Surface treatment agent and article treated with the surface treatment agent

Abstract

This invention provides a surface treatment agent that exhibits excellent stability under any temperature conditions, particularly even under heated conditions, and articles surface-treated with this agent. The surface treatment agent comprises (A) a silane containing hydrolyzable groups modified with a polymer containing fluorinated polyether groups and / or its partially hydrolyzed condensate, and (B) a fluorinated solvent, wherein the fluoride ions in the fluorinated solvent of component (B) constitute greater than 0% by mass and less than 1.0 × 10⁻⁵% by mass of the total amount of the surface treatment agent.

Description

Technical Field

[0001] This invention relates to surface treatment agents containing silanes and / or partially hydrolyzed condensates containing hydrolyzable groups modified with polymers containing fluorinated polyether groups, specifically, to articles having a cured film of the surface treatment agent on the surface, forming a film with excellent water and oil repellency, surface lubricity, and wear resistance. Background Technology

[0002] In recent years, the trend of touch panels, particularly in mobile phone displays, has accelerated. However, touch panels expose the screen, leading to frequent contact with fingers, cheeks, and other skin types, making them prone to accumulating dirt and grime. Consequently, the demand for technologies that improve appearance and visibility, making fingerprints less likely and easier to remove dirt from display surfaces, has increased year by year, leading to a need for materials that meet these requirements. In particular, because touch panel displays are prone to fingerprints and grime, a water- and oil-repellent coating is desired. However, while conventional water- and oil-repellent coatings offer high water and oil repellency and excellent dirt removal, their anti-fouling performance deteriorates during use.

[0003] Generally, polymers containing fluorinated polyether groups possess water and oil repellency, chemical resistance, lubricity, mold release properties, and antifouling properties due to their very low surface free energy. Utilizing these properties, they are widely used industrially as water and oil repellents and antifouling agents for paper and fibers, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, and protective films. However, these properties also mean non-adhesion and non-adhesion to other substrates; even if coating can be applied to a substrate, it is difficult to achieve a tight seal.

[0004] On the other hand, silane coupling agents are well-known as substances that bond organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as surface treatment agents for various substrates. Each silane coupling agent contains an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as alkoxysilyl). The hydrolyzable silyl group forms a coating by undergoing a self-condensation reaction induced by moisture in the air. This coating becomes a durable and robust film by chemically and physically bonding the hydrolyzable silyl group to the surface of glass, metal, etc.

[0005] Therefore, compositions containing fluorinated polyether groups, which introduce hydrolyzable silyl groups into compounds containing fluorinated oxyalkylene groups, are disclosed, which can form a coating on the substrate surface that is easy to adhere to and can form a coating on the substrate surface that has water and oil repellency, chemical resistance, lubricity, mold release properties, and antifouling properties (Patent Documents 1-6: Japanese Patent Application Publication No. 2008-534696, Japanese Patent Application Publication No. 2008-537557, Japanese Patent Application Publication No. 2012-072272, Japanese Patent Application Publication No. 2012-157856, Japanese Patent Application Publication No. 2013-136833, Japanese Patent Application Publication No. 2015-199906).

[0006] Surface treatment agents composed of a polymer containing a fluorinated polyether group with hydrolyzable silyl groups introduced into a compound containing fluorinated oxyalkylene groups and a diluent, when stored for a long period, may experience hydrolysis and condensation of the terminal alkoxysilyl groups, sometimes easily forming high molecular weight bodies or gels. Conditions for this formation include the moisture content of the surface treatment agent, the presence of acid catalysts, and the mixing of alkali catalysts. While the surface treatment agent exhibits good storage stability, its shelf life needs to be extended, thus requiring improvements in its storage stability.

[0007] As a means to improve 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 silane and / or a partially hydrolyzed condensate thereof modified with a polymer containing a fluorinated polyether group as component (A) and a solvent capable of uniformly dissolving component (A) as component (B), the water content of the solvent of component (B) is 20 ppm or less by mass conversion, thereby improving the storage stability.

[0008] Furthermore, as a means to improve the storage stability of surface treatment agents, Patent Document 8 (International Publication No. 2023 / 149339) discloses a surface treatment agent containing a fluorinated ether compound and fluoride ions. If the content of fluoride ions is 0.1-3.0 ppm by mass relative to the total mass of the surface treatment agent, the storage stability is improved, and a cured film with excellent weather resistance can be given.

[0009] However, under heating conditions, sufficient preservation stability is sometimes not achieved.

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Japanese Patent Publication No. 2008-534696

[0013] Patent Document 2: Japanese Patent Publication No. 2008-537557

[0014] Patent Document 3: Japanese Patent Application Publication No. 2012-072272

[0015] Patent Document 4: Japanese Patent Application Publication No. 2012-157856

[0016] Patent Document 5: Japanese Patent Application Publication No. 2013-136833

[0017] Patent Document 6: Japanese Patent Application Publication No. 2015-199906

[0018] Patent Document 7: Japanese Patent Application Publication No. 2015-214664

[0019] Patent Document 8: International Publication No. 2023 / 149339 Summary of the Invention

[0020] The problem that the invention aims to solve

[0021] Therefore, the object of the present invention is to provide a surface treatment agent that exhibits excellent stability under any temperature environment, especially even under heating conditions, i.e., a surface treatment agent comprising a silane containing a hydrolyzable group modified with a polymer containing a fluorinated polyether group and / or a partially hydrolyzed condensate thereof, and articles surface-treated with the surface treatment agent, etc.

[0022] Methods for solving problems

[0023] In order to solve the above-mentioned objective, the inventors conducted in-depth research and found that the following surface treatment agent has excellent storage stability even at temperatures higher than room temperature (20-25°C), thus completing the present invention.

[0024] That is, the present invention provides a surface treatment agent containing a silane with hydrolyzable groups modified by a polymer containing a fluorinated polyether group and / or a partially hydrolyzed condensate of the silane, and an article having a cured film of the surface treatment agent on the surface.

[0025] [1] A surface treatment agent comprising (A) a silane containing a hydrolyzable group modified with a polymer containing a fluorinated polyether group and / or its partially hydrolyzed condensate, and (B) a fluorinated solvent, wherein the fluoride ions (fluoride ions) contained in the fluorinated solvent of component (B) account for more than 0% by mass and 1.0 × 10⁻⁶ ppm of the total amount of the surface treatment agent. -5 Quality percentage below %.

[0026] [2] According to the surface treatment agent described in [1], the content of component (A) is 0.05 to 30% by mass relative to the total surface treatment agent.

[0027] [3] The surface treatment agent according to [1] or [2], wherein the number average molecular weight of component (A) is 1,000 to 25,000.

[0028] [4] The surface treatment agent according to any one of [1] to [3], wherein the silane containing hydrolyzable groups modified with a polymer containing a fluorinated polyether group of component (A) has at least one group represented by the following formula (1) at at least one end of the molecule.

[0029]

Chemistry 1

[0030]

[0031] (In formula (1), Y is a single bond, or may have one or more divalent hydrocarbon groups selected from fluorine atoms, silicon atoms and siloxane bonds, R is an alkyl or phenyl group with 1 to 4 carbon atoms, X is a hydrolyzable group, and a is 2 or 3.)

[0032] [5] The surface treatment agent according to any one of [1] to [4], wherein the silane containing a hydrolyzable group modified with a polymer containing a fluorinated polyether group in component (A) has a molecular structure consisting of -(C b F 2b O) m -(where b is an independent number from 1 to 6 in each unit, and m is a number from 1 to 250. These units can be linear or branched.) represents a polyfluoroalkylene oxide structure.

[0033] [6] The surface treatment agent according to any one of [1] to [5], wherein, in component (A), the silane is represented by the following formula (2), (4) or (7).

[0034]

Chemistry 2

[0035]

[0036] In equation (2), Rf is derived from -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-(where d is an independent number from 0 to 5, p, q, r, s, t, and u are each an independent number from 0 to 150, and the sum of p, q, r, s, t, and u is a number from 1 to 250. These units can be linear or branched. Furthermore, the repeating units shown within parentheses containing p, q, r, s, t, and u can be randomly combined.) represents a divalent group containing a polyfluorinated oxyalkylene structure, A 1 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3).

[0037]

Transformation 3

[0038]

[0039] [In formula (3), Q is a single-bonded or divalent organic group, Z is a group with 2 to 8 valences, α is 0 or 1, β is a number from 1 to 7, and W is independently a monovalent group containing a hydrolyzable silyl group represented by formula (1) above.]

[0040]

Chemistry 4

[0041]

[0042] In formula (4), Rf represents the same group as above, A 2 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5).

[0043]

Transformation 5

[0044]

[0045] In formula (5), W represents the same group as above, B is a hydrogen atom or -OS independently, S is a hydrogen atom, a monovalent hydrocarbon group with 1 to 10 carbon atoms, or a monovalent group represented by formula (6) below, and e is 1 or 2.

[0046]

Transformation 6

[0047]

[0048] (In formula (6), T is a single bond or a group with 2 to 8 valences, L is independently a divalent hydrocarbon group with 1 to 4 carbon atoms, E is a monovalent hydrocarbon group with 1 to 6 carbon atoms, or W, and l is a number from 0 to 20.)

[0049]

Transformation 7

[0050]

[0051] In formula (7), Rf represents the same group as above, A 3 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or J, where J is a monovalent group represented by the following formula (8).

[0052]

Transformation 8

[0053]

[0054] In formula (8), S and e have the same meaning as above, V is a single bond or a divalent hydrocarbon group with 2 to 15 carbon atoms that may have an ether bond, and M is a monovalent group represented by the following formula (9).

[0055]

Chemistry 9

[0056]

[0057] (In formula (9), Y, S, and W represent the same groups as above, and f is a number from 1 to 3.)

[0058] [7] According to the surface treatment agent described in [6], in formula (3), Q is an unsubstituted or substituted divalent hydrocarbon group having 1 to 15 carbon atoms and containing one or more bonds selected from amide bonds, ether bonds, ester bonds, thioether bonds, urethane bonds, siloxane bonds, triazine bonds, diorganomymethylene silane, silanephenyl bonds and silanealkyl bonds, and Z is a divalent to octyl group selected from silicon atoms, nitrogen atoms, silanealkyl, silanearyl, and divalent to octyl organopolysiloxane residues having siloxane bonds.

[0059] [8] The surface treatment agent according to [6] or [7], wherein, in formula (6), T is a single bond, or may contain a divalent hydrocarbon group, siloxane bond, silane group or organomycyl group with 2 to 20 carbon atoms selected from one or more bonds selected from silicon atom, siloxane bond, silane group, silane group or organomycyl group.

[0060] [9] The surface treatment agent according to any one of [1] to [8] further comprises a polymer containing a fluorinated polyether group without hydrolyzable groups as component (C).

[0061]

[10] According to the surface treatment agent of [9], the polymer containing fluorinated polyether groups that does not contain hydrolyzable groups is represented by the following formula (10).

[0062]

Chemistry 10

[0063]

[0064] (In equation (10), Rf is derived from -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 -(where d is an independent number from 0 to 5, p, q, r, s, t, and u are each an independent number from 0 to 150, and the sum of p, q, r, s, t, and u is a number from 1 to 250. These units can be linear or branched. Furthermore, the repeating units shown within parentheses containing p, q, r, s, t, and u can be randomly combined.) represents a divalent group containing a polyfluorinated oxyalkylene structure, A 4 Independently a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, -OR 3 -COOR 3 or -PO(OR) 3 )2 [R 3 It consists of a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0065]

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

[10] , wherein component (B) is at least one selected from fluorinated aliphatic hydrocarbon solvents, fluorinated ether solvents, and fluorinated alkylamine solvents.

[0066]

[12] Articles treated with any of the surface treatment agents according to any one of [1] to

[11] .

[0067]

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

[11] .

[0068]

[14] An antireflective treated article treated with any of the surface treatment agents according to any one of [1] to

[11] .

[0069]

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

[11] .

[0070] The effects of the invention

[0071] The surface treatment agent of the present invention exhibits excellent storage stability at temperatures higher than room temperature (20-25°C) and can suppress agglomerates in the surface treatment agent. Detailed Implementation

[0072] The present invention will now be described in detail.

[0073] This invention relates to a surface treatment agent comprising (A) a silane containing hydrolyzable groups modified with a polymer containing a fluorinated polyether group and / or its partially hydrolyzed condensate, and (B) a fluorinated solvent, characterized in that the fluoride ions contained in the fluorinated solvent of component (B) account for greater than 0% by mass and 1.0 × 10⁻⁶% by mass in the total amount of the surface treatment agent. -5 Less than % by mass. As long as the fluoride ion is within the above range, even when stored at high temperatures, it is not easy to form agglomerates in the surface treatment agent. Agglomerates are not easy to form in the cured film formed using the surface treatment agent of the present invention, and the increase in surface roughness and haze of the cured film can be suppressed.

[0074] Furthermore, in this invention, the term "high temperature state" refers to a temperature state that is higher than room temperature (20-25°C).

[0075] (A)Ingredients

[0076] (A) The component is a polymer containing a fluorinated polyether group in the molecule, with silanes containing hydrolyzable groups and / or their partially hydrolyzed condensates modified with the polymer containing the fluorinated polyether group as necessary components.

[0077] Furthermore, in this invention, the number-average molecular weight (Mn) of the silane and / or its partially hydrolyzed condensate containing hydrolyzable groups modified with a polymer containing a fluorinated polyether group contained in the surface treatment agent is preferably in the range of 1000 to 25000. From the viewpoint of being able to form a film with excellent water and oil repellency and scratch resistance, it is more preferable that the number-average molecular weight is 2000 to 20000, further preferably 2500 to 16000, and particularly preferably 3000 to 12000.

[0078] (A) The number-average molecular weight (Mn) of the component can be obtained as a conversion value for polystyrene analysis using a fluorinated solvent as the elution solvent.

[0079] Additionally, the number-average molecular weight (Mn) of silanes containing hydrolyzable groups modified with polymers containing fluorinated polyether groups and / or partially hydrolyzed condensates of such polymers can also be determined by... 19 The intensity ratio of the characteristic peaks was calculated from the F-NMR analysis.

[0080] The silanes and / or their partially hydrolyzed condensates containing hydrolyzable groups modified with polymers containing fluorinated polyether groups, having the above-mentioned number-average molecular weight, can be obtained by distillation or molecular distillation of a solution containing the polymers containing fluorinated polyether groups and / or their partially hydrolyzed condensates. Alternatively, they can be prepared by pre-selecting the fluorinated compounds used in the synthesis of polymers containing fluorinated polyether groups to have the above-mentioned number-average molecular weight.

[0081] The surface treatment agent used in this invention uses a silane modified with a polymer containing a fluorinated polyether group, which contains a hydrolyzable group. At least one, preferably one to three, ends of the silane in the molecule have at least one, preferably one to three (i.e., at least one, preferably one to nine, more preferably two to six) groups represented by the following formula (1) (groups containing a hydrolyzable silane).

[0082]

Chemistry 11

[0083]

[0084] (In formula (1), Y is a single bond, or may have one or more divalent hydrocarbon groups selected from fluorine atoms, silicon atoms, and siloxane bonds; R is an alkyl or phenyl group with 1 to 4 carbon atoms; X is a hydrolyzable group; and a is 2 or 3.) Preferably, the molecule has a group consisting of -(C b F 2b O) m -(where b is an independent number from 1 to 6 in each unit, and m is a number from 1 to 250. These units can be linear or branched.) represents a polyfluoroalkylene oxide structure.

[0085] Furthermore, in order to impart low haze and abrasion durability properties to articles surface-treated with the surface treatment agent of the present invention, which comprises a silane containing a hydrolyzable group modified with a polymer containing a fluorinated polyether group, it is preferable to use a polymer containing a fluorinated polyether group having at least 2, preferably 2 to 3 (i.e., having at least 2, preferably 2 to 9, more preferably 2 to 6 groups in the molecule) represented by the above formula (1) (groups containing hydrolyzable silanes).

[0086] In formula (1) above, Y is a single bond, or may have one or more divalent hydrocarbon groups selected from fluorine atoms, silicon atoms, and siloxane bonds. As a divalent hydrocarbon group that may have one or more divalent hydrocarbon groups selected from fluorine atoms, silicon atoms, and siloxane bonds, it may be a group selected from alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing fluorine atoms, alkylene groups having 6 to 8 carbon atoms containing aryl groups (alkylene-aryl), divalent groups in which alkylene groups are bonded to each other by a silane-alkylene structure or a silane-aryl structure, and divalent groups in which a 2 to 10 carbon alkylene group is bonded to the binding end of a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 carbon atoms. Among these, alkylene groups having 1 to 10 carbon atoms are preferred, 2 to 5 are preferred, and 2 or 3 are more preferred.

[0087] As for Y other than a single bond, specifically, the groups shown below can be exemplified. Furthermore, in the structures described below, it is preferable that the bonding end on the right is bonded to Si.

[0088]

Chemistry 12

[0089]

[0090] In formula (1) above, X represents a hydrolyzable group that can be different from each other. Examples of such X include alkoxy groups with 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups with 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups with 2 to 10 carbon atoms, such as acetoxy and propionyloxy; alkoxy groups with 2 to 10 carbon atoms, such as ethyleneoxy, allyloxy, propionyloxy, and isopropionyloxy; and halogen groups, such as chloro, bromo, and iodo. Among these, methoxy, ethoxy, isopropionyloxy, and chloro groups are preferred.

[0091] In the above formula (1), R is an alkyl or phenyl group with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, with methyl or ethyl being preferred.

[0092] In the above formula (1), a is 2 or 3, and from the viewpoint of reactivity and adhesion to the substrate, 3 is preferred.

[0093] As groups represented by formula (1) (groups containing hydrolyzable silyl groups), the following groups can be listed.

[0094]

Chemistry 13

[0095]

[0096]

Chemistry 14

[0097]

[0098] Additionally, in the above-(C) b F 2b O) m In the polyfluorinated oxyalkylene structure represented by -, b is independently a number from 1 to 6 in each unit, preferably from 1 to 4, and m is a number from 1 to 250, preferably from 10 to 250, more preferably from 10 to 140. These units can be linear or branched.

[0099] As a result of the above-C b F 2b O- indicates repeating units, such as units represented by the following formula.

[0100] -CF2O-

[0101] -CF2CF2O-

[0102] -CF2CF2CF2O-

[0103] -CF(CF3)CF2O-

[0104] -CF2CF2CF2CF2O-

[0105] -CF2CF2CF2CF2CF2CF2O-

[0106] -C(CF3)2O-

[0107] Of these, repeating units represented by the following formula are particularly preferred.

[0108] -CF2O-

[0109] -CF2CF2O-

[0110] Furthermore, the aforementioned polyfluorinated oxyalkylene structure can be composed of one of the aforementioned repeating units, or it can be composed of a combination of two or more of them.

[0111] The polymer containing fluorinated polyether groups is preferably a polymer containing fluorinated polyether groups, for example, represented by the following formulas (2), (4) or (7).

[0112]

Chemistry 15

[0113]

[0114] In equation (2), Rf is derived from -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 -(where d is an independent number from 0 to 5, p, q, r, s, t, and u are each an independent number from 0 to 150, and the sum of p, q, r, s, t, and u is a number from 1 to 250. These units can be linear or branched. Furthermore, the repeating units shown within parentheses containing p, q, r, s, t, and u can be randomly combined.) represents a divalent group containing a polyfluorinated oxyalkylene structure, A 1 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3).

[0115]

Chemistry 16

[0116]

[0117] [In formula (3), Q is a single-bonded or divalent organic group, Z is a 2- to 8-valent group, α is 0 or 1, β is a number from 1 to 7, and W is independently a monovalent group containing a hydrolyzable silyl group represented by formula (1) above.]

[0118]

Chemistry 17

[0119]

[0120] In formula (4), Rf represents the same group as above, A 2 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5).

[0121] [Chemistry 18]

[0122]

[0123] In formula (5), W represents the same group as above, B is independently a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group with 1 to 10 carbon atoms, or a group derived from the following formula (6).

[0124]

Chemistry 19

[0125]

[0126] (In formula (6), T is a single bond or a group with 2 to 8 valences, L is independently a divalent hydrocarbon group with 1 to 4 carbon atoms, E is a monovalent hydrocarbon group with 1 to 6 carbon atoms, or W, l is a number from 0 to 20.) representing a monovalent group, e is 1 or 2.

[0127]

Chemistry 20

[0128]

[0129] In formula (7), Rf represents the same group as above, A 3 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or J, where J is a monovalent group represented by the following formula (8).

[0130]

Chemistry 21

[0131]

[0132] In formula (8), S and e have the same meaning as above, V is a single bond or a divalent hydrocarbon group with 2 to 15 carbon atoms that may have an ether bond, and M is a group formed by the following formula (9).

[0133]

Chemistry 22

[0134]

[0135] (In formula (9), Y, S, and W represent the same groups as above, and f is a number from 1 to 3.) This represents a monovalent group.

[0136] First, the polymer containing fluorinated polyether groups, represented by the following formula (2), will be explained.

[0137]

Chemistry 23

[0138]

[0139] In equation (2) above, Rf is the product of -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 - indicates a divalent group containing a polyfluorinated oxyalkylene structure (perfluoropolyether structure), d is independently a number from 0 to 5, preferably a number 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 a number from 0 to 100, more preferably a number from 0 to 80, further preferably a number from 0 to 60, particularly preferably a number from 0 to 40, especially preferably a number 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. These units can be linear or branched. Furthermore, the repeating units shown in parentheses containing p, q, r, s, t and u can be randomly combined.

[0140] As a divalent group of Rf containing a polyfluorinated oxyalkylene structure (perfluoropolyether structure), specifically, it can be represented by the following structure.

[0141]

Chemistry 24

[0142]

[0143]

[0144] (In the formula, p', q', r', s', t', and u' are each independently a number from 1 to 150, and the sum of p', q', r', s', t', and u' is from 12 to 250. Furthermore, the repeating units shown within the parentheses containing p', q', r', s', t', and u' can be randomly combined. d' is independently a number from 0 to 5. These units can be linear or branched.)

[0145] Equation (2) above: A 1 In -Rf-D, A 1 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or D (i.e., -QZ represented by formula (3) described later). α (W) β The fluoroalkyl group is a monovalent fluoroalkyl group with a terminal CF3- or CF2H- and may contain an oxygen atom. It is preferably a fluoroalkyl group with 1 to 6 carbon atoms, and particularly preferably a fluoroalkyl group with a terminal CF3- or CF2H- of the polymer.

[0146] As such A 1 The terminal part is CF3- or CF2H- and may contain a monovalent fluorinated hydrocarbon group with an oxygen atom, such as the following groups.

[0147]

Chemistry 25

[0148]

[0149] In the above equation (2): A 1 In -Rf-D, D is a monovalent group represented by the following formula (3).

[0150]

Chemistry 26

[0151]

[0152] In the above formula (3), Q is a single bond or a divalent organic group. As Q other than a single bond, it is preferably an unsubstituted or substituted divalent hydrocarbon group with 1 to 15 carbon atoms, preferably 2 to 15 carbon atoms, which may contain one or more bonds selected from amide bonds (e.g., unsubstituted amide bonds, N-methyl substituted amide bonds, N-phenyl substituted amide bonds), ether bonds, ester bonds, thioether bonds, urethane bonds, siloxane bonds, triazine bonds, diorganosilyl groups (e.g., dialkylsilyl groups such as dimethylmethylenesilyl), silylenylic bonds and silylene bonds (e.g., silylethylic bonds). It is preferably an unsubstituted or fluorinated divalent hydrocarbon group with 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, which may contain the bonds.

[0153] Other than a single bond, Q can be represented by groups such as those listed below. Furthermore, in the structures described below, it is preferable that the left-hand binding end is bonded to Rf and the right-hand binding end is bonded to Z.

[0154]

Chemistry 27

[0155]

[0156] (In the formula, t is a number from 1 to 4, preferably a number from 2 to 4.)

[0157] Equation (3) above: -QZ α (W) β In this context, Z is a divalent to octavalent group, preferably a divalent to octavalent organopolysiloxane residue having a silicon atom, a nitrogen atom, a silanediol, a silaneryl group, and a siloxane bond. More preferably, it is a divalent to octavalent, preferably divalent to quaternary, group selected from linear organopolysiloxane residues having 2 to 13 silicon atoms, particularly 2 to 5 silicon atoms, or branched or cyclic organopolysiloxane residues having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms. Additionally, it may include silanediol structures such as silanediol structures with two silicon atoms bonded by alkylene groups such as ethylene, i.e., Si-(CH2). n -Si (where n is a number from 2 to 6, preferably a number from 2 to 4).

[0158] Among them, the following groups can be exemplified as silanediol or silanearyl groups.

[0159]

Chemistry 28

[0160]

[0161] (where R is in the formula) 1 R is an alkyl group with 1 to 8 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, or an aryl group with 6 to 10 carbon atoms, such as methyl, ethyl, propyl, or butyl. 1 They can be the same or different. R 2 It can be an alkylene group with 1 to 4 carbon atoms, such as methylene, ethylene, or propylene (trimethylene, methyl ethylene), or an aryl group with 6 to 10 carbon atoms, such as phenylene.

[0162] In addition, the groups shown below can be exemplified as 2- to 8-valent organopolysiloxane residues having siloxane bonds.

[0163]

Chemistry 29

[0164]

[0165] (where R is in the formula) 1 (This refers to the same group as described above, where g is a number from 1 to 12, preferably 1 to 4; h is a number from 2 to 8, preferably 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 3 to 5; and k is a number from 1 to 3, preferably 2 or 3.)

[0166] As such a Z, the following groups can be listed.

[0167]

Transformation 30

[0168]

[0169]

Chemistry 31

[0170]

[0171]

Chemistry 32

[0172]

[0173]

Transformation 33

[0174]

[0175]

Transformation 34

[0176]

[0177]

Chemistry 35

[0178]

[0179] Equation (3) above: -QZ α (W) β In this context, W is independently a monovalent group containing a hydrolyzable silyl group, as represented by the above formula (1).

[0180] Equation (3) above: -QZ α (W) β In this context, α is 0 or 1, β is a number from 1 to 7, preferably a number from 2 to 7, and β is (the valence of Z - 1).

[0181] As in the above equation (3): -QZ α (W) β (That is, D in formula (2)) can be listed as the groups shown below.

[0182]

Transformation 36

[0183]

[0184]

Chemistry 37

[0185]

[0186] As polymers containing fluorinated polyether groups as represented by the above formula (2), the following polymers can be listed.

[0187]

Transformation 38

[0188]

[0189] (where A is in the formula) 1 (Rf represents the same group as described above.)

[0190]

Chemistry 39

[0191]

[0192] (where A is in the formula) 1 (Rf represents the same group as described above.)

[0193] Next, we will describe polymers containing fluorinated polyether groups as represented by the following formula (4).

[0194]

Chemistry 40

[0195]

[0196] In the above formula (4), Rf represents the same group as above, and can represent the same group as the group represented in Rf of the above formula (2).

[0197] Equation (4) above: A 2 In -Rf-G, A 2 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or G (i.e., from formula (5) described later): -C(B) e (W) 3-e The monovalent group (represented by the CF3- or CF2H- terminal group) is a monovalent fluorinated hydrocarbon group that may contain an oxygen atom, preferably a fluoroalkyl group with 1 to 6 carbon atoms, and particularly preferably a fluoroalkyl group with CF3- or CF2H- terminal group.

[0198] As such A 2 The terminal part is CF3- or CF2H- and may contain a monovalent fluorinated hydrocarbon group with an oxygen atom, such as the following groups.

[0199]

Chemistry 41

[0200]

[0201] In the above equation (4): A 2 In -Rf-G, G is a monovalent group represented by the following formula (5).

[0202]

Chemistry 42

[0203]

[0204] In the above formula (5), W represents the same group as above, and can represent the same group as the group represented in W in the above formula (3).

[0205] In the above formula (5), e is 1 or 2, preferably 1.

[0206] Equation (5) above: -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 with 1 to 10 carbon atoms, or a monovalent group represented by the following formula (6).

[0207]

Chemistry 43

[0208]

[0209] Among them, the monovalent hydrocarbon group with 1 to 10 carbon atoms as S can be alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, vinyl, allyl, aryl such as phenyl, tolyl, aralkyl such as benzyl, phenylethyl, etc., preferably alkyl or phenyl with 1 to 3 carbon atoms.

[0210] Equation (6) above: -T-(LO) l In -E, T is a single bond or a group with a 2- to 8-valent charge, preferably a single bond, or a divalent hydrocarbon group with 2 to 20 carbon atoms selected from silicon atoms, siloxane bonds, silaneyl bonds (e.g., silylethylidene bonds, silylpropylidene bonds), silaryl bonds (e.g., silylphenylidene bonds), and diorganosilyl groups (e.g., dialkylsilyl groups such as dimethylmethylenesilyl, dialkoxysilyl, etc.). As T other than a single bond, specific examples of the groups shown below can be exemplified. Furthermore, in the structures described below, it is preferable that the right-hand side is bonded to L or E.

[0211]

Chemistry 44

[0212]

[0213] Equation (6) above: -T-(LO) l In -E, L is independently a divalent hydrocarbon group with 1 to 4 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methyl ethylene), butylene (tetramethylene), etc. The number of carbon atoms can be single or mixed.

[0214] Equation (6) above: -T-(LO) l In -E, l is a number from 0 to 20, preferably a number from 0 to 10, and more preferably a number from 0 to 6. Furthermore, when (LO) is present, l is preferably 1 or more, and particularly preferably 2 or more.

[0215] Equation (6) above: -T-(LO) l In -E, E is an alkyl group with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc., or a monovalent hydrocarbon group with 1 to 6 carbon atoms, such as phenyl, or W, where W represents the same group as described above, and can represent the same group as the group exemplified in W of the above formula (3).

[0216] As given by equation (6) above: -T-(LO) l -E represents a monovalent group, which can be listed as shown below.

[0217]

Chemistry 45

[0218]

[0219] As derived from the above equation (5): -C(B) e (W) 3-e The monovalent group (i.e., G in formula (4)) can be listed as the group shown below.

[0220]

Chemistry 46

[0221]

[0222]

Chemistry 47

[0223]

[0224] As polymers containing fluorinated polyether groups as represented by the above formula (4), the following polymers can be listed.

[0225]

Chemistry 48

[0226]

[0227] (where A is in the formula) 2 (Rf represents the same group as described above.)

[0228]

Chemistry 49

[0229]

[0230] (where A is in the formula) 2 (Rf represents the same group as described above.)

[0231] Next, we will describe polymers containing fluorinated polyether groups as represented by the following formula (7).

[0232] [Transformation 50]

[0233]

[0234] In the above formula (7), Rf represents the same group as above, and can represent the same group as the group represented in Rf of the above formula (2).

[0235] Equation (7) above: A 3 In -Rf-J, A 3 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or J (i.e., from formula (8) described later): -VC(=O)N(S) 2-e (M) e The monovalent group (represented by the CF3- or CF2H- terminal group) is a monovalent fluorinated hydrocarbon group that may contain an oxygen atom, preferably a fluoroalkyl group with 1 to 6 carbon atoms, and particularly preferably a fluoroalkyl group whose polymer terminal is CF3- or CF2H-.

[0236] Examples of such monovalent fluorinated hydrocarbon groups with a terminal CF3- or CF2H- and which may contain an oxygen atom include the following groups.

[0237]

Chemistry 51

[0238]

[0239] Equation (7) above: A 3 In -Rf-J, J is a monovalent group represented by the following formula (8).

[0240]

Chemistry 52

[0241]

[0242] In formula (8) above, V is a single bond or a divalent hydrocarbon group with 2 to 15 carbon atoms that may have an ether bond. Specifically, groups other than single bonds can be exemplified as shown below. Furthermore, in the structure described below, it is preferable that the bonding end on the right side is bonded to a carbon atom (-C(=O)-).

[0243]

Chemistry 53

[0244]

[0245] In the above formula (8), S represents the same group as above, and can represent the same group as the group represented in S in the above formula (5).

[0246] In the above formula (8), e has the same meaning as e in the above formula (5), which is 1 or 2, preferably 1.

[0247] In the above formula (8), M is a monovalent group represented by the following formula (9).

[0248]

Chemistry 54

[0249]

[0250] In the above formula (9), Y, S, and W represent the same groups as those described above, and can respectively represent the same groups as those exemplified in formula (1), formula (5), and formula (3).

[0251] In the above formula (9), f is a number from 1 to 3.

[0252] As given by equation (9): -YC(S) 3-f (W) f The monovalent groups (i.e., M in formula (8)) can be listed as shown below.

[0253]

Transformation 55

[0254]

[0255] As given by equation (8): -VC(=O)N(S) 2-e (M) e The monovalent groups can be listed as shown below.

[0256]

Transformation 56

[0257]

[0258]

Chemistry 57

[0259]

[0260]

Transformation 58

[0261]

[0262] As polymers containing fluorinated polyether groups as represented by the above formula (7), the following polymers can be listed.

[0263]

Chemistry 59

[0264]

[0265] (where A is in the formula) 3 (Rf represents the same group as described above.)

[0266]

Transformation 60

[0267]

[0268] (where A is in the formula) 3 (Rf represents the same group as described above.)

[0269]

Chemistry 61

[0270]

[0271] (where A is in the formula) 3 (Rf represents the same group as described above.)

[0272] (A) Components may be used alone or in combination of two or more.

[0273] (A) The content of component relative to the total surface treatment agent 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.

[0274] (B) Ingredients

[0275] The fluorinated solvent for component (B) is not particularly limited as long as component (A) is uniformly dissolved. In this invention, "uniformly dissolved" means that the solvent containing component (A) is visually transparent, for example, it is in a state where no white mist (dissolved residue such as agglomerates) is observed when the solvent is irradiated with light. Examples of such fluorinated solvents include fluorinated aliphatic hydrocarbon solvents, fluorinated ether solvents, and fluorinated alkylamine solvents.

[0276] Examples of fluorinated aliphatic hydrocarbon solvents include perfluoroheptane, perfluorooctane, tridecylfluorooctane, hexafluoropropylene trimer, etc., and fluorinated aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene.

[0277] Examples of fluorinated ether solvents include methyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, ethyl nonafluoroisobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptenyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, hexafluoroisopropylmethyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane.

[0278] Examples of fluorinated alkylamine solvents include perfluorotri-N-butylamine and perfluorotripentylamine.

[0279] Among these, 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotri-N-butylamine, ethyl perfluorobutyl ether, ethyl nonafluoroisobutyl 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 hexafluoropropylene trimer are preferred.

[0280] The above-mentioned fluorinated solvents can be used alone or in combination.

[0281] (B) The fluoride ions in the fluorinated solvent of component (B) account for more than 0% by mass and are 1.0 × 10⁻⁶. -5 Below 10% by mass, preferably greater than 0% by mass but less than 1.0 × 10⁻⁶. -5 Mass%, more preferably greater than 0% by mass and 9.8 × 10 -6 Less than 9.8% by mass, with a particularly preferred content greater than 0% by mass and 9.8 × 10⁻⁶. -6 Quality percentage below %.

[0282] In this invention, the fluoride ions in the fluorinated solvent of component (B) can be determined by ion chromatography. When used in the dissolution and dilution of component (A), if the fluoride ions contained in the fluorinated solvent of component (B) are within the above-mentioned range relative to the total amount of the surface treatment agent, there is no particular limitation on the concentration of fluoride ions in the fluorinated solvent of component (B). From the viewpoint of ease of manufacturing the surface treatment agent, a range greater than 0 µg / g and less than 0.1 µg / g is preferred, and more preferably greater than 0 µg / g and less than 0.095 µg / g.

[0283] (C) Components

[0284] In the surface treatment agent of the present invention, a fluorinated polyether polymer (hereinafter sometimes referred to as a non-hydrolyzable silane polymer or a nonfunctional polymer) represented by the following formula (10) may be further contained as component (C).

[0285]

Transformation 62

[0286]

[0287] (In equation (10), Rf is derived from -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 -(where d is an independent number from 0 to 5, p, q, r, s, t, and u are each an independent number from 0 to 150, and the sum of p, q, r, s, t, and u is a number from 1 to 250. These units can be linear or branched. Furthermore, the repeating units shown within parentheses containing p, q, r, s, t, and u can be randomly combined.) represents a divalent group containing a polyfluorinated oxyalkylene structure, A 4Independently a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, -OR 3 -COOR 3 or -PO(OR) 3 )2[R 3 It consists of a monovalent hydrocarbon group containing 1 to 10 hydrogen or carbon atoms.

[0288] In formula (10), Rf represents the same group as above, and can represent the same group as the group represented in Rf of formula (2) above.

[0289] In the above formula (10), A 4 Independently a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, -OR 3 -COOR 3 or -PO(OR) 3 )2, as a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and which may contain an oxygen atom, can be exemplified as A 1 The same group is an example of a monovalent fluorinated hydrocarbon group whose terminal part is CF3- or CF2H- and may contain an oxygen atom.

[0290] Among them, R 3 It is a monovalent hydrocarbon group with 1 to 10 carbon atoms, preferably a monovalent hydrocarbon group with 1 to 6 carbon atoms. Examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenylethyl. 3 Preferably, it contains hydrogen atoms or alkyl or phenyl groups with 1 to 3 carbon atoms.

[0291] As A 4 -OR 3 -COOR 3 -PO(OR) 3 )2, which can be used to represent -OH, -OCH3, -OC2H5, -COOH, -COOCH3, -COOC2H5, -PO(OH)2, -PO(OCH3)3, and -PO(OC2H5)3.

[0292] As a polymer that does not contain hydrolyzable silanes as represented by the above formula (10), the following polymers can be listed.

[0293]

Transformation 63

[0294]

[0295]

[0296] (In the formula, p', q', r', s', t', u' and the sum of p', q', r', s', t', u' represent the same meaning as above. These units can be linear or branched. In addition, the repeating units shown in parentheses with p', q', r', s', t', and u' can be randomly combined.)

[0297] The surface treatment agent of the present invention preferably comprises a silane containing a hydrolyzable group and / or a partially hydrolyzed condensate thereof modified with a fluorinated polyether group having at least one group represented by formula (1) at the end of the molecule, as described above. Typically, it comprises at least one polymer containing a fluorinated polyether group having at least one, preferably at least two, hydrolyzable silyl groups at a single end of the molecular chain, as described by formula (2), (4) or (7) above, and / or a partially hydrolyzed condensate thereof (single-terminal polymer); or at least one polymer containing a fluorinated polyether group having at least one, preferably at least two, hydrolyzable silyl groups at both ends of the molecular chain, as described by formula (2), (4) or (7) above, and / or a partially hydrolyzed condensate thereof (two-terminal polymer); or at least one of the single-terminal polymer and at least one of the two-terminal polymer; or in any of these cases, it further comprises a polymer without the hydrolyzable silyl groups described above.

[0298] In the surface treatment agent of the present invention, there is no particular limitation on the mixing ratio of the mixture of single-terminal polymers and / or two-terminal polymers with polymers without hydrolyzable silyl groups. Generally, the ratio of the polymers without hydrolyzable silyl groups is preferably 0 to 30% by mass, particularly 0 to 10% by mass, relative to the total mixture of polymers containing fluorinated polyether groups consisting of single-terminal polymers and / or two-terminal polymers with polymers without hydrolyzable silyl groups.

[0299] In the surface treatment agent of the present invention, as other components, a hydrolysis condensation catalyst may be added as needed, such as organotin compounds (dimethoxydibutyltin, dibutyltin dilaurate, etc.), organotitanium compounds (tetrabutyl titanate, etc.), organic acids (acetic acid, methanesulfonic acid, fluorinated carboxylic acids, etc.), and inorganic acids (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetrabutyl titanate, dibutyltin dilaurate, and fluorinated carboxylic acids are particularly preferred. The amount added is a catalytic amount, typically 0.01 to 5 parts by mass relative to 100 parts by mass of a polymer containing at least one hydrolyzable silyl group and / or a partially hydrolyzed condensate of the polymer, preferably 0.1 to 1 part by mass.

[0300] The surface treatment agent of the present invention can be applied to a substrate using known methods such as brush coating, dipping, spraying, and vapor deposition. The heating method during vapor deposition can be resistance heating or electron beam heating, and is not particularly limited. Furthermore, the curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferably set at 25–150°C, particularly 25–120°C, for 0.5–48 hours, particularly 12–24 hours. In the case of application by vapor deposition, it is preferably performed at 25–150°C, particularly 25–120°C, for 0.5–48 hours, particularly 12–24 hours. Additionally, it can be cured under humidification. The thickness of the cured film is appropriately selected according to the type of substrate, but is typically 5–30 nm, particularly 8–20 nm.

[0301] There are no particular limitations on the substrate treated with the surface treatment agent of the present invention; it can be a substrate of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, and quartz. The surface treatment agent of the present invention can impart water and oil repellency, surface lubrication, low dynamic friction, and scratch resistance to the substrate. In particular, it is suitable for use as a surface treatment agent for SiO2-treated glass or quartz substrates.

[0302] Examples of articles treated with the surface treatment agent of the present invention include glass, tempered glass, sapphire glass, quartz glass, touch panels, hard coatings, high-hardness films, anti-reflective films, spectacle lenses, optical lenses, and quartz substrates. In particular, it can be used as a surface treatment agent for forming a water- and oil-repellent layer on the surface of tempered glass and anti-reflective treated glass.

[0303] Example

[0304] The following examples, embodiments, and comparative examples illustrate the invention in more detail, but the invention is not limited to the embodiments described below.

[0305] [Methods for determining fluoride ion concentration]

[0306] Add 3g of solvent and 3ml of pure water, shake for 30 minutes, then centrifuge to separate the aqueous layer. After passing the aqueous layer through a cleaned pretreatment chamber, dilute it and perform ion mass spectrometry analysis. Fluoride ions were quantified using the absolute calibration curve method. It should be noted that the measurable range in this assay is above 0.005 μg / g.

[0307] Measuring apparatus and measuring conditions

[0308] Measuring device: Tosoh Corporation IC-8100

[0309] Pump: IC-8100 built-in pump

[0310] Assay conditions (column type): Tosho Bioscience TSKgel Super IC-Anion HS

[0311] Eluent: 7.5mM NaHCO3 + 0.8mM Na2CO3

[0312] Flow rate: 1.5 mL / min

[0313] Detection: Conductivity detector

[0314] [Methods for determining number-average molecular weight]

[0315] The number-average molecular weights of the fluorinated polyether polymers obtained in the following synthetic examples were determined using gel permeation chromatography (GPC). The determination conditions are described below. The results are shown in Table 1.

[0316] Measuring apparatus and measuring conditions

[0317] Measurement device: Agilent Technologies, Inc. 1260 Infinity II

[0318] Pump: HITACHI Chromaster 5110 Pump

[0319] Assay conditions (column): Tosoh Bioscience TSKgel Multipore H XL -M 7.8mmφ×30cm 2 pieces

[0320] Eluent: Hydrochlorofluorocarbon (HCFC)-225

[0321] Flow rate: 1.0 mL / min

[0322] Detector: Evaporative Light Scattering Detector

[0323] Column Oven: GL Science 705

[0324] Ink jet volume: 20μL

[0325] Flow rate: 1.0 mL / min

[0326] Column temperature: 35℃

[0327] Standard reference material: Agilent Technologies, Inc. PMMA calibrationlit ML-10

[0328] [Synthesis example 1]

[0329] A compound represented by the following formula (A) was prepared.

[0330] [Chemical Formula 64]

[0331]

[0332] 100 g (2.1 × 10 -2 mol) of the compound represented by the above formula (A), 100 g of 1,3-bis(trifluoromethyl)benzene, 6.4 g (5.4 × 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 in terms 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 as a result, 94 g of a liquid product was obtained. By 1 1H-NMR, it was confirmed that the obtained product was the compound represented by the following formula (B).

[0333] [Chemical Formula 65]

[0334]

[0335] [Synthesis Example 2]

[0336] A compound represented by the following formula (C) was prepared.

[0337] [Chemical Formula 66]

[0338]

[0339] 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 in terms 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 as a result, 8.5 g of a liquid product was obtained. By 1 1H-NMR, it was confirmed that the obtained product was the compound represented by the following formula (D).

[0340] [Chemical Formula 67]

[0341]

[0342] [Synthesis example 3]

[0343] With reference to International Publication No. 2022 / 131107, a compound represented by the following general formula (E) was synthesized.

[0344]

Transformation 68

[0345]

[0346] [Synthesis Example 4]

[0347] With reference to International Publication No. 2022 / 131107, a compound represented by the following general formula (F) was synthesized.

[0348]

Transformation 69

[0349]

[0350] [Synthesis example 5]

[0351] Referring to Japanese Patent No. 6524955, a compound represented by the following general formula (G) was synthesized.

[0352]

Transformation 70

[0353]

[0354] [Synthesis Example 6]

[0355] A compound represented by the following formula (H) was prepared.

[0356]

Chemistry 71

[0357]

[0358] 100g (2.3 × 10⁻⁶) of the compound represented by the above formula (H) -2 50g of 1,3-bis(trifluoromethyl)benzene and 5.0g of allylamine (8.8×10⁻⁶ mol) -2 The mixture (mol) was stirred at 50°C for 4 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 92 g of the liquid product. 1 H-NMR confirmed that the product obtained was a compound represented by the following formula (I).

[0359]

Chemistry 72

[0360]

[0361] 80g (1.8 × 10⁻⁶) of the compound represented by the above formula (I) -2 40g of 1,3-bis(trifluoromethyl)benzene and 4.5g of trimethoxysilane (3.8×10 mol)-2 mol), acetic acid 2.4 × 10 -5 g, and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.0 × 10 g -5 g (based on elemental Pt, containing 6.7 × 10⁻⁶) -10 The mixture (mol) was stirred at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 94 g of the liquid product. 1 H-NMR confirmed that the product obtained was a compound represented by the following formula (J).

[0362]

Transformation 73

[0363]

[0364] [Synthesis Example 7]

[0365] With reference to International Publication No. 2022 / 131107, a compound represented by the following general formula (K) was synthesized.

[0366]

Chemistry 74

[0367]

[0368] [Synthesis example 8]

[0369] A compound represented by the following formula (L) was prepared.

[0370]

Chemistry 75

[0371]

[0372] 100g (1.5 × 10⁻⁶) of the compound represented by the above formula (L) -2 1,3-bis(trifluoromethyl)benzene 100g, trimethoxysilane 4.5g (3.8×10 mol), -2 mol), acetic acid 1.0 × 10 -4 g, and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.0 × 10 g -4 g (based on elemental Pt, containing 2.0 × 10⁻⁶) -8 The mixture (mol) was stirred at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 8.5 g of the liquid product. 1 H-NMR confirmed that the product was a compound represented by the following formula (M).

[0373]

Transformation 76

[0374]

[0375] A compound represented by the following formula (N) was prepared.

[0376] [Chemical Formula 77]

[0377]

[0378] Solvent

[0379] 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)

[0380] 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)

[0381] Solvent (C): perfluorotri - N - butylamine (fluoride ion quantification value: <0.005 μg / g)

[0382] Solvent (D): perfluorotri - N - butylamine (fluoride ion quantification value: 0.5 μg / g)

[0383] Solvent (E): ethyl nonafluoroisobutyl ether (fluoride ion quantification value: 0.09 μg / g)

[0384] [Examples 1 - 10, Comparative Examples 1 - 2]

[0385] In the compounds obtained in the above synthesis examples, using the compositions shown in Table 1, the compounds were diluted to 20% by mass with a solvent to prepare a surface treatment agent.

[0386] [Table 1]

[0387]

[0388] Preparation of the surface treatment agent and storage stability under elevated temperature

[0389] [Confirmation of the appearance of the sample bottle]

[0390] The surface treatment agents prepared in Examples 1 - 10 and Comparative Examples 1 - 2 were respectively filled into 50 - g transparent sample bottles. Light from a flashlight was irradiated from the lower part of the sample bottle to make the back of the sample bottle black, and the appearance of the surface treatment agent just after preparation was visually observed. The results (appearance just after preparation) are shown in Table 2.

[0391] The sample bottle was placed in an oven at 55°C and stored statically for 1 year. Then, the sample bottle was brought to room temperature, and light from a flashlight was irradiated from the lower part to make the back of the sample bottle black, and the appearance after storage at 55°C for 1 year was visually observed. The results (appearance after storage at 55°C for 1 year) are shown in Table 3.

[0392] A: It is a transparent solution.

[0393] B: The solution is slightly turbid, cloudy, or foggy (residual dissolved aggregates, etc.), or the aggregates such as particles float in the air.

[0394] [Condensation content]

[0395] The surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 immediately after preparation, and those prepared in Examples 1-10 and Comparative Examples 1-2 after storage for one year, were determined using gel permeation chromatography (GPC). The determination conditions are as follows.

[0396] Measuring apparatus and conditions

[0397] Measurement device: Agilent Technologies, Inc. 1260 Infinity II

[0398] Pump: HITACHI Chromaster 5110 Pump

[0399] Assay conditions (column): Tosoh Bioscience TSKgel Multipore H XL -M 7.8mmφ×30cm 2 pieces

[0400] Eluent: Hydrochlorofluorocarbon (HCFC)-225

[0401] Flow rate: 1.0 mL / min

[0402] Detector: Evaporative Light Scattering Detector

[0403] Column Oven: GL Science 705

[0404] Ink jet volume: 20μL

[0405] Flow rate: 1.0 mL / min

[0406] Column temperature: 35℃

[0407] Standard material: Agilent Technologies PMMA calibration kit ML-10

[0408] For the analysis of GPC determination results, if a single peak is observed, the content of the condensate (alkoxy condensation structure) is recorded as 0%. If a peak is confirmed earlier in the detection time, in addition to the main peak, it is considered a condensate peak, and the condensate content is calculated from the total area ratio 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.

[0409] Formation of cured film

[0410] 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 a chemically strengthened glass (50 mm × 100 mm) (Gorilla 5 manufactured by Corning) with 10-12 nm SiO2 vapor-deposited on the outermost surface. (Processing conditions: pressure: 2.0 × 10⁻⁶) -2 The film was cured for 12 hours at 25°C and 50% humidity (Pa, heating temperature: 700°C) to form a 10nm thick cured film.

[0411] Evaluation of cured film

[0412] [Measurement of Haze]

[0413] For the chemically strengthened glass having the cured film formed as described above, the haze was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) according to the method described in JIS K7136. Table 2 shows the values ​​obtained by subtracting the blank value (the haze value of the chemically strengthened glass without a cured film) from the results of the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 immediately after preparation. Table 3 shows the values ​​obtained by subtracting the blank value (the haze value of the chemically strengthened glass without a cured film) from the results of the surface treatment agents prepared in Examples 1-10 and Comparative Examples 1-2 after storage for 1 year.

[0414] [Determination of initial water contact angle]

[0415] For chemically strengthened glass with the cured film formed as described above, the contact angle (water repellency) of the cured film 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 1 year.

[0416] Table 2

[0417]

[0418] Table 3

[0419]

[0420] [Examples 11-16, Comparative Examples 3-4]

[0421] In the above synthesis examples, the compounds were diluted with solvent to 0.1% by mass with the compositions shown in Table 4 to prepare surface treatment agents.

[0422] Table 4

[0423]

[0424] Preparation of surface treatment agents and their storage stability under heating conditions

[0425] [Sample bottle appearance confirmation]

[0426] The surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 were each placed into 50g transparent sample vials. A flashlight was shone from the bottom of the sample vial until the back of the vial turned black, and the appearance of the surface treatment agent immediately after preparation was visually observed. The results (appearance immediately after preparation) are shown in Table 2. The sample vial was placed in a 55°C oven and stored for one year. Then, the sample vial was brought to room temperature, and a flashlight was shone from the bottom until the back of the vial turned black, and the appearance after one year of storage at 55°C was visually observed. The results (appearance after one year of storage at 55°C) are shown in Table 3.

[0427] A: It is a transparent solution.

[0428] B: The solution is slightly turbid, cloudy, or foggy (residual dissolved aggregates, etc.), or the aggregates such as particles float in the air.

[0429] [Condensation content]

[0430] The surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 immediately after preparation, and those prepared in Examples 11-16 and Comparative Examples 3-4 after being stored for one year, were determined using gel permeation chromatography (GPC). The determination conditions are as follows.

[0431] Measuring apparatus and measuring conditions

[0432] Measurement device: Agilent Technologies, Inc. 1260 Infinity II

[0433] Pump: HITACHI Chromaster 5110 Pump

[0434] Assay conditions (column): Tosoh Bioscience TSKgel Multipore H XL -M 7.8mmφ×30cm 2 pieces

[0435] Eluent: Hydrochlorofluorocarbon (HCFC)-225

[0436] Flow rate: 1.0 mL / min

[0437] Detector: Evaporative Light Scattering Detector

[0438] Column Oven: GL Science 705

[0439] Ink jet volume: 20μL

[0440] Flow rate: 1.0 mL / min

[0441] Column temperature: 35℃

[0442] Standard material: Agilent Technologies PMMA calibration kit ML-10

[0443] For the analysis of GPC determination results, if a single peak is observed, the content of the condensate (alkoxy condensation structure) is recorded as 0%. If a peak is confirmed earlier in the detection time, in addition to the main peak, it is considered a condensate peak, and the condensate content is calculated from the total area ratio 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.

[0444] Formation of cured film

[0445] 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 storage for one year, a cured film was formed. The film was sprayed onto the surface of chemically strengthened glass (Corning Gorilla V) that had undergone plasma treatment cleaning using a spraying apparatus (T&K NST-51). Then, it was cured for 12 hours at 25°C and 50% relative humidity to form a cured film with a thickness of 10 nm, thus obtaining the test specimen.

[0446] Evaluation of cured film

[0447] [Measurement of Haze]

[0448] For the chemically strengthened glass having the cured film formed as described above, the haze was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) according to the method described in JIS K7136. Table 5 shows the values ​​obtained by subtracting the blank value (the haze value of the chemically strengthened glass without a cured film) 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 values ​​obtained by subtracting the blank value (the haze value of the chemically strengthened glass without a cured film) from the results of the surface treatment agents prepared in Examples 11-16 and Comparative Examples 3-4 after storage for 1 year.

[0449] [Determination of initial water contact angle]

[0450] For chemically strengthened glass with the cured film formed as described above, the contact angle (water repellency) of the cured film 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 1 year.

[0451] Table 5

[0452]

[0453] Table 6

[0454]

[0455] Based on the above results, in Comparative Examples 1-4, the formation of agglomerates and slight turbidity of the sample solution were confirmed in the samples stored for one year. These phenomena were not observed immediately after preparation. GPC analysis also confirmed the formation of a large number of condensates. Compared to the immediately prepared cured film, the cured film obtained from the one-year-old sample did not show a significant change in the water contact angle, but the haze increased substantially. The formation of small agglomerates, which have no effect on the water contact angle, resulted in the increased haze.

Claims

1. A surface treatment agent comprising (A) a silane containing hydrolyzable groups modified with a polymer containing a fluorinated polyether group and / or its partially hydrolyzed condensate, and (B) a fluorinated solvent. (B) The fluoride ions in the fluorinated solvent of component (B) account for more than 0% by mass and 1.0 × 10⁻⁶% of the total amount of the surface treatment agent. -5 Quality percentage below %.

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

3. The surface treatment agent according to claim 1, wherein, (A) The number average molecular weight of the component is 1000 to 25000.

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

5. The surface treatment agent according to claim 1, wherein, (A) The component is a silane containing hydrolyzable groups modified with a polymer containing fluorinated polyether groups, which has a molecular structure consisting of -(C b F 2b O) m - represents a polyfluorinated oxyalkylene structure, where b is an independent number from 1 to 6 in each unit, and m is a number from 1 to 250. These units can be linear or branched.

6. The surface treatment agent according to claim 1, wherein, In component (A), the silane is represented by formula (2), (4) or (7) below. 【Chemistry 2】 In equation (2), Rf is derived from -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 - indicates a divalent group containing a polyfluorinated oxyalkylene structure, 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, and the sum of p, q, r, s, t, and u is a number from 1 to 250. These units can be linear or branched. Furthermore, the repeating units shown within parentheses containing p, q, r, s, t, and u can be randomly combined. A 1 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, or D, where 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 group with 2 to 8 valences, α is 0 or 1, β is a number from 1 to 7, and W is independently a monovalent group containing a hydrolyzable silyl group represented by formula (1) above. 【Chemistry 4】 In formula (4), Rf represents the same group as above, and A 2 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- 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 group as above, B is independently a hydrogen atom or -OS, S is a hydrogen atom, a monovalent hydrocarbon group with 1 to 10 carbon atoms, or a monovalent group represented by formula (6) below, and e is 1 or 2. 【Transformation 6】 In formula (6), T is a single bond or a group with 2 to 8 valences, L is independently a divalent hydrocarbon group with 1 to 4 carbon atoms, E is a monovalent hydrocarbon group with 1 to 6 carbon atoms, or W, and l is a number from 0 to 20. 【Transformation 7】 In formula (7), Rf represents the same group as above, and A 3 It is a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- 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 have the same meaning as above, V is a divalent hydrocarbon group with 2 to 15 carbon atoms that has a single bond or may have an ether bond, and M is a monovalent group represented by the following formula (9). 【Chemistry 9】 In formula (9), Y, S and W represent the same groups 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 with 1 to 15 carbon atoms, which may contain one or more bonds selected from amide bonds, ether bonds, ester bonds, thioether bonds, urethane bonds, siloxane bonds, triazine bonds, diorganomymethylene silyl groups, silanephenyl bonds and silanealkyl bonds, and Z is a divalent to octyl group selected from silicon atoms, nitrogen atoms, silanealkyl groups, silanearyl groups and divalent to octyl organopolysiloxane residues having siloxane bonds.

8. The surface treatment agent according to claim 6, wherein, In formula (6), T is a single bond, or may contain a divalent hydrocarbon group, siloxane bond, silane group or organomyclic silane group with 2 to 20 carbon atoms selected from silicon atom, siloxane bond, silane group, silane group or organomyclic silane group.

9. The surface treatment agent according to claim 1, further comprising a polymer containing a fluorinated polyether group that does not contain hydrolyzable groups as component (C).

10. The surface treatment agent according to claim 9, wherein, Polymers containing fluorinated polyether groups but without hydrolyzable groups are represented by the following formula (10). 【Chemistry 10】 In equation (10), Rf is the value derived from -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 - indicates a divalent group containing a polyfluorinated oxyalkylene structure, 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, and the sum of p, q, r, s, t, and u is a number from 1 to 250. These units can be linear or branched. Furthermore, the repeating units shown within parentheses containing p, q, r, s, t, and u can be randomly combined. A 4 Independently a monovalent fluorinated hydrocarbon group with a terminal CF3- or CF2H- and may contain an oxygen atom, -OR 3 -COOR 3 or -PO(OR) 3 )2, R 3 It is a monovalent hydrocarbon group consisting of 1 to 10 hydrogen atoms or carbon atoms.

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

12. Articles treated with the surface treatment agent according to any one of claims 1 to 11.

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

14. An antireflective treated article treated with the surface treatment agent according to any one of claims 1 to 11.

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

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