Fluoropolyether group-containing polymer, surface treatment agent and article

Abstract

According to the present invention, a cured coating having exceptional water and oil repellency and abrasion resistance as well as exceptional chucking properties can be formed by using a fluoropolyether-group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) (Rf is a divalent fluoroxyalkylene-group-containing polymer residue, U is a divalent or trivalent organic group, Z is a silalkylene structure or a silarylene structure, Y is a divalent organic group, R is a C1-4 alkyl group or a phenyl group, X is a hydroxyl group or a hydrolyzable group, n is 1-3, and m is 1 or 2) as a surface treatment agent including said polymer and / or a partial (hydrolyzed) condensate thereof.

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 particularly to a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group that can form a coating film with excellent water and oil repellency and abrasion resistance, a surface treatment agent containing the polymer and / or a partial (hydrolyzed) condensate thereof, and an article surface-treated with the surface treatment agent. [Background technology]

[0002] In general, fluoropolyether group-containing compounds have very low surface free energy and therefore possess properties such as water and oil repellency, chemical resistance, lubricity, mold release properties, and stain resistance. These properties have led to a wide range of industrial applications, including water, oil, and stain repellency agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, mold release agents, cosmetics, and protective films. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and while they can be applied to the surface of a substrate, it has been difficult to form a coating that adheres to it.

[0003] Silane coupling agents are well known as agents for bonding organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as coating agents for various substrate surfaces. Silane coupling agents contain an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in each molecule. The hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating. The hydrolyzable silyl group chemically and physically bonds with the surface of various substrates, resulting in a durable, strong coating.

[0004] Therefore, compositions have been disclosed that use fluoropolyether group-containing polymers in which a hydrolyzable silyl group has been introduced at one end of a fluoropolyether group-containing compound, which can form coatings that easily adhere to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, etc. on the substrate surfaces (Patent Documents 1 to 4: JP 2012-072272 A, JP 2012-157856 A, JP 2013-136833 A, JP 2015-199906 A).

[0005] Lenses and substrates containing cured coatings such as anti-reflection films that have been surface-treated with a composition containing a fluoropolyether group-containing polymer in which a hydrolyzable silyl group has been introduced into the fluoropolyether group-containing compound have excellent slip properties and releasability, but when the substrate is fixed and processed, the slip properties affect the ability to fix the substrate (poor chucking), which causes the substrate to slip during processing, making it difficult to process it into the required shape.

[0006] Furthermore, although the above-mentioned problem of substrate fixation can be solved by using a fluoropolyether group-containing polymer in which hydrolyzable silyl groups are introduced at both ends of a fluoropolyether group-containing compound, it does not exhibit sufficient performance in terms of wear resistance. In addition to the above-mentioned documents, the following documents can be cited as prior art related to the present invention. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-072272 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-157856 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-136833 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-199906 [Patent Document 5] Japanese Patent Application Laid-Open No. 2003-238577 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above circumstances, and aims to provide a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group, which is capable of forming a cured coating film that has excellent water and oil repellency, abrasion resistance, and anti-chucking properties; a surface treatment agent containing the polymer and / or a partial (hydrolyzed) condensate thereof; and an article that has been surface-treated with the surface treatment agent. [Means for solving the problem]

[0009] As a result of intensive research conducted by the present inventors to achieve the above object, they have found that by using a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group, which is represented by the general formula (1) described below, in the above fluoropolyether group-containing polymer, a surface treatment agent containing the polymer and / or a partial (hydrolyzed) condensate thereof can form a cured coating that is excellent in water and oil repellency, abrasion resistance, and anti-chucking properties, and have thus completed the present invention.

[0010] Accordingly, the present invention provides the following fluoropolyether group-containing polymer, surface treatment agent, and article. [1] The following general formula (1) [ka] [wherein Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2)] [ka] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 3 for each unit. p, q, r, s, t, u, and v are each an integer of 0 to 450, such that p+q+r+s+t+u+v=20 to 450, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly, and the number average molecular weight of the polymer residue is 6,000 to 30,000.) U independently represents a trivalent group consisting of an arylene group having 6 to 8 carbon atoms, an oxygen atom, a sulfur atom, a diorganosilylene group, a tertiary amino group which may contain one or more atoms or groups selected from a secondary amino group, a carbonyl group, and an ester group, an amido group, an isocyanuric group, or a triazine ring-containing group, and a divalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms; Z independently represents a silalkylene structure or a silarylene structure; Y independently represents an oxygen atom, a sulfur atom, and an arylene group having 6 to 8 carbon atoms. R is independently an alkyl group having 1 to 20 carbon atoms, which may contain one or more atoms or groups selected from the group consisting of alkylene groups having 1 to 20 carbon atoms, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom, n is independently an integer of 1 to 3 for each silicon atom to which it is bonded, and m is 2. The fluoropolyether group-containing polymer has a silanol group or a hydrolyzable silyl group represented by the formula: [2] The fluoropolyether group-containing polymer according to [1], wherein, in the formula (2), 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, v is an integer of 0 to 100, p+q+r+s+t+u+v is 50 to 450, and p+q is 50 to 450. [ 3 〕 The fluoropolyether group-containing polymer according to [1], wherein in the formula (2), Rf is represented by the following formula: [ka] (In the formula, r2' and r3' are each an integer of 1 or more, and the sum of r2' and r3' is 35 to 180. The number average molecular weight of the polymer residue is 6,000 to 30,000.) [ 4 〕 The fluoropolyether group-containing polymer according to [1], wherein U in the formula (1) is represented by any one of the following formulae: [ka] [ka] (In the formula, f is independently an integer of 2 to 4, and a is an integer of 1 to 4.) [ 5 〕 The fluoropolyether group-containing polymer according to [1], wherein the polymer represented by formula (1) is represented by any one of the following formulas: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, 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. 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 parentheses with p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly.) [ 6 〕 [1] ~ [ 5 10. A surface treatment agent comprising, as a main component, the fluoropolyether group-containing polymer according to any one of claims 1 to 9 and / or a partial (hydrolyzed) condensate thereof. [ 7 〕 [ 6 ] An article surface-treated with the surface treatment agent according to the present invention. [ 8 〕 The lens substrate is 7 ] The article described in [ 9 〕 The following general formula (1) [ka] [wherein Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2)] [ka] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 3 for each unit. p, q, r, s, t, u, and v are each an integer of 0 to 450, such that p+q+r+s+t+u+v=20 to 450, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly, and the number average molecular weight of the polymer residue is 6,000 to 30,000.) U independently represents a divalent 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, a secondary amino group, a carbonyl group, and an ester group; Z independently represents a silalkylene structure or a silarylene structure; Y independently represents one or more atoms selected from an oxygen atom, a sulfur atom, and an arylene group having 6 to 8 carbon atoms. R is independently an alkyl group having 1 to 20 carbon atoms, which may contain a group or a group; R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group; X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; n is independently an integer of 1 to 3 for each silicon atom to which it is bonded; and m is 1. The surface treatment agent contains 80 to 100 mass % of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (I) and / or a partial (hydrolyzed) condensate thereof in a total amount excluding the solvent. [ 10 〕 [ 9 ] An article surface-treated with the surface treatment agent according to the present invention. [ 11 〕 The lens substrate is 10 ] The article described in [Effects of the Invention]

[0011] The fluoropolyether group-containing polymer of the present invention is a high-molecular-weight polymer in which the number-average molecular weight of the fluorooxyalkylene group-containing polymer residue (Rf) in the main chain is 6,000 to 30,000, and the polymer has silanol groups or hydrolyzable silyl groups at both ends of the molecular chain, and the fluorooxyalkylene group-containing polymer residue (Rf) in the main chain and the silanol groups or hydrolyzable silyl groups (-SiX n (R) 3-nThe presence of a silalkylene structure or a silarylene structure in the linking group to the polymer improves adhesion to the substrate. As a result, an article surface-treated with a surface treatment agent containing the polymer and / or its partial (hydrolysis) condensate has excellent water and oil repellency, abrasion resistance (especially resistance to abrasion by cloth), and substrate chucking properties. This effect is particularly pronounced when it comes to lens substrates. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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 silalkylene structure or a silarylene structure in the linking group between the divalent fluorooxyalkylene group-containing polymer residue (Rf) constituting the main chain and the reactive functional groups (silanol groups or hydrolyzable silyl groups) at both ends of the molecular chain, and in particular, a fluoropolyether group-containing polymer having no siloxane bond (Si-O-Si) in the molecule. [ka] [wherein Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2)] [ka] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 3 for each unit. p, q, r, s, t, u, and v are each an integer of 0 to 450, such that p+q+r+s+t+u+v=20 to 450, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly, and the number average molecular weight of the polymer residue is 6,000 to 30,000.) U is independently a divalent or trivalent organic group, Z is independently a silalkylene structure or a silarylene structure, Y is independently a divalent organic group, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each silicon atom to which it is bonded, and m is 1 or 2.

[0013] In the above formula (1), Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the above general formula (2). In the above formula (2), W is a fluoroalkylene group containing one or more hydrogen atoms, such as CF2, C2F4, C3F6, C4F8, and C5F 10 , C6F 12 Examples include perfluoroalkylene groups in which one or two fluorine atoms have been substituted with hydrogen atoms.

[0014] In the above formula (2), d is an integer of 1 to 3, preferably 1 or 2, independently for each unit. Furthermore, p, q, r, s, t, u, and v are each integers from 0 to 450, preferably p is an integer from 5 to 440, q is an integer from 5 to 250, r is an integer from 0 to 180, s is an integer from 0 to 100, t is an integer from 0 to 100, u is an integer from 0 to 100, and v is an integer from 0 to 100; p+q+r+s+t+u+v is 20 to 450, preferably 50 to 200, and p+q is 20 to 450, particularly preferably 50 to 200. When p+q+r+s+t+u+v is smaller than the upper limit, adhesion and curability are good, and when it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferred. Each unit may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.

[0015] The fluorooxyalkylene group-containing polymer residue (Rf) 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 fluorine-based solvent as a developing solvent, or 19 It can be calculated by means of F-NMR or the like.

[0016] Specific examples of Rf include the following: [ka] [ka] (In the formula, p', q', r', s', t', and u' each represent an integer of 1 or greater, the upper limit of which is the same as the upper limit of p, q, r, s, t, and u above, and the sum of p', q', r', s', t', and u' is 20 to 450. r2' and r3' each represent an integer of 1 or greater, and the sum of r2' and r3' is 35 to 180. In addition, the repeating units shown in parentheses followed by p', q', r', s', t', and u' may be bonded randomly.)

[0017] In the above formula (1), U is independently a divalent or trivalent organic group, and is preferably a divalent or trivalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms. The divalent or trivalent 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 hydroxyl group, a diorganosilylene group such as a dimethylsilylene group, a secondary amino group, a tertiary amino group, a carbonyl group (ketone structure), an amide group, an ester group, an isocyanuric group, and a triazine ring-containing group.

[0018] Examples of such U include the following groups: It is preferable that the bond on the left side is bonded to Rf, and the other bond is bonded to Z. [ka] [ka] [ka] [ka] (In the formula, f is independently an integer of 2 to 4, and a and b are integers of 1 to 4.)

[0019] In the above formula (1), Z is independently a silalkylene structure or a silarylene structure, and examples thereof include those represented by the following formulas. [ka] (In the formula, R 1 is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, and R 1 may be the same or different. 2 is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4, such as a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group), or an arylene group having 6 to 8 carbon atoms, such as a phenylene group.

[0020] Examples of such Z include the following groups. [ka] (In the formula, c is an integer of 1 to 4.)

[0021] In the above formula (1), Y is independently a divalent organic group, and is 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.

[0022] Examples of such Y include the following groups. [ka] (In the formula, h is an integer of 1 to 20, preferably an integer of 2 to 10, j and k are integers of 1 to 10, preferably an integer of 1 to 5, and j+k is an integer of 2 to 20, preferably an integer of 2 to 10.)

[0023] In the above formula (1), X independently represents a hydrolyzable group selected from the group consisting of hydroxyl group, alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group, alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, and ethoxyethoxy group, acyloxy groups having 2 to 10 carbon atoms such as acetoxy group and propionoxy group, alkenyloxy groups having 2 to 10 carbon atoms such as vinyloxy group, allyloxy group, propenoxy group, and isopropenoxy group, and halogen atoms such as chlorine group, bromo group, and iodo group. In the above formula (1), R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, and n is independently an integer of 1 to 3, preferably 2 or 3, for each silicon atom to which it is bonded, and m is 1 or 2.

[0024] Examples of methods for preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1) include the following methods. A fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organosilicon compound having a silalkylene structure or silarylene structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group (such as a halogenated silyl group or an alkoxysilyl group). The mixture is then aged in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, and more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours. In addition, when an organosilicon compound having a silalkylene structure or a silarylene structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group is used, and the organosilicon compound has a halogenated silyl group as the hydrolyzable silyl group, the substituent (halogen atom) on the silyl group may be subsequently converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.

[0025] Here, in preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), an example of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both ends of the molecular chain is the fluoropolyether group-containing polymer represented by the following general formula (3): [ka] (In the formula, Rf and m are the same as above, and U' independently represents a single bond or a divalent or trivalent organic group.)

[0026] In the above formula (3), U' independently represents a single bond or a divalent or trivalent organic group, and the divalent or trivalent organic group is preferably a divalent or trivalent hydrocarbon group having 1 to 18 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 such as a dimethylsilylene group, a secondary amino group, a tertiary amino group, a carbonyl group, an amide group, an ester group, an isocyanuric group, and a triazine ring-containing group.

[0027] Preferred examples of U' include those shown below: It is preferred that the bond on the left side is bonded to Rf, and the other bonds are bonded to alkenyl groups. [ka] [ka] [ka] [ka] (In the formula, f' is an integer of 0 to 2, a and b are integers of 1 to 4, and b' is an integer of 0 to 2.)

[0028] Examples of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals, represented by the above formula (3), include the following. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, 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. 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 parentheses with p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly.)

[0029] In preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), the organosilicon compound having a silalkylene structure or a silarylene structure 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 (4): [ka] (In the formula, R 1 , R 2 , Y, R, X, n are the same as above.)

[0030] Examples of such organosilicon compounds having a silalkylene structure or a silarylene structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group include the following: [ka] [ka]

[0031] In preparing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), a fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals is reacted with an organosilicon compound having a silalkylene structure or a silarylene structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group. The amount of the organosilicon compound used is such that the amount of 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 equivalent of the olefin moiety (alkenyl group) in the fluoropolyether group-containing polymer.

[0032] In addition, in an organosilicon compound having a silalkylene structure or a silarylene structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group, when an organosilicon compound having a halogenated silyl group as the hydrolyzable silyl group is used, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group, and examples of reagents that can be used to convert the substituent (halogen atom) on this silyl group to another hydrolyzable group include alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, and butanol. The amount used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, per 100 parts by mass of the addition reaction product of a fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals and an organosilicon compound having a silalkylene structure or silarylene structure in the molecule and having a SiH group and a halogenated silyl group.

[0033] In preparing the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by formula (1), examples of the solvent include fluorine-based solvents. Examples of fluorine-based solvents include hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series) such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, and perfluorosolvents (manufactured by 3M, trade name: Fluorinert series) composed of fully fluorinated compounds. The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals.

[0034] In preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), examples of hydrosilylation reaction catalysts include the following: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferred are platinum compounds such as vinylsiloxane coordination compounds. The amount of the hydrosilylation reaction catalyst used can be 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, calculated as transition metal (by mass) relative to the mass of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals.

[0035] Examples of the structure of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1) include the following structures. By changing the combination of Rf, U, Z, Y, X, R, n, and m in the above formula (1), several types of fluoropolyether group-containing polymers having a hydrolyzable silyl group can be obtained. 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. The repeating units shown in parentheses with p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

change

[0036] For example, as a fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both ends of the molecular chain, a compound represented by the following formula: [ka] and using a silane compound represented by the following formula as an organosilicon compound having a silalkylene structure or a silarylene structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group: [ka] When the above formula is used, a compound represented by the following formula is obtained. [ka]

[0037] The present invention further provides a surface treatment agent containing, as a main component, a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups, represented by the above-mentioned general formula (1), and / or a partial (hydrolyzed) condensate thereof. The surface treatment agent may contain, as a main component, the above-mentioned fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups, and / or a partial (hydrolyzed) condensate thereof. The surface treatment agent may also contain unreacted raw materials or reaction intermediates prior to the introduction of terminal silanol groups or terminal hydrolyzable silyl groups into the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups. Here, the term "partial (hydrolyzed) condensate" refers to a surface treatment agent obtained by partial condensation of hydroxyl groups of the fluoropolyether group-containing polymer represented by the general formula (1), or hydroxyl groups obtained by partial hydrolysis of the terminal hydrolyzable silyl groups of the fluoropolyether group-containing polymer represented by the general formula (1) in advance using a known method. The phrase "contained as a main component (main component)" means that the content of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group, represented by general formula (1), and / or its partial (hydrolyzed) condensate is 50 to 100 mass%, preferably 60 to 100 mass%, and more preferably 80 to 100 mass%, of the total amount of the surface treatment agent excluding the solvent, which will be described later.

[0038] 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 general formula (1) as the main component, a fluorine-containing compound (non-functional fluoropolyether polymer) represented by the following formula (5), if necessary: A-Rf-A (5) (In the formula, Rf is the same as above, and A independently represents a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group terminated in a —CF group, a —CFH group, or a —CHF group.)

[0039] In the above formula (5), Rf can be exemplified as the same as Rf exemplified in the above formula (1), and these Rf may be the same as or different from Rf in the above formula (1). In the above formula (5), A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a -CF3 group, a -CF2H group, or a -CH2F group. Specific examples of the monovalent fluorine-containing group whose terminal is a -CF3 group, a -CF2H group, or a -CH2F group include a -CF3 group, a -CF2CF3 group, a -CF2CF2CF3 group, a -CH2CF(CF3)-OC3F7 group, and a -CH2OCF2CFH-OC3F7 group. Of these, a fluorine atom, a -CF3 group, or a -CF2CF3 group is preferred as A.

[0040] Examples of the fluorine-containing compound (non-functional fluoropolyether polymer) represented by formula (5) include the following. [ka] (In the formula, p4, q4, and r6 each independently represent an integer of 0 to 450, the sum of p4, q4, and r6 is 20 to 450, and r7 and r8 each represent an integer of 20 to 450. The repeating units shown in parentheses with p4, q4, and r6 may be bonded randomly.)

[0041] The content of the fluorine-containing compound (non-functional fluoropolyether polymer) represented by the above formula (5) may be 0 to 100 parts by mass, preferably 0 to 60 parts by mass, and more preferably 0 to 30 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 (hydrolyzed) condensate.

[0042] If necessary, the surface treatment agent may contain a hydrolysis condensation catalyst, such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Of these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or its partial (hydrolysis) condensate.

[0043] The surface treatment agent may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluorohexane, perfluoroheptane, perfluorooctane, tridecafluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptenyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are desirable in terms of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether are particularly preferred. ,to Lidecafluorooctane is preferred.

[0044] Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group, its partial (hydrolyzed) condensate, and the non-functional fluoropolyether polymer. The optimum concentration of the total of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and its partial (hydrolysis) condensate and non-functional fluoropolyether polymer dissolved in the solvent varies depending on the treatment method, and may be any amount that is easy to measure. In the case of direct coating, the total of the solvent, the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and its partial (hydrolysis) condensate and non-functional fluoropolyether polymer is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of the total of the solvent, the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and its partial (hydrolysis) condensate and non-functional fluoropolyether polymer. In the case of vapor deposition treatment, the total of the solvent, the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and its partial (hydrolysis) condensate and non-functional fluoropolyether polymer is preferably 1 to 100 parts by mass, particularly 3 to 30 parts by mass.

[0045] The surface treatment agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition. The heating method used during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferably 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, particularly 1 to 18 hours. In the case of vapor deposition, a temperature range of 20 to 200°C is desirable. Curing may also be performed under humid conditions. The thickness of the cured coating film is determined appropriately depending on the type of substrate, but is typically 0.1 to 100 nm, particularly 1 to 20 nm. The film thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry, X-ray fluorescence measurement, or the like. Furthermore, for example, in the case of spray coating, if the resin is diluted in a fluorine-based solvent to which water has been added beforehand, and then hydrolyzed, that is, Si-OH is generated, and then spray coated, the resin hardens quickly after coating.

[0046] The substrate to be treated with the surface treatment agent of the present invention is not particularly limited and may be made of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, and quartz. The surface treatment agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO2-treated glass or film.

[0047] Examples of articles that can be treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, and other optical articles. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the articles and further impart scratch resistance, and is therefore particularly useful as a water- and oil-repellent layer for lenses, touch panel displays, anti-reflection films, and the like.

[0048] The surface treatment agent of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins; an anti-fouling coating for window glass or tempered glass for automobiles, trains, aircraft, etc., and headlamp covers, etc.; a water- and oil-repellent coating for exterior wall building materials; an anti-grease stain coating for kitchen building materials; an anti-fouling and anti-poster / anti-graffiti coating for telephone booths; a coating for imparting fingerprint resistance to artworks, etc.; an anti-fingerprint coating for compact discs, DVDs, etc.; a release agent or paint additive for molds; a resin modifier; a flowability modifier or dispersibility modifier for inorganic fillers; and a lubricity improver for tapes, films, etc.

[0049] In particular, the surface treatment agent of the present invention can provide a cured coating on a lens substrate that is excellent in water and oil repellency, abrasion resistance, and chucking properties. Chucking ability here refers to the degree to which the substrate to be processed is fixed with adhesive tape when processing is carried out while the substrate is fixed with the adhesive tape, and is judged based on the strength of adhesion (tensile shear bond strength) between the lens blocking tape and the lens when a lens is fixed with lens blocking tape for edging, for example. Chucking ability is said to be good when the adhesive tape can be firmly fixed to the substrate to an extent that the substrate can be processed with precision. [Example]

[0050] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. 19 The film thickness is a number average calculated by F-NMR. In the formula below, the repeating units indicated in parentheses with p1 and q1, p2 and q2, and p3 and q3 are randomly bonded. Furthermore, the film thickness is a value measured by spectroscopic ellipsometry using a spectroscopic ellipsometer.

[0051] [Synthesis Example 1] In a reaction vessel, the following formula (A) [ka] 100g (1.55 x 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 13.6g (4.64 x 10 -2 mol), and 5.92 × 10 chloroplatinic acid / vinylsiloxane complex in toluene -2 g (Pt alone is 1.83 × 10 -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 103 g of a liquid product.

[0052] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (C): [ka]

[0053] [Synthesis Example 2] In a reaction vessel, the following formula (A) [ka] 100g (1.55 x 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 15.9g (4.64 x 10 -2 mol), and 5.92 × 10 chloroplatinic acid / vinylsiloxane complex in toluene -2 g (Pt alone is 1.83 × 10 -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 104 g of a liquid product.

[0054] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (E): [ka]

[0055] [Synthesis Example 3] In a reaction vessel, the following formula (F) [ka] 50g (6.15 x 10 -3 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 6.98g (1.84 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.35 × 10 -2 g (7.26 x 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 50.1 g of a liquid product.

[0056] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (H): [ka]

[0057] [Synthesis Example 4] In a reaction vessel, the following formula (I) [ka] 50g (3.61 x 10 -3 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 3.19g (1.08 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.21 × 10 -2 g (3.73 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 50.6 g of a liquid product.

[0058] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (K): [ka]

[0059] [Synthesis Example 5] In a reaction vessel, the following formula (L) [ka] 100g (1.10 x 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100 g, [ka] 10.2g (3.31 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.20 × 10 -2 g (1.30×10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 105 g of a liquid product.

[0060] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (O): [ka]

[0061] [Synthesis Example 6] In a reaction vessel, the following formula (P) [ka] 100g (5.94 x 10 -3 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 7.56g (1.78 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.27 × 10 -2 g (7.01 x 10 as Pt alone) -8mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 104 g of a liquid product.

[0062] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (R): [ka]

[0063] [Synthesis Example 7] In a reaction vessel, the following formula (V) [ka] 50g (6.38 x 10 -3 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 11.8g (3.83 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.44 × 10 -2 g (7.53 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 55 g of a liquid product.

[0064] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (W): [ka]

[0065] [Synthesis Example 8] In a reaction vessel, the following formula (X) [ka] 100g (1.10 x 10-2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 22.5g (6.59 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.20 × 10 -2 g (1.30×10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 112 g of a liquid product.

[0066] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (Y): [ka]

[0067] [Synthesis Example 9] In a reaction vessel, the following formula (Z) [ka] 100g (1.41 x 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100 g, [ka] 13.0 g (4.23 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.39 × 10 -2 g (1.66×10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 106 g of a liquid product.

[0068] The resulting compound is 1H-NMR confirmed that the structure was represented by the following formula (AA): [ka]

[0069] [Synthesis Example 10] In a reaction vessel, the following formula (AB) [ka] 100g (5.99 x 10 -3 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 6.41g (1.80 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.29 × 10 -2 g (7.07 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 102 g of a liquid product.

[0070] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AC). [ka]

[0071] [Synthesis Example 11] In a reaction vessel, the following formula (AD) [ka] 100g (1.01 x 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 23.0 g (6.08 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.86 × 10 -2 g (1.19 × 10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 114 g of a liquid product.

[0072] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AE): [ka]

[0073] [Synthesis Example 12] In a reaction vessel, the following formula (AF) [ka] 50g (4.04 × 10 -3 mol), 50 g of 1,3-bis(trifluoromethyl)benzene, [ka] 8.64g (2.43 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.54 × 10 -2 g (4.77 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 51 g of a liquid product.

[0074] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AG): [ka]

[0075] [Synthesis Example 13] In a reaction vessel, the following formula (AH) [ka] 100g (1.28 x 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 13.1g (3.84 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.89 × 10 -2 g (1.51 x 10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 102 g of a liquid product.

[0076] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AI): [ka]

[0077] [Synthesis Example 14] In a reaction vessel, the following formula (AJ) [ka] 100g (1.42 x 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, [ka] 11.9g (4.25 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.42 × 10 -2 g (1.68×10 as Pt alone) -7mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 105 g of a liquid product.

[0078] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AL): [ka]

[0079] [Synthesis Example 15] In a reaction vessel, the following formula (AO) [ka] 70g (7.14 x 10 -3 mol), 70 g of 1,3-bis(trifluoromethyl)benzene, [ka] 15.2g (4.28 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.73 × 10 -2 g (8.43 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 78 g of a liquid product.

[0080] The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AP): [ka]

[0081] [Synthesis Example 16] In a reaction vessel, the following formula (AQ) [ka] 100g (1.23 x 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100 g, [ka] 22.8g (7.40 x 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.70 × 10 -2 g (1.45 × 10 as Pt alone) -7 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 111 g of a liquid product. The resulting compound is 1 H-NMR confirmed that the structure was represented by the following formula (AS): [ka]

[0082] [Example 1] The compound obtained in Synthesis Example 1 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0083] [Example 2] The compound obtained in Synthesis Example 2 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0084] [Example 3] The compound obtained in Synthesis Example 3 was dissolved in Opteon SF10 (manufactured by Mitsui-Chemours Fluoroproducts, methyl perfluoroheptenyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0085] [Example 4] The compound obtained in Synthesis Example 4 was dissolved in Asahiklin AC-6000 (manufactured by AGC, tridecafluorooctane) to a concentration of 20 mass % to prepare a surface treatment agent.

[0086] [Example 5] The compound obtained in Synthesis Example 6 was dissolved in Asahiklin AC-6000 (manufactured by AGC, tridecafluorooctane) to a concentration of 20 mass % to prepare a surface treatment agent.

[0087] [Example 6] The compound obtained in Synthesis Example 7 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0088] [Example 7] The compound obtained in Synthesis Example 8 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0089] [Example 8] The compound obtained in Synthesis Example 10 was dissolved in Opteon SF10 (manufactured by Mitsui-Chemours Fluoroproducts, methyl perfluoroheptenyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0090] [Example 9] The compound obtained in Synthesis Example 11 was dissolved in Opteon SF10 (manufactured by Mitsui-Chemours Fluoroproducts, Inc., methyl perfluoroheptenyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0091] [Example 10] The compound obtained in Synthesis Example 13 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0092] [Example 11] The compound obtained in Synthesis Example 14 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0093] [Example 12] The compound obtained in Synthesis Example 15 was dissolved in Novec 7300 (manufactured by 3M, methyl perfluorohexyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0094] [Example 13] The compound obtained in Synthesis Example 16 was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0095] [Comparative Example 1] The following formula (AT) [ka] The compound represented by the following formula was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0096] Comparative Example 2 The following formula (AU) [ka] The compound represented by the following formula was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0097] Comparative Example 3 The following formula (AV) C6F 13 -Si(OCH3)3(AV) The compound represented by the following formula was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0098] Preparation of surface treatment agent and formation of hardened coating The surface treatment agents were prepared as in the above examples. Each surface treatment agent was vacuum-deposited (treatment conditions: pressure: 2.0 × 10) onto an AR-treated plastic lens (size: 80 mmφ) having an SiO layer on the outermost surface. -2The coating was cured for 12 hours in an atmosphere of 25°C and 50% humidity (Pa, heating temperature: 700°C) to form a cured coating with a thickness of 10 nm.

[0099] Water and oil repellency evaluation [Initial water repellency measurement] For the lenses having the cured coating formed thereon, the contact angle (water repellency) of the cured coating with water was measured using a contact angle meter, Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., humidity: 40%). The results (initial water contact angle) are shown in Table 1. In the initial stage, both the Example and Comparative Examples showed good water repellency.

[0100] Evaluation of slipperiness [Measurement of dynamic friction coefficient] The dynamic friction coefficient of the lenses having the cured coating formed thereon was measured against Bemcot (manufactured by Asahi Kasei Corporation) using a surface property tester 14FW (manufactured by Shinto Scientific Co., Ltd.) under the following conditions. The results are shown in Table 1. Contact area: 10mm x 30mm Load: 100g

[0101] Wear resistance evaluation The lenses having the cured coatings prepared as described above were rubbed using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.) under the following conditions, and the contact angle of the cured coating with water (water repellency) was measured in the same manner as above to evaluate abrasion resistance. The test environmental conditions were 25°C and 40% humidity. The percentage reduction from the initial water contact angle was also calculated, and these results (water contact angle after cloth abrasion, percentage reduction in water contact angle) are shown in Table 1. [Measurement of fabric abrasion resistance] Fabric: Bemcot (manufactured by Asahi Kasei Corporation) Contact area: 1cm 2 Travel distance (one way): 40 mm Traveling speed: 4,800mm / min Load: 1kg / 1cm 2 Number of wear cycles: 30,000

[0102] Chucking property evaluation Lens blocking tape (3M: LEAP III 1695M) was applied to the lens with the cured coating prepared above, and the tensile shear adhesive strength was measured. Specifically, the lens with the cured coating and the lens blocking tape applied to the lens were pulled so that shear stress was applied to the adhesive surface, and the maximum strength at which the adhesive bond broke was measured. The results (tensile shear adhesive strength) are shown in Table 1. [Lasting shear adhesive strength measurement] Adhesive area: 2.7cm 2 Pulling speed: 50 mm / min

[0103] In Examples 1 to 13, by using a compound having a high molecular weight and a silalkylene structure or silarylene structure in the linking group (the fluoropolyether group-containing polymer of the present invention), the adhesion to the substrate was improved and high fabric abrasion durability was demonstrated. Furthermore, by having functional groups at both ends, high tensile shear adhesive strength was confirmed, and high chucking properties were confirmed. Comparative Example 1 had a low dynamic friction coefficient and low chucking properties. Comparative Example 2 had high chucking properties but low fabric abrasion durability. Furthermore, Comparative Example 3 also had low fabric abrasion properties. As described above, the Examples using the fluoropolyether group-containing polymer of the present invention were able to achieve both high levels of fabric abrasion durability and chucking properties.

[0104] [Table 1]

Claims

1. The following general formula (1) 【Chemistry 1】 [wherein Rf is a divalent fluorooxyalkylene group-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, such that p+q+r+s+t+u+v=20 to 450; each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly, and the number average molecular weight of the polymer residue is 6,000 to 30,000.) U independently represents a trivalent group consisting of an arylene group having 6 to 8 carbon atoms, an oxygen atom, a sulfur atom, a diorganosilylene group, a tertiary amino group which may contain one or more atoms or groups selected from a secondary amino group, a carbonyl group, and an ester group, an amide group, an isocyanuric group, or a triazine ring-containing group, and a divalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms; Z independently represents a silalkylene structure or a silarylene structure; Y independently represents an oxygen atom, a sulfur atom, and an arylene group having 6 to 8 carbon atoms. groups, R is independently an alkyl group having 1 to 20 carbon atoms or a phenyl group, X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom, n is independently an integer of 1 to 3 for each silicon atom to which it is bonded, and m is 2. A fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula:

2. In the formula (2), 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, v is an integer of 0 to 100, p + q + r + s + t + u + v is 50 to 450, and p + q is 50 to 450. Fluoropolyether group-containing polymer according to claim 1.

3. The fluoropolyether group-containing polymer according to claim 1, wherein in formula (2), Rf is represented by the following formula: 【Transformation 3】 (In the formula, r2' and r3' are each an integer of 1 or greater, and the sum of r2' and r3' is 35 to 180. The number average molecular weight of the polymer residue is 6,000 to 30,000.)

4. 2. The fluoropolyether group-containing polymer according to claim 1, wherein U in the formula (1) is represented by any one of the following formulae: 【Chemistry 4】 【Transformation 5】 (In the formula, f is independently an integer of 2 to 4, and a is an integer of 1 to 4.)

5. 2. The fluoropolyether group-containing polymer according to claim 1, wherein the polymer represented by formula (1) is represented by any one of the following formulas: 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 (In the formula, 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. 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 parentheses labeled p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly.)

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

7. An article surface-treated with the surface treatment agent according to claim 6.

8. 8. The article of claim 7 which is a lens substrate.

9. The following general formula (1) 【Chemistry 15】 [wherein Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2)] 【Chemistry 16】 (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, such that p+q+r+s+t+u+v=20 to 450; each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly, and the number average molecular weight of the polymer residue is 6,000 to 30,000.) U independently represents a divalent 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, a secondary amino group, a carbonyl group, and an ester group; Z independently represents a silalkylene structure or a silarylene structure; Y independently represents one or more atoms selected from an oxygen atom, a sulfur atom, and an arylene group having 6 to 8 carbon atoms. R is an alkylene group having 1 to 20 carbon atoms, which may contain a group or a group; R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group; X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; n is independently an integer of 1 to 3 for each silicon atom to which it is bonded; and m is 1. The surface treatment agent contains 80 to 100 mass % of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (I) and / or a partial (hydrolyzed) condensate thereof in a total amount excluding the solvent.

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

11. 11. The article of claim 10 which is a lens substrate.

Images