue having 2 to 10 silicon atoms or 3 to 10 silicon atoms in the molecule, and having a SiH group and a silanol group or a hydrolyzable silyl group, when an organosilicon compound having a halogen atom as a hydrolyzable silyl group is used, the substituent (halogen atom) on the silyl group can be converted into another hydrolyzable group such as an alkoxy group such as a methoxy group. Examples of reagents that can be used to convert the substituent (halogen atom) on the silyl group into another hydrolyzable group include alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.

[0280] The amount used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and still more preferably about 65 parts by mass, based on 100 parts by mass of the addition reaction product of a fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both ends of the molecular chain and an organosilicon compound having a linear or branched or cyclic divalent to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule, and having a SiH group and a silanol group or a hydrolyzable silyl group (halosilyl group, alkoxysilyl group, etc.).

[0281] In the preparation of the polymer containing a fluoropolyether group having a silanol group or a hydrolyzable silyl group represented by formula (1), as a solvent, for example, a fluorine-based solvent can be cited. As the fluorine-based solvent, hydrofluoroether (HFE)-based solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name: Novec series), and perfluoro-based solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series) can be cited.

[0282] The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably about 100 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both ends of the molecular chain.

[0283] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), the following catalysts can be cited as the hydrosilylation reaction catalyst. Examples thereof include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0284] The amount of the hydrosilylation reaction catalyst used is 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (mass) relative to the mass of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both ends of the molecular chain.

[0285] As another method (another method) for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1), for example, the following method can be mentioned.

[0286] A fluoropolyether group-containing polymer having a linear or branched or cyclic divalent to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule and SiH groups at both ends of the molecular chain is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having an olefin part (alkenyl group) and a silanol group or a hydrolyzable silyl group (halosilyl group, alkoxysilyl group, etc.) is mixed, and the mixture is aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C., for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex. It should be noted that, in the case of using an organosilicon compound having an olefin portion (alkenyl) and a silanol group or a hydrolyzable silyl group (halosilyl group, alkoxysilyl group, etc.), when using an organosilicon compound having a halogen atom as a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can then be converted into another hydrolyzable group such as an alkoxy group such as a methoxy group.

[0287] Among them, in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) (another method), as the fluoropolyether group-containing polymer having a linear or branched or cyclic 2-6-valent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule and having SiH groups at both ends of the molecular chain, a fluoropolyether group-containing polymer represented by the following general formula (7) can be exemplified.

[0288] [Chemistry 89]

[0289]

[0290] (In the formula, Rf, U, and m are the same as above, and Z' is independently a monovalent organo(poly)siloxane residue having a SiH group and having 2 to 10 silicon atoms in a linear or 3 to 10 silicon atoms in a branched or cyclic state.)

[0291] In the above formula (7), Z' is independently a SiH group-containing, linear, branched or cyclic monovalent organo(poly)siloxane residue having 2 to 10 silicon atoms or 3 to 10 silicon atoms. Examples of the monovalent organo(poly)siloxane residue include groups represented by the following formulae.

[0292] [Chemistry 90]

[0293]

[0294] (Where R 1 , R 2 , g, g2, k, i, j, i+j are the same as above, and each repeating unit shown in the brackets may be randomly bonded. )

[0295] Preferred examples of Z' include the following groups.

[0296] [Chemistry 91]

[0297]

[0298] [Chemistry 92]

[0299]

[0300] (In the formula, g is the same as above.)

[0301] Examples of the fluoropolyether group-containing polymer represented by the above formula (7) having a linear or branched or cyclic di- to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule and having SiH groups at both ends of the molecular chain include the following polymers.

[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] [Chemistry 102]

[0321]

[0322] [Chemistry 103]

[0323]

[0324] [Chemistry 104]

[0325]

[0326] [Chemistry 105]

[0327]

[0328] [Chemistry 106]

[0329]

[0330] [Chemistry 107]

[0331]

[0332] [Chemistry 108]

[0333]

[0334] [Chemistry 109]

[0335]

[0336] [Chemistry 110]

[0337]

[0338] [Chemistry 111]

[0339]

[0340] [Chemistry 112]

[0341]

[0342] [Chemistry 113]

[0343]

[0344] [Chemistry 114]

[0345]

[0346] [Chemistry 115]

[0347]

[0348] [Chemistry 116]

[0349]

[0350] [Chemistry 117]

[0351]

[0352] [Chemistry 118]

[0353]

[0354] (wherein, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and p1+q1 is an integer of 50 to 450. r1 is an integer of 35 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 35 to 180. p2 is an integer of 1 to 400, q2 is an integer of 1 to 250, r4 is an integer of 1 to 100, and r5 is an integer of 1 ~100, p2+q2+r4+r5 is an integer of 40~403. qs1 is an integer of 1~85, qs2 is an integer of 1~85, and qs1+qs2 is an integer of 16~86. The repeating units shown in the brackets with p1 and q1, p2 and q2 may be randomly bonded, and the number average molecular weight of the polymer residue containing fluorooxyalkylene is 6000~30000. )

[0355] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) (another method), the organosilicon compound having an olefin moiety and a silanol group or a hydrolyzable silyl group is preferably a compound represented by the following general formula (8).

[0356] [Chemistry 119]

[0357]

[0358] (In the formula, R, X, and n are the same as above. Y' is independently a single bond or a divalent organic group.)

[0359] In the above formula (8), Y' is independently a single bond or a divalent organic group, and the divalent organic group is preferably an alkylene group having 1 to 18 carbon atoms which may contain one or more atoms or groups selected from oxygen atoms, sulfur atoms and arylene groups having 6 to 8 carbon atoms.

[0360] Examples of such a divalent organic group of Y' include the following groups: It is preferred that the left bonding end is bonded to a carbon atom and the right bonding end is bonded to a silicon atom.

[0361] [Chemistry 120]

[0362]

[0363] (In the formula, x' is an integer of 1 to 18, preferably an integer of 1 to 8, y' is an integer of 0 to 8, preferably an integer of 0 to 3, z is an integer of 1 to 10, preferably an integer of 1 to 5, and y'+z is an integer of 1 to 18, preferably an integer of 1 to 8.)

[0364] Examples of the organosilicon compound having an olefin moiety and a silanol group or a hydrolyzable silyl group include the following organosilicon compounds.

[0365] [Chemistry 121]

[0366] H2C=CH--Si(OCHH3)3

[0367] H2C=CHCH2--Si(OCH3)3

[0368] H2C=CHCH2CH2CH2CH2CH2CH2-Si(OCH3)3

[0369]

[0370] H2C=CHCH2-O-CH2CH2CH2-Si(OCH3)3

[0371] H2C=CH-S-CH2CH2CH2-Si(OCH3)3

[0372] In the preparation of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) (another method), when a fluoropolyether group-containing polymer having a linear or branched or cyclic divalent to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule and SiH groups at both ends of the molecular chain is reacted with an organosilicon compound having an olefin moiety and a silanol group or a hydrolyzable silyl group, the organosilicon compound can be used in such an amount that the olefin moiety in the organosilicon compound is in an amount of 1 to 4 equivalents, more preferably 1 to 2.5 equivalents, and even more preferably about 1.5 equivalents, per 1 equivalent of SiH groups in the fluoropolyether group-containing polymer.

[0373] It should be noted that, in the case of using an organosilicon compound having an olefin portion and a silanol group or a hydrolyzable silyl group, a substituent (halogen atom) on the silyl group can be converted into another hydrolyzable group such as an alkoxy group such as a methoxy group. Examples of reagents that can be used to convert the substituent (halogen atom) on the silyl group into another hydrolyzable group include alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.

[0374] The amount used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably about 65 parts by mass, based on 100 parts by mass of an addition reaction product of a fluoropolyether group-containing polymer having a linear or branched or cyclic divalent to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule and SiH groups at both ends of the molecular chain, and an organosilicon compound having an olefin portion and a silanol group or a hydrolyzable silyl group.

[0375] In the preparation of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) (another method), as a solvent, for example, a fluorine-based solvent can be cited. As the fluorine-based solvent, hydrofluoroether (HFE)-based solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name: Novec series), and perfluoro-based solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series) can be cited.

[0376] The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably about 100 parts by mass, relative to 100 parts by mass of a fluoropolyether group-containing polymer having a linear or branched or cyclic di- to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule and having SiH groups at both ends of the molecular chain.

[0377] In the preparation of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) (another method), the following catalysts can be cited as a catalyst for the hydrosilylation reaction. Examples thereof include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0378] The amount of the hydrosilylation reaction catalyst used is 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal conversion (mass) relative to the mass of the fluoropolyether group-containing polymer having a linear, branched or cyclic, divalent to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in the molecule and SiH groups at both ends of the molecular chain.

[0379] In addition, in the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (1), a method for producing a compound represented by the following formula:

[0380] [Chemistry 122]

[0381]

[0382] (In the formula, p1 and q1 are the same as above.)

[0383] The compound represented by the following formula can be prepared by utilizing the reaction described in

[0038] to

[0044] of Japanese Patent No. 6531833:

[0384] [Chemistry 123]

[0385]

[0386] (In the formula, p1 and q1 are the same as above.)

[0387] The above compound can be obtained by reacting the above compound with the compound shown below in the same manner as above.

[0388] [Chemistry 124]

[0389]

[0390] As the structure of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1), the following structures can be cited. By changing the combination of Rf, U, Z, Y, X, R, n, and m in the above formula (1), various fluoropolyether group-containing polymers having a hydrolyzable silyl group can be obtained. It should be noted that in the following formula, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 50 to 450, r1 is an integer of 35 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, r2+r3 is an integer of 35 to 180, p2 is an integer of 1 to 400, q2 is an integer of 1 to 250, r4 is an integer of 1 to 100, r5 is an integer of 1 to 100, and p2+q2+r4+r5 is an integer of 40 to 403. p3 is an integer of 5 to 440, q3 is an integer of 5 to 250, and p3+q3 is an integer of 50 to 445. qs1 is an integer of 1 to 85, qs2 is an integer of 1 to 85, and qs1+qs2 is an integer of 16 to 86. The repeating units shown in the parentheses with p1 and q1, p2 and q2, and p3 and q3 may be randomly bonded. The number average molecular weight of the polymer residue containing a fluorooxyalkylene group is 6,000 to 30,000.

[0391] [Chemistry 125]

[0392]

[0393] [Chemistry 126]

[0394]

[0395] [Chemistry 127]

[0396]

[0397] [Chemistry 128]

[0398]

[0399] [Chemistry 129]

[0400]

[0401] [Chemistry 130]

[0402]

[0403] [Chemistry 131]

[0404]

[0405] [Chemistry 132]

[0406]

[0407] [Chemistry 133]

[0408]

[0409] [Chemistry 134]

[0410]

[0411] [Chemistry 135]

[0412]

[0413] [Chemistry 136]

[0414]

[0415] [Chemistry 137]

[0416]

[0417] [Chemistry 138]

[0418]

[0419] [Chemistry 139]

[0420]

[0421] [Chemistry 140]

[0422]

[0423] [Chemistry 141]

[0424]

[0425] [Chemistry 142]

[0426]

[0427] [Chemistry 143]

[0428]

[0429] [Chemistry 144]

[0430]

[0431] [Chemistry 145]

[0432]

[0433] [Chemistry 146]

[0434]

[0435] [Chemistry 147]

[0436]

[0437] [Chemistry 148]

[0438]

[0439] [Chemistry 149]

[0440]

[0441] [Chemistry 150]

[0442]

[0443] [Chemistry 151]

[0444]

[0445] [Chemistry 152]

[0446]

[0447] [Chemistry 153]

[0448]

[0449] [Chemistry 154]

[0450]

[0451] [Chemistry 155]

[0452]

[0453] [Chemistry 156]

[0454]

[0455] [Chemistry 157]

[0456]

[0457] [Chemistry 158]

[0458]

[0459] [Chemistry 159]

[0460]

[0461] [Chemistry 160]

[0462]

[0463] [Chemistry 161]

[0464]

[0465] [Chemistry 162]

[0466]

[0467] [Chemistry 163]

[0468]

[0469] [Chemistry 164]

[0470]

[0471] [Chemistry 165]

[0472]

[0473] [Chemistry 166]

[0474]

[0475] [Chemistry 167]

[0476]

[0477] [Chemistry 168]

[0478]

[0479] [Chemistry 169]

[0480]

[0481] [Chemistry 170]

[0482]

[0483] [Chemistry 171]

[0484]

[0485] [Chemistry 172]

[0486]

[0487] [Chemistry 173]

[0488]

[0489] [Chemistry 174]

[0490]

[0491] [Chemistry 175]

[0492]

[0493] For example, as the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both ends of the molecular chain, a compound represented by the following formula is used:

[0494] [Chemistry 176]

[0495] H2C=CHCH2-O-CH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -CF2--CH2-O-CH2CH=CH2

[0496]

[0497] When a silane compound represented by the following formula is used as an organosilicon compound having a linear or branched or cyclic divalent to hexavalent organo(poly)siloxane residue having 2 to 10 silicon atoms in a molecule, and having a SiH group and a silanol group or a hydrolyzable silyl group,

[0498] [Chemistry 177]

[0499]

[0500] A compound represented by the following formula was obtained.

[0501] [Chemistry 178]

[0502]

[0503] The present invention also provides a surface treatment agent, which contains the above-mentioned fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (1) and / or its partial (hydrolysis) condensate as a main component. The surface treatment agent 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, as described above, 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.

[0504] It should be noted that, in the surface treatment agent of the present invention, the phrase “containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (1) and / or a partial (hydrolyzed) condensate thereof as a main component” means that the content of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (1) and / or a partial (hydrolyzed) condensate thereof is 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more, relative to the total mass of the components in the surface treatment agent excluding the solvent.

[0505] The surface treatment agent may contain, in addition to the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (1) and / or its partial (hydrolysis) condensate as a main component, a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following formula (3) and / or its partial (hydrolysis) condensate as necessary.

[0506] The following general formula (3)

[0507] [Chemistry 179]

[0508]

[0509] (In the formula, Rf, U, Z, Y, X, R, n, m, and l are the same as those in the general formula (1), and A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group, or -CH2F group.)

[0510] In the above formula (3), Rf can be exemplified by the same groups as those exemplified in the above formula (1), and these Rf may be the same as or different from Rf in the above formula (1).

[0511] In the above formula (3), A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group. As a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group, specifically, -CF3 group, -CF2CF3 group, -CF2CF2CF3 group, -CH2CF(CF3)-OC3F7 group, -CH2OCF2CFH-OC3F7 group, etc. can be exemplified. As A, a fluorine atom, -CF3 group, -CF2CF3 group are preferred.

[0512] In the above formula (3), U, Z, Y, X, R, n, and m can be exemplified by the same contents as U, Z, Y, X, R, n, and m exemplified in the above formula (1). These U, Z, Y, X, R, n, and m may be the same as or different from U, Z, Y, X, R, n, and m in the above formula (1).

[0513] Examples of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (3) and / or its partial (hydrolysis) condensate include the following.

[0514] [Chemistry 180]

[0515]

[0516] [Chemistry 181]

[0517]

[0518] [Chemistry 182]

[0519]

[0520] [Chemistry 183]

[0521]

[0522] [Chemistry 184]

[0523]

[0524] [Chemistry 185]

[0525]

[0526] [Chemistry 186]

[0527]

[0528] [Chemistry 187]

[0529]

[0530] [Chemistry 188]

[0531]

[0532] [Chemistry 189]

[0533]

[0534] [Chemistry 190]

[0535]

[0536] [Chemistry 191]

[0537]

[0538] [Chemistry 192]

[0539]

[0540] [Chemistry 193]

[0541]

[0542] [Chemistry 194]

[0543]

[0544] [Chemistry 195]

[0545]

[0546] (In the formula, p1, q1, p1+q1, r1, r2, r3, and r2+r3 are the same as those described above. qs3 is an integer of 16 to 86, r6 is an integer of 33 to 180, p4 is an integer of 5 to 440, q4 is an integer of 5 to 250, r7 is an integer of 1 to 175, and p4+q4+r7 is an integer of 30 to 443. The repeating units shown in the parentheses with p1, q1, p4, q4, and r7 may be randomly bonded. In addition, the number average molecular weight of the polymer residue containing a fluorooxyalkylene group is 6,000 to 30,000.)

[0547] The content of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or its partial (hydrolysis) condensate represented by the above formula (3) may be 0 to 100 parts by mass, preferably 0 to 60 parts by mass, and more preferably about 0 to 40 parts by mass, relative to 100 parts by mass of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or its partial (hydrolysis) condensate represented by the general formula (1) as the main component. When the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or its partial (hydrolysis) condensate represented by the above formula (3) is added, the content is preferably 1 part by mass or more, and particularly preferably 5 parts by mass or more, relative to 100 parts by mass of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or its partial (hydrolysis) condensate represented by the general formula (1).

[0548] The surface treatment agent may further contain a fluorine-containing compound (non-functional fluoropolyether polymer) represented by the following formula (9) as necessary, in addition to the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (1) and / or its partial (hydrolysis) condensate, and the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above-mentioned formula (3) and / or its partial (hydrolysis) condensate.

[0549] A-Rf-A(9)

[0550] (In the formula, Rf is the same as above, and A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group.)

[0551] In the above formula (9), Rf can be exemplified by the same groups as those exemplified in the above formula (1), and these Rf may be the same as or different from Rf in the above formula (1).

[0552] In the above formula (9), A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group. As a monovalent fluorine-containing group having a terminal -CF3 group, -CF2H group or -CH2F group, specifically, -CF3 group, -CF2CF3 group, -CF2CF2CF3 group, -CH2CF(CF3)-OC3F7 group, -CH2OCF2CFH-OC3F7 group, etc. can be exemplified. As A, a fluorine atom, -CF3 group, -CF2CF3 group are preferred.

[0553] Examples of the fluorine-containing compound (non-functional fluoropolyether polymer) represented by the formula (9) include the following compounds.

[0554] [Chemistry 196]

[0555]

[0556] (In the formula, p5, q5, and r8 are each independently an integer of 0 to 450, and the total of p5, q5, and r8 is 20 to 450, and r9 and r10 are each an integer of 20 to 450. The repeating units shown in the parentheses with p5, q5, and r8 may be randomly bonded. In addition, the number average molecular weight of the polymer residue containing a fluorooxyalkylene group is 6000 to 30000.)

[0557] The content of the fluorine-containing compound (non-functional fluoropolyether polymer) represented by the above formula (9) can be 0 to 100 parts by mass, preferably 0 to 60 parts by mass, and more preferably about 0 to 40 parts by mass, relative to 100 parts by mass of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (1) as the main component and / or its partial (hydrolysis) condensate.

[0558] 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 zirconium compound (tetra-n-butyl zirconate, 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.

[0559] When a hydrolysis condensation catalyst is added, the amount thereof added is a catalytic amount and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, relative to 100 parts by mass of the total of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) and formula (3) and / or its partial (hydrolysis) condensate.

[0560] The surface treatment agent may contain an appropriate solvent. As such a solvent, 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 perfluoroheptenyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferred from the perspectives of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether, ethyl perfluorobutyl ether, tridecafluorooctane are particularly preferred.

[0561] As for the above-mentioned solvents, two or more thereof may be mixed, preferably so that the polymer containing a fluoropolyether group and its partial (hydrolysis) condensate (the polymer containing a fluoropolyether group having a silanol group or a hydrolyzable silyl group and its partial (hydrolysis) condensate represented by the above formula (1) and its partial (hydrolysis) condensate, the polymer containing a fluoropolyether group having a silanol group or a hydrolyzable silyl group and its partial (hydrolysis) condensate represented by the above formula (3) and the fluorine-containing compound (non-functional fluoropolyether polymer) represented by the above formula (9), the same below) is uniformly dissolved. It should be noted that the optimal concentration of the fluoropolyether group-containing polymer and its partial (hydrolysis) condensate dissolved in the solvent varies depending on the treatment method, and any amount that can be easily weighed may be used. However, 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 fluoropolyether group-containing polymer 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 50 parts by mass, relative to 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer and its partial (hydrolysis) condensate.

[0562] The surface treatment agent of the present invention can be applied to the substrate by known methods such as brushing, 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 (brushing, 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 18 hours. In addition, in the case of applying by evaporation treatment, the range of 20 to 200°C is preferred. In addition, it can be cured under humidification. The film thickness of the cured film is appropriately selected according to the type of substrate, usually 0.1 to 100 nm, especially 1 to 20 nm. In addition, for example, in terms of spraying, if it is diluted in a fluorine-based solvent to which water has been added in advance, hydrolyzed, that is, sprayed after generating Si-OH, the curing after coating is fast.

[0563] 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.

[0564] The substrate to be processed with the surface treatment agent of the present invention is not particularly limited, and can be a substrate of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc. The surface treatment agent of the present invention can impart water and oil repellency to the above-mentioned substrate. Especially, it can be suitable for use as the surface treatment agent of glass and film processed through SiO2.

[0565] As articles processed with the surface treatment agent of the present invention, medical instruments 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 above-mentioned articles, and then imparts 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.

[0566] In addition, the surface treatment agent of the present invention can also be used as an antifouling paint for sanitary products such as bathtubs and washbasins, an antifouling paint for window glass or tempered glass of automobiles, trains, airplanes, etc., an antifouling paint for headlight covers, etc., a water-repellent and oil-repellent paint for exterior building materials, an anti-oil paint for kitchen building materials, an antifouling and anti-sticker for telephone booths, a graffiti paint, a paint that prevents fingerprint adhesion for artworks, etc., an anti-fingerprint adhesion paint for CDs, DVDs, etc., a mold release agent or paint additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, and a lubricity enhancer for tapes, films, etc.

[0567] In particular, the surface treatment agent of the present invention can provide a cured film having water- and oil-repellency, excellent abrasion resistance, and excellent gripping properties to a lens substrate.

[0568] 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, it is judged by the strength of the adhesion (tensile shear adhesion strength) between the lens blocking tape and the lens when the lens is fixed with a lens blocking tape for grinding processing. The situation where the substrate can be firmly fixed to the extent that it can be processed with good precision by the adhesion of the adhesive tape to the substrate is called good clamping property.

[0569] Example

[0570] The present invention is described in more detail below with reference to synthesis examples, embodiments and comparative examples, but the present invention is not limited to the following examples. 19 The number average value calculated by F-NMR. In the following formula, the repeating units shown in the brackets with p1 and q1, p1 and q1 and r1, p2 and q2, p3 and q3 are randomly bonded. Furthermore, the film thickness is a value measured by ellipsometry using a spectroscopic ellipsometer.

[0571] [Synthesis example 1]

[0572] In a reaction vessel, the following formula (1A)

[0573] [Chemistry 197]

[0574]

[0575] The compound represented by 100g (1.55×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, the following formula (1B):

[0576] [Chemistry 198]

[0577]

[0578] The organosilicon compound represented was 13.1 g (4.64 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 5.92×10 -2 g (calculated as Pt single substance, containing 1.83×10 -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 100 g of a liquid product.

[0579] use1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (1C).

[0580] [Chemistry 199]

[0581]

[0582] [Synthesis example 2]

[0583] In a reaction vessel, the following formula (2A)

[0584] [Chemistry 200]

[0585]

[0586] The compound represented by 100g (1.55×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, the following formula (2B)

[0587] [Chemistry 201]

[0588]

[0589] The organosilicon compound represented was 16.5 g (4.64 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 5.92×10 -2 g (calculated as Pt single substance, containing 1.83×10 -7 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were removed by vacuum distillation and washed to obtain 96 g of a liquid product.

[0590] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (2C).

[0591] [Chemistry 202]

[0592]

[0593] [Synthesis example 3]

[0594] In a reaction vessel, the following formula (3A)

[0595] [Chemistry 203]

[0596] H2C=CHCH2-O-CH2-CF2-O-(CF2O) p1 -(C2F4O) q1 -(C3F6O) r1 -CF2-CH2-O--CH2CH=CH2

[0597]

[0598] The compound represented by 50g (6.15×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 50g, by the following formula (3B)

[0599] [Chemistry 204]

[0600]

[0601] The organosilicon compound represented was 6.74 g (1.84 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 2.35×10 -2 g (calculated as Pt single substance, containing 7.26×10 -8 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 49.7 g of a liquid product.

[0602] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (3C).

[0603] [Chemistry 205]

[0604]

[0605] [Synthesis Example 4]

[0606] In a reaction vessel, the following formula (4A)

[0607] [Chemistry 206]

[0608]

[0609] The compound represented by 50g (3.61×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 50g, by the following formula (4B)

[0610] [Chemistry 207]

[0611]

[0612] The organosilicon compound represented was 3.19 g (1.08 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.21×10 -2 g (based on Pt single substance, containing 3.73×10 -8 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 51.0 g of a liquid product.

[0613] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (4C).

[0614] [Chemistry 208]

[0615]

[0616] [Synthesis example 5]

[0617] In a reaction vessel, the following formula (5A)

[0618] [Chemistry 209]

[0619]

[0620] The compound represented by 100g (1.10×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, by the following formula (5B):

[0621] [Chemistry 210]

[0622]

[0623] The organosilicon compound represented was 13.4 g (3.30 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.20×10 -2 g (calculated as Pt single substance, containing 1.30×10 -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.

[0624] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (5C).

[0625] [Chemistry 211]

[0626]

[0627] [Synthesis example 6]

[0628] In a reaction vessel, the following formula (6A)

[0629] [Chemistry 212]

[0630]

[0631] The compound represented by 100g (5.94×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 100g, the following formula (6B)

[0632] [Chemistry 213]

[0633]

[0634] The organosilicon compound represented was 6.52 g (1.78 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 2.27×10 -2 g (calculated as Pt single substance, containing 7.01×10 -8 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.

[0635] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (6C).

[0636] [Chemistry 214]

[0637]

[0638] [Synthesis Example 7]

[0639] In a reaction vessel, the following formula (7A)

[0640] [Chemistry 215]

[0641]

[0642] The compound represented by 50g (6.38×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 50g, by the following formula (7B)

[0643] [Chemistry 216]

[0644]

[0645] The organosilicon compound represented was 11.3 g (3.83 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 2.44×10 -2 g (calculated as Pt single substance, containing 7.53×10 -8 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were removed by vacuum distillation and washed to obtain 53 g of a liquid product.

[0646] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (7C).

[0647] [Chemistry 217]

[0648]

[0649] [Synthesis example 8]

[0650] In a reaction vessel, the following formula (8A)

[0651] [Chemistry 218]

[0652]

[0653] The compound represented by 100g (1.10×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, and the following formula (8B):

[0654] [Chemistry 219]

[0655]

[0656] The organosilicon compound represented was 18.6 g (6.59 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.20×10 -2 g (calculated as Pt single substance, containing 1.30×10 -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 110 g of a liquid product.

[0657] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (8C).

[0658] [Chemistry 220]

[0659]

[0660] [Synthesis Example 9]

[0661] In a reaction vessel, the following formula (9A)

[0662] [Chemistry 221]

[0663]

[0664] The compound represented by 100g (1.41×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, the following formula (9B)

[0665] [Chemistry 222]

[0666]

[0667] The organosilicon compound represented was 21.8 g (4.23 × 10-2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 5.39×10 -2 g (calculated as Pt single substance, containing 1.66×10 -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 115 g of a liquid product.

[0668] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (9C).

[0669] [Chemistry 223]

[0670]

[0671] [Synthesis Example 10]

[0672] In a reaction vessel, the following formula (10A)

[0673] [Chemistry 224]

[0674]

[0675] The compound represented by 100g (5.99×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 100g, by the following formula (10B):

[0676] [Chemistry 225]

[0677]

[0678] The organosilicon compound represented was 5.33 g (1.80 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 2.29×10 -2 g (calculated as Pt single substance, containing 7.07×10 -8 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.

[0679] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (10C).

[0680] [Chemistry 226]

[0681]

[0682] [Synthesis Example 11]

[0683] In a reaction vessel, the following formula (11A)

[0684] [Chemistry 227]

[0685]

[0686] The compound represented by 100g (1.01×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, the following formula (11B):

[0687] [Chemistry 228]

[0688]

[0689] The organosilicon compound represented was 22.3 g (6.08 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 3.86×10 -2 g (based on Pt single substance, containing 1.19×10 -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 113 g of a liquid product.

[0690] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (11C).

[0691] [Chemistry 229]

[0692]

[0693] [Synthesis Example 12]

[0694] In a reaction vessel, the following formula (12A)

[0695] [Chemistry 230]

[0696]

[0697] The compound represented by 50g (4.04×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 50g, the following formula (12B)

[0698] [Chemistry 231]

[0699]

[0700] The organosilicon compound represented was 8.99 g (2.43 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.54×10 -2 g (based on Pt single substance, containing 4.77×10 -8mol) 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 50 g of a liquid product.

[0701] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (12C).

[0702] [Chemistry 232]

[0703]

[0704] [Synthesis Example 13]

[0705] In a reaction vessel, the following formula (13A)

[0706] [Chemistry 233]

[0707]

[0708] The compound represented by 100g (1.28×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, and the following formula (13B):

[0709] [Chemistry 234]

[0710]

[0711] The organosilicon compound represented was 10.8 g (3.84 × 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 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 102 g of a liquid product.

[0712] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (13C).

[0713] [Chemistry 235]

[0714]

[0715] [Synthesis Example 14]

[0716] In a reaction vessel, the following formula (14A)

[0717] [Chemistry 236]

[0718]

[0719] The compound represented by 100g (1.42×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, and the following formula (14B):

[0720] [Chemistry 237]

[0721]

[0722] The organosilicon compound represented by 15.1 g (4.25 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 5.42×10 -2 g (calculated as Pt single substance, containing 1.68×10 -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 106 g of a liquid product.

[0723] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (14C).

[0724] [Chemistry 238]

[0725]

[0726] [Synthesis Example 15]

[0727] In a reaction vessel, the following formula (15A)

[0728] [Chemistry 239]

[0729]

[0730] The compound represented by 70g (7.14×10 -3 mol), 70 g of 1,3-bis(trifluoromethyl)benzene, and the following formula (15B):

[0731] [Chemistry 240]

[0732]

[0733] The organosilicon compound represented was 12.6 g (4.28 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 2.73×10 -2 g (based on Pt single substance, containing 8.43×10 -8 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure and washed to obtain 78 g of a liquid product.

[0734] use 1H-NMR confirmed that the obtained compound had a structure represented by the following formula (15C).

[0735] [Chemistry 241]

[0736]

[0737] [Synthesis Example 16]

[0738] In a reaction vessel, the following formula (16A)

[0739] [Chemistry 242]

[0740]

[0741] The compound represented by 100g (1.23×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, and the following formula (16B):

[0742] [Chemistry 243]

[0743]

[0744] The organosilicon compound represented was 21.9 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 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure and washed to obtain 110 g of a liquid product.

[0745] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (16C).

[0746] [Chemistry 244]

[0747]

[0748] [Synthesis Example 17]

[0749] In a reaction vessel, the following formula (17A)

[0750]

[0751] The compound represented by 100g (1.44×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, and the following formula (17B):

[0752] [Chemistry 246]

[0753] H2C=CHCH2—si(OCH3)3 (17B)

[0754] The organosilicon compound represented by 21.0 g (1.30 × 10 -1 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 5.49×10 -2 g (calculated as Pt single substance, containing 1.70×10 -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 101 g of a liquid product.

[0755] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (17C).

[0756] [Chemistry 247]

[0757]

[0758] [Synthesis Example 18]

[0759] In a reaction vessel, the following formula (18A)

[0760] [Chemistry 248]

[0761]

[0762] The compound represented by 30g (1.76×10 -3 mol), 30 g of 1,3-bis(trifluoromethyl)benzene, and the following formula (18B):

[0763] [Chemistry 249]

[0764] H2C=CH—Si(OCH3)3 (18B)

[0765] The organosilicon compound represented was 2.35 g (1.58 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 6.70×10 -3 g (calculated as Pt single substance, containing 2.07×10 -8 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 30 g of a liquid product.

[0766] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (18C).

[0767] [Chemistry 250]

[0768]

[0769] [Synthesis Example 19]

[0770] In a reaction vessel, the following formula (19A)

[0771] [Chemistry 251]

[0772]

[0773] The compound represented by 50g (7.57×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 50g, the following formula (19B)

[0774] [Chemistry 252]

[0775]

[0776] The organosilicon compound represented was 13.5 g (4.54 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 2.89×10 -2 g (based on Pt single substance, containing 8.94×10 -8 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure and washed to obtain 48 g of a liquid product.

[0777] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (19C).

[0778] [Chemistry 253]

[0779]

[0780] [Synthesis Example 20]

[0781] In a reaction vessel, the following formula (20A)

[0782] [Chemistry 254]

[0783]

[0784] The compound represented by 100g (1.52×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100g, and the following formula (20B):

[0785] [Chemistry 255]

[0786]

[0787] The organosilicon compound represented by 33.4 g (9.12 × 10 -2mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 5.82×10 -2 g (calculated as Pt single substance, containing 1.80×10 -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 120 g of a liquid product.

[0788] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (20C).

[0789] [Chemistry 256]

[0790]

[0791] [Synthesis Example 21]

[0792] In a reaction vessel, the following formula (21A)

[0793] [Chemistry 257]

[0794]

[0795] The compound represented by 80g (1.01×10 -2 mol), 80 g of 1,3-bis(trifluoromethyl)benzene, and the following formula (21B):

[0796] [Chemistry 258]

[0797]

[0798] The organosilicon compound represented by 25.6 g (9.09 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 3.87×10 -2 g (calculated as Pt single substance, containing 1.20×10 -7 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were removed by vacuum distillation and washed to obtain 90 g of a liquid product.

[0799] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (21C).

[0800] [Chemistry 259]

[0801]

[0802] [Synthesis Example 22]

[0803] In a reaction vessel, the following formula (22A)

[0804] [Chemistry 260]

[0805]

[0806] The compound represented by 50g (7.37×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 100g, and the following formula (22B):

[0807] [Chemistry 261]

[0808]

[0809] The organosilicon compound represented was 25.6 g (6.63 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 2.81×10 -2 g (based on Pt single substance, containing 8.70×10 -8 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 63 g of a liquid product.

[0810] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (22C).

[0811] [Chemistry 262]

[0812]

[0813] [Synthesis Example 23]

[0814] In a reaction vessel, the following formula (23A)

[0815] [Chemistry 263]

[0816]

[0817] The compound represented by 50g (6.27×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 100g, by the following formula (23B)

[0818] [Chemistry 264]

[0819]

[0820] The organosilicon compound represented was 16.7 g (5.64 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.40×10 -2 g (calculated as Pt single substance, containing 7.41×10 -8mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were removed by vacuum distillation and washed to obtain 57 g of a liquid product.

[0821] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (23C).

[0822] [Chemistry 265]

[0823]

[0824] [Synthesis example 24]

[0825] In a reaction vessel, the following formula (24A)

[0826] [Chemistry 266]

[0827] H2C=CHCH2-O-CH2-CF2CF2-O-(C3F6O) 40 -CF2CF2-CH2-O-CH2CH=CH2 (24A)

[0828] The compound represented by 50g (7.14×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 50g, the following formula (24B)

[0829] [Chemistry 267]

[0830]

[0831] The organosilicon compound represented was 6.04 g (2.14 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 2.73×10 -2 g (based on Pt single substance, containing 8.43×10 -8 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were removed under reduced pressure and washed to obtain 48 g of a liquid product.

[0832] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (24C).

[0833] [Chemistry 268]

[0834]

[0835] [Synthesis Example 25]

[0836] In a reaction vessel, the following formula (25A)

[0837] [Chemistry 269]

[0838]

[0839] The compound represented by 50g (5.62×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 50g, by the following formula (25B)

[0840] [Chemistry 270]

[0841]

[0842] The organosilicon compound represented by 5.00 g (1.69 × 10 -2 mol), and toluene solution of chloroplatinic acid / vinylsiloxane complex 2.15×10 -2 g (calculated as Pt single substance, containing 6.60×10 -8 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 47 g of a liquid product.

[0843] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (25C).

[0844] [Chemistry 271]

[0845]

[0846] [Example 1]

[0847] 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 to prepare a surface treatment agent.

[0848] [Example 2]

[0849] 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 to prepare a surface treatment agent.

[0850] [Example 3]

[0851] The compound obtained in Synthesis Example 3 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0852] [Example 4]

[0853] The compound obtained in Synthesis Example 4 was dissolved in Asahiklin AC-6000 (manufactured by AGC Corporation, tridecafluorooctane) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0854] [Example 5]

[0855] The compound obtained in Synthesis Example 6 was dissolved in Asahiklin AC-6000 (manufactured by AGC Corporation, tridecafluorooctane) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0856] [Example 6]

[0857] The compound obtained in Synthesis Example 7 was dissolved in Opteon SF10 (manufactured by Chemours-Mitsui Fluoroproducts, methyl perfluoroheptenyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0858] [Example 7]

[0859] The compound obtained in Synthesis Example 8 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0860] [Example 8]

[0861] The compound obtained in Synthesis Example 10 was dissolved in Opteon SF10 (manufactured by Chemours-Mitsui Fluoroproducts, methyl perfluoroheptenyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0862] [Example 9]

[0863] The compound obtained in Synthesis Example 11 was dissolved in Opteon SF10 (manufactured by Chemours-Mitsui Fluoroproducts, methyl perfluoroheptenyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0864] [Example 10]

[0865] The compound obtained in Synthesis Example 13 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0866] [Example 11]

[0867] 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 to prepare a surface treatment agent.

[0868] [Example 12]

[0869] The compound obtained in Synthesis Example 16 was dissolved in Novec 7300 (manufactured by 3M Co., Ltd., methyl perfluorohexyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0870] [Example 13]

[0871] The compound obtained in Synthesis Example 17 was dissolved in Novec 7300 (manufactured by 3M Co., Ltd., methyl perfluorohexyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0872] [Example 14]

[0873] The compound obtained in Synthesis Example 19 was dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0874] [Example 15]

[0875] The compound obtained in Synthesis Example 20 was dissolved in Asahiklin AE-3000 (manufactured by AGC Corporation, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0876] [Example 16]

[0877] The compound obtained in Synthesis Example 21 was dissolved in Opteon SF10 (manufactured by Chemours-Mitsui Fluoroproducts, methyl perfluoroheptenyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0878] [Example 17]

[0879] The compound obtained in Synthesis Example 23 was dissolved in Novec 7300 (manufactured by 3M Co., Ltd., methyl perfluorohexyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0880] [Example 18]

[0881] The compound obtained in Synthesis Example 24 was dissolved in Novec 7300 (manufactured by 3M Co., Ltd., methyl perfluorohexyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0882] [Example 19]

[0883] The compound obtained in Synthesis Example 25 was dissolved in Opteon SF10 (manufactured by Chemours-Mitsui Fluoroproducts, methyl perfluoroheptenyl ether) so as to have a concentration of 20% by mass to prepare a surface treatment agent.

[0884] [Example 20]

[0885] The compound obtained in Synthesis Example 1 was mixed with the following formula (D)

[0886] [Chemistry 272]

[0887]

[0888] The compound represented by formula (D) was mixed with the compound obtained in Synthesis Example 1 at a ratio of 95:5 and dissolved in Novec 7200 (3M Co., Ltd., ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0889] [Comparative Example 1]

[0890] By the following formula (E)

[0891] [Chemistry 273]

[0892]

[0893] The compounds shown were dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0894] [Comparative Example 2]

[0895] By the following formula (F)

[0896] [Chemistry 274]

[0897] (H3CO)3Si-CH2CH2CH2-O-CH2-CF2O-(CF2O) p1 -(c2F4O) q1 -CF2-CH2-O-cH2CH2CH2-Si(OCH3)3

[0898]

[0899] The compounds shown were dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0900] [Comparative Example 3]

[0901] By the following formula (G)

[0902] C6F 13 -Si(OCH3)3 (G)

[0903] The compounds shown were dissolved in Novec 7200 (manufactured by 3M Co., Ltd., ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0904] Preparation of surface treatment agent and formation of cured film

[0905] The surface treatment agents were prepared as in the above-mentioned Examples and Comparative Examples. 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.

[0906] Evaluation of water repellency

[0907] 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.

[0908] In the initial stage, both Examples and Comparative Examples showed good water repellency.

[0909] Evaluation of gripping properties (1) Dynamic friction measurement on microfiber cloth

[0910] The dynamic friction coefficient of the lens with the cured film formed thereon was measured with BEMCOT (manufactured by Asahi Kasei Corporation) under the following conditions using a surface property tester 14FW (manufactured by Shinto Scientific Co., Ltd.).

[0911] Contact area: 10mm×30mm

[0912] Load: 100gf

[0913] Evaluation of clamping properties (2) Measurement of tape shear adhesive strength

[0914] The lens barrier tape (manufactured by 3M: LEAP III1695M) was attached to the lens with the cured film formed thereon, and the tensile shear bonding strength was measured. Specifically, the lens with the cured film formed thereon and the lens barrier tape attached thereto were stretched so that shear stress acted on the bonding surface, and the maximum strength (tensile shear bonding strength) when the bonding joint was broken was measured and evaluated according to the following standards. The results are shown in Table 1.

[0915] [Tensile shear bond strength measurement]

[0916] Bonding area: 2.7cm 2

[0917] Stretching speed: 50mm / min

[0918] [Evaluation criteria for shear bond strength]

[0919] ×: Less than 30N

[0920] △: 30N or more and less than 40N

[0921] 0:40N or more and less than 50N

[0922] ◎: 50N or more and less than 60N

[0923] Evaluation of wear resistance

[0924] For the lens formed with the cured film produced above, the contact angle (water repellency) of the cured film 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 wear resistance. The test environment conditions were 25° C. and a relative humidity of 40%. In addition, the reduction rate from the initial water contact angle was calculated, and these results (water contact angle after paper abrasion, water contact angle reduction rate) are shown in Table 1.

[0925] [Determination of paper abrasion resistance]

[0926] Paper: Dusper (manufactured by Ozu Sangyo Co., Ltd.)

[0927] Contact area: 1cm 2

[0928] Moving distance (one way): 40mm

[0929] Moving speed: 4800mm / min

[0930] Load: 1kgf / 1cm 2

[0931] Wear times: 10000 times

[0932] Examples 1 to 20 show the results of improving substrate adhesion and showing high paper wear durability by using a compound (fluoropolyether group-containing polymer of the present invention) having a high molecular weight and a siloxane structure (siloxane bond) in the connecting group. In addition, it can be confirmed that the tensile shear bonding strength is high by having functional groups at both ends. The dynamic friction coefficient of Comparative Example 1 is low and the tensile shear bonding strength is low. Although the tensile shear bonding strength of Comparative Example 2 is high, the paper wear durability is low. In addition, as for Comparative Example 3, the result is that the paper wear resistance is also low. As described above, in the embodiments using the fluoropolyether group-containing polymer of the present invention, it is possible to have both paper wear durability and clamping properties at a high level.

[0933] [Table 1]

[0934]

Claims

1. A fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group, which is represented by the following general formula (1): [Chemistry 1] In the formula, Rf is a divalent fluorooxyalkylene-containing polymer residue represented by the following general formula (2): [Chemistry 2] In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 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 6,000 to 30,000. U is independently a 2-4 valent organic group, Z is independently a 2-6 valent straight-chain organic (poly)siloxane residue having 2-10 silicon atoms or a branched or cyclic 3-10 silicon atoms, Y is independently a divalent organic group, R is independently an alkyl group having 1-4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1-3 for each bonded silicon atom, m is independently an integer of 1-3, and l is independently an integer of 1-5.

2. The fluoropolyether group-containing polymer according to claim 1, in, In the formula (1), U is a divalent or trivalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from the group consisting of an arylene group having 6 to 8 carbon atoms, an oxygen atom, a sulfur atom, a hydroxyl group, a diorganosilylene group, an unsubstituted or substituted secondary amino group, a tertiary amino group, a carbonyl group, an amide group, an ester group, an isocyanuride group, and a triazine ring-containing group, or is a tetravalent group having a carbon atom or a silicon atom as a central atom, and to three or four of the four bonding ends of the central atom are bonded an aliphatic saturated 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, an unsubstituted or substituted secondary amino group, a carbonyl group, and an amide group, or an oxygen atom.

3. The fluoropolyether group-containing polymer according to claim 1, in, In the above formula (1), Y is an alkylene group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom, and an arylene group having 6 to 8 carbon atoms.

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

5. The fluoropolyether group-containing polymer according to claim 1, in, The polymer represented by formula (1) is represented by any of the following formulae, [Chemistry 3] [Chemistry 4] [Chemistry 5] [Chemistry 6] [Chemistry 7] [Chemistry 8] [Chemistry 9] [Chemistry 10] [Chemistry 11] [Chemistry 12] [Chemistry 13] [Chemistry 14] [Chemistry 15] [Chemistry 16] [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] [Chemistry 32] [Chemistry 33] [Chemistry 34] [Chemistry 35] [Chemistry 36] [Chemistry 37] [Chemistry 38] [Chemistry 39] [Chemistry 40] [Chemistry 41] In the formula, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 50 to 450, r1 is an integer of 35 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, r2+r3 is an integer of 35 to 180, p2 is an integer of 1 to 400, q2 is an integer of 1 to 250, r4 is an integer of 1 to 100, r5 is an integer of 1 to 100, p2+q2+r4+r5 is an integer of 40 to 403, p3 is an integer of 5 to 440, q3 is an integer of 5 to 250, p3+q3 is an integer of 50 to 445, qs1 is an integer of 1 to 85, qs2 is an integer of 1 to 85, qs 1+qs2 is an integer of 16 to 86, the repeating units represented by the parentheses p1 and q1, p2 and q2, p3 and q3 may be randomly bonded, and the number average molecular weight of the polymer residue containing a fluorooxyalkylene group is 6,000 to 30,000.

6. A surface treatment agent comprising the fluoropolyether group-containing polymer according to any one of claims 1 to 5 and / or its partial (hydrolysis) condensate as a main component.

7. The surface treatment agent according to claim 6, further comprising a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (3) and / or a partial (hydrolyzed) condensate thereof, [Chemistry 42] In the formula, A is independently a fluorine atom, a hydrogen atom, or a terminal -CF 3 Base, -CF 2 H group or -CH 2 The F group is a monovalent fluorine-containing group, and Rf is a divalent fluorooxyalkylene-containing polymer residue represented by the following general formula (2). [Chemistry 43] In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 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 6,000 to 30,000. U is independently a 2-4 valent organic group, Z is independently a 2-6 valent straight-chain organic (poly)siloxane residue having 2-10 silicon atoms or a branched or cyclic 3-10 silicon atoms, Y is independently a divalent organic group, R is independently an alkyl group having 1-4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1-3 for each bonded silicon atom, m is independently an integer of 1-3, and l is independently an integer of 1-5.

8. An article surface-treated with the surface treating agent according to claim 6.

9. The article of claim 8 which is a lens.

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