Surface treatment agent and article treated with said surface treatment agent

Abstract

A surface treatment agent which contains a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis-condensation product of the polymer, said polymer having at least one group represented by formula (1) (wherein Y represents a single bond or a divalent hydrocarbon group which may have F, Si and a siloxane bond; R represents a C1-C4 alkyl group or a phenyl group; X represents a hydrolyzable group; and a represents 2 or 3) at least at one end of each molecule, wherein the molecular weight distribution of the fluorooxyalkylene group-containing polymer or a fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer contained in the surface treatment agent is within the range of from 1.2 to 1.8. This surface treatment agent is able to form a cured coating film that has excellent surface sliding properties, excellent water falling properties, low haze and excellent wear resistance.

Description

[Technical field]

[0001] The present invention relates to a surface treatment agent containing a fluorooxyalkylene group-containing polymer and / or a partial hydrolyzed condensate of the polymer, and more particularly to a surface treatment agent containing a fluorooxyalkylene group-containing polymer and / or a partial hydrolyzed condensate of the polymer that forms a coating excellent in water and oil repellency, surface slipperiness and abrasion resistance, or a fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer and / or the partial hydrolyzed condensate of the polymer, and an article having a cured coating of the surface treatment agent on its surface. [Background technology]

[0002] In recent years, the use of touch panels for screens, including mobile phone displays, has accelerated. However, touch panels have exposed screens and are often directly touched by fingers or cheeks, which makes them susceptible to dirt such as sebum. Therefore, there is an increasing demand for technology that makes it difficult for fingerprints to be left on the surface of displays to improve appearance and visibility, and technology that makes it easy to remove dirt, and there is a demand for development of materials that can meet these demands. In particular, since fingerprints are easily attached to the surface of touch panel displays, it is desirable to provide a water- and oil-repellent layer. However, although conventional water- and oil-repellent layers have high water- and oil-repellent properties and are easy to wipe off, there is a problem in that their anti-fouling performance deteriorates during use.

[0003] In general, fluorooxyalkylene group-containing polymers have water and oil repellency, chemical resistance, lubricity, releasability, and stain resistance due to their very small surface free energy. Taking advantage of these properties, they are widely used industrially as water and oil repellency and stain resistance agents for paper and fibers, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, etc. However, these properties also mean that they are non-adhesive and non-adhesive to other substrates, and even if they can be applied to the surface of a substrate, it has been difficult to make the coating adhere to it.

[0004] On the other hand, silane coupling agents are well known as agents that bond organic compounds to the surfaces of substrates such as glass and cloth, and are 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 due to moisture in the air, etc., to form a coating. The coating becomes a strong and durable coating as the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.

[0005] In view of this, compositions have been disclosed that use fluorooxyalkylene group-containing polymers in which a hydrolyzable silyl group has been introduced into a fluorooxyalkylene group-containing compound, and that can form coatings on the substrate surface that are easily adhered to the substrate surface and have water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, and the like (Patent Documents 1 to 6: JP-T-2008-534696, JP-T-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, JP-A-2015-199906).

[0006] Cured coatings such as lenses and antireflective films that have been surface-treated with a composition containing a fluorooxyalkylene group-containing polymer in which a hydrolyzable silyl group has been introduced into the fluorooxyalkylene group-containing compound have excellent release properties and abrasion resistance to steel wool, but there is a demand for improvement in slip properties, such as water removability, of the cured coating surface.

[0007] In addition, as a means for not impairing the visibility of the substrate surface, that is, not increasing the haze, Patent Document 7 (JP Patent Publication 2013-136833 A) discloses that by mixing a non-functional fluorooxyalkylene group-containing polymer having a larger average molecular weight than the fluorooxyalkylene group-containing silane with a fluorooxyalkylene group-containing silane, the unevenness of the coated surface can be suppressed to a few nm when coated by vacuum deposition. In deposition coating, since the low boiling point component is deposited first, a layer containing a large amount of fluorooxyalkylene group-containing polymer-modified silane is formed on the substrate side, and a non-functional fluorooxyalkylene group-containing polymer layer having a larger molecular weight is formed on the surface side. Even if aggregation occurs in the fluorooxyalkylene group-containing polymer layer, the outermost non-functional fluorooxyalkylene group-containing polymer layer fills in the unevenness, so the haze is unlikely to increase. However, when the composition is diluted with a fluorine-based solvent and surface-treated by spray coating or dip coating, the compatibility between the fluorooxyalkylene group-containing silane and the non-functional fluorooxyalkylene group-containing polymer becomes a problem, and the haze may increase.As such, it has been found that the degree of increase in haze varies depending on the coating method even with the same composition.

[0008] Patent Document 8 (JP 2016-141699 A) discloses a fluorine-containing coating agent which contains (A) a silane having a hydrolyzable group at one end modified with a fluorooxyalkylene group-containing polymer and / or a partial hydrolyzed condensate thereof, and (B) a silane having hydrolyzable groups at both ends modified with a fluorooxyalkylene group-containing polymer and / or a partial hydrolyzed condensate thereof, in which the mixing mass ratio of component (A) to component (B) is 20:80 to 60:40. The cured film of the fluorine-containing coating agent has reduced haze even when it is as thick as 20 nm, but the abrasion resistance may be reduced due to the inclusion of component (B). [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Special Publication No. 2008-534696 [Patent Document 2] Special Publication No. 2008-537557 [Patent Document 3] JP 2012-072272 A [Patent Document 4] JP 2012-157856 A [Patent Document 5] JP 2013-136833 A [Patent Document 6] JP 2015-199906 A [Patent Document 7] JP 2013-136833 A [Patent Document 8] JP 2016-141699 A Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a surface treatment agent containing a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate of the polymer, which is capable of forming a cured coating having excellent surface slipperiness, excellent water sliding properties (small sliding angle with respect to water), low haze, and excellent abrasion resistance, as well as an article or the like that has been surface-treated with the surface treatment agent. [Means for solving the problem]

[0011] As a result of intensive research to achieve the above object, the present inventors have found that a surface treatment agent containing a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate of the polymer, which has at least one group represented by the formula (1) described below at at least one terminal in the molecule and preferably has a divalent polyfluorooxyalkylene structure (perfluoropolyether structure)-containing group in the main chain, and in which the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer contained in the surface treatment agent, or a fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer, has a molecular weight distribution (i.e., the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn)) within a specific range (having a certain degree of molecular weight nonuniformity), is capable of forming a cured coating that is excellent in water and oil repellency and surface slipperiness, and in particular has a small water sliding angle. Furthermore, the present inventors have found that the above-mentioned fluorooxyalkylene group-containing polymer has at least two groups represented by the above formula (1) at at least one end in the molecule, and that a surface treatment agent which gives a cured coating having a difference in haze value of 0.2 or less before and after the production of the cured coating film, as measured according to a method in accordance with JIS K 7136, can form a cured coating film with low haze and excellent abrasion resistance, which has led to the completion of the present invention.

[0012] Accordingly, the present invention provides a surface treatment agent containing the following fluorooxyalkylene group-containing polymer and / or a partial hydrolyzed condensate of the polymer, or a fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer and / or the partial hydrolyzed condensate of the polymer, and an article having a cured coating of the surface treatment agent on its surface, and the like. [1] At least one terminal of the molecule has the following formula (1): [ka] (In the formula, Y is a single bond or a divalent hydrocarbon group which may have one or more groups selected from a fluorine atom, a silicon atom, and a siloxane bond, R is an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is a hydrolyzable group, and a is 2 or 3.) and / or a partial hydrolysis condensate of said polymer, The fluorooxyalkylene group-containing polymer has -(C b F 2b O) m - (wherein b is independently an integer of 1 to 6 for each unit, and m is an integer of 1 to 250. Each of these units may be linear or branched), The fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate of the polymer contained in the surface treatment agent, or a fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate of the polymer. The number average molecular weight is 1,000 to 20,000, and A surface treatment agent having a molecular weight distribution in the range of 1.2 to 1.8. [2] Said -(C b F 2b O) m The surface treatment agent according to [1], wherein m is an integer of 10 to 250. [3] The surface treatment agent according to [1] or [2], wherein X in the formula (1) is an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, or a halogen group. [4] The fluorooxyalkylene group-containing polymer is represented by the following formula (2), (4) or (7): ] The surface treatment agent described above. [ka] [Wherein, Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F10 O) t (C 6 F 12 O) u -C d F 2d -(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t and u is an integer of 1 to 250, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t and u may be bonded randomly), and A 1 ends with CF 3 - or CF 2 It is H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3). [ka] [In the formula, Q is a single bond or a divalent organic group, Z is a divalent to octavalent group, α is 0 or 1, β is an integer of 1 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the above formula (1)], [ka] [In the formula, Rf is the same as above, and A 2 ends with CF 3 - or CF 2 a monovalent fluorine-containing hydrocarbon group which is H- and which may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5). [ka] [In the formula, W is the same as above, B is independently a hydrogen atom or -OS, S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following formula (6): [ka] (In the formula, T is a single bond or a divalent to octavalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, E is a monovalent hydrocarbon group having 1 to 6 carbon atoms or W, and l is an integer of 0 to 20.) and e is 1 or 2. [ka] [In the formula, Rf is the same as above, and A 3 ends with CF 3 - or CF 2 It is H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or J, where J is a monovalent group represented by the following formula (8). [ka] [In the formula, S and e are the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond, and M is a group represented by the following formula (9): [ka] (In the formula, Y, S, and W are the same as above, and f is an integer of 1 to 3.) is a monovalent group represented by the following formula: [5] The surface treatment agent according to [4], wherein in the formula (3), Q is an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms which may contain one or more bonds selected from the group consisting of an amide bond, an ether bond, an ester bond, a sulfide bond, a urethane bond, a siloxane bond, a triazine bond, a diorganosilylene group, a silphenylene bond, and a silalkylene bond, and Z is a di- to octavalent group selected from a silicon atom, a nitrogen atom, a silalkylene group, a silarylene group, and a di- to octavalent organopolysiloxane residue having a siloxane bond. [6] The surface treatment agent according to [4], wherein in the formula (6), T is a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a silalkylene bond, a silarylene bond, and a diorganosilylene group, a siloxane bond, a silalkylene group, or a diorganosilylene group. [7] The surface treatment agent according to any one of [1] to [6], wherein the fluorooxyalkylene group-containing polymer has at least two groups represented by the above formula (1) at at least one terminal in the molecule. [8] The surface treatment agent according to [7], which provides a cured coating having a difference in haze value between a substrate and a cured coating made of a cured product of the surface treatment agent formed on the substrate of 0.2 or less, as measured according to a method in accordance with JIS K 7136. [9] Furthermore, the following formula (10) [ka] (Wherein, Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d-(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t and u is an integer of 1 to 250, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t and u may be bonded randomly), and A 4 are independently terminated with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, -OR 3 , -COOR 3 OR-PO(OR 3 ) 2 [R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. The surface treatment agent according to any one of [1] to [8], which contains a fluorooxyalkylene group-containing polymer represented by the following formula:

[10] The surface treatment agent according to any one of [1] to [9], further comprising a fluorine-based solvent.

[11] An article having, on its surface, a coating of the cured product of the surface treatment agent according to any one of [1] to

[10] .

[12] The article according to

[11] , which is any one selected from a glass plate, a hard-coated film, a high-hardness film, an anti-reflection film, a spectacle lens, an optical lens, and a quartz substrate. Effect of the Invention

[0013] The fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer (hereinafter, in this specification, these may be simply referred to as fluorooxyalkylene group-containing polymer) containing at least one, preferably at least two hydrolyzable silyl groups contained in the surface treatment agent of the present invention, or the fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer, has a molecular weight distribution somewhat larger than 1, thereby improving surface slipperiness, and furthermore, even if the cured coating is thick, it can maintain a low haze surface, and also has excellent wear resistance. As a result, an article surface-treated with the surface treatment agent containing the fluorooxyalkylene group-containing polymer or the fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer can be excellent in water sliding, and can also be imparted with low haze and wear resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present invention will be described in detail below.

[0015] The present invention is a surface treatment agent containing a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate of the polymer, which contains at least one, preferably at least two, hydrolyzable silyl groups at at least one end of the molecule, and is characterized in that the molecular weight distribution (i.e., the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn)) of the fluorooxyalkylene group-containing polymer (fluorooxyalkylene group-containing polymer and / or partial hydrolysis condensate of the polymer containing at least one, preferably at least two, hydrolyzable silyl groups) contained in the surface treatment agent or the fluorooxyalkylene group-containing polymer mixture (a mixture of the fluorooxyalkylene group-containing polymer and a nonfunctional fluorooxyalkylene group-containing polymer described below (i.e., a fluorooxyalkylene group-containing polymer composition)) is in the range of 1.2 to 1.8. Preferably, the molecular weight distribution is in the range of 1.20 to 1.80, more preferably 1.22 to 1.70, particularly preferably 1.25 to 1.65. If the molecular weight distribution is less than 1.2, aggregates will form in the cured coating, reducing the water sliding properties of the cured coating (the water sliding angle will increase) and the haze of the cured coating will increase. If the molecular weight distribution exceeds 1.8, the physical properties of the cured coating will not be stable.

[0016] In order to make the molecular weight distribution within the above range, in the fluorooxyalkylene group-containing polymer and / or fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer as the final product, a plurality of polymers and / or mixtures containing the polymer having different molecular weights and molecular weight distributions are appropriately blended together, or in the fluoropolyether group-containing polymer and / or mixture containing the polymer as a starting material or intermediate material before obtaining the final product, a plurality of polymers and / or mixtures containing the polymer having different molecular weights and molecular weight distributions are appropriately blended together to prepare a fluoropolyether group-containing polymer and / or mixture containing the polymer as a starting material or intermediate material having a molecular weight distribution within the above range, and the fluoropolyether group-containing polymer and / or mixture containing the polymer is used as a starting material or intermediate material to produce a fluorooxyalkylene group-containing polymer and / or fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer as the final product, thereby making it possible to prepare a fluorooxyalkylene group-containing polymer and / or fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer having a molecular weight distribution controlled within the above range.

[0017] In the present invention, in the surface treatment agent containing a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate of the polymer containing at least one, preferably at least two hydrolyzable silyl groups, the number average molecular weight of the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer contained in the surface treatment agent, or the fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer (a mixture of the fluorooxyalkylene group-containing polymer and a nonfunctional fluorooxyalkylene group-containing polymer described below (fluorooxyalkylene group-containing polymer composition)) is preferably in the range of 1,000 to 20,000. More preferably, the number average molecular weight is 2,000 to 10,000, even more preferably 2,500 to 9,000, and particularly preferably 3,000 to 8,000.

[0018] In the present invention, the number average molecular weight (Mn) and weight average molecular weight (Mw) used in measuring the molecular weight distribution (ratio of weight average molecular weight (Mw) / number average molecular weight (Mn)) of the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer, or the fluorooxyalkylene group-containing polymer composition can each be determined as a polystyrene-equivalent value in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. The number average molecular weight (Mn) of the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer, or the fluorooxyalkylene group-containing polymer composition is 19 It can also be calculated from the characteristic peak intensity ratio in F-NMR analysis.

[0019] The fluorooxyalkylene group-containing polymer used in the surface treatment agent of the present invention has a fluorooxyalkylene group represented by the following formula (1) at at least one, preferably 1 to 3, terminals in the molecule. [ka] (In the formula, Y is a single bond or a divalent hydrocarbon group which may have one or more groups selected from a fluorine atom, a silicon atom, and a siloxane bond, R is an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is a hydrolyzable group, and a is 2 or 3.) and has at least one, preferably 1 to 3 (i.e., at least one, preferably 1 to 9, more preferably 2 to 6 in the molecule) group (hydrolyzable silyl group-containing group) represented by -(C b F 2b O) m - (wherein b is independently an integer of 1 to 6 for each unit, and m is an integer of 1 to 250. Each of these units may be linear or branched). In order to impart low haze and abrasion resistance to an article that has been surface-treated with a surface treatment agent containing the fluorooxyalkylene group-containing polymer of the present invention, it is preferable to use a fluorooxyalkylene group-containing polymer having at least two, preferably 2 to 3 (i.e., at least 2, preferably 2 to 9, more preferably 2 to 6 in the molecule) groups represented by the above formula (1) (hydrolyzable silyl group-containing groups).

[0020] In the above formula (1), Y is a single bond, or a divalent hydrocarbon group which may have one or more selected from fluorine atoms, silicon atoms, and siloxane bonds, and the divalent hydrocarbon group which may have one or more selected from fluorine atoms, silicon atoms, and siloxane bonds is a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms and containing a fluorine atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms (alkylene-arylene group), a divalent group in which alkylene groups are mutually bonded via a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms. Among these, an alkylene group having 1 to 10 carbon atoms, preferably 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, is preferred.

[0021] Specific examples of Y other than a single bond include the following: In the following structure, it is preferable that the bond on the right side is bonded to Si. [ka]

[0022] In the above formula (1), X is a hydrolyzable group which may be different from each other. Examples of such X include 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; alkoxy-substituted alkoxy 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, propionoxy group; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy group, allyloxy group, propenoxy group, and isopropenoxy group; and halogen groups, such as chlorine group, bromo group, and iodo group. Among them, methoxy group, ethoxy group, isopropenoxy group, and chlorine group are preferable.

[0023] In the above formula (1), R is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, with a methyl group and an ethyl group being particularly preferred. In the above formula (1), a is 2 or 3, with 3 being preferred from the standpoints of reactivity and adhesion to the substrate.

[0024] Examples of the group represented by formula (1) (hydrolyzable silyl group-containing group) include those shown below. [ka] [ka]

[0025] In addition, the above-(C b F 2b O) m In the polyfluorooxyalkylene structure represented by -, b is independently an integer of 1 to 6, preferably an integer of 1 to 4 for each unit, and m is an integer of 1 to 250, preferably an integer of 10 to 250, more preferably an integer of 10 to 140. Each of these units may be linear or branched.

[0026] Above-C b F 2b Examples of the repeating unit represented by O- include units represented by the following formulas. -CF 2 O-, -CF 2 CF 2 O-, -CF 2 CF 2 CF 2 O-, -CF(CF 3 )CF 2 O-, -CF 2 CF 2 CF 2 CF 2 O-, -CF 2 CF 2 CF2 CF 2 CF 2 CF 2 O-, -C(CF 3 ) 2 O- Among these, the repeating units represented by the following formula are particularly preferred. -CF 2 O-, -CF 2 CF 2 O-

[0027] The polyfluorooxyalkylene structure may be composed of one type of the repeating units described above, or may be composed of a combination of two or more types.

[0028] The fluorooxyalkylene group-containing polymer is preferably a fluorooxyalkylene group-containing polymer represented by the following formula (2), (4) or (7). [ka] [Wherein, Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d-(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t and u is an integer of 1 to 250, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t and u may be bonded randomly), and A 1 ends with CF 3 - or CF 2 It is H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3). [ka] [In the formula, Q is a single bond or a divalent organic group, Z is a divalent to octavalent group, α is 0 or 1, β is an integer of 1 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the above formula (1)], [ka] [In the formula, Rf is the same as above, and A 2 ends with CF 3 - or CF 2 a monovalent fluorine-containing hydrocarbon group which is H- and which may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5). [ka] [In the formula, W is the same as above, B is independently a hydrogen atom or -OS, S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following formula (6): [ka] (In the formula, T is a single bond or a divalent to octavalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, E is a monovalent hydrocarbon group having 1 to 6 carbon atoms or W, and l is an integer of 0 to 20.) and e is 1 or 2. [ka] [In the formula, Rf is the same as above, and A 3 ends with CF 3 - or CF 2 It is H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or J, where J is a monovalent group represented by the following formula (8). [ka] [In the formula, S and e are the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond, and M is a group represented by the following formula (9): [ka] (In the formula, Y, S, and W are the same as above, and f is an integer of 1 to 3.) is a monovalent group represented by the following formula:

[0029] First, the fluorooxyalkylene group-containing polymer represented by the following formula (2) will be described. [ka]

[0030] In the above formula (2), Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d- is a divalent polyfluorooxyalkylene structure (perfluoropolyether structure)-containing group, and d is an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0 or 1, for each unit. p, q, r, s, t, and u are each independently an integer of 0 to 150, preferably an integer of 0 to 100, more preferably an integer of 0 to 80, even more preferably an integer of 0 to 60, particularly preferably an integer of 0 to 40, and particularly preferably an integer of 0 to 10, and the sum of p, q, r, s, t, and u is at least 1, preferably 3 or more, more preferably 7 or more, and particularly preferably 10 or more, and the sum of p, q, r, s, t, and u is 250 or less, preferably 140 or less, and more preferably 70 or less. Each of these units may be linear or branched. The repeating units shown in parentheses with p, q, r, s, t, and u may be randomly bonded.

[0031] The divalent polyfluorooxyalkylene structure-containing group of Rf can specifically be represented by the following structure. [ka] [ka] (In the formula, p', q', r', s', t' and u' are each independently an integer of 1 to 150, and the sum of p', q', r', s', t' and u' is 12 to 250. Furthermore, each repeating unit shown in parentheses with p', q', r', s', t' and u' may be bonded randomly. d' is independently an integer of 0 to 5. Each of these units may be linear or branched.)

[0032] The above formula (2); A 1 - In Rf-D, A 1 ends with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or D (i.e., -QZ represented by the formula (3) described below).α (W) β ) and terminated with CF 3 - or CF 2 The monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms, particularly a CF 3 - or CF 2 H- is preferred.

[0033] Such an A 1 The end of 3 - or CF 2 Examples of the monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom include the following groups. [ka]

[0034] The above formula (2); A 1 In -Rf-D, D is a monovalent group represented by the following formula (3). [ka]

[0035] In the above formula (3), Q is a single bond or a divalent organic group, and Q other than a single bond is preferably an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms, preferably 2 to 15 carbon atoms, which may contain one or more bonds selected from the group consisting of an amide bond (e.g., an unsubstituted amide bond, an N-methyl substituted amide bond, an N-phenyl substituted amide bond), an ether bond, an ester bond, a sulfide bond, a urethane bond, a siloxane bond, a triazine bond, a diorganosilylene group (e.g., a dialkylsilylene group such as a dimethylsilylene group), a silphenylene bond, and a silalkylene bond (e.g., a silethylene bond), and is preferably an unsubstituted or fluorine-substituted divalent hydrocarbon group having 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, which may contain the bond.

[0036] Examples of Q other than a single bond include the following groups: In the following structure, it is preferable that the left bond is bonded to Rf and the right bond is bonded to Z (or W). [ka] (In the formula, t is an integer of 1 to 4, preferably an integer of 2 to 4.)

[0037] The above formula (3);-QZ α (W) β In the formula, Z is a divalent to octavalent group, preferably a divalent to octavalent, preferably divalent to tetravalent group selected from a silicon atom, a nitrogen atom, a silalkylene group, a silarylene group, and a divalent to octavalent organopolysiloxane residue having a siloxane bond, more preferably a linear organopolysiloxane residue having 2 to 13 silicon atoms, particularly 2 to 5 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms. Also, a silalkylene structure such as a silethylene structure in which two silicon atoms are bonded by an alkylene group such as an ethylene group, i.e., Si-(CH 2 ) n It may contain -Si (in the above formula, n is an integer of 2 to 6, preferably an integer of 2 to 4).

[0038] Here, examples of the silalkylene group and silarylene group include those shown below. [ka] (In the formula, R 1 is an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group; R 1 may be the same or different. 2 is an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group (a trimethylene group, a methylethylene group), or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.

[0039] Examples of the divalent to octavalent organopolysiloxane residue having a siloxane bond include those shown below. [ka] (In the formula, R 1 is the same as above. g is an integer of 1 to 12, preferably an integer of 1 to 4, h is an integer of 2 to 8, preferably an integer of 2 to 4, j is an integer of 0 to 8, preferably 0 or 1, h+j is an integer of 3 to 13, preferably an integer of 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3.

[0040] Examples of such Z include the following: [ka] [ka] [ka] [ka] [ka] [ka]

[0041] The above formula (3);-QZ α (W) β In the formula, W is independently a monovalent hydrolyzable silyl-containing group represented by the above formula (1), and examples thereof include the same as those exemplified for the above formula (1).

[0042] The above formula (3);-QZ α (W) βIn the above formula, α is 0 or 1, β representing the number of W is an integer of 1 to 7, preferably an integer of 2 to 7, and β is (the valence of Z−1).

[0043] The group in the above formula (3): -QZ α (W) β (That is, examples of D in formula (2)) include those shown below. [ka] [ka]

[0044] Examples of the fluorooxyalkylene group-containing polymer represented by the above formula (2) include those shown below. [ka] [ka] (In the formula, A 1 , Rf is the same as above.)

[0045] Next, the fluorooxyalkylene group-containing polymer represented by the following formula (4) will be described. [ka] In the above formula (4), Rf is the same as above, and examples thereof include those similar to those exemplified as Rf in the above formula (2).

[0046] The above formula (4); A 2 - In Rf-G, A 2 ends with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or G (i.e., the formula (5) described below; -C(B) e (W) 3-e (a monovalent group represented by the formula: 3- or CF 2 The monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms, particularly a CF 3 - or CF 2 H- is preferred.

[0047] Such an A 2 The end of 3 - or CF 2 Examples of the monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom include the following groups. [ka]

[0048] The above formula (4); A 2 In -Rf-G, G is a monovalent group represented by the following formula (5). [ka] In the above formula (5), W is the same as above, and examples thereof include those similar to those exemplified in the above formula (1). In the above formula (5), e is 1 or 2, and is preferably 1.

[0049] The above formula (5);-C(B) e (W) 3-e In the formula (6), each B is independently a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (6): [ka]

[0050] Here, examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for S include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups, alkenyl groups such as vinyl and allyl groups, aryl groups such as phenyl and tolyl groups, and aralkyl groups such as benzyl and phenylethyl groups, with alkyl groups having 1 to 3 carbon atoms and phenyl groups being preferred.

[0051] The above formula (6); -T-(LO) l In -E, T is a single bond or a divalent group having 2 to 8 valences, preferably a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of silicon atoms, siloxane bonds, silalkylene bonds (e.g., silethylene bonds, silpropylene bonds), silarylene bonds (e.g., silphenylene bonds), and diorganosilylene groups (e.g., dialkylsilylene groups such as dimethylsilylene groups, and dialkoxysilylene groups such as dimethoxysilylene groups), siloxane bonds, silalkylene groups, or diorganosilylene groups, and specific examples of T other than a single bond include those shown below. In the following structure, it is preferable that the bond on the right side is bonded to L or E. [ka]

[0052] The above formula (6); -T-(LO) l In -E, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, such as an alkylene group including a methylene group, an ethylene group, a propylene group (a trimethylene group, a methylethylene group), a butylene group (a tetramethylene group), etc., and the carbon numbers may be single or mixed. The above formula (6); -T-(LO) l In -E, 1 is an integer of 0 to 20, preferably an integer of 0 to 10, and more preferably an integer of 0 to 6. When (LO) is present, 1 is preferably 1 or more, particularly preferably 2 or more. The above formula (6); -T-(LO) lIn -E, E is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a phenyl group, or W, where W is the same as defined above and examples thereof include the same groups as those exemplified in formula (1) above.

[0053] The above formula (6); -T-(LO) l Examples of the monovalent group represented by -E include those shown below. [ka]

[0054] The above formula (5);-C(B) e (W) 3-e Examples of the monovalent group represented by the formula (that is, G in formula (4)) include those shown below. [ka] [ka]

[0055] Examples of the fluorooxyalkylene group-containing polymer represented by the above formula (4) include those shown below. [ka] [ka] (In the formula, A 2 , Rf is the same as above.)

[0056] Next, the fluorooxyalkylene group-containing polymer represented by the following formula (7) will be described. [ka] In the above formula (7), Rf is the same as above, and examples thereof include those similar to those exemplified as Rf in the above formula (2).

[0057] The above formula (7);A 3 -Rf-J, A 3 ends with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or J (i.e., the formula (8) described below; -VC(=O)N(S) 2-e (M) e (a monovalent group represented by the formula: 3 - or CF 2 The monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms, particularly a CF 3 - or CF 2 H- is preferred.

[0058] Such a terminal is CF 3 - or CF 2 Examples of the monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom include the following groups. [ka]

[0059] The above formula (7);;A 3 In —Rf-J, J is a monovalent group represented by the following formula (8). [ka]

[0060] In the above formula (8), V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond, and specific examples of V other than a single bond include those shown below. In the following structure, it is preferable that the bond on the right side is bonded to a carbon atom (-C(=O)-). [ka]

[0061] In the above formula (8), S is the same as above, and examples thereof include those similar to those exemplified for S in the above formula (5). In the above formula (8), e is the same as e in the above formula (5) and is 1 or 2, and is preferably 1.

[0062] In the above formula (8), M is a monovalent group represented by the following formula (9). [ka]

[0063] In the above formula (9), Y, S, and W are the same as above, and examples thereof include Y in the above formula (1), S in the above formula (5), and the same as those exemplified in the above formula (1). In the above formula (9), f is an integer of 1 to 3.

[0064] The above formula (9); -YC(S) 3-f (W) f Examples of the monovalent group represented by the formula (that is, M in formula (8)) include those shown below. [ka]

[0065] Above formula (8);-VC(=O)N(S) 2-e (M) e Examples of the monovalent group represented by the formula: include those shown below. [ka] [ka] [ka]

[0066] Examples of the fluorooxyalkylene group-containing polymer represented by the above formula (7) include those shown below. [ka] [ka] [ka] (In the formula, A 3 , Rf is the same as above.)

[0067] The surface treatment agent containing the fluorooxyalkylene group-containing polymer of the present invention may be a mixture (i.e., a fluorooxyalkylene group-containing polymer composition) containing, in addition to the above-mentioned fluorooxyalkylene group-containing polymer containing at least one hydrolyzable silyl group and / or a partial hydrolysis condensate of the polymer, a fluorooxyalkylene group-containing polymer not containing a hydrolyzable silyl group represented by the following formula (10) (hereinafter, sometimes referred to as a polymer not containing a hydrolyzable silyl group or a non-functional polymer). [ka] (In the formula, Rf is the same as above, and examples thereof include those exemplified as Rf in the above formula (2). A 4 are independently terminated with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, -OR 3 , -COOR 3 OR-PO(OR 3 ) 2 [R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0068] In the above formula (10), A 4 are independently terminated with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, -OR 3 , -COOR 3OR-PO(OR 3 ) 2 and ends with CF 3 - or CF 2 The monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom is, for example, A 1 The end of 3 - or CF 2 Examples of the monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom include the same as those exemplified above. Here, R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the monovalent hydrocarbon group is preferably one having 1 to 6 carbon atoms, and examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups, alkenyl groups such as vinyl and allyl groups, aryl groups such as phenyl and tolyl groups, and aralkyl groups such as benzyl and phenylethyl groups. R 3 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. A 4 -OR 3 , -COOR 3 , -PO(OR 3 ) 2 As examples, -OH, -OCH 3 , -OC 2 H 5 , -COOH, -COOCH 3 , -COOC 2 H 5 , -PO(OH) 2 , -PO(OCH 3 ) 2 , -PO(OC 2 H 5 ) 2 Examples include:

[0069] Examples of the polymer not containing a hydrolyzable silyl group represented by the above formula (10) include the following. [ka] [ka] (In the formula, p', q', r', s', t', u', and the sum of p', q', r', s', t', u' are the same as above. Each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p', q', r', s', t', and u' may be randomly bonded.)

[0070] The surface treatment agent of the present invention comprises the above-mentioned fluorooxyalkylene group-containing polymer having at least one group represented by the following formula (1) at at least one terminal in the molecule and / or a partial hydrolysis condensate of the polymer, or a fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate of the polymer, and typically comprises a fluorooxyalkylene group-containing polymer having at least one, preferably at least two, hydrolyzable silyl groups at one terminal of the molecular chain represented by the above formula (2), (4) or (7) and / or a partial hydrolysis condensate of the polymer (one terminal or at least one fluorooxyalkylene group-containing polymer having at least one, preferably at least two, hydrolyzable silyl groups at both ends of the molecular chain, as represented by the above formula (2), (4) or (7), and / or a partial hydrolyzed condensate of said polymer (double-ended polymer); or a mixture containing at least one of said single-ended polymer and at least one of said double-ended polymer; or a mixture (fluorooxyalkylene group-containing polymer composition) containing any of the above polymers that does not contain a hydrolyzable silyl group.

[0071] In the fluorooxyalkylene group-containing polymer mixture (fluorooxyalkylene group-containing polymer composition) contained in the surface treatment agent of the present invention, the mixing ratio of the one-terminated polymer and / or both-terminated polymer to the polymer not containing a hydrolyzable silyl group is not particularly limited, but usually, it is desirable that the ratio of the polymer not containing a hydrolyzable silyl group is 0 to 30 mol %, particularly 0 to 10 mol %, based on the entire fluorooxyalkylene group-containing polymer composition consisting of the one-terminated polymer and / or both-terminated polymer and the polymer not containing a hydrolyzable silyl group.

[0072] In the surface treatment agent of the present invention, the amount of the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer, or the fluorooxyalkylene group-containing polymer composition may be in such an amount that the molecular weight distribution is in the range of 1.2 to 1.8, preferably 1.20 to 1.80, more preferably 1.22 to 1.70, and even more preferably 1.25 to 1.65.

[0073] In the surface treatment agent of the present invention, the number average molecular weight of the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer, or the fluorooxyalkylene group-containing polymer composition is preferably in the range of 1,000 to 20,000. The number average molecular weight is more preferably 2,000 to 10,000, even more preferably 2,500 to 9,000, and particularly preferably 3,000 to 8,000, from the viewpoint of forming a film having excellent water / oil repellency and scratch resistance.

[0074] The fluorooxyalkylene group-containing polymer and / or partial hydrolysis condensate of the polymer, or the fluorooxyalkylene group-containing polymer composition having the above molecular weight distribution and / or number average molecular weight can be obtained by rectifying or molecular distilling a mixture of the above single-terminated polymer and / or double-terminated polymer and a polymer not containing a hydrolyzable silyl group, and / or a composition containing a partial hydrolysis condensate of these polymers. In addition, the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer, or the fluorooxyalkylene group-containing polymer composition having the above-mentioned molecular weight distribution and / or number average molecular weight can also be prepared by previously preparing a fluorine compound used in synthesizing the fluorooxyalkylene group-containing polymer having the above-mentioned molecular weight distribution and / or number average molecular weight.

[0075] If necessary, the surface treatment agent of the present invention may contain a hydrolysis and condensation catalyst, for example, an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium 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.). Among these, acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. The amount of addition 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 a fluorooxyalkylene group-containing polymer containing at least one hydrolyzable silyl group and / or a partial hydrolysis and condensation product of the polymer.

[0076] The surface treatment agent of the present invention may contain a solvent. The solvent is preferably a fluorine-modified aliphatic hydrocarbon solvent (perfluoroheptane, perfluorooctane, etc.), a fluorine-modified olefin solvent (methoxyperfluoroheptene, etc.), a fluorine-modified aromatic hydrocarbon solvent (m-xylene hexafluoride, benzotrifluoride, 1,3-trifluoromethylbenzene, etc.), a fluorine-modified ether solvent (methylperfluorobutylether, ethylperfluorobutylether, perfluoro(2-butyltetrahydrofuran), etc.), a fluorine-modified alkylamine solvent (perfluorotributylamine, perfluorotripentylamine, etc.), a hydrocarbon solvent (petroleum benzine, mineral spirits, toluene, xylene, etc.), or a ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents (referred to as fluorine-based solvents) are desirable in terms of solubility, wettability, etc., and 1,3-trifluoromethylbenzene, m-xylene hexafluoride, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are particularly preferred.

[0077] The above-mentioned solvent may be a mixture of two or more of them, and is preferably one that can uniformly dissolve the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer. The optimal concentration of the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer to be dissolved in the solvent may be appropriately selected depending on the method of using the surface treatment agent, and is not limited. The concentration of the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate of the polymer to be dissolved in the solvent is usually 0.01 to 30 mass%, preferably 0.02 to 25 mass%, and more preferably 0.05 to 20 mass%.

[0078] The surface treatment agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition. The heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method, but for example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferably at 25 to 150°C, particularly 25 to 120°C, for 0.5 to 48 hours, particularly 12 to 24 hours. In the case of application by vapor deposition, it is preferably at 25 to 150°C, particularly 25 to 120°C, for 0.5 to 48 hours, particularly 12 to 24 hours. It may also be cured under humidification. The thickness of the cured coating is appropriately selected depending on the type of substrate, but is usually 5 to 30 nm, particularly 8 to 20 nm.

[0079] 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 oxide, glass plate, plastic, ceramic, quartz, etc. The surface treatment agent of the present invention can impart water and oil repellency, surface slipperiness, low dynamic friction, and scratch resistance to the substrate. In particular, SiO 2 It can be suitably used as a surface treatment agent for treated glass or quartz substrates.

[0080] In the present invention, the difference in haze between the substrate and the substrate on which a cured coating made of the cured product of the surface treatment agent of the present invention is formed, measured by a method conforming to JIS K 7136 (i.e., the haze value of the substrate surface-treated with the cured coating made of the cured product of the surface treatment agent of the present invention minus the haze value of the substrate alone) is preferably 0.2 or less, particularly preferably 0.15 or less. When the difference in haze is 0.2 or less, a cured coating having good visibility and excellent abrasion resistance can be formed. In order to make the difference in haze value 0.2 or less, a fluorooxyalkylene group-containing polymer used in the surface treatment agent of the present invention is one having at least two groups represented by the above formula (1) at at least one terminal in the molecule, and further, a surface treatment agent in which the molecular weight distribution of the fluorooxyalkylene group-containing polymer is a relatively wide molecular weight distribution within a specific range is used to form a cured coating.

[0081] Examples of articles that can be treated with the surface treatment agent of the present invention include glass, hard-coated films, high-hardness films, anti-reflection films, eyeglass lenses, optical lenses, quartz substrates, etc. In particular, the agent is useful as a treatment agent for forming a water- and oil-repellent layer on the surface of tempered glass and anti-reflection treated glass. EXAMPLES

[0082] 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.

[0083] [Molecular weight distribution measurement method] The fluorooxyalkylene group-containing polymer or the fluorooxyalkylene group-containing polymer composition was measured by gel permeation chromatography (GPC) to calculate the molecular weight distribution (ratio of weight average molecular weight (Mw) / number average molecular weight (Mn)). The measurement conditions were as follows: Measurement conditions Developing solvent: Hydrochlorofluorocarbon (HCFC)-225 Flow rate: 1mL / min Detector: Evaporative light scattering detector Column: Tosoh TSKgel Multipore HXL-M 7.8mmφ×30cm 2 pieces used Column temperature: 35℃ Sample injection volume: 100 μL (0.1% by mass solution)

[0084] [Number average molecular weight calculation method] Regarding the fluorooxyalkylene group-containing polymer or the fluorooxyalkylene group-containing polymer composition, 19 The number average molecular weight (Mn) was calculated from the characteristic peak intensity ratio of F-NMR analysis.

[0085] [Example 1-1] A compound (starting material) represented by the following formula (1a) and having a number average molecular weight of 4,000 and a molecular weight distribution of 1.32 was used in the following synthesis. [ka]

[0086] 50 g of the compound of formula (1a), which is the starting material, was dissolved in a mixed solvent of 5 g of 1,3-trifluoromethylbenzene and 20 g of methanol. After stirring at 60°C for 4 hours, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The product obtained was 19 F-NMR confirmed that the compound was the compound of formula (1b) below.

[0087] [ka] 40 g of the compound of formula (1b), 36 g of allyl magnesium chloride, and 30 g of Asahiklin AC6000 (AGC) were placed in a reaction vessel and stirred at 60°C for 2 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was removed and the solvent was distilled off under reduced pressure, yielding 30 g of a liquid product. The product obtained was 19 F-NMR and 1It was confirmed by 1 H-NMR that the compound was the compound of the following formula (1c). [ka]

[0088] A reaction vessel was charged with 30 g of the compound of formula (1c), 15 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone). -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (1d) shown below. The compound of formula (1d) had a number average molecular weight of 4,400 and a molecular weight distribution of 1.32. [ka]

[0089] The product (fluoropolyether group-containing polymer) obtained above was dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare surface treatment agent 1-1.

[0090] [Example 1-2] A mixture (starting material) consisting of 80 mol % of the compound of formula (2a-1) shown below and 20 mol % of the compound of formula (2a-2) shown below, having a number average molecular weight of 4,000 and a molecular weight distribution of 1.35, was used in the following synthesis. [ka]

[0091] 50 g of a mixture consisting of 80 mol % of the compound of formula (2a-1) and 20 mol % of the compound of formula (2a-2), which are the starting materials, was dissolved in a mixed solvent of 5 g of 1,3-trifluoromethylbenzene and 20 g of methanol. After stirring at 60° C. for 4 hours, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The product obtained was 19 It was confirmed by F-NMR that the product was a mixture consisting of 80 mol % of the compound of the following formula (2b-1) and 20 mol % of the compound of formula (2b-2). [ka]

[0092] A reaction vessel was charged with 40 g of a mixture consisting of 80 mol % of the compound of formula (2b-1) and 20 mol % of the compound of formula (2b-2), 36 g of allyl magnesium chloride, and 30 g of AC6000, and the mixture was stirred at 60° C. for 2 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was taken out, and the solvent was distilled off under reduced pressure, yielding 30 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the product was a mixture consisting of 80 mol % of the compound of the following formula (2c-1) and 20 mol % of the compound of formula (2c-2). [ka]

[0093] A mixture of 30 g of 80 mol % of the compound of the above formula (2c-1) and 20 mol % of the compound of the formula (2c-2), 15 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5×10 as Pt alone) was added. -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1It was confirmed by H-NMR that the mixture was composed of 80 mol % of the compound of formula (2d-1) and 20 mol % of the compound of formula (2d-2) shown below. The mixture composed of 80 mol % of the compound of formula (2d-1) and 20 mol % of the compound of formula (2d-2) had a number average molecular weight of 4,500 and a molecular weight distribution of 1.35. [ka]

[0094] The mixture (fluoropolyether group-containing polymer) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 1-2.

[0095] [Examples 1-3] A mixture (starting material) consisting of 76 mol % of the compound of formula (3a-1), 19 mol % of the compound of formula (3a-2), and 5 mol % of the compound of formula (3a-3) shown below, having a number average molecular weight of 4,000 and a molecular weight distribution of 1.37, was used in the following synthesis. [ka]

[0096] 50 g of a mixture consisting of 76 mol % of the compound of formula (3a-1), 19 mol % of the compound of formula (3a-2), and 5 mol % of the compound of formula (3a-3), which are the starting materials, was dissolved in a mixed solvent of 5 g of 1,3-trifluoromethylbenzene and 20 g of methanol. After stirring at 60° C. for 4 hours, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The product obtained was 19 F-NMR confirmed that the product was a mixture consisting of 76 mol % of the compound of the following formula (3b-1), 19 mol % of the compound of formula (3b-2), and 5 mol % of the compound of formula (3b-3). [ka]

[0097] A reaction vessel was charged with 40 g of a mixture consisting of 76 mol % of the compound of formula (3b-1), 19 mol % of the compound of formula (3b-2), and 5 mol % of the compound of formula (3b-3), 36 g of allyl magnesium chloride, and 30 g of AC6000, and the mixture was stirred at 60° C. for 2 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was removed, and the solvent was distilled off under reduced pressure, yielding 30 g of a liquid product. The product obtained was 19 F-NMR and 1 H-NMR confirmed that the product was a mixture consisting of 76 mol % of the compound of the following formula (3c-1), 19 mol % of the compound of formula (3c-2), and 5 mol % of the compound of formula (3c-3). [ka]

[0098] 30 g of a mixture consisting of 76 mol % of the compound of the above formula (3c-1), 19 mol % of the compound of the formula (3c-2), and 5 mol % of the compound of the formula (3c-3), 15 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the mixture was composed of 76 mol% of the compound of formula (3d-1), 19 mol% of the compound of formula (3d-2), and 5 mol% of the compound of formula (3d-3) shown below. The mixture composed of 76 mol% of the compound of formula (3d-1), 19 mol% of the compound of formula (3d-2), and 5 mol% of the compound of formula (3d-3) had a number average molecular weight of 4,400 and a molecular weight distribution of 1.37. [ka]

[0099] The mixture (fluoropolyether group-containing polymer) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 1-3.

[0100] [Examples 1-4] 30 g of the compound of formula (1c) in Example 1-1 above, 30 g of 1,3-trifluoromethylbenzene, 2.7 g of allyl bromide, and 0.06 g of tetrabutylammonium iodide were mixed. Then, 2.4 g of potassium hydroxide was added, and the mixture was stirred at 60°C for 11 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was taken out, and the solvent was distilled off, to obtain 28 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (4a). [ka]

[0101] A mixture of 25 g of the compound of formula (4a), 15 g of 1,3-trifluoromethylbenzene, 3.6 g of trimethoxysilane, and 0.023 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 23 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (4b) shown below. The compound of formula (4b) had a number average molecular weight of 4,500 and a molecular weight distribution of 1.32. [ka]

[0102] The product obtained above (fluoropolyether group-containing polymer) was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 1-4.

[0103] [Examples 1-5] 30 g of the compound of formula (1c) in Example 1-1 above, 30 g of 1,3-trifluoromethylbenzene, 7.8 g of diethylene glycol 2-bromoethyl methyl ether, and 0.07 g of tetrabutylammonium iodide were mixed. Then, 6.2 g of potassium hydroxide was added, and the mixture was aged at 60°C for 11 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was taken out, and the solvent was distilled off under reduced pressure, obtaining 28 g of a liquid product. The obtained product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (5a). [ka]

[0104] A mixture of 25 g of the compound of formula (5a), 15 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (2.5 × 10 -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 23 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (5b) shown below. The compound of formula (5b) had a number average molecular weight of 4,400 and a molecular weight distribution of 1.32. [ka]

[0105] The product obtained above (fluoropolyether group-containing polymer) was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 1-5.

[0106] [Examples 1-6] A compound (starting material) represented by the following formula (6a) and having a number average molecular weight of 6,000 and a molecular weight distribution of 1.45 was used in the following synthesis. [ka]

[0107] 50 g of the compound of formula (6a), which is the starting material, was dissolved in a mixed solvent of 40 g of AC6000 and 20 g of methanol. After stirring at 60°C for 11 hours, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The product obtained was 19 F-NMR confirmed that the compound was the compound of the following formula (6b). [ka]

[0108] 40 g of the compound of formula (6b), 40 g of allyl magnesium chloride, 41 g of AC6000, and 54 g of PF5060 (3M) were placed in a reaction vessel and stirred at 50° C. for 2 hours. After that, an appropriate amount of hydrochloric acid was added and stirred, and then thoroughly washed with water. Furthermore, the lower layer was taken out and the solvent was distilled off under reduced pressure, obtaining 30 g of a liquid product. The obtained product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (6c). [ka]

[0109] 30 g of the compound of the above formula (6c), 15 g of AC6000, 2.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (6d) shown below. The compound of formula (6d) had a number average molecular weight of 6,400 and a molecular weight distribution of 1.45. [ka]

[0110] The product obtained above (fluoropolyether group-containing polymer) was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 1-6.

[0111] [Examples 1-7] A compound (starting material) represented by the following formula (7a) and having a number average molecular weight of 9,000 and a molecular weight distribution of 1.53 was used in the following synthesis. [ka]

[0112] 50 g of the compound of formula (7a), which is the starting material, was dissolved in a mixed solvent of 40 g of AC6000 and 20 g of methanol. After stirring at 60°C for 11 hours, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The product obtained was 19 F-NMR confirmed that the compound was the compound of the following formula (7b). [ka]

[0113] 40 g of the compound of formula (7b), 40 g of allyl magnesium chloride, 41 g of AC6000, and 54 g of PF5060 were placed in a reaction vessel and stirred at 50°C for 2 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was removed and the solvent was distilled off under reduced pressure to obtain 30 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (7c). [ka]

[0114] 30 g of the compound of the above formula (7c), 15 g of AC6000, 2.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (7d) shown below. The compound of formula (7d) had a number average molecular weight of 9,400 and a molecular weight distribution of 1.53. [ka]

[0115] The product obtained above (fluoropolyether group-containing polymer) was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 1-7.

[0116] [Examples 1-8] A compound (starting material) represented by the following formula (8a) and having a number average molecular weight of 4,000 and a molecular weight distribution of 1.32 was used in the following synthesis. [ka]

[0117] In a reaction vessel, 50 g of the compound of formula (8a), 8.5 g of allyl bromide, 1.0 g of tetrabutylammonium hydrogen sulfate, and 7.0 g of a 30% by mass aqueous solution of sodium hydroxide were placed and stirred at 60° C. for 11 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, followed by thorough washing. The lower layer was then removed and the solvent was distilled off under reduced pressure, yielding 40 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (8b). [ka]

[0118] A mixture of 40 g of the compound of formula (8b), 8 g of 1,3-trifluoromethylbenzene, 7.0 g of 1,4-phenylenebisdimethylsilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8 The mixture was stirred at 80° C. for 5 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 35 g of a liquid product. 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (8c). [ka]

[0119] 30 g of the compound of the above formula (8c), 8 g of 1,3-trifluoromethylbenzene, 1.8 g of vinyltrimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8 The mixture (containing 1 mole of ethyl acetate) was stirred at 80° C. for 5 hours. After that, the solvent and unreacted materials were distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of the following formula (8d): The compound of formula (8d) had a number average molecular weight of 4,400 and a molecular weight distribution of 1.32. [ka]

[0120] The product obtained above (fluoropolyether group-containing polymer) was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 1-8.

[0121] [Examples 1-9] 30 g of the compound of formula (1b) in Example 1-1 above, 10 g of 1,3-trifluoromethylbenzene, and 6.0 g of 2,2-diallyl-4-penten-1-amine were stirred at 50° C. for 5 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 25 g of a liquid product. The product obtained was 1It was confirmed by 1 H-NMR that the compound was the compound of the following formula (9a). [ka]

[0122] A mixture of 25 g of the compound of formula (9a), 10 g of 1,3-trifluoromethylbenzene, 2.0 g of trimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8 The mixture was mixed with 100 moles of ethyl alcohol and aged at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (9b) shown below. The compound of formula (9b) had a number average molecular weight of 4,600 and a molecular weight distribution of 1.32. [ka]

[0123] The product obtained above (fluoropolyether group-containing polymer) was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 1-9.

[0124] [Comparative Example 1-1] A compound consisting only of the compound of formula (10a) shown below, having a number average molecular weight of 4,400 and a molecular weight distribution of 1.02, was produced in the same manner as in Example 1-1, except that a compound represented by formula (1a) having a number average molecular weight of 4,000 and a molecular weight distribution of 1.02 was used as a starting material instead of the compound represented by formula (1a) as the starting material in Example 1-1, and the compound was dissolved in Novec 7200 to a concentration of 20 mass%, to prepare a surface treatment agent 1-10. [ka]

[0125] [Comparative Example 1-2] In Example 1-2, instead of the starting material mixture of 80 mol% of the compound of formula (2a-1) and 20 mol% of the compound of formula (2a-2), which has a number average molecular weight of 4,000 and a molecular weight distribution of 1.35, a mixture of 80 mol% of the compound of formula (2a-1) and 20 mol% of the compound of formula (2a-2), which has a number average molecular weight of 4,000 and a molecular weight distribution of 1.05, was used as the starting material in the same manner as in Example 1-2, except that a mixture of 80 mol% of the compound of formula (11a-1) and 20 mol% of the compound of formula (11a-2) shown below, which has a number average molecular weight of 4,500 and a molecular weight distribution of 1.05, was produced, and the mixture was dissolved in Novec 7200 to a concentration of 20 mass%, to prepare a surface treatment agent 1-11. [ka]

[0126] [Comparative Example 1-3] A compound represented by formula (1c) was prepared in the same manner as in Example 1-1, except that a compound represented by formula (1a) having a number average molecular weight of 4,000 and a molecular weight distribution of 1.07 was used as a starting material instead of the compound represented by formula (1a) in Example 1-1, which has a number average molecular weight of 4,000 and a molecular weight distribution of 1.32. A compound represented by formula (1c) was prepared in the same manner as in Example 1-5, except that the compound was used as an intermediate material. A compound consisting only of the compound represented by formula (12a) shown below, having a number average molecular weight of 4,400 and a molecular weight distribution of 1.07, was produced. The compound was dissolved in Novec 7200 to a concentration of 20 mass%, to prepare a surface treatment agent 1-12. [ka]

[0127] [Comparative Example 1-4] A compound consisting only of the compound of formula (13a) shown below and having a number average molecular weight of 6,400 and a molecular weight distribution of 1.07 was produced in the same manner as in Example 1-6, except that a compound represented by formula (6a) having a number average molecular weight of 6,000 and a molecular weight distribution of 1.07 was used as a starting material instead of the compound represented by formula (6a) and having a number average molecular weight of 6,000 and a molecular weight distribution of 1.45 in Example 1-6. The compound was dissolved in Novec 7200 to a concentration of 20 mass%, to prepare a surface treatment agent 1-13. [ka]

[0128] [Preparation of cured film] SiO on the top surface 2 5 μl of each surface treatment agent was vacuum-deposited (treatment condition pressure: 2.0 × 10 -2 The coating was cured for 12 hours in an atmosphere of 80°C and 80% humidity (Pa, heating temperature: 700°C) to obtain a cured coating with a thickness of 10 nm.

[0129] The water sliding angle of each of the resulting cured coatings was measured by the following method. The results are shown in Table 1.

[0130] [Measurement of water fall angle] For the glass having the cured coating formed thereon, the sliding angle of the cured coating in water was measured using a contact angle meter Drop Master (Kyowa Interface Science Co., Ltd.) (droplet: 20 μl, temperature: 25° C., humidity: 40%).

[0131] [Table 1]

[0132] The surface treatment agents of Examples 1-1 to 1-9, which contain the fluoropolyether group-containing polymer having a relatively wide molecular weight distribution within a specific range of the present invention, had a broader molecular weight distribution than the fluoropolyether group-containing polymer contained in the surface treatment agents of Comparative Examples 1-1 to 1-4, and therefore had a reduced water sliding angle.

[0133] [Synthesis Example 1] A compound (starting material) represented by the following formula (1A) and having a number average molecular weight of 4,000 and a molecular weight distribution of 1.02 was used in the following synthesis. [ka]

[0134] 50 g of the compound of formula (1A), which is the starting material, was dissolved in a mixed solvent of 5 g of 1,3-trifluoromethylbenzene and 20 g of methanol. After stirring at 60° C. for 4 hours, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The product obtained was 19 F-NMR confirmed that the compound was the compound of formula (1B) below. [ka]

[0135] 40 g of the compound of formula (1B), 36 g of allyl magnesium chloride, and 30 g of Asahiklin AC6000 (AGC) were placed in a reaction vessel and stirred at 60°C for 2 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was removed and the solvent was distilled off under reduced pressure, yielding 30 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (1C). [ka]

[0136] In a reaction vessel, 30 g of the compound of the above formula (1C), 15 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) were placed. -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (1D) shown below. The compound of formula (1D) had a number average molecular weight of 4,400 and a molecular weight distribution of 1.02. [ka]

[0137] [Synthesis Example 2] A compound (starting material) represented by the following formula (2A) and having a number average molecular weight of 4,000 and a molecular weight distribution of 1.32 was used in the following synthesis. [ka]

[0138] 50 g of the compound of formula (2A), which is the starting material, was dissolved in a mixed solvent of 5 g of 1,3-trifluoromethylbenzene and 20 g of methanol. After stirring at 60° C. for 4 hours, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The product obtained was 19 F-NMR confirmed that the compound was the compound of formula (2B) below. [ka]

[0139] 40 g of the compound of formula (2B), 36 g of allyl magnesium chloride, and 30 g of AC6000 were placed in a reaction vessel and stirred at 60° C. for 2 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was removed, and the solvent was distilled off under reduced pressure to obtain 30 g of a liquid product. The product obtained was 19 F-NMR and1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (2C). [ka]

[0140] In a reaction vessel, 30 g of the compound of the above formula (2C), 15 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) were placed. -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (2D) shown below. The compound of formula (2D) had a number average molecular weight of 4,400 and a molecular weight distribution of 1.32. [ka]

[0141] [Synthesis Example 3] A compound (starting material) represented by the following formula (3A) and having a number average molecular weight of 8,000 and a molecular weight distribution of 1.50 was used in the following synthesis. [ka]

[0142] 50 g of the compound of formula (3A), which is the starting material, was dissolved in a mixed solvent of 40 g of AC6000 and 20 g of methanol. After stirring at 60°C for 11 hours, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The product obtained was 19 F-NMR confirmed that the compound was the compound of formula (3B) below. [ka]

[0143] 40 g of the compound of formula (3B), 40 g of allyl magnesium chloride, 41 g of AC6000, and 54 g of PF5060 were placed in a reaction vessel and stirred at 50° C. for 2 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was removed, and the solvent was distilled off under reduced pressure to obtain 30 g of a liquid product. The product obtained was 19 F-NMR and 1 H-NMR confirmed that the compound was the compound of formula (3C) below. [ka]

[0144] 30 g of the compound of the above formula (3C), 15 g of AC6000, 2.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (3D) shown below. The compound of formula (3D) had a number average molecular weight of 8,400 and a molecular weight distribution of 1.50. [ka]

[0145] [Synthesis Example 4] 30 g of the compound of formula (2C) in Synthesis Example 2 above, 30 g of 1,3-trifluoromethylbenzene, 7.8 g of diethylene glycol 2-bromoethyl methyl ether, and 0.07 g of tetrabutylammonium iodide were mixed. Then, 6.2 g of potassium hydroxide was added, and the mixture was aged at 60°C for 11 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was taken out, and the solvent was distilled off under reduced pressure, obtaining 28 g of a liquid product. The obtained product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (4A). [ka]

[0146] A mixture of 25 g of the compound of formula (4A), 15 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (2.5 × 10 -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 23 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (4B) shown below. The compound of formula (4B) had a number average molecular weight of 4,400 and a molecular weight distribution of 1.32. [ka]

[0147] [Synthesis Example 5] 30 g of the compound of formula (2C) in Synthesis Example 2 above, 30 g of 1,3-trifluoromethylbenzene, 2.7 g of allyl bromide, and 0.06 g of tetrabutylammonium iodide were mixed. Then, 2.4 g of potassium hydroxide was added, and the mixture was stirred at 60° C. for 11 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was taken out, and the solvent was distilled off, to obtain 28 g of a liquid product. The obtained product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (5A). [ka]

[0148] A mixture of 25 g of the compound of formula (5A), 15 g of 1,3-trifluoromethylbenzene, 3.6 g of trimethoxysilane, and 0.023 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 23 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (5B) shown below. The compound of formula (5B) had a number average molecular weight of 4,500 and a molecular weight distribution of 1.32. [ka]

[0149] [Synthesis Example 6] A compound (starting material) represented by the following formula (6A) and having a number average molecular weight of 4,000 and a molecular weight distribution of 1.32 was used in the following synthesis. [ka]

[0150] In a reaction vessel, 50 g of the compound of formula (6A), 4.2 g of allyl bromide, 1.0 g of tetrabutylammonium hydrogen sulfate, and 6.0 g of a 30% by mass aqueous solution of sodium hydroxide were placed and stirred at 60° C. for 11 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, followed by thorough washing. The lower layer was then removed and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (6B). [ka]

[0151] A mixture of 40 g of the compound of formula (6B), 40 g of 1,3-trifluoromethylbenzene, 0.2 g of triacetoxymethylsilane, 3.8 g of trichlorosilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8 The mixture was stirred at 60° C. for 5 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 36 g of a liquid product.19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (6C). [ka]

[0152] 36 g of the compound of formula (6C), 40 g of 1,3-trifluoromethylbenzene, and 6.0 g of allylmagnesium bromide were placed in a reaction vessel and stirred at 25°C for 10 hours. Then, an appropriate amount of methanol was added and stirred, and the mixture was thoroughly washed. Furthermore, the lower layer was removed and the solvent was distilled off under reduced pressure to obtain 34 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (6D). [ka]

[0153] 34 g of the compound of the above formula (6D), 35 g of 1,3-trifluoromethylbenzene, 0.15 g of triacetoxymethylsilane, 6.5 g of trichlorosilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8 The mixture was stirred at 60° C. for 5 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 36 g of a liquid product. 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (6E). [ka]

[0154] 36 g of the compound of formula (6E), 35 g of 1,3-trifluoromethylbenzene, 2.0 g of methanol, and 10 g of trimethyl orthoformate were mixed and stirred at 65° C. for 3 hours. After that, the solvent and unreacted materials were distilled off under reduced pressure to obtain 33 g of a liquid product. The obtained product was 1It was confirmed by H-NMR that the compound was the compound of formula (6F) shown below. The compound of formula (6F) had a number average molecular weight of 4,600 and a molecular weight distribution of 1.32. [ka]

[0155] [Synthesis Example 7] A compound (starting material) represented by the following formula (7A) and having a number average molecular weight of 8,000 and a molecular weight distribution of 1.50 was used in the following synthesis. [ka]

[0156] In a reaction vessel, 50 g of the compound of formula (7A), 3.0 g of allyl bromide, 0.68 g of tetrabutylammonium hydrogen sulfate, and 5.9 g of a 30% by mass aqueous solution of sodium hydroxide were placed and stirred at 60° C. for 11 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed. The lower layer was then removed and the solvent was distilled off under reduced pressure to obtain 45 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (7B). [ka]

[0157] 45 g of the compound of the above formula (7B), 40 g of AC6000, 0.2 g of triacetoxymethylsilane, 3.7 g of trichlorosilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8 The mixture was stirred at 60° C. for 5 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 40 g of a liquid product. 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (7C). [ka]

[0158] 40 g of the compound of formula (7C), 40 g of AC6000, and 4.3 g of allyl magnesium bromide were placed in a reaction vessel and stirred at 25°C for 10 hours. Then, an appropriate amount of methanol was added and stirred, and the mixture was thoroughly washed. Furthermore, the lower layer was removed and the solvent was distilled off under reduced pressure to obtain 36 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (7D). [ka]

[0159] 36 g of the compound of the above formula (7D), 40 g of AC6000, 0.10 g of triacetoxymethylsilane, 3.0 g of trichlorosilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8 The mixture was stirred at 60° C. for 5 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 30 g of a liquid product. 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (7E). [ka]

[0160] 30 g of the compound of formula (7E), 35 g of AC6000, 1.0 g of methanol, and 3.2 g of trimethyl orthoformate were mixed and stirred at 65° C. for 3 hours. After that, the solvent and unreacted materials were distilled off under reduced pressure to obtain 33 g of a liquid product. The obtained product was 1 It was confirmed by H-NMR that the compound was the compound of formula (7F) shown below. The compound of formula (7F) had a number average molecular weight of 8,600 and a molecular weight distribution of 1.50. [ka]

[0161] [Synthesis Example 8] A mixed solution of 35 g of bis(2-methoxyethoxy)aluminum hydride-sodium toluene solution, 30 g of tetrahydrofuran, and 30 g of 1,3-trifluoromethylbenzene was prepared. Next, 50 g of the compound represented by formula (2A) which is the starting material in Synthesis Example 2 above and has a number average molecular weight of 4,000 and a molecular weight distribution of 1.32 was slowly added dropwise to the mixed solution cooled in an ice bath. After the dropwise addition, the mixture was stirred at 50°C for 3 hours. Then, hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was removed and the solvent was distilled off under reduced pressure, yielding 40 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (8A). [ka]

[0162] 40 g of the compound of formula (8A), 3.1 g of allyl bromide, and 0.83 g of tetrabutylammonium hydrogen sulfate were mixed. Then, 5.5 g of potassium hydroxide was added, and the mixture was stirred at 60° C. for 6 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was taken out, and the solvent was distilled off, to obtain 32 g of a liquid product. The obtained product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (8B). [ka]

[0163] 32 g of the compound of the above formula (8B), 23 g of 1,3-trifluoromethylbenzene, 7.9 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8The mixture was mixed with 100 moles of ethyl alcohol and aged at 75° C. for 7 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 31 g of a liquid product. 1 H-NMR confirmed that the compound was the compound of formula (8C) shown below. [ka]

[0164] A mixture of 31 g of the compound of formula (8C), 15 g of 1,3-trifluoromethylbenzene, 7.2 g of octenyltrimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8 The mixture was mixed with 100 moles of ethyl alcohol and aged at 80° C. for 6 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 28 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (8D) shown below. The compound of formula (8D) had a number average molecular weight of 4,600 and a molecular weight distribution of 1.33. [ka]

[0165] [Synthesis Example 9] 30 g of the compound of formula (2B) in Synthesis Example 2 above, 30 g of 1,3-trifluoromethylbenzene, and 6.0 g of 2,2-diallyl-4-penten-1-amine were stirred at 50° C. for 5 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 25 g of a liquid product. The product obtained was 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (9A). [ka]

[0166] A mixture of 25 g of the compound of formula (9A), 10 g of 1,3-trifluoromethylbenzene, 2.0 g of trimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) was used.-8 The mixture was mixed with 100 moles of ethyl alcohol and aged at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (9B) shown below. The compound of formula (9B) had a number average molecular weight of 4,600 and a molecular weight distribution of 1.32. [ka]

[0167] [Synthesis Example 10] In a nickel autoclave, 40 g of the compound of formula (2B) in Synthesis Example 2 and 60 g of methanol were placed. Then, 40 g of liquid ammonia was placed in the autoclave under a pressure of 1.0 MPa and stirred at 50° C. for 150 hours. After that, the solvent was distilled off under reduced pressure to obtain 35 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (10A). [ka]

[0168] A solution was prepared by mixing 1.6 g of lithium aluminum hydride and 20 g of tetrahydrofuran (THF). Next, 35 g of the compound of the above formula (10A) was dissolved in 10 g of 1,3-trifluoromethylbenzene, and slowly added dropwise to the THF solution cooled in an ice bath. After the dropwise addition, the mixture was stirred at 70°C for 10 hours. Then, an appropriate amount of an aqueous potassium hydroxide solution was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was removed, and the solvent was distilled off under reduced pressure, yielding 31 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (10B). [ka]

[0169] 31 g of the compound of formula (10B), 0.3 g of potassium hydrogen carbonate, and 2.8 g of allyl bromide were mixed and stirred at 70° C. for 11 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed. The lower layer was then removed and the solvent was distilled off under reduced pressure to obtain 28 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (10C). [ka]

[0170] 28 g of the compound of the above formula (10C), 30 g of 1,3-trifluoromethylbenzene, 2.5 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8 The mixture was mixed with 100 moles of ethyl alcohol and aged at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (10D) shown below. The compound of formula (10D) had a number average molecular weight of 4,300 and a molecular weight distribution of 1.32. [ka]

[0171] [Synthesis Example 11] A compound (starting material) represented by the following formula (11A) and having a number average molecular weight of 4,200 and a molecular weight distribution of 1.34 was used in the following synthesis. [ka]

[0172] The starting material, 20 g of the compound of formula (11A), 30 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8The mixture was mixed with 1.5 moles of ethyl alcohol and 1.0 moles of ethyl alcohol, and the mixture was aged at 80° C. for 3 hours. After that, the solvent and unreacted materials were distilled off under reduced pressure to obtain 18 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (11B) shown below. The compound of formula (11B) had a number average molecular weight of 4,400 and a molecular weight distribution of 1.34. [ka]

[0173] [Synthesis Example 12] A compound (starting material) represented by the following formula (12A) and having a number average molecular weight of 4,000 and a molecular weight distribution of 1.00 was used in the following synthesis. [ka]

[0174] 40 g of the compound of formula (12A), which is the starting material, 5.9 g of butenyl magnesium bromide, and 30 g of AC6000 were placed in a reaction vessel and stirred at 60° C. for 2 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was taken out, and the solvent was distilled off under reduced pressure, yielding 30 g of a liquid product. The product obtained was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (12B). [ka]

[0175] 30 g of the compound of formula (12B), 30 g of 1,3-trifluoromethylbenzene, 3.3 g of allyl bromide, and 0.06 g of tetrabutylammonium iodide were mixed. Then, 3.9 g of potassium hydroxide was added, and the mixture was stirred at 60°C for 18 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was taken out, and the solvent was distilled off, to obtain 28 g of a liquid product. The obtained product was 19 F-NMR and 1H-NMR confirmed that the compound was the compound of the following formula (12C). [ka]

[0176] 25 g of the compound of the above formula (12C), 30 g of 1,3-trifluoromethylbenzene, 3.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 23 g of a liquid product. 1 It was confirmed by H-NMR that the compound was the compound of formula (12D) shown below. The compound of formula (12D) had a number average molecular weight of 4,300 and a molecular weight distribution of 1.00. [ka]

[0177] [Synthesis Example 13] A compound represented by the following formula (13A), having a number average molecular weight of 4,300 and a molecular weight distribution of 1.40, was synthesized in the same manner as in Synthesis Example 12, except that a compound represented by formula (12A), having a number average molecular weight of 4,000 and a molecular weight distribution of 1.40 and represented by formula (12A), was used as a starting material instead of the compound represented by formula (12A), having a number average molecular weight of 4,000 and a molecular weight distribution of 1.00 in Synthesis Example 12. [ka]

[0178] [Synthesis Example 14] A compound (starting material) represented by the following formula (14A) and having a number average molecular weight of 5,000 and a molecular weight distribution of 1.30 was used in the following synthesis. [ka]

[0179] A compound represented by the following formula (14B) and having a number average molecular weight of 5,300 and a molecular weight distribution of 1.35 was synthesized in the same manner as in Synthesis Example 2, except that the compound represented by the above formula (14A) was used as a starting material instead of the compound represented by formula (2B) in Synthesis Example 2. [ka]

[0180] [Synthesis Example 15] A mixture (starting material) consisting of 80 mol % of the compound of formula (15A) shown below and 20 mol % of the compound of formula (15B) having a number average molecular weight of 8,000 and a molecular weight distribution of 1.55 was used in the following synthesis. [ka]

[0181] 50 g of a mixture consisting of 80 mol % of the compound of formula (15A) and 20 mol % of the compound of formula (15B), which are the starting materials, was dissolved in a mixed solvent of 40 g of AC6000 and 20 g of methanol. After stirring at 60° C. for 4 hours, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 48 g of a liquid product. The product obtained was 19 It was confirmed by F-NMR that the product was a mixture consisting of 80 mol % of the compound of the following formula (15C) and 20 mol % of the compound of formula (15D). [ka]

[0182] A reaction vessel was charged with 48 g of a mixture consisting of 80 mol % of the compound of formula (15C) and 20 mol % of the compound of formula (15D), 48 g of allyl magnesium chloride, 40 g of AC6000, and 40 g of PF5060, and the mixture was stirred at 50° C. for 2 hours. Then, an appropriate amount of hydrochloric acid was added and stirred, and the mixture was thoroughly washed with water. Furthermore, the lower layer was taken out, and the solvent was distilled off under reduced pressure, to obtain 40 g of a liquid product. The product obtained was 19 F-NMR and 1It was confirmed by 1 H-NMR that the product was a mixture consisting of 80 mol % of the compound of the following formula (15E) and 20 mol % of the compound of formula (15F). [ka]

[0183] A mixture of 40 g of 80 mol % of the compound of the above formula (15E) and 20 mol % of the compound of the formula (15F), 15 g of AC6000, 2.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5×10 as Pt alone) was added. -8 The mixture was stirred at 80° C. for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the product was a mixture of 80 mol % of the compound of formula (15G) and 20 mol % of the compound of formula (15H) shown below. The mixture of 80 mol % of the compound of formula (15G) and 20 mol % of the compound of formula (15H) had a number average molecular weight of 8,600 and a molecular weight distribution of 1.55. [ka]

[0184] [Example 2-1] The compound of formula (2D) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare a surface treatment agent 2-1.

[0185] [Example 2-2] The compound of formula (3D) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-2.

[0186] [Example 2-3] The compound of formula (4B) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-3.

[0187] [Example 2-4] The compound of formula (5B) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-4.

[0188] [Example 2-5] The compound of formula (6F) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-5.

[0189] [Example 2-6] The compound of formula (7F) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare a surface treatment agent 2-6.

[0190] [Example 2-7] The compound of formula (8D) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-7.

[0191] [Example 2-8] The compound of formula (9B) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-8.

[0192] [Example 2-9] The compound of formula (10D) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare a surface treatment agent 2-9.

[0193] [Example 2-10] The compound of formula (11B) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-10.

[0194] [Example 2-11] The compound of formula (13A) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-11.

[0195] [Example 2-12] The compound of formula (14B) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-12.

[0196] [Example 2-13] The mixture prepared by mixing the compound of formula (2D) and the compound of formula (3D) obtained above in equal masses was dissolved in Novec 7200 to a concentration of 20 mass%, to prepare surface treatment agent 2-13. The number average molecular weight of the mixture of the compound of formula (2D) and the compound of formula (3D) in equal masses was 6,500, and the molecular weight distribution was 1.70.

[0197] [Example 2-14] A mixture of 70% by mass of the compound of formula (1D) and 30% by mass of the compound of formula (5B) obtained above was dissolved in Novec 7200 to a concentration of 20% by mass to prepare surface treatment agent 2-14. The mixture of the compound of formula (1D) and the compound of formula (5B) above had a number average molecular weight of 4,500 and a molecular weight distribution of 1.22.

[0198] [Example 2-15] The mixture prepared by mixing the compound of formula (5B) and the compound of formula (12D) obtained above in equal masses was dissolved in Novec 7200 to a concentration of 20 mass%, to prepare surface treatment agent 2-15. The mixture of the compound of formula (5B) and the compound of formula (12D) in equal masses had a number average molecular weight of 4,400 and a molecular weight distribution of 1.36.

[0199] [Example 2-16] The mixture consisting of 80 mol % of the compound of formula (15G) and 20 mol % of the compound of formula (15H) obtained above was dissolved in Novec 7200 to a concentration of 20 mass %, thereby preparing surface treatment agent 2-16.

[0200] [Example 2-17] The mixture prepared by mixing the compound of formula (7F) and the compound of formula (9B) obtained above in equal amounts was dissolved in Novec 7200 to a concentration of 20% by mass to prepare surface treatment agent 2-17. The number average molecular weight of the mixture of the compound of formula (7F) and the compound of formula (9B) in equal amounts was 6,700, and the molecular weight distribution was 1.42.

[0201] [Example 2-18] The compound of formula (2D) obtained above was dissolved in methoxyperfluoroheptane to a concentration of 20 mass % to prepare surface treatment agent 2-18.

[0202] [Example 2-19] The compound of formula (2D) obtained above was dissolved in Novec 7200 to a concentration of 0.1 mass % to prepare surface treatment agent 2-19.

[0203] [Example 2-20] The compound of formula (3D) obtained above was dissolved in Novec 7200 to a concentration of 0.1 mass % to prepare surface treatment agent 2-20.

[0204] [Example 2-21] The compound of formula (6F) obtained above was dissolved in Novec 7200 to a concentration of 0.1 mass % to prepare surface treatment agent 2-21.

[0205] [Example 2-22] The compound of formula (8D) obtained above was dissolved in Novec 7200 to a concentration of 0.1 mass % to prepare surface treatment agent 2-22.

[0206] [Example 2-23] The compound of formula (9B) obtained above was dissolved in Novec 7200 to a concentration of 0.1 mass % to prepare surface treatment agent 2-23.

[0207] [Comparative Example 2-1] The compound of formula (1D) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-24.

[0208] [Comparative Example 2-2] The compound of formula (12D) obtained above was dissolved in Novec 7200 to a concentration of 20 mass % to prepare surface treatment agent 2-25.

[0209] [Comparative Example 2-3] The mixture prepared by mixing the compound of formula (1D) and the compound of formula (12D) obtained above in equal masses was dissolved in Novec 7200 to a concentration of 20 mass%, to prepare surface treatment agent 2-26. The number average molecular weight of the mixture of the compound of formula (1D) and the compound of formula (12D) in equal masses was 4,400, and the molecular weight distribution was 1.05.

[0210] [Comparative Example 2-4] The compound of formula (1D) obtained above was dissolved in Novec 7200 to a concentration of 0.1 mass % to prepare surface treatment agent 2-27.

[0211] [Preparation of cured film] SiO on the top surface 2 A film with 100 nm of SiO on the surface of a transparent hard-coated PET film (Ray Hyper VC01, manufactured by Nakai Industrial Co., Ltd.) 2 The surface treatment agents 2-1 to 2-18, 2-24 to 2-26 were vacuum-deposited at 6 μl onto a film (50 mm × 100 mm) that had been vapor-deposited to a thickness of 100 nm (treatment condition pressure: 2.0 × 10 -2 The coating was cured for 12 hours in an atmosphere of 80°C and 80% humidity (Pa, heating temperature: 700°C) to obtain a cured coating with a thickness of 14 nm.

[0212] Surface treatment agents 2-19 to 2-23, and 2-27 were spray-coated onto chemically strengthened glass (Corning, Gorilla 5) using a spray coating device (T&K Corporation, NST-51), and cured for 12 hours in an atmosphere at a temperature of 80°C and a humidity of 80%, to obtain a cured coating with a thickness of 14 nm.

[0213] For each of the resulting cured coatings, haze measurements and abrasion tests were carried out by the following methods.

[0214] [Haze measurement] The haze (%) of the film on which the cured coating was formed as described above was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) according to the method described in JIS K7136. The values ​​obtained by subtracting the blank values ​​(haze values ​​of films without the cured coating) from the measured values ​​(i.e., the increase in haze value) are shown in Table 2.

[0215] The haze (%) of the chemically strengthened glass on which the hardened coating film was formed was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) according to the method described in JIS K7136. The values ​​obtained by subtracting the blank value (the haze value of the chemically strengthened glass on which the hardened coating film was not formed) from the measured value (i.e., the increase in the haze value) are shown in Table 3.

[0216] [Wear resistance test] Abrasion resistance tests of the cured coating (water- and oil-repellent layer) were conducted under the following conditions using a reciprocating abrasion tester (HEIDON 30S, manufactured by Shinto Scientific Co., Ltd.). The contact angle of the cured coating (water- and oil-repellent layer) with water before and after the abrasion resistance test was measured using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.). The results for the film with the cured coating are shown in Table 2, and the results for the chemically strengthened glass with the cured coating are shown in Table 3. Evaluation environment conditions: 25°C, humidity 40% Friction material: CS-5 felt (manufactured by TABER) Load capacity: 1kg Rubbing distance (one way): 30mm Scraping speed: 3,600mm / min Number of round trips: 1,000

[0217] [Table 2]

[0218] [Table 3]

[0219] From the above results, in Comparative Examples 2-1, 2-2, and 2-4, the molecular weight distribution is smaller than 1.2, so the haze increases and the abrasion resistance is insufficient. In Comparative Example 2-3, even if two kinds of fluorooxyalkylene group-containing polymers are mixed, the molecular weight distribution of the entire mixture is smaller than the range of the present invention, so the haze increases. On the other hand, in Examples 2-1 to 2-23, the increase in haze is suppressed and the abrasion resistance is also good. In particular, it was found that by mixing multiple fluorooxyalkylene group-containing polymers, if the molecular weight distribution is within the range of the present invention, the increase in haze is suppressed and the abrasion resistance is excellent.

Claims

1. At least one terminal of the molecule has the following formula (1): 【Chemistry 1】 (In the formula, Y is a single bond or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond, R is an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is a hydrolyzable group, and a is 2 or 3.) and / or a partial hydrolyzed condensate of said polymer, wherein the fluorooxyalkylene group-containing polymer has a polyfluorooxyalkylene structure represented by -(C b F 2b O) m - (wherein b is independently an integer of 1 to 6 for each unit, and m is an integer of 1 to 250, and each of these units may be linear or branched) in the molecule, and the fluorooxyalkylene group-containing polymer and / or the partial hydrolyzed condensate of said polymer contained in the surface treatment agent, or a fluorooxyalkylene group-containing polymer mixture containing the fluorooxyalkylene group-containing polymer and / or the partial hydrolyzed condensate of said polymer, has a number average molecular weight of 1,000 to 20,000 and a molecular weight distribution in the range of 1.2 to 1.

8.

2. The surface treatment agent according to claim 1, wherein m in the -(C b F 2b O) m - is an integer of 10 to 250.

3. The surface treatment agent according to claim 1, wherein X in formula (1) is an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, or a halogen group.

4. 2. The surface treatment agent according to claim 1, wherein the fluorooxyalkylene group-containing polymer is represented by the following formula (2), (4) or (7): 【Chemistry 2】 [In the formula, Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d -(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t and u is an integer of 1 to 250, and each of these units may be linear or branched. In addition, each of the repeating units shown in parentheses with p, q, r, s, t and u may be bonded randomly), and A 1 is terminated with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3): 【Chemistry 3】 [In the formula, Q is a single bond or a divalent organic group, Z is a divalent to octavalent group, α is 0 or 1, β is an integer of 1 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the above formula (1)], 【Chemistry 4】 [In the formula, Rf is the same as above, A 2 is terminated with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5): 【Chemistry 5】 [In the formula, W is the same as defined above, B is independently a hydrogen atom or —OS, S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following formula (6): 【Chemistry 6】 (In the formula, T is a single bond or a divalent to octavalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, E is a monovalent hydrocarbon group having 1 to 6 carbon atoms or W, and l is an integer from 0 to 20.) and e is 1 or 2. 【Chemistry 7】 [In the formula, Rf is the same as above, A 3 is terminated with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, or J, where J is a monovalent group represented by the following formula (8): 【Chemistry 8】 [In the formula, S and e are the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond, and M is a group represented by the following formula (9): 【Chemistry 9】 (In the formula, Y, S, and W are the same as above, and f is an integer of 1 to 3.) is a monovalent group represented by the following formula:

5. The surface treatment agent according to claim 4, wherein in formula (3), Q is an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms which may contain one or more bonds selected from the group consisting of an amide bond, an ether bond, an ester bond, a sulfide bond, a urethane bond, a siloxane bond, a triazine bond, a diorganosilylene group, a silphenylene bond, and a silalkylene bond, and Z is a di- to octavalent group selected from a silicon atom, a nitrogen atom, a silalkylene group, a silarylene group, and a di- to octavalent organopolysiloxane residue having a siloxane bond.

6. The surface treatment agent according to claim 4, wherein in formula (6), T is a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a silalkylene bond, a silarylene bond, and a diorganosilylene group, a siloxane bond, a silalkylene group, or a diorganosilylene group.

7. 7. The surface treatment agent according to claim 1, wherein the fluorooxyalkylene group-containing polymer has at least two groups represented by the above formula (1) at at least one terminal in the molecule.

8. 8. The surface treatment agent according to claim 7, which provides a cured coating having a difference in haze value between a substrate and a cured coating comprising a cured product of the surface treatment agent formed on the substrate of 0.2 or less, as measured by a method in accordance with JIS K 7136.

9. Furthermore, the following formula (10) 【Chemistry 10】 (Wherein, Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d -(wherein, d is independently an integer of 0 to 5 for each unit, p, q, r, s, t and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t and u is an integer of 1 to 250, and each of these units may be linear or branched. In addition, each of the repeating units shown in parentheses with p, q, r, s, t and u may be bonded randomly), and A 4 are independently terminated with CF 3 - or CF 2 H-, a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom, -OR 3 , -COOR 3 Or -PO(OR 3 ) 2 [R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. The surface treatment agent according to any one of claims 1 to 8, which contains a fluorooxyalkylene group-containing polymer represented by the formula:

10. The surface treatment agent according to any one of claims 1 to 9, further comprising a fluorine-containing solvent.

11. An article having a coating of the cured product of the surface treatment agent according to any one of claims 1 to 10 on its surface.

12. 12. The article according to claim 11, which is any one selected from the group consisting of a glass plate, a hard coat film, a high hardness film, an anti-reflection film, a spectacle lens, an optical lens, and a quartz substrate.

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