Surface treatment agent and articles treated with the surface treatment agent

Abstract

To provide a surface treatment agent that exhibits excellent storage stability under any temperature environment, especially under heated conditions, and articles, etc., that have been surface-treated with the surface treatment agent. [Solution] (A) A hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof modified with a fluoropolyether group-containing polymer, (B) A surface treatment agent containing a fluorine-containing solvent, (B) The fluoride ions contained in the fluorine-containing solvent of component (B) are greater than 0% by mass of the total surface treatment agent, or 1.0 × 10 -5 A surface treatment agent that is less than or equal to mass percent.

Description

[Technical Field]

[0001] The present invention relates to a surface treatment agent containing a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, and more particularly to a surface treatment agent containing a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof that forms a film with excellent water-repellent, oil-repellent, surface-slippery, and abrasion-resistant properties, and to an article having a cured film of the surface treatment agent on its surface. [Background technology]

[0002] In recent years, the use of touch panels has accelerated, particularly in mobile phone displays. However, because touch panels have exposed screens, fingers and cheeks frequently come into direct contact with the screen, making them prone to accumulating dirt such as sebum. Therefore, there is a growing demand for technologies that make the surface of displays and screens less prone to fingerprints and easier to clean, in order to improve appearance and visibility. The development of materials that can meet these demands is highly desirable. Touch panel displays, in particular, are prone to fingerprint smudges, so the provision of a water- and oil-repellent layer is desirable. However, while conventional water- and oil-repellent layers have high water- and oil-repellent properties and are excellent at wiping away dirt, they have the problem of their stain-resistant performance deteriorating during use.

[0003] Generally, polymers containing fluoropolyether groups have very low surface free energy, resulting in properties such as water and oil repellency, chemical resistance, lubricity, mold release, and antifouling. These properties are utilized industrially in a wide range of applications, including water, oil, and stain repellents for paper and textiles, lubricants for magnetic recording media, oil inhibitors and mold release agents for precision equipment, cosmetics, and protective films. However, these properties also mean non-stickiness and poor adhesion to other substrates; while they can be applied to substrate surfaces, achieving a strong bond between the film and the substrate is difficult.

[0004] On the other hand, silane coupling agents are well known for bonding organic compounds to the surface of substrates such as glass and cloth, and are widely used as surface treatment agents for various substrate surfaces. A silane coupling agent has 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 with moisture in the air to form a film. This film becomes a strong and durable coating because the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.

[0005] Therefore, compositions have been disclosed that use a fluoropolyether group-containing polymer obtained by introducing a hydrolyzable silyl group into a fluorooxyalkylene group-containing compound, which can easily adhere to the substrate surface and form a coating on the substrate surface that has water-repellent and oil-repellent properties, chemical resistance, lubricity, mold release properties, and antifouling properties (Patent Documents 1-6:, JP 2008-534696, JP 2008-537557, JP 2012-072272, JP 2012-157856, JP 2013-136833, JP 2015-199906).

[0006] A surface treatment agent comprising a composition containing a fluoropolyether group-containing polymer in which a hydrolyzable silyl group has been introduced into the fluorooxyalkylene group-containing compound, and a diluent solvent, may easily form high molecular weight materials and gels when stored for a long period of time, due to hydrolysis and condensation of the terminal alkoxysilyl groups. Factors contributing to this formation include the water content in the surface treatment agent and the presence of acid / base catalysts. Since better storage stability of the surface treatment agent extends its lifespan, there is a need to improve its storage stability.

[0007] As a means of improving the storage stability of surface treatment agents, Patent Document 7 (Japanese Patent Application Publication No. 2015-214664) discloses that in a surface treatment agent containing a hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof modified with a fluoropolyether group-containing polymer as component (A) and a solvent capable of uniformly dissolving component (A) as component (B), the storage stability is improved by making the water content of the solvent component (B) 20 ppm or less by mass.

[0008] In addition, as a means of improving the storage stability of surface treatment agents, Patent Document 8 (International Publication No. 2023 / 149339) discloses a surface treatment agent containing a fluorine-containing ether compound and fluorine-containing ions, wherein the fluorine-containing ions are present in an amount of 0.1-3.0 ppm by mass relative to the total mass of the surface treatment agent, thereby improving storage stability and obtaining a cured film with excellent weather resistance. However, sufficient storage stability could not be obtained under heated conditions. [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] Japanese Patent Publication No. 2012-072272 [Patent Document 4] Japanese Patent Publication No. 2012-157856 [Patent Document 5] Japanese Patent Publication No. 2013-136833 [Patent Document 6] Japanese Patent Publication No. 2015-199906 [Patent Document 7] Japanese Patent Publication No. 2015-214664 [Patent Document 8] International Publication No. 2023 / 149339 [Overview of the project] [Problems that the invention aims to solve]

[0010] Therefore, the present invention aims to provide a surface treatment agent that exhibits excellent storage stability under any temperature environment, particularly under heated conditions, and which comprises a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, as well as articles and the like that have been surface-treated with the surface treatment agent. [Means for solving the problem]

[0011] As a result of diligent research to solve the above objectives, the inventors of the present invention discovered that the following surface treatment agent exhibits excellent storage stability even in environments with temperatures higher than room temperature (20-25°C), leading to the present invention.

[0012] In other words, the present invention provides a surface treatment agent containing a hydrolyzable group-containing silane modified with the following fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate of the silane, and articles having a cured film of the surface treatment agent on their surface.

[0013] [1] (A) A hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof modified with a fluoropolyether group-containing polymer, (B) A surface treatment agent containing a fluorine-containing solvent, (B) The fluoride ions contained in the fluorine-containing solvent of component (B) are greater than 0% by mass of the total surface treatment agent, or 1.0 × 10 -5 A surface treatment agent that is less than or equal to mass percent. [2] The surface treatment agent according to [1], wherein the content of component (A) is 0.05 to 30% by mass of the entire surface treatment agent. [3] (A) A surface treatment agent according to [1] or [2], wherein the number average molecular weight of the component is 1,000 to 25,000. [4] The surface treating agent according to any one of [1] to [3], wherein the hydrolyzable group-containing silane modified with the fluoropolyether group-containing polymer of component (A) has at least one group represented by the following formula (1) at at least one terminal in the molecule. [Chemical formula] (In formula (1), Y is a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom and a siloxane bond, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3.) [5] (A) The surface treating agent according to any one of [1] to [4], wherein the hydrolyzable group-containing silane modified with the fluoropolyether group-containing polymer has a polyfluorooxyalkylene structure represented by -(C b F 2b O) m -(wherein b is a number independently 1 to 6 for each unit, and m is a number 1 to 250. Each of these units may be linear or branched.) [6] (A) The surface treating agent according to any one of [1] to [5], wherein the silane in component (A) is represented by the following formula (2), (4) or (7). [Chemical formula] [In formula (2), Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d-(wherein d is independently a number from 0 to 5, p, q, r, s, t, and u are independently a number from 0 to 150, the sum of p, q, r, s, t, and u is a number from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit represented in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal end is CF3- or CF2H- and may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3). [ka] [In formula (3), Q is a single bond or a divalent organic group, Z is a 2- to 8valent group, α is 0 or 1, β is a number from 1 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by formula (1) above.] [ka] [In equation (4), Rf is the same as above, and A 2 is a monovalent fluorine-containing hydrocarbon group having a terminal end of CF3- or CF2H- and may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5). [ka] [In formula (5), W represents the same as above, 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 the following formula (6)] [ka] (In formula (6), T is a single bond or a 2- to 8-valent 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 a number from 0 to 20.) It is a monovalent group represented by this formula, and e is 1 or 2. [ka] [In equation (7), Rf is the same as above, and A 3 is a monovalent fluorine-containing hydrocarbon group having a terminal end of CF3- or CF2H- and may contain an oxygen atom, or J, where J is a monovalent group represented by the following formula (8). [ka] [In formula (8), S and e are the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have single bonds or ether bonds, and M is the following formula (9)] [ka] (In formula (9), Y, S, and W are the same as above, and f is a number from 1 to 3.) This is a monovalent group represented by this formula. [7] The surface treatment agent according to [6], 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 amide bonds, ether bonds, ester bonds, sulfide bonds, urethane bonds, siloxane bonds, triazine bonds, diorganosilylene groups, silphenylene bonds, and sylalkylene bonds, and Z is a 2 to 8-valent group selected from a silicon atom, a nitrogen atom, a sylalkylene group, a sylarylene group, and a 2 to 8-valent organopolysiloxane residue having a siloxane bond. [8] The surface treatment agent according to [6] or [7], wherein in formula (6), T is a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms, a siloxane bond, a sylalkylene group, or a diorganosilylene group, which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a sylalkylene bond, a sylarylene bond, and a diorganosilylene group. [9] Furthermore, the surface treatment agent according to any one of [1] to [8] further comprises a fluoropolyether group-containing polymer that does not contain hydrolyzable groups as component (C).

[10] The surface treatment agent according to [9], wherein the fluoropolyether group-containing polymer that does not contain hydrolyzable groups is represented by the following formula (10). [ka] (In equation (10), Rf is -C) d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d -(wherein d is independently a number from 0 to 5, p, q, r, s, t, and u are independently a number from 0 to 150, the sum of p, q, r, s, t, and u is a number from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit represented in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 4 These are monovalent fluorine-containing hydrocarbon groups whose terminal ends are CF3- or CF2H- and may contain an oxygen atom, -OR 3 ,-COOR 3 or -PO(OR 3 )2[R 3 It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[11] (B) The surface treatment agent according to any one of [1] to

[10] , wherein component (B) is at least one selected from the group consisting of fluorine-modified aliphatic hydrocarbon solvents, fluorine-modified ether solvents, and fluorine-modified alkylamine solvents.

[12] Articles treated with any of the surface treatment agents described in [1] to

[11] .

[13] A touch panel treated with any of the surface treatment agents described in [1] to

[11] .

[14] An anti-reflective treated article treated with any of the surface treatment agents described in [1] to

[11] .

[15] Glass, tempered glass, sapphire glass, quartz glass, or SiO2-treated substrate treated with any of the surface treatment agents described in [1] to

[11] . [Effects of the Invention]

[0014] The surface treatment agent of the present invention exhibits excellent storage stability in environments with temperatures higher than room temperature (20-25°C) and can suppress aggregation in the surface treatment agent. [Modes for carrying out the invention]

[0015] The present invention will be described in detail below.

[0016] The present invention relates to a surface treatment agent comprising (A) a hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof modified with a fluoropolyether group-containing polymer, and (B) a fluorine-containing solvent, wherein the amount of fluoride ions contained in the fluorine-containing solvent of component (B) is greater than 0 to 1.0 × 10 in the total amount of the surface treatment agent. -5 The present invention is characterized by being less than or equal to mass%. If the fluoride ions are within the above range, aggregates are less likely to form in the surface treatment agent even when stored at high temperatures, aggregates are less likely to form in the cured film formed by the surface treatment agent of the present invention, and surface roughness of the cured film and an increase in haze of the cured film can be suppressed. In this invention, "high temperature state" refers to a temperature state higher than room temperature (20-25°C).

[0017] (A) component Component (A) contains a polymer containing a fluoropolyether group within its molecule, and is an essential component of a hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof modified with a fluoropolyether group-containing polymer.

[0018] In the present invention, the number-average molecular weight (Mn) of the hydrolyzable group-containing silane and / or its partially hydrolyzed condensate, modified with a fluoropolyether group-containing polymer contained in the surface treatment agent, is preferably in the range of 1,000 to 25,000. More preferably, the number-average molecular weight is 2,000 to 20,000, even more preferably 2,500 to 16,000, and particularly preferably 3,000 to 12,000, from the viewpoint of forming a film with excellent water-repellent, oil-repellent, and scratch-resistant properties. (A) The number-average molecular weight (Mn) of component can be determined as a polystyrene-equivalent value in gel permeation chromatography (GPC) analysis using a fluorinated solvent as the developing solvent. Furthermore, the number-average molecular weight (Mn) of a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate of said polymer is: 19 It can also be calculated from the characteristic peak intensity ratio of F-NMR analysis.

[0019] Hydrolyzable group-containing silanes and / or their partially hydrolyzed condensates, modified with fluoropolyether group-containing polymers having the above number-average molecular weight, can be obtained by rectification or molecular distillation of a solution containing the fluoropolyether group-containing polymer and / or its partially hydrolyzed condensate. Alternatively, they can be prepared by pre-setting the fluorine compound used in the synthesis of the fluoropolyether group-containing polymer to have the above number-average molecular weight.

[0020] The hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer used in the surface treatment agent of the present invention has at least one, preferably 1 to 3, terminals of the molecule that are related to the following formula (1) [ka] (In formula (1), Y is a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond; R is an alkyl group or phenyl group having 1 to 4 carbon atoms; X is a hydrolyzable group; and a is 2 or 3.) The molecule contains at least one, preferably 1 to 3 (i.e., at least 1, preferably 1 to 9, more preferably 2 to 6) groups represented by (hydrolyzable silyl group-containing group), and the molecule contains -(C b F 2b O) m It is preferable to have a polyfluorooxyalkylene structure represented by -(wherein the formula, b is a number from 1 to 6 independently for each unit, and m is a number from 1 to 250. Each of these units may be linear or branched.) Furthermore, in order to impart low haze and wear resistance properties to articles surface-treated with a surface treatment agent containing a hydrolyzable group-containing silane modified with the fluoropolyether group-containing polymer of the present invention, it is preferable to use a fluoropolyether group-containing polymer having at least two, preferably two to three (i.e., at least two, preferably two to nine, and more preferably two to six) groups represented by the above formula (1) (hydrolyzable silyl group-containing groups).

[0021] In formula (1) above, Y is a divalent hydrocarbon group which may have a single bond or one or more selected from a fluorine atom, a silicon atom, and a siloxane bond. The divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond 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 containing a fluorine atom, an alkylene group having 6 to 8 carbon atoms containing an arylene group (alkylene-arylene group), a divalent group in which alkylene groups are bonded to each other via a sylalkylene structure or a sylarylene structure, and a divalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the binding site of a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms. Among these, an alkylene group having 1 to 10 carbon atoms, preferably 2 to 5, more preferably 2 or 3 carbon atoms, is preferred.

[0022] Examples of Y other than single bonds include those shown below. In the structures below, it is preferable that the right-hand bond is connected to Si. [ka]

[0023] In formula (1) above, X is a hydrolyzable group that may be different from one another. Examples of such X include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups having 2 to 10 carbon atoms, such as acetoxy and propionoxy; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups such as chlor, bromo, and iodine. Among these, methoxy, ethoxy, isopropenoxy, and chlor are preferred.

[0024] In formula (1) above, R is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, with methyl and ethyl groups being preferred. In the above formula (1), a is 2 or 3, and 3 is preferred from the viewpoint of reactivity and adhesion to the substrate.

[0025] The following are examples of groups represented by formula (1) (hydrolyzable silyl group-containing groups). [ka] [ka]

[0026] Also, the above-(C b F 2b O) m In the polyfluorooxyalkylene structure represented by -, b is a number from 1 to 6, preferably from 1 to 4, independently for each unit, and m is a number from 1 to 250, preferably from 10 to 250, more preferably from 10 to 140. Each of these units may be linear or branched.

[0027] The above -C b F 2b Examples of repeating units represented by O- include the unit shown in the following formula. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2O- -C(CF3)2O- Among these, the repeating unit represented by the following formula is particularly preferred. -CF2O- -CF2CF2O-

[0028] The polyfluorooxyalkylene structure described above may be composed of one of the repeating units described above, or it may be composed of a combination of two or more units.

[0029] The fluoropolyether group-containing polymer is preferably, for example, a fluoropolyether group-containing polymer represented by the following formulas (2), (4), or (7). [ka] [In equation (2), Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d -(wherein d is independently a number from 0 to 5, p, q, r, s, t, and u are independently a number from 0 to 150, the sum of p, q, r, s, t, and u is a number from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit represented in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal end is CF3- or CF2H- and may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3). [ka] [In formula (3), Q is a single bond or a divalent organic group, Z is a 2- to 8valent group, α is 0 or 1, β is a number from 1 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by formula (1) above.] [ka] [In equation (4), Rf is the same as above, and A 2is a monovalent fluorine-containing hydrocarbon group having a terminal end of CF3- or CF2H- and may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5). [ka] [In formula (5), W represents the same as above, 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 the following formula (6)] [ka] (In formula (6), T is a single bond or a 2- to 8-valent 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 a number from 0 to 20.) It is a monovalent group represented by this formula, and e is 1 or 2. [ka] [In equation (7), Rf is the same as above, and A 3 is a monovalent fluorine-containing hydrocarbon group having a terminal end of CF3- or CF2H- and may contain an oxygen atom, or J, where J is a monovalent group represented by the following formula (8). [ka] [In formula (8), S and e are the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have single bonds or ether bonds, and M is the following formula (9)] [ka] (In formula (9), Y, S, and W are the same as above, and f is a number from 1 to 3.) This is a monovalent group represented by this formula.

[0030] First, we will explain the fluoropolyether group-containing polymer represented by the following formula (2). [ka]

[0031] In equation (2) above, Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d - is a divalent polyfluorooxyalkylene structure (perfluoropolyether structure) containing group, where d is independently a number from 0 to 5, preferably from 0 to 2, more preferably 0 or 1. p, q, r, s, t and u are each independently a number from 0 to 150, preferably from 0 to 100, more preferably from 0 to 80, even more preferably from 0 to 60, particularly preferably from 0 to 40, especially preferably from 0 to 10, the sum of p, q, r, s, t and u is at least 1, preferably 3 or more, more preferably 7 or more, particularly preferably 10 or more, and the sum of p, q, r, s, t and u is 250 or less, preferably 140 or less, more preferably 70 or less. Each of these units may be linear or branched. Note that each repeating unit represented in parentheses with p, q, r, s, t and u may be randomly linked.

[0032] The divalent polyfluorooxyalkylene structure (perfluoropolyether structure) containing Rf can be specifically represented by the following structure. [ka] (In the formula, p', q', r', s', t', and u' are each independently numbers between 1 and 150, and the sum of p', q', r', s', t', and u' is between 12 and 250. Furthermore, each repeating unit represented within the parentheses of p', q', r', s', t', and u' may be randomly combined. d' is independently a number between 0 and 5. These units may be linear or branched.)

[0033] The above formula (2); A 1 In -Rf-D, A 1 The term is a monovalent fluorine-containing hydrocarbon group whose terminus is CF3- or CF2H- and may contain an oxygen atom, or D (i.e., -Q-Zα(W)β represented by formula (3) described later), whose terminus is CF3- or CF2H- and may contain an oxygen atom. Preferably, the terminus of the polymer is a fluoroalkyl group having 1 to 6 carbon atoms, and in particular, those in which the terminus of the polymer is CF3- or CF2H-.

[0034] Such A 1 Examples of monovalent fluorine-containing hydrocarbon groups whose terminal ends are CF3- or CF2H- and which may contain an oxygen atom include the following groups. [ka]

[0035] The above formula (2); A 1 In -Rf-D, D is a monovalent group represented by the following formula (3). [ka]

[0036] In formula (3) above, 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 amide bonds (e.g., unsubstituted amide bonds, N-methyl substituted amide bonds, N-phenyl substituted amide bonds), ether bonds, ester bonds, sulfide bonds, urethane bonds, siloxane bonds, triazine bonds, diorganosilylene groups (e.g., dialkylsilylene groups such as dimethylsilylene groups), silphenylene bonds, and silalkylene bonds (e.g., silethylene bonds), and 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 aforementioned bonds.

[0037] Examples of Q other than single bonds include the following groups. In the structure below, it is preferable that the left bond is bonded to Rf and the right bond is bonded to Z. [ka] (In the formula, t is a number between 1 and 4, preferably between 2 and 4.)

[0038] In the above formula (3);-Q-Zα(W)β, Z is a 2- to 8-valent group, preferably a 2- to 8-valent organopolysiloxane residue having a silicon atom, a nitrogen atom, a sylalkylene group, a sylarylene group, and a siloxane bond, more preferably a 2- to 8-valent group, preferably a 2- to 4-valent group, selected from linear organopolysiloxane residues with 2 to 13 silicon atoms, particularly 2 to 5 silicon atoms, or branched or cyclic organopolysiloxane residues with 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms. Also, a sylalkylene structure such as a silethylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group, i.e., Si-(CH2) n -Si may be included (in the above formula, n is a number from 2 to 6, preferably from 2 to 4).

[0039] Examples of sylalkylene groups and sylarylene groups are shown below. [ka] (In the formula, R 1 R is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, or butyl group, and an aryl group having 6 to 10 carbon atoms, such as a phenyl group. 1 They may be the same or different. 2 These include alkylene groups with 1 to 4 carbon atoms, such as methylene groups, ethylene groups, and propylene groups (trimethylene groups, methylethylene groups), and arylene groups with 6 to 10 carbon atoms, such as phenylene groups.

[0040] Examples of 2- to 8-valent organopolysiloxane residues containing siloxane bonds are listed below. [ka] (In the formula, R 1 The above applies to the same values, where g is a number from 1 to 12, preferably from 1 to 4; h is a number from 2 to 8, preferably from 2 to 4; j is a number from 0 to 8, preferably 0 or 1; h+j is a number from 3 to 13, preferably from 3 to 5; and k is a number from 1 to 3, preferably 2 or 3.

[0041] Examples of such Z include the following: [ka] [ka] [ka] [ka] [ka] [ka]

[0042] In the above formula (3);-Q-Zα(W)β, W is independently a monovalent hydrolyzable silyl group-containing group represented by the above formula (1).

[0043] In the above formula (3);-Q-Zα(W)β, α is 0 or 1, β is a number from 1 to 7, preferably a number from 2 to 7, and β is (valence of Z - 1).

[0044] The following are examples of -Q-Zα(W)β (i.e., D in equation (2)) in the above equation (3). [ka] [ka]

[0045] Examples of fluoropolyether group-containing polymers represented by the above formula (2) are listed below. [ka] (In the formula, A 1 (Rf represents the same thing as above.) [ka] (In the formula, A 1 (Rf represents the same thing as above.)

[0046] Next, we will describe the fluoropolyether group-containing polymer represented by the following formula (4). [ka] In equation (4) above, Rf represents the same thing as above, and the same example as the one exemplified for Rf in equation (2) above can be given.

[0047] The above formula (4); A 2-Rf-G, A 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and may contain an oxygen atom, or G (that is, formula (5) described later; -C(B) e (W) 3-e represented by a monovalent group). As the monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and may contain an oxygen atom, a fluoroalkyl group having 1 to 6 carbon atoms is preferable, and particularly, those in which the terminal of the polymer is CF3- or CF2H- are preferable.

[0048] Such A 2 Examples of the monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and may contain an oxygen atom include the following groups.

Chemical formula

[0049] In the above formula (4); A 2 -Rf-G, G is a monovalent group represented by the following formula (5).

Chemical formula

[0050] In the above formula (5); -C(B) e (W) 3-e In this formula, 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).

Chemical formula

[0051] Here, examples of monovalent hydrocarbon groups of S having 1 to 10 carbon atoms 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. Alkyl groups having 1 to 3 carbon atoms and phenyl groups are preferred.

[0052] Equation (6) above: -T-(LO) l In -E, T is a single bond or a 2- to 8-valent group, preferably a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms, a siloxane bond, a sylalkylene bond (e.g., silethylene bond, sylpropylene bond), a sylarylene bond (e.g., sylphenylene bond), and a diorganosilylene group (e.g., a dialkylsilylene group such as dimethylsilylene group, a dialkoxysilylene group such as dimethoxysilylene group), a siloxane bond, a sylalkylene group, or a diorganosilylene group, which may contain one or more bonds selected from the group consisting of a silicon atom, a siloxane bond, a sylalkylene group, a sylalkylene group, or a diorganosilylene group. Specific examples of T other than a single bond are shown below. In the structure below, it is preferable that the right-hand bond is bonded to L or E. [ka]

[0053] Equation (6) above: -T-(LO) l In -E, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, such as a methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group), or other alkylene groups, and the number of carbon atoms may be single or mixed. Equation (6) above: -T-(LO) l In -E, l is a number from 0 to 20, preferably from 0 to 10, and more preferably from 0 to 6. If (LO) is present, l is preferably 1 or more, and particularly preferably 2 or more. Equation (6) above: -T-(LO) l-E, where 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 represents the same as above, and examples thereof are the same as those exemplified by W in the above formula (3).

[0054] The above formula (6); -T-(LO) l Examples of the monovalent group represented by -E include those shown below. [Chemical formula]

[0055] The above formula (5); -C(B) e (W) 3-e Examples of the monovalent group (i.e., G in formula (4)) represented by [formula] include those shown below. [Chemical formula] [Chemical formula]

[0056] Examples of the fluoropolyether group-containing polymer represented by the above formula (4) include those shown below. [Chemical formula] (In the formula, A 2 , Rf represents the same as above.) [Chemical formula] (In the formula, A 2 , Rf represents the same as above.)

[0057] Next, the fluoropolyether group-containing polymer represented by the following formula (7) will be described. [Chemical formula] In equation (7) above, Rf represents the same thing as above, and the same example as the one exemplified for Rf in equation (2) above can be given.

[0058] The above formula (7); A 3 In -Rf-J, A 3 This is a monovalent fluorine-containing hydrocarbon group whose terminus is CF3- or CF2H- and may contain an oxygen atom, or J(i.e., formula (8) described later; -VC(=O)N(S) 2-e (M) e The monovalent fluorine-containing hydrocarbon group is a monovalent group represented by , and its terminal end is CF3- or CF2H-, which may contain an oxygen atom. Preferably, it is a fluoroalkyl group having 1 to 6 carbon atoms, and in particular, one in which the polymer terminal end is CF3- or CF2H-.

[0059] Examples of monovalent fluorine-containing hydrocarbon groups having CF3- or CF2H- terminals and potentially containing an oxygen atom include the following groups. [ka]

[0060] The above formula (7); A 3 In -Rf-J, J is a monovalent group represented by the following formula (8). [ka]

[0061] In formula (8) above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms, which may have a single bond or an ether bond. Specific examples of V other than a single bond are shown below. In the structure below, it is preferable that the bond on the right side is bonded to a carbon atom (-C(=O)-). [ka]

[0062] In equation (8) above, S represents the same thing as above, and examples similar to those exemplified for S in equation (5) above can be given. In formula (8) above, e represents the same value as e in formula (5) above, and is either 1 or 2, with 1 being preferable. In the above formula (8), M is a monovalent group represented by the following formula (9). [ka]

[0063] In equation (9) above, Y, S, and W represent the same values ​​as above, and examples can be given that are the same as those exemplified in equation (1), equation (5), and equation (3), respectively. In equation (9) above, f is a number between 1 and 3.

[0064] Equation (9) above: -YC(S) 3-f (W) f Examples of monovalent groups represented by (i.e., M in formula (8)) are listed below. [ka]

[0065] Above formula (8);-VC(=O)N(S) 2-e (M) e Examples of monovalent groups represented by the formula are listed below. [ka] [ka] [ka]

[0066] Examples of fluoropolyether group-containing polymers represented by the above formula (7) are listed below. [ka] (In the formula, A 3 (Rf represents the same thing as above.) [ka] (In the formula, A 3 (Rf represents the same thing as above.) [ka] (In the formula, A 3 (Rf represents the same thing as above.)

[0067] (A) Component may be used alone or as a mixture of two or more components. The content of component (A) is preferably 0.05 to 30% by mass, more preferably 0.07 to 25% by mass, and particularly preferably 0.1 to 20% by mass, relative to the total surface treatment agent.

[0068] (B) Component The fluorine-containing solvent of component (B) is not particularly limited as long as it uniformly dissolves component (A). In the present invention, "uniformly dissolves" means that it is transparent to the naked eye, for example, when light is shone on the solvent in which component (A) has been dissolved, there is no white haze (undissolved aggregates, etc.). Examples of such fluorine-containing solvents include fluorine-modified aliphatic hydrocarbon solvents, fluorine-modified ether solvents, and fluorine-modified alkylamine solvents. Examples of fluorine-modified aliphatic hydrocarbon solvents include perfluoroheptane, perfluorooctane, tridecafluorooctane, and hexafluoropropene trimer, as well as fluorine-modified aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene. Examples of fluorine-modified ether solvents include methyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, ethyl nanofluoroisobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptenyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, hexafluoroisopropyl methyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane. Examples of fluorine-modified alkylamine solvents include perfluorotri-N-butylamine and perfluorotripentylamine. Among these, 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotri-N-butylamine, ethyl perfluorobutyl ether, ethyl nanofluoroisobutyl ether, methyl perfluorohexyl ether, tridecafluorooctane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, and hexafluoropropene trimer are preferred.

[0069] The above-mentioned fluorine-containing solvents may be used individually or as a mixture of two or more types. (B) The fluoride ions contained in the fluorine-containing solvent of component (B) are greater than 0 and 1.0 × 10 in the total amount of surface treatment agent. -5 It is less than or equal to a mass percentage, and is greater than 0 and greater than 1.0 × 10⁻ -5 Preferably less than 0% by mass, and greater than 0 or 9.8 × 10 -6 It is more preferable that it be less than or equal to mass%, and greater than 0 and 9.8 × 10 -6 It is particularly preferable that the amount be less than or equal to a mass percent.

[0070] In the present invention, the fluoride ions in the fluorine-containing solvent of component (B) can be measured by ion chromatography. When used for dissolving and diluting component (A), the fluoride ion concentration in the fluorine-containing solvent of component (B) is not particularly limited as long as the fluoride ions contained in the fluorine-containing solvent of component (B) are within the above range relative to the entire surface treatment agent. However, from the viewpoint of ease of manufacturing the surface treatment agent, it is preferable that it be in the range of greater than 0 and 0.1 μg / g or less, and more preferably greater than 0 and 0.095 μg / g or less.

[0071] (C) Component The surface treatment agent of the present invention may further contain, as component (C), a fluoropolyether group-containing polymer that does not contain hydrolyzable silyl groups represented by the following formula (10) (hereinafter referred to as a polymer that does not contain hydrolyzable silyl groups or a non-functional polymer). [ka] (In equation (10), Rf is -C) d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d -(wherein d is independently a number from 0 to 5, p, q, r, s, t, and u are independently a number from 0 to 150, the sum of p, q, r, s, t, and u is a number from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit represented in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 4 These are monovalent fluorine-containing hydrocarbon groups whose terminal ends are CF3- or CF2H- and may contain an oxygen atom, -OR 3 ,-COOR 3 or -PO(OR 3 )2[R3 It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0072] In equation (10), Rf represents the same thing as above, and examples similar to those exemplified for Rf in equation (2) above can be given. In the above formula (10), A 4 These are monovalent fluorine-containing hydrocarbon groups whose terminal ends are CF3- or CF2H- and may contain an oxygen atom, -OR 3 ,-COOR 3 or -PO(OR 3 )2, and the terminal end is CF3- or CF2H- and may contain an oxygen atom, as a monovalent fluorine-containing hydrocarbon group, A 1 Examples of monovalent fluorine-containing hydrocarbon groups that have CF3- or CF2H- at their termini and may contain an oxygen atom are similar to those exemplified above. Here, R 3 R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as 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. 3 Preferred elements include hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and phenyl groups. A 4 -OR 3 ,-COOR 3 , -PO(OR 3 Examples of -OH, -OCH3, -OC2H5, -COOH, -COOCH3, -COOC2H5, -PO(OH)2, -PO(OCH3)3, and -PO(OC2H5)3 can be given as )2.

[0073] Examples of polymers that do not contain the hydrolyzable silyl group represented by the above formula (10) are listed below. [ka] (In the formula, p', q', r', s', t', u', and the sum of p', q', r', s', t', u' represent the same as above. Each of these units may be linear or branched. Also, each repeating unit represented in parentheses with p', q', r', s', t', and u' may be randomly combined.)

[0074] The surface treatment agent of the present invention preferably contains a hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof, modified with a fluoropolyether group-containing polymer having at least one group represented by formula (1) at at least one terminal in the molecule, and typically contains at least one fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate (single-ended polymer) having at least one, preferably at least two, hydrolyzable silyl groups at one end of the molecular chain represented by formula (2), (4), or (7), or at least one fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate (double-ended polymer) having at least one, preferably at least two, hydrolyzable silyl groups at both ends of the molecular chain represented by formula (2), (4), or (7), or contains at least one of the single-ended polymers and at least one of the double-ended polymers, or further contains a polymer that does not contain the hydrolyzable silyl groups.

[0075] In the surface treatment agent of the present invention, the mixing ratio of a mixture of a single-ended polymer and / or a double-ended polymer and a polymer that does not contain hydrolyzable silyl groups is not particularly limited, but it is generally desirable that the polymer that does not contain hydrolyzable silyl groups is in a ratio of 0 to 30% by mass, and particularly 0 to 10% by mass, of the total fluoropolyether group-containing polymer mixture consisting of a single-ended polymer and / or a double-ended polymer and a polymer that does not contain hydrolyzable silyl groups.

[0076] The surface treatment agent of the present invention may optionally contain other components, such as hydrolysis condensation catalysts, organotin compounds (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), organotitanium compounds (e.g., tetra-n-butyl titanate), organic acids (e.g., acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid), and inorganic acids (e.g., hydrochloric acid, sulfuric acid). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, and fluorine-modified carboxylic acid are particularly desirable. The amount added is a catalytic amount, and is usually 0.01 to 5 parts by mass, preferably 0.1 to 1 part by mass, per 100 parts by mass of a fluoropolyether group-containing polymer containing at least one hydrolyzable silyl group and / or a partially hydrolyzed condensate of said polymer.

[0077] The surface treatment agent of the present invention can be applied to a substrate by known methods such as brush application, dipping, spraying, and vapor deposition. The heating method during vapor deposition can 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 (brush application, dipping, spraying, etc.), it is preferable to cure at 25 to 150°C, particularly 25 to 120°C, for 0.5 to 48 hours, and especially 12 to 24 hours. When applied by vapor deposition, it is preferable to cure at 25 to 150°C, particularly 25 to 120°C, for 0.5 to 48 hours, and especially 12 to 24 hours. Curing may also be performed under humid conditions. The film thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 5 to 30 nm, and especially 8 to 20 nm.

[0078] The substrate 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, metals and their oxides, glass plates, plastics, ceramics, and quartz. The surface treatment agent of the present invention can impart water-repellent and oil-repellent properties, surface slipperiness, low dynamic friction, and scratch resistance to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO2-treated glass or quartz substrates.

[0079] Articles treated with the surface treatment agent of the present invention include, for example, glass, tempered glass, sapphire glass, quartz glass, touch panels, hard coat films, high-hardness films, anti-reflective films, spectacle lenses, optical lenses, and quartz substrates. In particular, it is useful as a surface treatment agent for forming a water-repellent and oil-repellent layer on the surface of tempered glass and anti-reflective treated glass. [Examples]

[0080] 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.

[0081] [Method for measuring fluoride ion concentration] 3 g of solvent and 3 ml of pure water were added, shaken for 30 minutes, and then centrifuged to separate the aqueous layer. The aqueous layer was passed through a washed pre-treatment cartridge, diluted, and ion chromatography was performed. Fluoride ions were quantified using the absolute calibration curve method. The measurable range in this measurement is 0.005 μg / g or higher. Measurement equipment and conditions Measuring device: Tosoh Corporation IC-8100 Pump: Built-in pump of IC-8100 Measurement conditions (column type): Tosho Bioscience TSKgel Super IC-Anion HS Eluent: 7.5mM NaHCO3+0.8mM Na2CO3 Flow rate: 1.5mL / min Detection: Electrical conductivity detector

[0082] [Method for measuring number-average molecular weight] The number-average molecular weight of the fluoropolyether group-containing polymers obtained in the following synthesis examples was measured using gel permeation chromatography (GPC). The measurement conditions were as follows. The results are shown in Table 1. Measurement equipment and conditions Measurement equipment: Agilent Technologies, Inc. Agilent 1260 Infinity II Pump: HITACHI Chromaster 5110 Pump Measurement conditions (column): Tosoh Bioscience TSKgel Multipore H XL -M 7.8mmφ×30cm 2 pieces Eluent: Hydrochlorofluorocarbon (HCFC)-225 Flow rate: 1.0mL / min Detector: Evaporative light scattering detector Column Oven: GL Science 705 Ink injection volume: 20 μL Flow rate: 1.0mL / min Column temperature: 35℃ Reference material: Agilent Technologies, Inc. PMMA calibrationlit ML-10

[0083] [Synthesis Example 1] A compound represented by the following formula (A) was prepared. [ka] 100g of the compound represented by the above formula (A) (2.1 × 10 -2 (mol), 1,3-bis(trifluoromethyl)benzene 100g, trimethoxysilane 6.4g (5.4 × 10) -2 (mol), acetic acid 1.0 × 10 -4 g and 3.0 × 10⁻¹ toluene solution of chloroplatinate / vinylsiloxane complex -4 g(Pt alone: ​​2.0 × 10) -8 The mixture (containing mol) was stirred at 80°C for 24 hours. Then, the solvent and unreacted materials were removed by distillation under reduced pressure, yielding 94 g of liquid product. The obtained product was, 1 ¹H-NMR confirmed that the compound is represented by the following formula (B). [ka]

[0084] [Synthesis Example 2] A compound represented by the following formula (C) was prepared. [Chemical formula] 100 g (1.5×10 -2 mol) of the compound represented by the above formula (C), 100 g of 1,3-bis(trifluoromethyl)benzene, 12.9 g (4.5×10 -2 mol) of 1,1,3,3-tetramethyl-1-[2-(trimethoxysilyl)ethyl]disiloxane, 3.0×10 -2 g of acetic acid, and 1.0×10 -2 g of a 2-ethylhexanol solution of chloroplatinic acid (containing 1.0×10 -6 mol of platinum as a simple substance) were mixed and stirred at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure, and 8.5 g of a liquid product was obtained. The obtained product was confirmed to be a compound represented by the following formula (D) by 1 1H-NMR. [Chemical formula]

[0085] [Synthesis Example 3] Referring to International Publication No. 2022 / 131107, a compound represented by the following general formula (E) was synthesized. [Chemical formula]

[0086] [Synthesis Example 4] Referring to International Publication No. 2022 / 131107, a compound represented by the following general formula (F) was synthesized. [Chemical formula]

[0087] [[ID=高51]] [Synthesis Example 5] Referring to Patent No. 6524955, a compound represented by the following general formula (G) was synthesized. [Chemical formula]

[0088] [Synthesis Example 6] A compound represented by the following formula (H) was prepared. [ka] 100g of the compound represented by the above formula (H) (2.3 × 10) -2 50g of 1,3-bis(trifluoromethyl)benzene and 5.0g of allylamine (8.8 × 10) -2 The mixture (mol) was stirred at 50°C for 4 hours. Then, the solvent and unreacted materials were removed by reduced pressure distillation, yielding 92 g of liquid product. The obtained product was: 1 ¹H-NMR confirmed that the compound is represented by the following formula (I). [ka] 80g (1.8 × 10) of the compound represented by the above formula (I) -2 40g of 1,3-bis(trifluoromethyl)benzene (mol), 4.5g of trimethoxysilane (3.8 × 10) -2 mol), acetic acid 2.4 × 10 -5 g and 1.0 × 10⁻¹ toluene solution of chloroplatinate / vinylsiloxane complex -5 g(Pt alone: ​​6.7 × 10) -10 The mixture (containing mol) was stirred at 80°C for 24 hours. Then, the solvent and unreacted materials were removed by distillation under reduced pressure, yielding 94 g of liquid product. The obtained product was, 1 ¹H-NMR confirmed that the compound is represented by the following formula (J). [ka]

[0089] [Synthesis Example 7] Based on International Publication No. 2022 / 131107, the compound represented by the following general formula (K) was synthesized. [ka]

[0090] [Synthesis Example 8] A compound represented by the following formula (L) was prepared. [Chemical Formula] 100 g (1.5×10 -2 mol) of the compound represented by the above formula (L), 100 g of 1,3-bis(trifluoromethyl)benzene, 4.5 g (3.8×10 -2 mol) of trimethoxysilane, 1.0×10 -4 g of acetic acid, and 3.0×10 -4 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 2.0×10 -8 mol of elemental Pt) were mixed and stirred at 80 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure, and 8.5 g of a liquid product was obtained. The obtained product was 1 confirmed by [Chemical Formula]

[0091] to be a compound represented by the following formula (M). [Chemical Formula]

[0092] Solvent Solvent (A): 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (fluoride ion quantification value: <0.005 μg / g) Solvent (B): 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (fluoride ion quantification value: 5.8 μg / g) Solvent (C): Perfluorotri-N-butylamine (fluoride ion quantification value: <0.005 μg / g) Solvent (D): Perfluorotri-N-butylamine (fluoride ion quantification value: 0.5 μg / g) Solvent (E): Ethyl nanofluoroisobutyl ether (fluoride ion quantitative value: 0.09 μg / g)

[0093] [Examples 1-10, Comparative Examples 1-2] The compounds obtained in the above synthesis example were diluted with a solvent to the composition shown in Table 1, so that the compound constituted 20% by mass, to prepare a surface treatment agent.

[0094] [Table 1]

[0095] Preparation of surface treatment agents and storage stability under heated conditions [Check the appearance of the sample bottle] 50g of each surface treatment agent prepared in Examples 1-10 and Comparative Examples 1-2 was placed in a transparent sample bottle. The back of the sample bottle was made black, and a flashlight was shone from the bottom of the sample bottle to visually observe the appearance of the surface treatment agent [immediately after preparation]. The results (appearance [immediately after preparation]) are shown in Table 2. The sample bottles were placed in an oven at 55°C and stored undisturbed for one year. After that, the sample bottles were allowed to cool to room temperature, and the back of the sample bottles was positioned so that they were black. A flashlight was shone from below, and the appearance [after 1 year of storage at 55°C] was visually observed. The results (appearance [after 1 year of storage at 55°C]) are shown in Table 3. A: It was a clear solution. B: The solution was slightly cloudy or opaque, or contained a white haze (undissolved aggregates, etc.) or aggregates resembling particles.

[0096] [Condensate content] The surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 immediately after preparation, and the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 after being stored for one year, were measured using gel permeation chromatography (GPC). The measurement conditions are as follows. Measurement equipment and conditions Measurement equipment: Agilent Technologies, Inc. Agilent 1260 Infinity II Pump: HITACHI Chromaster 5110 Pump Measurement conditions (column): Tosoh Bioscience TSKgel Multipore H XL -M 7.8mmφ×30cm 2 pieces Eluent: Hydrochlorofluorocarbon (HCFC)-225 Flow rate: 1.0mL / min Detector: Evaporative light scattering detector Column Oven: GL Science 705 Ink injection volume: 20 μL Flow rate: 1.0mL / min Column temperature: 35℃ Reference material: Agilent Technologies, Inc. PMMA calibration kit ML-10

[0097] Analysis of GPC measurement results was performed, and if there was a single peak, the content of the condensate (a structure in which alkoxy groups are condensed) was recorded as 0%. If a peak was observed at an early detection time in addition to the main peak, it was considered to be a condensate peak, and the content of the condensate was calculated from the area ratio of the total of all peaks. Table 2 shows the results (condensate content) of the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 immediately after preparation, and Table 3 shows the results (condensate content) of the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 after storage for one year.

[0098] Formation of a hardened film A cured film was formed using the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 immediately after preparation, and the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 after being stored for one year. 5 μl of each surface treatment agent was vacuum-deposited onto chemically strengthened glass (50 mm x 100 mm) (Corning Gorilla 5) with a 10-12 nm SiO2 deposition coating on the outermost surface (processing conditions: pressure: 2.0 x 10°C). -2 A cured film with a thickness of 10 nm was formed by curing for 12 hours in an atmosphere of Pa, heating temperature: 700°C, 25°C, and 50% humidity.

[0099] Evaluation of the cured film [Measurement of haze] The haze of the chemically strengthened glass having the hardened coating formed as described above was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with the method described in JIS K7136. Table 2 shows the results of the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 immediately after preparation, minus the blank value (haze value of chemically strengthened glass without a hardened coating). Table 3 shows the results of the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 after storage for one year, minus the blank value (haze value of chemically strengthened glass without a hardened coating).

[0100] [Measurement of initial water contact angle] For the chemically strengthened glass having the hardened coating formed as described above, the contact angle (water repellency) of the hardened coating with respect to water was measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). Table 2 shows the results (initial water contact angle) of the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 immediately after preparation, and Table 3 shows the results (initial water contact angle) of the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 after storage for one year.

[0101] [Table 2]

[0102] [Table 3]

[0103] [Examples 11-16, Comparative Examples 3-4] The compounds obtained in the above synthesis example were diluted with a solvent to the composition shown in Table 4, so that the compound amounted to 0.1% by mass, to prepare a surface treatment agent.

[0104] [Table 4]

[0105] Preparation of surface treatment agents and storage stability under heated conditions [Check the appearance of the sample bottle] 50g of each surface treatment agent prepared in Examples 11-16 and Comparative Examples 3-4 was placed in a transparent sample bottle. The back of the sample bottle was made black, and a flashlight was shone from below the sample bottle to visually observe the appearance of the surface treatment agent [immediately after preparation]. The results (appearance [immediately after preparation]) are shown in Table 2. The sample bottles were placed in an oven at 55°C and stored undisturbed for one year. After that, the sample bottles were allowed to reach room temperature, the back of the sample bottles was made black, and a flashlight was shone from below to visually observe the appearance [after 1 year of storage at 55°C]. The results (appearance [after 1 year of storage at 55°C]) are shown in Table 3. A: It was a clear solution. B: The solution was slightly cloudy or opaque, or contained a white haze (undissolved aggregates, etc.) or aggregates resembling particles.

[0106] [Condensate content] The surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 immediately after preparation, and the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 after being stored for one year, were measured using gel permeation chromatography (GPC). The measurement conditions are as follows. Measurement equipment and conditions Measurement equipment: Agilent Technologies, Inc. Agilent 1260 Infinity II Pump: HITACHI Chromaster 5110 Pump Measurement conditions (column): Tosoh Bioscience TSKgel Multipore H XL -M 7.8mmφ×30cm 2 pieces Eluent: Hydrochlorofluorocarbon (HCFC)-225 Flow rate: 1.0mL / min Detector: Evaporative light scattering detector Column Oven: GL Science 705 Ink injection volume: 20 μL Flow rate: 1.0mL / min Column temperature: 35℃ Reference material: Agilent Technologies, Inc. PMMA calibration kit ML-10

[0107] Analysis of GPC measurement results was performed, and if there was a single peak, the content of the condensate (a structure in which alkoxy groups are condensed) was recorded as 0%. If a peak was observed at an early detection time in addition to the main peak, it was considered to be a condensate peak, and the content of the condensate was calculated from the area ratio of the total of all peaks. Table 5 shows the results (condensate content) of the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 immediately after preparation, and Table 6 shows the results (condensate content) of the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 after storage for one year.

[0108] Formation of a hardened film A cured film was formed using the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 immediately after preparation, and the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 after being stored for one year. The surface of chemically strengthened glass (Corning, Gorilla V) that had been plasma-cleaned was spray-coated using a spray coating apparatus (T&K Corporation, NST-51). Subsequently, the coating was cured for 12 hours in an atmosphere of 25°C and 50% relative humidity to form a cured film with a thickness of 10 nm, and test specimens were obtained.

[0109] Evaluation of the cured film [Measurement of haze] The haze of the chemically strengthened glass having the hardened coating formed as described above was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with the method described in JIS K7136. Table 5 shows the results obtained by subtracting the blank value (haze value of chemically strengthened glass without a hardened coating) from the results of the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 immediately after preparation. Table 6 shows the results obtained by subtracting the blank value (haze value of chemically strengthened glass without a hardened coating) from the results of the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 after storage for one year.

[0110] [Measurement of initial water contact angle] For the chemically strengthened glass having the hardened coating formed as described above, the contact angle (water repellency) of the hardened coating with respect to water was measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). Table 5 shows the results (initial water contact angle) of the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 immediately after preparation, and Table 6 shows the results (initial water contact angle) of the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 after storage for one year.

[0111] [Table 5]

[0112] [Table 6]

[0113] Based on the results above, in Comparative Examples 1-4, the samples stored for one year showed the formation of aggregates that were not observed immediately after preparation, as well as slight turbidity of the sample solution. GPC measurements confirmed the formation of many condensates. Compared to the cured film obtained immediately after preparation, the cured film obtained from the samples stored for one year showed no significant change in the water contact angle, but the haze increased significantly. Small aggregates that did not affect the water contact angle were formed, resulting in the increased haze.

Claims

1. (A) A hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof modified with a fluoropolyether group-containing polymer, (B) A surface treatment agent containing a fluorine-containing solvent, (B) The fluoride ions contained in the fluorine-containing solvent of component (B) are greater than 0% by mass and 1.0 × 10 in the total amount of surface treatment agent -5 A surface treatment agent that is less than or equal to a mass percent.

2. The surface treatment agent according to claim 1, wherein the content of component (A) is 0.05 to 30% by mass of the entire surface treatment agent.

3. (A) The surface treatment agent according to claim 1, wherein the number average molecular weight of component is 1,000 to 25,000.

4. The surface treatment agent according to claim 1, wherein the hydrolyzable group-containing silane modified with the fluoropolyether group-containing polymer of component (A) has at least one group represented by the following formula (1) at at least one terminal in the molecule. 【Chemistry 1】 (In formula (1), Y is a single bond or a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond; R is an alkyl group or phenyl group having 1 to 4 carbon atoms; X is a hydrolyzable group; and a is 2 or 3.)

5. (A) A hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer of component (C) has -(C) in its molecule b F 2b O) m The surface treatment agent according to claim 1, having a polyfluorooxyalkylene structure represented by - (wherein b is a number from 1 to 6 independently for each unit, and m is a number from 1 to 250. Each of these units may be linear or branched).

6. The surface treatment agent according to claim 1, wherein in component (A), the silane is represented by the following formula (2), (4), or (7). 【Chemistry 2】 [In 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 -(wherein d is independently a number from 0 to 5, p, q, r, s, t and u are each independently a number from 0 to 150, the sum of p, q, r, s, t and u is a number from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit represented within the parentheses to which p, q, r, s, t and u are attached may be randomly combined.) is a divalent polyfluorooxyalkylene structure-containing group, and A 1 is a monovalent fluorine-containing hydrocarbon group having a terminal of CF 3 - or CF 2 H- and may contain an oxygen atom, or D, and D is a monovalent group represented by the following formula (3). 【Transformation 3】 [In formula (3), Q is a single bond or a divalent organic group, Z is a 2- to 8valent group, α is 0 or 1, β is a number from 1 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by formula (1) above.] 【Chemistry 4】 [In equation (4), Rf is the same as above, A 2 The terminal is CF 3 - or CF 2 A monovalent fluorine-containing hydrocarbon group that is H- and may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5). 【Transformation 5】 [In formula (5), W represents the same as above, 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 the following formula (6)] 【Transformation 6】 (In formula (6), T is a single bond or a 2- to 8-valent 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 a number from 0 to 20.) The monovalent group is represented by this formula, and e is 1 or 2. 【Transformation 7】 [In equation (7), Rf is the same as above, A 3 The terminal is CF 3 - or CF 2 A monovalent fluorine-containing hydrocarbon group that is H- and may contain an oxygen atom, or J, where J is a monovalent group represented by the following formula (8). 【Transformation 8】 [In formula (8), S and e are the same as above, V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have single bonds or ether bonds, and M is the following formula (9)] 【Chemistry 9】 It is a monovalent group represented by (9) (wherein Y, S, and W are the same as above, and f is a number from 1 to 3).

7. The surface treatment agent according to claim 6, 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 amide bonds, ether bonds, ester bonds, sulfide bonds, urethane bonds, siloxane bonds, triazine bonds, diorganosilylene groups, silphenylene bonds, and sylalkylene bonds, and Z is a 2 to 8-valent group selected from a silicon atom, a nitrogen atom, a sylalkylene group, a sylarylene group, and a 2 to 8-valent organopolysiloxane residue having a siloxane bond.

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

9. Furthermore, the surface treatment agent according to claim 1, comprising a fluoropolyether group-containing polymer that does not contain hydrolyzable groups as component (C).

10. The surface treatment agent according to claim 9, wherein the fluoropolyether group-containing polymer that does not contain hydrolyzable groups is represented by the following formula (10). 【Chemistry 10】 (In equation (10), 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 a number from 0 to 5, p, q, r, s, t, and u are each independently a number from 0 to 150, the sum of p, q, r, s, t, and u is a number from 1 to 250, and each of these units may be linear or branched. Also, each repeating unit represented in parentheses with p, q, r, s, t, and u may be randomly linked.) is a divalent polyfluorooxyalkylene structure-containing group, A 4 The terminals are independently CF 3 - or CF 2 H- and possibly containing an oxygen atom, monovalent fluorine-containing hydrocarbon group, -OR 3 , -COOR 3 OR -PO(OR 3 ) 2 [R 3 It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

11. The surface treatment agent according to claim 1, wherein component (B) is at least one selected from the group consisting of fluorine-modified aliphatic hydrocarbon solvents, fluorine-modified ether solvents, and fluorine-modified alkylamine solvents.

12. An article treated with the surface treatment agent described in any one of claims 1 to 11.

13. A touch panel treated with the surface treatment agent described in any one of claims 1 to 11.

14. An anti-reflective treated article treated with the surface treatment agent described in any one of claims 1 to 11.

15. Glass, tempered glass, sapphire glass, quartz glass, or SiO2 treated with the surface treatment agent described in any one of claims 1 to 11. 2 Processing substrate.

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