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

Abstract

The present invention is capable of forming a cured coating film which is excellent in water / oil repellency, dry eraser abrasion resistance, and further wet eraser abrasion resistance, by using a fluorine-containing polyether group-containing polymer of the following formula (1), a surface treatment agent containing the polymer and / or a partial (hydrolytic) condensate thereof. In the formula, Rf is a monovalent or divalent fluorine-containing polyether group, B is a single bond or a divalent organic group not containing a fluorine atom, E is independently a monovalent group having a urethane bond and a polyether chain, U is a single bond or a divalent organic group, Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to heptavalent organic group, Y is a divalent hydrocarbon group which can have at least one selected from an oxygen atom, a sulfur 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 hydroxyl group or a hydrolyzable group, n is independently 1 to 3 for each silicon atom to which it is bonded, m is 1 to 7, and a is 1 or 2.

Description

Technical Field

[0001] This invention relates to polymers containing fluorinated polyether groups (compounds having monovalent or divalent fluorinated polyether groups in the molecule), and more specifically, to polymers containing fluorinated polyether groups capable of forming coatings with excellent water and oil repellency, abrasion resistance, particularly for dry and wet erasers, as well as surface treatment agents comprising the polymer and / or a portion thereof (hydrolyzed) condensates, and articles surface-treated with the surface treatment agent. Background Technology

[0002] In recent years, the trend of touch panel displays, exemplified by smartphones, has accelerated. However, touch panel screens are exposed, frequently coming into direct contact with fingers, cheeks, and other skin, making them prone to accumulating dirt and sebum, which poses a problem. Therefore, to achieve good appearance and visibility, the requirements for technologies that prevent fingerprints from adhering to the display surface and facilitate the removal of dirt have been increasing year by year, leading to the development of materials that meet these requirements. In particular, since touch panel displays are prone to fingerprints and dirt accumulation, the application of water- and oil-repellent coatings is desired. However, while previous water- and oil-repellent coatings offer high water and oil repellency and excellent dirt-wiping properties, their anti-fouling performance deteriorates during use.

[0003] Generally, compounds 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 and mold release agents for precision instruments, cosmetics, and protective films. However, this property also implies non-adhesion and non-adhesion to other substrates; although it is possible to coat them onto substrate surfaces, achieving a tight seal is difficult.

[0004] On the other hand, silane coupling agents are widely known as agents for bonding organic compounds to the surfaces of substrates such as glass and cloth, and are extensively used as coating agents for various substrate surfaces. A silane coupling agent contains an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as alkoxysilyl) in one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction with moisture in the air to form a coating. Because the hydrolyzable silyl group chemically or physically bonds with the surface of glass, metal, etc., this coating becomes a durable and robust coating.

[0005] Therefore, a composition is disclosed that, by using a fluorinated polyether polymer in which hydrolyzable silyl groups are introduced into a compound containing fluorinated polyether groups, it can be easily adhered to the surface of a substrate and can form a coating on the surface of the substrate with properties such as water and oil repellency, chemical resistance, lubricity, mold release, and antifouling (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] Lenses, antireflective films, and other cured coatings that have been surface-treated with a composition comprising "a polymer containing a fluorinated polyether group in which hydrolyzable silyl groups are introduced" exhibit excellent sliding and release properties, as well as excellent abrasion resistance against steel wool. However, their performance is not fully realized, particularly in terms of abrasion resistance against erasers.

[0007] In addition, a composition is disclosed that, by using a fluorinated polyether polymer in which a polyether group is introduced into a compound containing a fluorinated polyether group, a coating with excellent sliding properties, release properties, and abrasion resistance to erasers is formed (Patent Document 7: International Publication No. 2017 / 212850).

[0008] While curing coatings for displays, lenses, antireflective films, etc., which have been surface-treated with a composition comprising "a polymer containing a polyether group in which a polyether group is introduced into a compound containing a fluorinated polyether group" exhibit excellent abrasion durability for dry erasers, their abrasion durability for wet (ethanol) erasers is not fully realized. Therefore, a balance between abrasion durability for both dry and wet erasers is required.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Publication No. 2008-534696

[0012] Patent Document 2: Japanese Patent Publication No. 2008-537557

[0013] Patent Document 3: Japanese Patent Application Publication No. 2012-072272

[0014] Patent Document 4: Japanese Patent Application Publication No. 2012-157856

[0015] Patent Document 5: Japanese Patent Application Publication No. 2013-136833

[0016] Patent Document 6: Japanese Patent Application Publication No. 2015-199906

[0017] Patent Document 7: Japanese International Publication No. 2017 / 212850 Summary of the Invention

[0018] The problem that the invention aims to solve

[0019] The present invention was made in view of the above circumstances, and aims to provide a fluorinated polyether-based polymer capable of forming a cured coating with excellent water and oil repellency, abrasion resistance, especially excellent abrasion resistance of dry and wet erasers, a surface treatment agent comprising the polymer and / or a portion thereof (hydrolyzed) condensate, and articles surface-treated with the surface treatment agent.

[0020] Methods for solving problems

[0021] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that, in the above-mentioned polymers containing fluorinated polyether groups, by using a surface treatment agent containing a polymer containing fluorinated polyether groups represented by the general formula (1) described below and / or a portion thereof (hydrolyzed) condensate, a cured coating with excellent water and oil repellency, excellent dry eraser abrasion resistance, and thus excellent wet eraser abrasion resistance can be formed, thereby completing the present invention.

[0022] Therefore, the present invention provides polymers, surface treatment agents and articles containing fluorinated polyether groups.

[0023] [1] The polymer containing fluorinated polyether groups represented by the following general formula (1)

[0024]

[0025] (In the formula, Rf is a monovalent or divalent fluorinated polyether group, B is independently a single bond or a divalent organic group without fluorine atoms, E is independently a monovalent group having a urethane bond and a polyether chain, U is independently a single bond or a divalent organic group, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octvalent organic group, Y is independently a divalent hydrocarbon group that may have at least one of the following: oxygen atom, sulfur atom, silicon atom, and siloxane bond, R is independently an alkyl or phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl or hydrolyzable group, n is independently an integer of 1 to 3 for each bonded silicon atom, m is independently an integer of 1 to 7, and α is 1 or 2.)

[0026] [2] According to the polymer containing fluorinated polyether groups described in [1], wherein α in the above formula (1) is 1, and Rf is a group represented by the following general formula (2),

[0027]

[0028] (In the formula, A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group terminated with a -CF3 group, and W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer from 1 to 3 for each unit independently, p, q, r, s, t, u, and v are integers from 0 to 200, and the sum of p, q, r, s, t, u, and v is 3 to 200. These units can be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be randomly bonded.)

[0029] [3] According to the polymer containing fluorinated polyether groups described in [1], wherein α in the above formula (1) is 2, and Rf is a group represented by the following general formula (3),

[0030]

[0031] (In the formula, W is a fluorinated alkylene group containing one or more hydrogen atoms. d is an integer from 1 to 3 for each unit independently, p, q, r, s, t, u, and v are integers from 0 to 200, and the sum of p, q, r, s, t, u, and v is 3 to 200. These units can be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be randomly bonded.)

[0032] [4] The polymer containing a fluorinated polyether group according to any one of [1] to [3], wherein, in the above formula (1), E is a group represented by the following general formula (4),

[0033] -O-CONH-W'(-(LO) k -R') z (4)

[0034] (In the formula, W' is a single bond, or X' or a divalent or trivalent group formed by X' and an oxygen atom, X' is a divalent or trivalent group containing a divalent hydrocarbon group with 1 to 20 carbon atoms that may have a carbamate bond, a urea bond, a silicon atom, a siloxane bond, a silanediol structure or a silanediol structure, L is independently an alkylene group with 1 to 4 carbon atoms, k is an integer from 1 to 20, R' is an alkyl or phenyl group with 1 to 4 carbon atoms, and z is 1 or 2.)

[0035] [5] The polymer containing a fluorinated polyether group according to any one of [1] to [4], wherein, in the above formula (1), Y is a group selected from the following: an alkylene group containing 1 to 10 carbon atoms that may contain oxygen or sulfur atoms, an alkylene group containing 6 to 8 carbon atoms that contains 1 to 10 carbon atoms, a divalent group formed by bonding alkylene groups of 1 to 10 carbon atoms to each other via a diorganosilylene, a silaneylene structure or a silaneylene structure, and a divalent group having an alkylene group of 1 to 10 carbon atoms bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue containing 2 to 10 silicon atoms.

[0036] [6] The polymer containing a fluorinated polyether group according to any one of [1] to [5], wherein, in the above formula (1), B is a single bond or a divalent group that does not contain fluorine atoms and may contain at least one of oxygen atoms, sulfur atoms, secondary amines, tertiary amines, ketones, amides and esters, wherein the divalent group is selected from: alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing 6 to 8 carbon atoms, divalent groups having alkylene groups having 1 to 10 carbon atoms bonded to each other via diorganosilyl, silaneylene or silaneylene structures, divalent groups having alkylene groups having 1 to 10 carbon atoms bonded to the bonding ends of linear or branched or cyclic organopolysiloxane residues having 2 to 10 silicon atoms, and carbonyl groups.

[0037] [7] The polymer containing a fluorinated polyether group according to any one of [1] to [6], wherein, in the above formula (1), U is a single bond or a group selected from the following: an alkylene group containing 1 to 10 carbon atoms that may contain oxygen or sulfur atoms, an alkylene group containing 6 to 8 carbon atoms that contains 1 to 10 carbon atoms, a divalent group formed by bonding alkylene groups of 1 to 10 carbon atoms to each other via a diorganosilylene, a silaneylene structure or a silaneylene structure, and a divalent group having an alkylene group of 1 to 10 carbon atoms bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue containing 2 to 10 silicon atoms.

[0038] [8] The polymer containing a fluorinated polyether group according to any one of [1] to [7], wherein, in the above formula (1), Z is selected from: single bond, carbon atom, silicon atom, nitrogen atom, -CH=, and 3 to 6 valent organopolysiloxane residues with 2 to 10 silicon atoms in a straight chain or with 3 to 10 silicon atoms in a branched or cyclic manner.

[0039] [9] A polymer containing a fluorinated polyether group according to any one of [1] to [8], wherein, in the above formula (1), X is selected from: hydroxyl, alkoxy group with 1 to 10 carbon atoms, alkoxy group with 2 to 10 carbon atoms, acyloxy group with 1 to 10 carbon atoms, olefinic group with 2 to 10 carbon atoms and halogen group.

[0040]

[10] The polymer containing a fluorinated polyether group according to any one of [1] to [9], wherein the polymer containing a fluorinated polyether group represented by formula (1) is represented by any one of the following formulas,

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050] (In the formula, p1, q1, r1, and s1 are integers from 1 to 200, and the sum of p1, q1, r1, and s1 in each formula is from 3 to 200. The units shown in parentheses with p1, q1, r1, and s1 can be randomly bonded. k is an integer from 1 to 20.)

[0051]

[11] A surface treatment agent comprising a polymer and / or a portion thereof (hydrolyzed) condensate containing a fluorinated polyether group, characterized in that it is a surface treatment agent comprising a polymer and / or a portion thereof (hydrolyzed) condensate containing a fluorinated polyether group having two or more hydroxyl-containing silyl groups or hydrolyzable silyl groups, wherein the monovalent or divalent fluorinated polyether group in the polymer containing the fluorinated polyether group is bonded to the hydroxyl-containing silyl group or hydrolyzable silyl group via a linker, the linker having a tertiary carbon atom bonded to a monovalent group, the monovalent group having a urethane bond and a polyether chain.

[0052]

[12] A surface treatment agent comprising, as described in any one of [1] to

[10] , a polymer containing a fluorinated polyether group and / or a portion thereof (hydrolyzed) condensate.

[0053]

[13] An article which has been surface treated with the surface treatment agent described in

[11] or

[12] .

[0054] Invention Effects

[0055] The fluorinated polyether polymer of the present invention has a monovalent group containing a urethane bond and a polyether chain on the tertiary carbon atom of the molecule. The polyether chain (polyether group) improves lubricity, and the urethane bond has the property of mutual attraction between urethane bonds. As a result, articles surface-treated with a surface treatment agent containing this polymer and / or a portion thereof (hydrolyzed) condensate exhibit excellent water and oil repellency, dry eraser wear durability, and wet eraser wear durability. Detailed Implementation

[0056] The fluorinated polyether polymer of the present invention is represented by the following general formula (1), having a monovalent or divalent fluorinated polyether group and a reactive functional group in the molecule, and having a monovalent group containing a urethane bond and a polyether chain on a tertiary carbon atom.

[0057]

[0058] (In the formula, Rf is a monovalent or divalent fluorinated polyether group, B is independently a single bond or a divalent organic group without fluorine atoms, E is independently a monovalent group having a urethane bond and a polyether chain, U is independently a single bond or a divalent organic group, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octvalent organic group, Y is independently a divalent hydrocarbon group that may have at least one of the following: oxygen atom, sulfur atom, silicon atom, and siloxane bond, R is independently an alkyl or phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl or hydrolyzable group, n is independently an integer of 1 to 3 for each bonded silicon atom, m is independently an integer of 1 to 7, and α is 1 or 2.)

[0059] The fluorinated polyether polymer of the present invention is a structure in which a monovalent fluorinated oxyalkylene group or a divalent fluorinated oxyalkylene group (i.e., a monovalent or divalent fluorinated polyether group) is bonded to a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl-containing silyl group via a linker. Further, a monovalent group containing a urethane bond and a polyether chain is present on the tertiary carbon atom in the molecule. The polyether chain (polyether group) is characterized by improving lubricity, and the urethane bond exhibiting the characteristic of mutual attraction between urethane bonds, thereby enabling the acquisition of a cured coating with excellent water and oil repellency, dry eraser wear durability, and wet eraser wear durability.

[0060] In formula (1) above, Rf is a monovalent or divalent fluoropolyether group. When α is 1 (i.e., when Rf is a monovalent fluoropolyether group), it is preferably a monovalent fluoropolyether group represented by the following general formula (2). When α is 2 (i.e., when Rf is a divalent fluoropolyether group), it is preferably a divalent fluoropolyether group represented by the following general formula (3). It should be noted that a cured coating formed using a polymer containing a fluoropolyether group with a monovalent or divalent fluoropolyether group will exhibit good water repellency and, at the same time, oil repellency to a certain extent.

[0061]

[0062] (In the formula, A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group terminated with a -CF3 group, and W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer from 1 to 3 for each unit independently, p, q, r, s, t, u, and v are integers from 0 to 200, and the sum of p, q, r, s, t, u, and v is 3 to 200. These units can be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be randomly bonded.)

[0063] In the above formula (2), A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group with a -CF3 group at the end, preferably a fluorine atom.

[0064] In equations (2) and (3) above, W is a fluoroalkyl group containing one or more hydrogen atoms, for example, in CF2, C2F4, C3F6, C4F8, and C5F... 10 Unit, C6F 12 In various perfluoroalkyl groups, one or two fluorine atoms are replaced by hydrogen atoms, etc.

[0065] In equations (2) and (3) above, d is an integer from 1 to 3 for each unit, preferably 1 or 2.

[0066] Furthermore, p, q, r, s, t, u, and v are integers from 0 to 200, preferably from 0 to 100, and the total of p, q, r, s, t, u, and v is 3 to 200, preferably from 10 to 100. When the total of p, q, r, s, t, u, and v is less than the upper limit mentioned above, the resulting cured film has good adhesion and curing properties; when it is greater than the lower limit mentioned above, the characteristics of the fluoropolyether group can be fully utilized, and therefore it is preferred.

[0067] It should be noted that when r, s, t, u, and v are all 0, p and q are integers from 5 to 100, and the sum of p and q is preferably from 10 to 105, and more preferably from 15 to 60.

[0068] In equations (2) and (3) above, each unit can be either linear or branched. Furthermore, the repeating units indicated within parentheses containing p, q, r, s, t, u, and v can be randomly bonded.

[0069] As Rf, the following groups can be specifically exemplified.

[0070]

[0071]

[0072] (In the formula, p', q', r', s', t', and u' are integers greater than or equal to 1, with the same upper limit as the upper limit of p, q, r, s, t, and u mentioned above. The sum of these p', q', r', s', t', and u' is 3 to 200. r2' and r3' are integers greater than or equal to 1, and the sum of r2' and r3' is 2 to 199. In addition, the repeating units shown in parentheses containing p', q', r', s', t', and u' can be randomly bonded.)

[0073] In formula (1) above, B is independently a single bond or a divalent organic group without fluorine atoms. This divalent organic group is selected from: alkylene groups with 1 to 10 carbon atoms; alkylene groups with 1 to 10 carbon atoms containing arylene groups with 6 to 8 carbon atoms (e.g., alkylene-arylene groups with 7 to 18 carbon atoms); divalent groups formed by bonding alkylene groups with 1 to 10 carbon atoms to each other via diorganosilyl, silaneyl, or silaneyl structures; divalent groups with alkylene groups having 1 to 10 carbon atoms bonded to the bonding ends of linear or branched or cyclic organopolysiloxane residues with 2 to 10 silicon atoms; and carbonyl groups. This divalent organic group may contain at least one of oxygen, sulfur, secondary, tertiary amines, ketones, amides, and ester groups. Furthermore, this divalent organic group does not contain fluorine atoms.

[0074] Here, the group bonded to the silicon atom of the diorganosilyl group, silanediol group, silanediol group, and organopolysiloxane residue is preferably an alkyl group such as methyl, ethyl, propyl, or butyl, or a phenyl group having 1 to 8 carbon atoms, preferably 1 to 4. Furthermore, the alkyl group in the silanediol group is preferably an ethyl group, propylene group (trimethylene, methyl ethylene), or butyl group (tetramethylene, methyl propyleneene), having 2 to 8 carbon atoms, preferably 2 to 4.

[0075] Examples of such a B group include the following groups. It should be noted that in the following structure, the left-hand bonding end is bonded to Rf, and the right-hand bonding end is bonded to a carbon atom.

[0076]

[0077]

[0078]

[0079] (In the formula, f is an integer from 2 to 8, a, a', and b are integers from 1 to 4 respectively, c is an integer from 1 to 10, and e is an integer from 1 to 9.)

[0080] In the above formula (1), E is independently a monovalent group having a urethane bond and a polyether chain, which can be represented by the following general formula (4).

[0081] -O-CONH-W'(-(LO) k -R') z (4)

[0082] In formula (4) above, W' is a single bond, or a divalent or trivalent group formed by X' or X' combined with an oxygen atom, and X' is a divalent or trivalent group. The divalent or trivalent group includes a divalent hydrocarbon group with 1 to 20 carbon atoms that may have a carbamate bond, a urea bond, a silicon atom, a siloxane bond, a silanediol structure, or a silanediol structure. The silicon atom preferably has alkyl groups such as methyl, ethyl, propyl, butyl, etc., or phenyl groups with 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and may also have alkoxy groups such as hydroxyl or methoxy. In addition, the alkylene group in the silanediol structure is preferably ethylene, propylene (trimethylene, methyl ethylene), butylene (tetramethylene, methyl propylene), etc., with 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0083] Examples of such a W' group include the following. It should be noted that in the following structure, the left-hand bonding end is bonded to a nitrogen atom, and the other bonding ends are bonded to an L atom.

[0084]

[0085]

[0086] (In the formula, e is the same as above.)

[0087] In the above formula (4), L is independently an alkylene group with 1 to 4 carbon atoms, such as methylene, ethylene, propylene, or butylene, wherein ethylene is preferred. The number of carbon atoms can be singular or mixed.

[0088] In the above formula (4), k is an integer from 1 to 20, preferably an integer from 2 to 10.

[0089] In the above formula (4), R' is an alkyl group or phenyl group with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc., wherein methyl is preferred.

[0090] In the above formula (4), z is 1 or 2, preferably 1.

[0091] Examples of such E groups include the following groups.

[0092]

[0093]

[0094] (In the formula, e and k are the same as above.)

[0095] In the above formula (1), U is independently a single bond or a divalent organic group, which is selected from the following groups: alkylene with 1 to 10 carbon atoms, alkylene with 1 to 10 carbon atoms containing arylene with 6 to 8 carbon atoms (e.g., alkylene-arylene with 7 to 18 carbon atoms), divalent groups formed by alkylene with 1 to 10 carbon atoms bonded to each other via diorganosilylene, silaneylene or silaneylene structures, and divalent groups with alkylene with 1 to 10 carbon atoms bonded to the bonding ends of linear or branched or cyclic organopolysiloxane residues with 2 to 10 silicon atoms, which may contain oxygen atoms and sulfur atoms.

[0096] It should be noted that when Z is a single bond, U is preferably a single bond.

[0097] Here, the group bonded to the silicon atom of the diorganosilyl group, silanediol group, silanediol group, and organopolysiloxane residue is preferably an alkyl group such as methyl, ethyl, propyl, or butyl, or a phenyl group having 1 to 8 carbon atoms, preferably 1 to 4. Furthermore, the alkyl group in the silanediol group is preferably an ethyl group, propylene group (trimethylene, methyl ethylene), or butyl group (tetramethylene, methyl propyleneene), having 2 to 8 carbon atoms, preferably 2 to 4.

[0098] In addition to single bonds, such a U group can be exemplified by the following groups. It should be noted that in the following structure, the left-hand bonding end is bonded to a carbon atom, and the right-hand bonding end is bonded to a Z atom.

[0099]

[0100]

[0101] (In the formula, f is an integer from 2 to 8, a and b are integers from 1 to 4 respectively, c is an integer from 1 to 10, and e is an integer from 1 to 9.)

[0102] In formula (1) above, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a 3- to 8-valent organic group. As a 3- to 8-valent organic group, it is preferably a 3- to 6-valent organopolysiloxane residue with -CH=, 2 to 10 silicon atoms, particularly 3 to 8 silicon atoms, in a straight chain, or with 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, in a branched or cyclic form. Furthermore, this organopolysiloxane residue may contain a silane-alkylene structure with two silicon atoms bonded by alkylene bonds, i.e., Si-(CH2). x -Si (where x is an integer from 2 to 6 in the above formula).

[0103] The organopolysiloxane residue may have alkyl groups such as methyl, ethyl, propyl, butyl, or phenyl with 1 to 8 carbon atoms, more preferably 1 to 4.

[0104] In addition to single bonds, the following structures can be cited as examples of such Z. It should be noted that in the following structures, the left bonding end is preferably bonded to U, and the other bonding ends are bonded to Y.

[0105]

[0106] In formula (1) above, Y is independently a divalent hydrocarbon group having at least one of oxygen, sulfur, silicon, and siloxane bonds, preferably having 1 to 20 carbon atoms. Specifically, this divalent hydrocarbon group is selected from the following groups: alkylene groups having 1 to 10 carbon atoms that may contain oxygen or sulfur atoms; alkylene groups having 1 to 10 carbon atoms that contain 6 to 8 carbon atoms (e.g., alkylene-arylene groups having 7 to 18 carbon atoms); divalent groups formed by bonding alkylene groups having 1 to 10 carbon atoms to each other via a diorganosilyl group, a silaneyl group, or a silaneyl group; and divalent groups having alkylene groups having 1 to 10 carbon atoms bonded to the bonding ends of linear or branched or cyclic organopolysiloxane residues having 2 to 10 silicon atoms.

[0107] Here, the group bonded to the silicon atom of the diorganosilyl group, silanediol group, silanediol group, and organopolysiloxane residue is preferably an alkyl group such as methyl, ethyl, propyl, or butyl, or a phenyl group having 1 to 8 carbon atoms, preferably 1 to 4. Furthermore, the alkyl group in the silanediol group is preferably an ethyl group, propylene group (trimethylene, methyl ethylene), or butyl group (tetramethylene, methyl propyleneene), having 2 to 8 carbon atoms, preferably 2 to 4.

[0108] Examples of such a Y group include the following groups. It should be noted that in the following structure, the left-hand bonding end is bonded to Z, and the right-hand bonding end is bonded to Si.

[0109]

[0110]

[0111] (In the formula, f is an integer from 2 to 8, a and b are integers from 1 to 4 respectively, b' and c are integers from 1 to 10 respectively, and e is an integer from 1 to 9.)

[0112] In the above formula (1), R is independently an alkyl or phenyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc., wherein methyl is preferred.

[0113] In formula (1) above, X is independently a hydroxyl group or a hydrolyzable group. Examples of such X include hydroxyl groups; alkoxy groups with 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy; alkoxy groups with 2 to 10 carbon atoms, such as methoxymethoxy and methoxyethoxy; acyloxy groups with 1 to 10 carbon atoms, such as acetoxy; alkenoxy groups with 2 to 10 carbon atoms, such as isopropoxy; and halogen groups, such as chlorine, bromine, and iodo. Among these, methoxy, ethoxy, isopropoxy, and chlorine are suitable.

[0114] In the above formula (1), α is 1 or 2.

[0115] In addition, n is an integer from 1 to 3 for each bonded silicon atom, preferably 3, and m is an integer from 1 to 7, preferably 1 or 3.

[0116] As a structure of the polymer containing fluorinated polyether groups represented by the above formula (1), the following structures can be cited. By changing the combination of Rf, B, E, U, Z, Y, R, X, and n in the above formula (1), several polymers containing fluorinated polyether groups can be obtained.

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127] (In the formula, k is the same as above. p1, q1, r1, and s1 are integers from 1 to 200, and the sum of p1, q1, r1, and s1 in each formula is from 3 to 200. The units shown in parentheses with p1, q1, r1, and s1 can be randomly bonded.)

[0128] As an example, the following methods can be cited as methods for preparing polymers containing fluorinated polyether groups, represented by the above formula (1), when α is 1 (i.e., Rf is a monovalent fluorinated polyether group) or when α is 2 (i.e., Rf is a divalent fluorinated polyether group).

[0129] A polymer containing fluorinated polyether groups with monovalent groups containing urethane bonds and polyether chains and two or more olefin sites at one or both ends of the molecular chain, an organosilicon compound having SiH groups and hydroxyl groups or hydrolyzable groups (halogen atoms, alkoxy groups, etc.) in the molecule, such as trichlorosilane or trialkoxysilane, and a solvent (e.g., fluorinated solvents such as 1,3-bis(trifluoromethyl)benzene) are mixed and aged at a temperature of 40–120°C, preferably 60–100°C, more preferably 70–90°C, for 1–72 hours, preferably 20–36 hours, more preferably 22–30 hours, in the presence of a hydrogenation silylation catalyst (e.g., a toluene solution of a chloroplatinic acid / vinylsiloxane complex). To clarify, when using organosilicon compounds containing SiH groups and hydroxyl or hydrolyzable groups, such as trichlorosilane, a SiH-containing halogenated (organo)silane compound, the substituents (halogen atoms) on the silane group can be converted to other hydrolyzable groups, such as alkoxy groups like methoxy groups. Furthermore, two different compounds can be used to produce the organosilicon compounds containing SiH groups and hydroxyl or hydrolyzable groups, in which case they can be manufactured through a stepwise addition process.

[0130] Here, when preparing a polymer containing a fluorinated polyether group as represented by formula (1), a polymer containing a fluorinated polyether group having a monovalent group containing a urethane bond and a polyether chain and two or more olefin sites at one end or both ends of the molecular chain can be exemplified by the polymer containing a fluorinated polyether group represented by the following general formula (5).

[0131]

[0132] (In the formula, Rf, B, E, U, Z, m, and α are the same as above, and Y' is independently a single bond or may have at least one divalent hydrocarbon group selected from oxygen atom, sulfur atom, silicon atom, and siloxane bond.)

[0133] In formula (5) above, Y' is independently a single bond, or may have at least one of the following: an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond, preferably a divalent hydrocarbon group with 1 to 18 carbon atoms. Specifically, this divalent hydrocarbon group is selected from the following groups: an alkylene group with 1 to 8 carbon atoms containing an oxygen atom or a sulfur atom; an alkylene group with 1 to 8 carbon atoms containing an arylene group with 6 to 8 carbon atoms (e.g., an alkylene-arylene group with 7 to 16 carbon atoms); a divalent group formed by bonding an alkylene group with 1 to 10 carbon atoms to a diorganosilyl group, a silaneyl group, or a silaneyl group; and a divalent group with an alkylene group with 1 to 8 carbon atoms bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue with 2 to 10 silicon atoms. Preferably, Y' is a linear alkylene group with 1 to 6 carbon atoms.

[0134] As a method for preparing the polymer containing fluorinated polyether groups represented by the above formula (5), the following methods can be cited as an example.

[0135] A polymer containing a fluorinated polyether group and an isocyanate-containing polyether group, which has hydroxyl groups and two or more olefin sites at one or both ends of the molecular chain represented by the following general formula (6), and an isocyanate-containing polyether group introducer are aged in the presence of a catalyst and, if necessary, in a solvent at a temperature of 0 to 190°C, preferably 40 to 150°C, more preferably 80 to 100°C, for 1 to 48 hours, preferably 10 to 40 hours, more preferably 20 to 30 hours.

[0136]

[0137] (In the formula, Rf, B, U, Z, Y', m, and α are the same as above.)

[0138] Here, the following polymers can be cited as examples of polymers containing fluorinated polyether groups that have hydroxyl groups at one end or two ends of the molecular chain as represented by the above formula (6).

[0139]

[0140]

[0141]

[0142] (In the formula, the sums of p1, q1, r1, s1, and p1, q1, r1, and s1 in each formula are the same as above. In addition, the repeating units shown in parentheses with p1, q1, r1, and s1 can be randomly bonded.)

[0143] Examples of isocyanate-containing polyether-introducing agents that react with polymers containing fluorinated polyether groups that have hydroxyl groups at one or both ends of the molecular chain represented by formula (6) above include the following compounds.

[0144]

[0145]

[0146] (In the formula, e and k are the same as above.)

[0147] The amount of isocyanate-containing polyether-based introducing agent used can be 1 to 15 equivalents, more preferably 3 to 6 equivalents, relative to the hydroxyl content of a fluorinated polyether-based polymer with hydroxyl groups at one or both ends of the molecular chain represented by formula (6).

[0148] Catalysts for the reaction of polymers containing fluorinated polyether groups with hydroxyl groups and two or more olefin sites at the single or double ends of the molecular chain represented by formula (6) above with polyether-introducing agents containing isocyanate groups include, for example, titanium compounds such as tetra-2-ethylhexyloxytitanium, tetra-n-butyl titanate, and tetra-n-propyl titanate; zirconium compounds such as tetra-n-butyl zirconate and tetra-n-propyl zirconate; tin compounds such as dibutyldimethoxytin and dibutyltin dilaurate; bismuth compounds such as tris(2-ethylhexanoate)bismuth; and amine catalysts such as diazabicycloundecene.

[0149] Regarding the amount of catalyst used, relative to 100 parts by mass of a polymer containing a fluorinated polyether group with hydroxyl groups at one end or two ends of the molecular chain represented by the above formula (6), 0.01 to 100 parts by mass can be used, preferably 0.05 to 20 parts by mass.

[0150] In the preparation method of the polymer containing fluorinated polyether groups represented by formula (5) above, a solvent can be used. The solvent is not necessarily required, but examples of fluorinated solvents include: fluorinated aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene; hydrofluoroether (HFE) solvents such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name: Novec series); and perfluorinated solvents composed of perfluorinated compounds (manufactured by 3M, trade name: Fluorinert series). Furthermore, as organic solvents, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, THF, etc., can be used.

[0151] When using solvent, the amount used is 10 to 300 parts by weight, preferably 30 to 150 parts by weight, and more preferably 50 to 100 parts by weight, relative to 100 parts by weight of the fluorinated polyether group-containing polymer with hydroxyl groups and two or more olefin sites at one or both ends of the molecular chain represented by formula (6).

[0152] After the reaction is complete, the aqueous layer and the fluorinated solvent layer are separated by liquid-liquid separation. The obtained fluorinated solvent layer is further washed with an organic solvent and the solvent is removed by distillation, thereby obtaining the polymer containing fluorinated polyether groups represented by the above formula (5).

[0153] Examples of polymers containing fluorinated polyether groups as represented by the above formula (5) include the following polymers.

[0154]

[0155]

[0156]

[0157]

[0158]

[0159] (In the formula, the sums of k, p1, q1, r1, s1, and p1, q1, r1, and s1 in each formula are the same as above. Additionally, the repeating units indicated in parentheses containing p1, q1, r1, and s1 can be randomly bonded.)

[0160] When preparing a polymer containing a fluorinated polyether group as represented by formula (1), the preferred organosilicon compound having a SiH group and a hydrolyzable group in the molecule is a compound represented by the following general formulas (7) to (10).

[0161]

[0162] (In the formula, R, X, n, and e are the same as above. R) 1 Independently an alkyl or phenyl group having 1 to 8 carbon atoms, R 2 It is an alkylene group having 2 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms. R 3 For divalent hydrocarbon groups with 2 to 8 carbon atoms, h is 1, j is an integer from 1 to 8, and h+j is an integer from 2 to 9. In equation (10), the repeating units shown in parentheses can be randomly bonded.

[0163] Here, R 1 It is an alkyl group such as methyl, ethyl, propyl, butyl, or phenyl with 1 to 8 carbon atoms, preferably 1 to 4, wherein methyl is preferred. 1 They can be the same or different.

[0164] R 2 It is an alkylene group with 6 to 8 carbon atoms, such as ethylene, propylene (trimethylene, methyl ethylene), butylene (tetramethylene, methyl propyleneene), etc., with 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, or an arylene group with 6 to 8 carbon atoms, such as phenylene, with ethylene, trimethylene, and phenylene being preferred.

[0165] As R 3 The group has 2 to 8 carbon atoms, preferably 2 or 3, and includes divalent hydrocarbon groups such as methylene, ethylene, propylene (trimethylene, methyl ethylene), butylene (tetramethylene, methyl propyleneene), hexamethylene, octamethylene, etc., alkylene, phenylene, etc., or combinations of two or more of these groups (alkylene-arylene, etc.), with ethylene and trimethylene being preferred.

[0166] Examples of organosilicon compounds having SiH groups and hydroxyl or hydrolyzable groups in their molecules include: trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and silane or siloxane compounds, as well as their (partial) hydrolysates.

[0167]

[0168]

[0169] When preparing a polymer containing a fluorinated polyether group as represented by formula (1), the amount of organosilicon compound having SiH groups and hydroxyl or hydrolyzable groups in the molecule can be 1 to 4 equivalents, more preferably 1.5 to 4 equivalents, relative to 1 equivalent of the olefin portion of a polymer containing a fluorinated polyether group having a monovalent group containing a urethane bond and a polyether chain and two or more olefin portions at one or both ends of the molecular chain.

[0170] When preparing polymers containing fluorinated polyether groups as represented by formula (1), the following catalysts can be used as catalysts for the hydrosilylation reaction: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, ethynyl alcohols, etc., and platinum group metal catalysts such as tetra(triphenylphosphine)palladium and trichloro(triphenylphosphine)rhodium. Platinum group compounds such as vinylsiloxane coordination compounds are preferred.

[0171] Regarding the amount of catalyst used in the hydrogenation silylation reaction, it shall be used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm, relative to the mass of a polymer containing a fluorinated polyether group with a monovalent group containing a urethane bond and a polyether chain at one or both ends of the molecular chain, in the form of transition metal conversion (mass).

[0172] When preparing polymers containing fluorinated polyether groups as represented by formula (1), fluorinated solvents can be cited as examples. Examples of fluorinated solvents include: 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), and perfluorinated solvents composed of perfluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc.

[0173] Regarding the amount of solvent used, for 100 parts by weight of a polymer containing fluorinated polyether groups with monovalent groups containing urethane bonds and polyether chains and two or more olefin sites at one or both ends of the molecular chain, 10 to 300 parts by weight can be used, preferably 50 to 150 parts by weight, and more preferably 50 to 100 parts by weight.

[0174] To explain, when using organosilicon compounds containing SiH groups and hydroxyl or hydrolyzable groups, such as trichlorosilane, the substituents (halogen atoms) on the silane group can be converted into other hydrolyzable groups, such as alkoxy groups, methoxy groups, etc. As reagents that can be used to convert the substituents (halogen atoms) on the silane group into other hydrolyzable groups, examples include alcohols with 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, and butanol.

[0175] Regarding the amount used, relative to 100 parts by mass of the addition reaction product of a fluorinated polyether group containing a monovalent group containing a urethane bond and a polyether chain and two or more olefin sites at one or both ends of the molecular chain with a halogenated (organo)silicon compound containing a SiH group, 10 to 200 parts by mass can be used, more preferably 40 to 100 parts by mass, and even more preferably 50 to 70 parts by mass.

[0176] After the reaction is complete, the solvent and unreacted substances are removed by vacuum distillation to obtain the polymer containing fluorinated polyether groups represented by the above formula (1).

[0177] As another method for preparing a polymer containing a fluorinated polyether group, as represented by the above formula (1), when α is 1 (i.e., Rf is a monovalent fluorinated polyether group) or when α is 2 (i.e., Rf is a divalent fluorinated polyether group), the following method can be cited as an example.

[0178] A polymer containing fluorinated polyether groups, having monovalent groups containing urethane bonds and polyether chains and two or more SiH groups at one or both ends of the molecular chain; an organosilicon compound having olefin sites and hydroxyl or hydrolyzable groups in the molecule; and a solvent (e.g., fluorinated solvents such as 1,3-bis(trifluoromethyl)benzene) are mixed and aged at a temperature of 40–120°C, preferably 60–100°C, more preferably 70–90°C, for 1–72 hours, preferably 20–36 hours, more preferably 22–30 hours, in the presence of a hydrogenation silylation catalyst (e.g., a toluene solution of a chloroplatinic acid / vinylsiloxane complex). Note that two different organosilicon compounds having olefin sites and hydroxyl or hydrolyzable groups in the molecule can also be used, in which case they can be manufactured by stepwise addition.

[0179] In another method of preparing a polymer containing a fluorinated polyether group as represented by formula (1), a polymer containing a fluorinated polyether group having a monovalent group containing a urethane bond and a polyether chain and two or more SiH groups at one end or both ends of the molecular chain can be exemplified by the polymer containing a fluorinated polyether group represented by the following general formula (11) or (12).

[0180]

[0181] (In the formula, Rf, B, E, U, m, and α are the same as above. Z) 1 It consists of linear chains of 2–10 silicon atoms, particularly 3–8 silicon atoms, or branched or cyclic 3–6 valent organopolysiloxane residues of 3–10 silicon atoms, particularly 3–8 silicon atoms. The hydrogen atoms are bonded to silicon atoms.

[0182]

[0183] (In the formula, Rf, B, E, U, Z, m, α are the same as above, Y) 2 It is an independent divalent hydrocarbon group containing silicon atoms. The hydrogen atom is bonded to the silicon atom.

[0184] In the above formula (11), Z 1 It is a 3- to 6-valent organopolysiloxane residue with 2 to 10 silicon atoms, particularly 3 to 8 silicon atoms, in a straight-chain form, or in a branched or cyclic form with 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms. This organopolysiloxane residue may contain a silaneide structure with two silicon atoms bonded by an alkylene group, i.e., Si-(CH2).x -Si (where x is an integer from 2 to 6 in the above formula).

[0185] The organopolysiloxane residue may have alkyl groups such as methyl, ethyl, propyl, butyl, or phenyl with 1 to 8 carbon atoms, more preferably 1 to 4.

[0186] As such Z 1 Examples of such structures include the following. It should be noted that in the following structures, the left-side bonding end is preferably bonded to U, while the other bonding ends are bonded to Y.

[0187]

[0188]

[0189] In the above formula (12), Y 2 It is a divalent hydrocarbon group having silicon atoms, preferably with 1 to 18 carbon atoms. Specifically, this divalent hydrocarbon group is selected from the following groups: a divalent group formed by bonding an alkylene group having 1 to 10 carbon atoms and a diorganomylidene, silanealkylene, or silanearyl structure; and a divalent group having an alkylene group having 1 to 10 carbon atoms bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms.

[0190] As such Y 2 For example, the following groups can be cited. It should be noted that in the following structure, the left-hand bonding end is bonded to Z, and the right-hand bonding end is bonded to H.

[0191]

[0192]

[0193] (In the formula, a, e, and f are the same as above.)

[0194] As a method for preparing the polymer containing fluorinated polyether groups represented by the above formula (11), the following methods can be cited as an example.

[0195] A polymer containing a fluorinated polyether group with hydroxyl groups and two olefin sites at one or both ends of the molecular chain, represented by the following general formula (13), and a polyether group containing an isocyanate group are prepared by aging a polymer containing a fluorinated polyether group with hydroxyl groups at one or both ends of the molecular chain and a polyether group containing an isocyanate group in the presence of a catalyst and, if necessary, a solvent, at a temperature of 0 to 190°C, preferably 40 to 150°C, more preferably 80 to 100°C for 1 to 48 hours, preferably 10 to 40 hours, more preferably 20 to 30 hours.

[0196]

[0197] (In the formula, Rf, B, and α are the same as above. U' is independently a single bond or a divalent organic group.)

[0198] Next, the obtained polymer containing fluorinated polyether groups with monovalent groups containing urethane bonds and polyether chains and two olefin sites at one or both ends of the molecular chain, an organosilicon compound having three or more SiH groups without hydrolyzable groups, and a solvent (e.g., fluorinated solvents such as 1,3-bis(trifluoromethyl)benzene) are mixed and aged at a temperature of 40–120°C, preferably 60–100°C, more preferably 70–90°C, for 1–72 hours, preferably 20–36 hours, more preferably 22–30 hours, in the presence of a hydrogenation silylation catalyst (e.g., a toluene solution of chloroplatinic acid / vinylsiloxane complex).

[0199] In the above formula (13), U' is independently a single bond or a divalent organic group, which is selected from the following groups: alkylene with 1 to 8 carbon atoms, alkylene with 1 to 8 carbon atoms containing arylene with 6 to 8 carbon atoms (e.g., alkylene-arylene with 7 to 16 carbon atoms), divalent groups formed by alkylene with 1 to 10 carbon atoms bonded to each other via diorganosilyl, silaneyl or silaneyl structures, and divalent groups with alkylene with 1 to 10 carbon atoms bonded to the bonding ends of linear or branched or cyclic organopolysiloxane residues with 2 to 10 silicon atoms, which may contain oxygen atoms and sulfur atoms.

[0200] In addition to single bonds, such a U' can be represented by, for example, the following groups. It should be noted that in the following structure, the left-hand bonding end is bonded to a carbon atom bonded to a hydroxyl group, and the right-hand bonding end is bonded to a carbon atom in an olefinic region.

[0201]

[0202]

[0203] (In the formula, f, a, and e are the same as above, b'' is 0, 1, or 2, and c' is an integer from 1 to 8.)

[0204] As a polymer containing a fluorinated polyether group that has a hydroxyl group and two olefin sites at one or both ends of the molecular chain represented by the above formula (13), the following polymers can be cited as examples.

[0205]

[0206]

[0207] (In the formula, the sums of p1, q1, s1, and p1, q1, and s1 in each formula are the same as above. In addition, the repeating units shown in parentheses with p1, q1, and s1 can be randomly bonded.)

[0208] As a polyether-based introducing agent containing isocyanate groups that reacts with a polymer containing fluorinated polyether groups that has hydroxyl groups at one end or two ends of the molecular chain represented by the above formula (13), for example, the above-described polyether-based introducing agent containing isocyanate groups can be exemplified, and the following compounds are preferred.

[0209]

[0210] (In the formula, k is the same as above.)

[0211] The amount of isocyanate-containing polyether-based introducing agent used can be 1 to 15 equivalents, more preferably 3 to 6 equivalents, relative to the hydroxyl content of a fluorinated polyether-based polymer with hydroxyl groups at one or both ends of the molecular chain represented by formula (13) having hydroxyl groups and two olefin sites.

[0212] Catalysts for the reaction of a polymer containing a fluorinated polyether group with a hydroxyl group and two olefin sites at the single or double ends of the molecular chain represented by formula (13) with a polyether group introducing agent containing an isocyanate group include, for example, titanium compounds such as tetra-2-ethylhexyloxytitanium, tetra-n-butyl titanate, and tetra-n-propyl titanate; zirconium compounds such as tetra-n-butyl zirconate and tetra-n-propyl zirconate; tin compounds such as dibutyldimethoxytin and dibutyltin dilaurate; bismuth compounds such as tris(2-ethylhexanoate)bismuth; and amine catalysts such as diazabicycloundecene.

[0213] Regarding the amount of catalyst used, relative to 100 parts by mass of a polymer containing a fluorinated polyether group with hydroxyl groups at one end or two ends of the molecular chain represented by formula (13), 0.01 to 100 parts by mass can be used, preferably 0.05 to 20 parts by mass.

[0214] In the reaction of a polymer containing a fluorinated polyether group with hydroxyl groups at one or both ends of the molecular chain and two olefin sites as represented by formula (13) above with a polyether group introducing agent containing isocyanate groups, a solvent may be used. The solvent is not necessarily required, but the same fluorinated solvents and organic solvents as exemplified in the preparation method above can be used as the solvent. As for the amount of the solvent used, relative to 100 parts by weight of the polymer containing a fluorinated polyether group with hydroxyl groups at one or both ends of the molecular chain as represented by formula (13), 10 to 300 parts by weight, preferably 30 to 150 parts by weight, and more preferably 50 to 100 parts by weight can be used.

[0215] After the reaction is complete, the aqueous layer and the fluorinated solvent layer are separated by liquid-liquid separation. The obtained fluorinated solvent layer is further washed with an organic solvent and the solvent is removed by distillation, thereby obtaining a polymer containing fluorinated polyether groups with monovalent groups containing urethane bonds and polyether chains and two olefin sites at one or both ends of the molecular chain represented by the following general formula (14).

[0216]

[0217] (In the formula, Rf, B, E, U', and α are the same as above.)

[0218] As a polymer containing a fluorinated polyether group, which has a monovalent group containing a urethane bond and a polyether chain and two olefin sites at one end or both ends of the molecular chain represented by the above formula (14), the following polymers can be cited as examples.

[0219]

[0220] (In the formula, the sums of k, p1, q1, s1, and p1, q1, and s1 in each formula are the same as above. In addition, the repeating units shown in parentheses with p1, q1, and s1 can be randomly bonded.)

[0221] The following compounds can be cited as examples of organosilicon compounds that react with a polymer containing a fluorinated polyether group and having a monovalent group containing a urethane bond and a polyether chain and two olefin sites at one or both ends of the molecular chain represented by the above formula (14), and which do not have hydrolyzable groups but have three or more SiH groups in the molecule.

[0222]

[0223]

[0224] The amount of organosilicon compounds that do not have hydrolyzable groups but have three or more SiH groups used is 7 to 30 equivalents, more preferably 5 to 20 equivalents, and even more preferably 8 to 12 equivalents, relative to the olefin equivalent of a polymer containing a fluoropolyether group with a monovalent group containing a urethane bond and a polyether chain and two olefin sites at the single or double ends of the molecular chain represented by formula (14).

[0225] As a catalyst for the hydrosilylation reaction of a polymer containing a fluorinated polyether group with a monovalent group containing a urethane bond and a polyether chain and two olefin sites at one or both ends of the molecular chain represented by formula (14) above, and an organosilicon compound having three or more SiH groups but no hydrolyzable groups in the molecule, the same catalyst as the hydrosilylation reaction catalyst exemplified in the preparation method described above can be used. As its amount of formulation, relative to the mass of the polymer containing a fluorinated polyether group with a monovalent group containing a urethane bond and a polyether chain and two olefin sites at one or both ends of the molecular chain represented by formula (14), it can be used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal conversion (mass).

[0226] As a solvent for reacting a polymer containing a fluorinated polyether group with a monovalent group containing a urethane bond and a polyether chain and two olefin sites at one or both ends of the molecular chain represented by formula (14) with an organosilicon compound having three or more SiH groups but no hydrolyzable groups, the same solvent as the fluorinated solvent exemplified in the preparation method described above can be used. As the amount of the solvent used, relative to 100 parts by mass of the polymer containing a fluorinated polyether group with a monovalent group containing a urethane bond and a polyether chain and two olefin sites at one or both ends of the molecular chain represented by formula (14), 10 to 300 parts by mass can be used, preferably 50 to 150 parts by mass, and more preferably 50 to 100 parts by mass.

[0227] After the reaction is complete, the solvent and unreacted substances are removed by vacuum distillation to obtain the polymer containing fluorinated polyether groups represented by the above formula (11).

[0228] Examples of polymers containing fluorinated polyether groups as represented by the above formula (11) include the following polymers.

[0229]

[0230]

[0231] (In the formula, the sums of k, p1, q1, s1, and p1, q1, and s1 in each formula are the same as above. In addition, the repeating units shown in parentheses with p1, q1, and s1 can be randomly bonded.)

[0232] Next, as a method for preparing the polymer containing fluorinated polyether groups represented by the above formula (12), the following method can be cited as an example.

[0233] A polymer containing a fluorinated polyether group with hydroxyl groups and two or more olefin sites at one or both ends of the molecular chain, represented by the following general formula (15), and a polyether group containing an isocyanate group are prepared by aging a polymer containing a fluorinated polyether group with hydroxyl groups at one or both ends of the molecular chain and a solvent, in the presence of a catalyst, at a temperature of 0 to 190°C, preferably 40 to 150°C, more preferably 80 to 100°C for 1 to 48 hours, preferably 10 to 40 hours, more preferably 20 to 30 hours, with monovalent groups containing urethane bonds and polyether chains and two or more olefin sites at one or both ends of the molecular chain.

[0234]

[0235] (In the formula, Rf, B, U, Z, m, and α are the same as above. Y) 1 (Independently a single bond or a divalent hydrocarbon group that may have an oxygen atom.)

[0236] Next, the obtained polymer containing fluorinated polyether groups with monovalent groups containing urethane bonds and polyether chains and two or more olefin sites at one or both ends of the molecular chain, an organosilicon compound having two SiH groups but no hydrolyzable groups in the molecule, and a solvent (e.g., fluorinated solvents such as 1,3-bis(trifluoromethyl)benzene) are mixed and aged at a temperature of 40–120°C, preferably 60–100°C, more preferably 70–90°C, for 1–72 hours, preferably 20–36 hours, more preferably 22–30 hours, in the presence of a hydrogenation silylation catalyst (e.g., a toluene solution of chloroplatinic acid / vinylsiloxane complex).

[0237] In the above formula (15), Y 1 It is a divalent hydrocarbon group that is independently a single bond or preferably has 1 to 10 carbon atoms and may have an oxygen atom. Examples of divalent hydrocarbon groups include the following groups. It should be noted that in the following structures, the left-hand bonding end is bonded to a Z atom, and the right-hand bonding end is bonded to a carbon atom.

[0238]

[0239] (In the formula, a'' is 1 or 2.)

[0240] As a polymer containing a fluorinated polyether group that has a hydroxyl group and two or more olefin sites at one or both ends of the molecular chain represented by the above formula (15), the following polymers can be cited as examples.

[0241]

[0242]

[0243] (In the formula, p1, q1, and the sum of p1 and q1 in each formula are the same as above. In addition, the repeating units shown in parentheses with p1 and q1 can be randomly bonded.)

[0244] As a polyether-introducing agent containing isocyanate groups that reacts with a polymer containing fluorinated polyether groups that has hydroxyl groups at one end or two ends of the molecular chain represented by the above formula (15), for example, the above-described polyether-introducing agent containing isocyanate groups can be exemplified, and the following compounds are preferred.

[0245]

[0246] (In the formula, k is the same as above.)

[0247] The amount of isocyanate-containing polyether-based introducing agent used can be 1 to 15 equivalents, more preferably 3 to 6 equivalents, relative to the hydroxyl content of a fluorinated polyether-based polymer with hydroxyl groups at one or both ends of the molecular chain represented by formula (15) having hydroxyl groups and two or more olefin sites.

[0248] Catalysts for the reaction of a polymer containing a fluorinated polyether group with a hydroxyl group and two or more olefin sites at the single or double ends of the molecular chain represented by formula (15) above with a polyether group introducing agent containing an isocyanate group include, for example, titanium compounds such as tetra-2-ethylhexyloxytitanium, tetra-n-butyl titanate, and tetra-n-propyl titanate; zirconium compounds such as tetra-n-butyl zirconate and tetra-n-propyl zirconate; tin compounds such as dibutyldimethoxytin and dibutyltin dilaurate; bismuth compounds such as tris(2-ethylhexanoate)bismuth; and amine catalysts such as diazabicycloundecene.

[0249] Regarding the amount of catalyst used, relative to 100 parts by mass of a polymer containing a fluorinated polyether group having hydroxyl groups at one end or two ends of the molecular chain represented by formula (15), 0.01 to 100 parts by mass can be used, preferably 0.05 to 20 parts by mass.

[0250] In the reaction of a polymer containing a fluorinated polyether group with hydroxyl groups at one or both ends of the molecular chain and two or more olefinic sites, as represented by formula (15) above, with a polyether-introducing agent containing isocyanate groups, a solvent may be used. The solvent is not necessarily required, but examples of solvents similar to the fluorinated solvents and organic solvents exemplified in the above preparation method may be used. The amount of solvent used may be 10 to 300 parts by weight, preferably 30 to 150 parts by weight, and more preferably 50 to 100 parts by weight, relative to 100 parts by weight of the polymer containing a fluorinated polyether group with hydroxyl groups at one or both ends of the molecular chain, as represented by formula (15).

[0251] After the reaction is complete, the aqueous layer and the fluorinated solvent layer are separated by liquid-liquid separation. The obtained fluorinated solvent layer is further washed with an organic solvent and the solvent is removed by distillation, thereby obtaining a polymer containing fluorinated polyether groups with monovalent groups containing urethane bonds and polyether chains and two or more olefin sites at one or both ends of the molecular chain represented by the following general formula (16).

[0252]

[0253] (In the formula, Rf, B, E, U, Z, Y 1 (m, α are the same as above.)

[0254] As a polymer containing a fluorinated polyether group, which has a monovalent group containing a urethane bond and a polyether chain and two or more olefin sites at one or both ends of the molecular chain represented by the above formula (16), the following polymers can be cited as examples.

[0255]

[0256]

[0257] (In the formula, k, p1, q1, and the sum of p1 and q1 in each formula are the same as above. In addition, the repeating units shown in parentheses with p1 and q1 can be randomly bonded.)

[0258] The following compounds can be cited as examples of organosilicon compounds that react with a polymer containing a fluorinated polyether group and having a monovalent group containing a urethane bond and a polyether chain and two or more olefin sites at one or both ends of the molecular chain represented by the above formula (16), and which do not have hydrolyzable groups but have two SiH groups in the molecule.

[0259]

[0260]

[0261] (In the formula, e and f are the same as above.)

[0262] The amount of organosilicon compound having two SiH groups but no hydrolyzable groups in the molecule can be 7 to 30 equivalents, more preferably 5 to 20 equivalents, and even more preferably 8 to 12 equivalents, relative to the olefin equivalent of a polymer containing a fluoropolyether group with a monovalent group containing a urethane bond and a polyether chain and two or more olefin sites at the single or double ends of the molecular chain represented by formula (16).

[0263] As a catalyst for the hydrosilylation reaction of a polymer containing a fluorinated polyether group with a monovalent group containing a urethane bond and a polyether chain and two or more olefin sites at one or both ends of the molecular chain represented by formula (16) above, and an organosilicon compound having two SiH groups but no hydrolyzable groups in the molecule, the same catalyst as the hydrosilylation reaction catalyst exemplified in the preparation method above can be used. As its amount of formulation, relative to the mass of the polymer containing a fluorinated polyether group with a monovalent group containing a urethane bond and a polyether chain and two or more olefin sites at one or both ends of the molecular chain represented by formula (16), it can be used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal conversion (mass).

[0264] As a solvent for reacting a polymer containing a fluorinated polyether group with a monovalent group containing a urethane bond and a polyether chain and two or more olefin sites at one or both ends of the molecular chain represented by formula (16) with an organosilicon compound having two SiH groups but no hydrolyzable groups in the molecule, the same solvent as the fluorinated solvent exemplified in the preparation method described above can be used. As the amount of the solvent, relative to 100 parts by mass of the polymer containing a fluorinated polyether group with a monovalent group containing a urethane bond and a polyether chain and two or more olefin sites at one or both ends of the molecular chain represented by formula (16), 10 to 300 parts by mass can be used, preferably 50 to 150 parts by mass, more preferably 50 to 100 parts by mass.

[0265] After the reaction is complete, the solvent and unreacted substances are removed by vacuum distillation to obtain the polymer containing fluorinated polyether groups represented by the above formula (12).

[0266] Examples of polymers containing fluorinated polyether groups as represented by the above formula (12) include the following polymers.

[0267]

[0268]

[0269]

[0270]

[0271] (In the formula, k, p1, q1, and the sum of p1 and q1 in each formula are the same as above. In addition, the repeating units shown in parentheses with p1 and q1 can be randomly bonded.)

[0272] In another method for preparing a polymer containing a fluorinated polyether group as represented by formula (1), the preferred organosilicon compound is one that reacts with a polymer containing a fluorinated polyether group having a monovalent group containing a urethane bond and a polyether chain and two or more SiH groups at one or both ends of the molecular chain, and has an olefinic site and hydroxyl or hydrolyzable groups in the molecule.

[0273]

[0274] (In the formula, R, X, and n are the same as above. Y'' is a single bond or may have a divalent hydrocarbon group selected from oxygen, sulfur, silicon, and siloxane bonds.)

[0275] In formula (17) above, Y'' is a single bond, or a divalent hydrocarbon group having at least one of oxygen, sulfur, silicon, and siloxane bonds, preferably with 1 to 18 carbon atoms. Specifically, this divalent hydrocarbon group is selected from the following groups: alkylene groups with 1 to 8 carbon atoms containing oxygen or sulfur atoms; alkylene groups with 1 to 8 carbon atoms containing 6 to 8 arylene groups (e.g., alkylene-arylene groups with 7 to 18 carbon atoms); divalent groups formed by bonding alkylene groups with 1 to 10 carbon atoms to diorganosilyl groups, silaneyl groups, or silaneyl groups; and divalent groups with alkylene groups having 1 to 10 carbon atoms bonded to the bonding ends of straight-chain or branched or cyclic organopolysiloxane residues with 2 to 10 silicon atoms. Y'' is preferably a single bond or a straight-chain alkylene group with 1 to 6 carbon atoms.

[0276] Examples of organosilicon compounds having an olefinic site and hydroxyl or hydrolyzable groups in their molecules include: vinyltrimethoxysilane, allyltrimethoxysilane, hexenyltrimethoxysilane, octenyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, hexenyltriethoxysilane, octenyltriethoxysilane, vinyltriisopropoxysilane, allyltriisopropoxysilane, vinyltributoxysilane, allyltributoxysilane, vinyltriacetoxysilane, allyltriacetoxysilane, vinyltrichlorosilane, vinyltribromosilane, vinyltriiodosilane, and silane or siloxane compounds, as well as their (partial) hydrolysates. Vinyltrimethoxysilane and allyltrimethoxysilane are preferred.

[0277]

[0278] In another method for preparing a polymer containing a fluorinated polyether group as represented by formula (1), the amount of organosilicon compound having an olefinic site and hydroxyl or hydrolyzable groups in the molecule is 1 to 4 equivalents, more preferably 1.5 to 2.5 equivalents, and even more preferably 1.8 to 2.2 equivalents, relative to 1 equivalent of the SiH group in a polymer containing a fluorinated polyether group having a monovalent group containing a urethane bond and a polyether chain and two or more SiH groups at one or both ends of the molecular chain.

[0279] As another method for preparing a polymer containing a fluorinated polyether group as represented by formula (1), the same catalyst as the one exemplified in the above preparation method can be used as the amount of the catalyst for the hydrosilylation reaction. The amount of the catalyst used is 0.1 to 100 ppm, more preferably 0.3 to 50 ppm, relative to the mass of a polymer containing a fluorinated polyether group having a monovalent group containing a urethane bond and a polyether chain at one or both ends of the molecular chain.

[0280] As a solvent for another method of preparing the polymer containing fluorinated polyether groups represented by formula (1), the same solvent as the fluorinated solvent exemplified in the above preparation method can be used. As its proportion, 10 to 300 parts by mass can be used relative to 100 parts by mass of the polymer containing fluorinated polyether groups having monovalent groups containing urethane bonds and polyether chains and two or more SiH groups at one or both ends of the molecular chain. Preferably, 50 to 150 parts by mass, more preferably 50 to 100 parts by mass.

[0281] After the reaction is complete, the solvent and unreacted substances are removed by vacuum distillation to obtain the polymer containing fluorinated polyether groups represented by the above formula (1).

[0282] The present invention also provides a surface treatment agent comprising a polymer containing a fluorinated polyether group and / or a portion thereof (hydrolyzed) condensate, characterized in that it is a surface treatment agent comprising a polymer containing a fluorinated polyether group having two or more hydroxysilyl or hydrolyzed silyl groups and / or a portion thereof (hydrolyzed) condensate, wherein the monovalent or divalent fluorinated polyether group in the polymer containing the fluorinated polyether group is bonded to the hydroxysilyl or hydrolyzed silyl group via a linker, the linker having a tertiary carbon atom bonded to a monovalent group, the monovalent group having a urethane bond and a polyether chain. Preferably, the polymer containing the fluorinated polyether group is represented by the above formula (1).

[0283] That is, the present invention provides a surface treatment agent containing a polymer containing a fluorinated polyether group as represented by formula (1) above and / or a portion of its (hydrolyzed) condensate. This surface treatment agent only needs to contain the polymer containing a fluorinated polyether group as represented by formula (1) above and / or a portion of its (hydrolyzed) condensate as the main agent, and may also contain unreacted raw materials, reaction intermediates, etc., prior to the introduction of the terminal hydroxyl groups or hydrolyzable groups of the polymer containing a fluorinated polyether group as represented by formula (1).

[0284] In addition, in this invention, "partial (hydrolyzed) condensate" refers to a partial condensate or a partially hydrolyzed condensate, which is obtained by condensing the hydroxyl groups of the polymer containing the fluorinated polyether group represented by the above formula (1) or the hydroxyl groups obtained by partially hydrolyzing the terminal hydrolyzable groups of the polymer containing the fluorinated polyether group in advance using a known method.

[0285] Surface treatment agents can be supplemented with hydrolysis-condensation catalysts as needed, such as organotin compounds (dibutyldimethoxytin, dibutyltin dilaurate, etc.), organotitanium compounds (tetrabutyl titanate, tetrapropyl titanate, etc.), organozirconium compounds (tetrabutyl zirconate, tetrapropyl zirconate, 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 desirable.

[0286] The amount of hydrolysis condensation catalyst added is the catalytic amount, which is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, relative to 100 parts by mass of the polymer containing fluorinated polyether groups and / or its partial (hydrolysis) condensate represented by the above formula (1).

[0287] The surface treatment agent may contain a suitable solvent. Examples of such solvents include: fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, tridecafluorooctane, etc.), fluorinated aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorinated ether solvents (methyl perfluorobutyl ether, methyl perfluoropentyl ether, methyl perfluorohexyl ether, methyl perfluoroheptenyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), tetrafluoroethyltrifluoroethyl ether, etc.), fluorinated alkylamine solvents (perfluorotripropylamine, perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum volatile oils, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, considering solubility, wettability, and other aspects, fluorinated solvents are ideal, with 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, methyl perfluorohexyl ether, methyl perfluoroheptenyl ether, ethyl perfluorobutyl ether, tridecylfluorooctane, and tetrafluoroethyltrifluoroethyl ether being particularly preferred.

[0288] Two or more of the above solvents can be mixed, preferably to uniformly dissolve the polymer containing fluorinated polyether groups and its partial (hydrolyzed) condensate (hereinafter referred to as the polymer containing fluorinated polyether groups) represented by formula (1). It should be noted that the optimal concentration of the polymer containing fluorinated polyether groups dissolved in the solvent varies depending on the processing method, and any amount that is easy to weigh is acceptable. However, when coating directly, it is preferably 0.01 to 10 parts by mass relative to the total of 100 parts by mass of the solvent and the polymer containing fluorinated polyether groups, and particularly preferably 0.05 to 5 parts by mass. When performing vapor deposition, it is preferably 1 to 100 parts by mass relative to the total of 100 parts by mass of the solvent and the polymer containing fluorinated polyether groups, and particularly preferably 3 to 30 parts by mass.

[0289] The surface treatment agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition. The heating method during vapor deposition can be resistance heating or electron beam heating, without particular limitation. The curing temperature varies depending on the curing method. For example, when directly coating (brushing, dipping, spraying, etc.), it is preferable to treat at 25–200°C, particularly 25–150°C, for 30 minutes to 36 hours, particularly 1–24 hours. When applied by vapor deposition, it is ideal to treat at 20–200°C for 1–24 hours. Alternatively, curing can be performed under humidified conditions. Furthermore, for example, in spray coating, pre-diluting in a fluorinated solvent with added water and hydrolyzing to generate Si-OH before spray coating results in faster curing after coating.

[0290] The thickness of the cured coating is appropriately selected according to the type of substrate, typically ranging from 0.1 to 100 nm, especially 1 to 20 nm. It should be noted that the film thickness can be measured, for example, by methods such as spectrophotometry, X-ray reflectance measurement, spectrophotometric ellipsometer measurement, and fluorescence X-ray measurement.

[0291] The substrate treated with the surface treatment agent of this invention is not particularly limited and can be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. The surface treatment agent of this invention can impart water and oil repellency to the substrate. It is particularly suitable as a surface treatment agent for SiO2-treated glass or films.

[0292] Examples of articles treated with the surface treatment agent of the present invention include: car navigation systems, mobile phones, smartphones, digital cameras, digital camcorders, PDAs (personal digital assistants), portable audio players, car audio systems, gaming devices, eyeglass lenses, camera lenses, lens elements, sunglasses, endoscopes and other medical devices, copiers, PCs (personal computers), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films and other optical articles or electronic components. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the above-mentioned articles and can impart scratch resistance, therefore it is particularly useful as a water- and oil-repellent layer for touch panel displays, anti-reflective films, etc.

[0293] In addition, the surface treatment agent of the present invention can also be used as: anti-fouling coatings for bathroom products such as bathtubs and washbasins; anti-fouling coatings for window glass or tempered glass of automobiles, trams, aircraft, etc., headlight covers, etc.; water- and oil-repellent coatings for exterior wall building materials; oil-resistant coatings for kitchen building materials; anti-fouling and anti-sticking / anti-graffiti coatings for telephone booths; anti-fingerprint coatings for artworks, etc.; anti-fingerprint coatings for optical discs (CDs), DVDs, etc.; mold release agents or coating additives for molds; resin modifiers; flow modifiers or dispersant modifiers for inorganic fillers; lubricity improvers for tapes, films, etc.

[0294] Example

[0295] The following describes the invention in more detail, showing synthesis examples, examples, and comparative examples, but the invention is not limited to the following examples. It should be noted that in the following examples, the amounts of p1, q1, and mol are based on... 19 F-NMR, 1 The values ​​were calculated from the results of analyses such as H-NMR.

[0296] [Synthesis Example 1]

[0297] In a reaction vessel, the following formula (1-A) is mixed.

[0298]

[0299] The compound represented is 120g (2.84 × 10⁻⁶). -2 mol), 120g of 1,3-bis(trifluoromethyl)benzene, and the following formula (1-B)

[0300]

[0301] The indicated compound was 21.5 g (0.113 mol), and tetra-2-ethylhexyloxytitanium was 0.6 g (1.06 × 10⁻⁶ mol). -3(mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by separation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 125 g of the compound represented by the following formula (1-C).

[0302]

[0303] In a reaction vessel, 100 g (2.30 × 10⁻⁶) of the compound represented by the above formula (1-C) obtained above was mixed. -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, 11.2g of trimethoxysilane (9.18×10⁻⁶ mol), -2 8.51 × 10⁻⁶ mol) and a toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (containing 2.23 × 10⁻⁶ Pt elements) -6 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 101g of liquid product.

[0304] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (1-D).

[0305]

[0306] [Synthesis Example 2]

[0307] In a reaction vessel, the following formula (2-A) is mixed.

[0308]

[0309] The compound represented is 60g (1.41 × 10⁻⁶). -2 mol), 60g of 1,3-bis(trifluoromethyl)benzene, and the following formula (2-B)

[0310]

[0311] The compound represented is 18.1 g (5.62 × 10⁻⁶). -2 0.3 g (5.31 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by separation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 58 g of the compound represented by the following formula (2-C).

[0312]

[0313] In a reaction vessel, 50 g (1.10 × 10⁻⁶) of the compound represented by the above formula (2-C) obtained above was mixed. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 5.39g of trimethoxysilane (4.41×10⁻⁶ mol), -2 4.09 × 10⁻⁶ mol) and a toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (containing 1.07 × 10⁻⁶ Pt elements) -6 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 50g of liquid product.

[0314] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (2-D).

[0315]

[0316] [Synthesis Example 3]

[0317] In a reaction vessel, the following formula (3-A) is mixed.

[0318]

[0319] The compound represented is 60g (1.32 × 10⁻⁶). -2 mol), 60g of 1,3-bis(trifluoromethyl)benzene, and the following formula (3-B)

[0320]

[0321] The compound represented is 17.0 g (5.28 × 10⁻⁶). -2 0.3 g (5.31 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by separation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 62 g of the compound represented by the following formula (3-C).

[0322]

[0323] In a reaction vessel, 50 g (1.06 × 10⁻⁶) of the compound represented by the above formula (3-C) was mixed. -2mol), 25g of 1,3-bis(trifluoromethyl)benzene, 5.16g of trimethoxysilane (4.41×10⁻⁶ mol), -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.92 × 10⁻⁶ -2 g (containing 1.03 × 10⁻⁶ Pt elements) -6 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 48g of liquid product.

[0324] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (3-D).

[0325]

[0326] [Synthesis Example 4]

[0327] In a reaction vessel, the following formula (4-A) is mixed.

[0328]

[0329] The compound represented is 120g (2.84 × 10⁻⁶). -2 mol), 120g of 1,3-bis(trifluoromethyl)benzene, and the following formula (4-B)

[0330]

[0331] The indicated compound was 46.5 g (0.114 mol), and tetra-2-ethylhexyloxytitanium was 0.6 g (1.06 × 10⁻⁶ mol). -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by liquid-liquid extraction and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 128 g of the compound represented by the following formula (4-C).

[0332]

[0333] In a reaction vessel, 100 g (2.19 × 10⁻⁶) of the compound represented by the above formula (4-C) obtained above was mixed. -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, 10.7g of trimethoxysilane (8.74×10⁻⁶ mol), -2 8.10 × 10⁻⁶ mol) and a toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (containing 2.12 × 10⁻⁶ Pt elements) -6The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 102 g of liquid product.

[0334] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (4-D).

[0335]

[0336] [Synthesis Example 5]

[0337] In a reaction vessel, the following formula (5-A) is mixed.

[0338]

[0339] The compound represented is 60g (1.42 × 10⁻⁶). -2 mol), 60g of 1,3-bis(trifluoromethyl)benzene, and the following formula (5-B)

[0340]

[0341] The compound represented is 34.9 g (5.68 × 10⁻⁶). -2 0.3 g (5.31 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by liquid-liquid extraction and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 68 g of the compound represented by the following formula (5-C).

[0342]

[0343] In a reaction vessel, 50 g (1.05 × 10⁻⁶) of the compound represented by the above formula (5-C) obtained above was mixed. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 5.11g of trimethoxysilane (4.18×10⁻⁶ mol), -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.88 × 10⁻⁶ -2 g (containing 1.02 × 10⁻⁶ Pt elements) -6 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 49g of liquid product.

[0344] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (5-D).

[0345]

[0346] [Synthesis Example 6]

[0347] In a reaction vessel, the following formula (6-A) is mixed.

[0348]

[0349] The compound represented is 60g (9.60 × 10⁻⁶). -3 mol), 60g of 1,3-bis(trifluoromethyl)benzene, and the following formula (6-B)

[0350]

[0351] The compound represented is 15.7 g (3.84 × 10⁻⁶). -2 0.3 g (5.31 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by separation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 60 g of the compound represented by the following formula (6-C).

[0352]

[0353] In a reaction vessel, 50 g (7.51 × 10⁻⁶) of the compound represented by the above formula (6-C) obtained above was mixed. -3 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 3.66g of trimethoxysilane (3.00×10⁻⁶ mol), -2 2.78 × 10⁻⁶ mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (containing 7.29 × 10⁻⁶ Pt elements) -7 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 50g of liquid product.

[0354] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (6-D).

[0355]

[0356] [Synthesis Example 7]

[0357] In a reaction vessel, the following formula (7-A) is mixed.

[0358]

[0359] The compound represented is 60g (1.50 × 10⁻⁶). -2 mol), 60g of 1,3-bis(trifluoromethyl)benzene, and the following formula (7-B)

[0360]

[0361] The indicated compound was 33.3 g (0.120 mol), and tetra-2-ethylhexyloxytitanium was 0.3 g (5.31 × 10⁻⁶ mol). -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by separation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby giving 64 g of the compound represented by the following formula (7-C).

[0362]

[0363] In a reaction vessel, 50 g (1.10 × 10⁻⁶) of the compound represented by the above formula (7-C) obtained above was mixed. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 10.7g of trimethoxysilane (8.78×10⁻⁶ mol), -2 4.07 × 10⁻⁶ mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (containing 1.07 × 10⁻⁶ Pt elements) -6 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 23g of liquid product.

[0364] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (7-D).

[0365]

[0366] [Synthesis Example 8]

[0367] In a reaction vessel, the following formula (8-A) is mixed.

[0368]

[0369] The compound represented is 120g (2.84 × 10⁻⁶). -2 mol), 120g of 1,3-bis(trifluoromethyl)benzene, and the following formula (8-B)

[0370]

[0371] The indicated compound was 41.5 g (0.114 mol), and tetra-2-ethylhexyloxytitanium was 0.6 g (1.06 × 10⁻⁶ mol). -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by separation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 119 g of the compound represented by the following formula (8-C).

[0372]

[0373] In a reaction vessel, 100 g (2.24 × 10⁻⁶) of the compound represented by the above formula (8-C) obtained above was mixed. -2 mol), 100g of 1,3-bis(trifluoromethyl)benzene, and the following formula (8-D)

[0374]

[0375] The indicated compound was 107 g (0.448 mol), and an 8.31 × 10⁻⁶ toluene solution of the chloroplatinic acid / vinylsiloxane complex was also present. -2 g (containing 2.18 × 10 g of Pt elemental) -6 The compound was aged at 80°C for 24 hours (mol). Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 103 g of the compound represented by the following formula (8-E).

[0376]

[0377] In a reaction vessel, 50 g (9.95 × 10⁻⁶) of the compound represented by the above formula (8-E) obtained above was mixed. -3 25 g of 1,3-bis(trifluoromethyl)benzene, 27.7 g (0.119 mol) of octenyltrimethoxysilane, and 3.69 × 10⁻⁶ toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (containing 9.66 × 10 g of Pt elemental) -7 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 62g of liquid product.

[0378] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (8-F).

[0379]

[0380] [Synthesis Example 9]

[0381] In a reaction vessel, the following formula (9-A) is mixed.

[0382]

[0383] The compound represented is 120g (2.86 × 10⁻⁶). -2 mol), 120g of 1,3-bis(trifluoromethyl)benzene, and the following formula (9-B)

[0384]

[0385] The indicated compound was 26.7 g (0.114 mol), and tetra-2-ethylhexyloxytitanium was 0.6 g (1.06 × 10⁻⁶ mol). -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by separation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 121 g of the compound represented by the following formula (9-C).

[0386]

[0387] In a reaction vessel, 100 g (2.26 × 10⁻⁶) of the compound represented by the above formula (9-C) obtained above was mixed. -2 100 g of 1,3-bis(trifluoromethyl)benzene, 49.6 g (0.370 mol) of 1,1,3,3-tetramethyldisiloxane, and 8.56 × 10⁻⁶ toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (containing 2.24 × 10⁻⁶ Pt elements) -6 The compound was aged at 80°C for 24 hours (mol). Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 102 g of the compound represented by the following formula (9-D).

[0388]

[0389] In a reaction vessel, 50 g (1.07 × 10⁻⁶) of the compound represented by the above formula (9-D) was mixed. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 6.97g of allyltrimethoxysilane (4.30×10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.98 × 10⁻⁶ -2 g (containing 1.04 × 10⁻⁶ Pt elements) -6 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 52g of liquid product.

[0390] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (9-E).

[0391]

[0392] [Synthesis Example 10]

[0393] In a reaction vessel, the following formula (10-A) is mixed.

[0394]

[0395] The compound represented is 60g (1.42 × 10⁻⁶). -2 mol), 60g of 1,3-bis(trifluoromethyl)benzene, and the following formula (10-B)

[0396]

[0397] The compound represented is 25.7 g (5.66 × 10⁻⁶). -2 0.3 g (5.31 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by separation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby giving 64 g of the compound represented by the following formula (10-C).

[0398]

[0399] In a reaction vessel, 50 g (1.08 × 10⁻⁶) of the compound represented by the above formula (10-C) obtained above was mixed. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 5.25g of trimethoxysilane (4.30×10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.99 × 10⁻⁶ -2 g (containing 1.05 × 10⁻⁶ Pt elements) -6 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 52g of liquid product.

[0400] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in the following formula (10-D).

[0401]

[0402] [Synthesis Example 11]

[0403] In a reaction vessel, the following formula (11-A) is mixed.

[0404]

[0405] The compound represented is 60g (1.42 × 10⁻⁶). -2 mol), 60g of 1,3-bis(trifluoromethyl)benzene, and the following formula (11-B)

[0406]

[0407] The compound represented is 18.3 g (5.70 × 10⁻⁶). -2 0.3 g (5.31 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by liquid-liquid extraction and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 57 g of the compound represented by the following formula (11-C).

[0408]

[0409] In a reaction vessel, 50 g (1.10 × 10⁻⁶) of the compound represented by the above formula (11-C) obtained above was mixed. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 7.24g of triethoxysilane (4.41×10⁻⁶ mol), -2 4.09 × 10⁻⁶ mol) and a toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (containing 1.07 × 10⁻⁶ Pt elements) -6 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 51g of liquid product.

[0410] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (11-D).

[0411]

[0412] [Synthesis Example 12]

[0413] In a reaction vessel, the following formula (12-A) is mixed.

[0414]

[0415] The compound represented is 60g (1.42 × 10⁻⁶).-2 mol), 60g of 1,3-bis(trifluoromethyl)benzene, and the following formula (12-B)

[0416]

[0417] The compound represented is 25.8 g (5.70 × 10⁻⁶). -2 0.3 g (5.31 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium -4 (mol), and then heated at 90°C for 24 hours. After heating, cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluorine compound layer was recovered by separation and washed with acetone. The washed lower fluorine compound layer was recovered again, and the residual solvent was removed by distillation under reduced pressure, thereby obtaining 55 g of the compound represented by the following formula (12-C).

[0418]

[0419] In a reaction vessel, 50 g (1.07 × 10⁻⁶) of the compound represented by the above formula (12-C) obtained above was mixed. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 5.23g of trimethoxysilane (4.29×10⁻⁶ mol), -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 3.97 × 10⁻⁶ -2 g (containing 1.04 × 10⁻⁶ Pt elements) -6 The product (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain 50g of liquid product.

[0420] The obtained compound was obtained by 1 H-NMR confirmed that it is a polymer containing fluorinated polyether groups with the structure shown in formula (12-D).

[0421]

[0422] [Example 1]

[0423] The compound represented by formula (1-D) obtained in Synthesis Example 1 was dissolved in Novec 7200 (3M Corporation, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0424] [Example 2]

[0425] The compound represented by formula (2-D) obtained in Synthesis Example 2 was dissolved in Opteon SF10 (Mitsui Chemours Fluoride Products Co., Ltd., methyl perfluoroheptenyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0426] [Example 3]

[0427] The compound represented by formula (4-D) obtained in Synthesis Example 4 was dissolved in Novec 7200 (3M Corporation, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0428] [Example 4]

[0429] The compound represented by formula (5-D) obtained in Synthesis Example 5 was dissolved in Asahiklin AC-6000 (manufactured by AGC, tridecylfluorooctane) to a concentration of 20% by mass to prepare a surface treatment agent.

[0430] [Example 5]

[0431] The compound represented by formula (6-D) obtained in Synthesis Example 6 was dissolved in Novec 7300 (3M Corporation, methyl perfluorohexyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0432] [Example 6]

[0433] The compound represented by formula (8-F) obtained in Synthesis Example 8 was dissolved in Novec 7200 (3M Corporation, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0434] [Example 7]

[0435] The compound represented by formula (10-D) obtained in Synthesis Example 10 was dissolved in Asahiklin AE-3000 (manufactured by AGC, tetrafluoroethyl trifluoroethyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0436] [Example 8]

[0437] The compound represented by formula (11-D) obtained in Synthesis Example 11 was dissolved in Novec 7200 (3M Corporation, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0438] [Example 9]

[0439] The compound represented by formula (12-D) obtained in Synthesis Example 12 was dissolved in Novec 7200 (3M Corporation, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0440] [Comparative Example 1]

[0441] The following formula (Y)

[0442]

[0443] The compound was dissolved in Novec 7200 (3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0444] [Comparative Example 2]

[0445] The following formula (Z)

[0446]

[0447] The compound was dissolved in Novec 7200 (3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0448] Preparation of surface treatment agent and formation of cured coating

[0449] Surface treatment agents were prepared according to the above examples and comparative examples. Various surface treatment agents were vacuum-deposited onto glass (Gorilla, Corning Incorporated) coated with 10 nm thick SiO2 (obtained by SiO2 coating treatment on the outermost surface) (treatment conditions: pressure: 2.0 × 10⁻⁶). -2 A 10 nm thick cured coating was formed by curing the film at 25°C and 50% relative humidity for 12 hours (heating temperature: 700°C). The film thickness was determined using a spectrophotometer.

[0450] Evaluation of water repellency

[0451] [Evaluation of initial water repellency]

[0452] For the glass with the cured coating prepared above, the contact angle (hydrophobicity) of the cured coating 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%). The results (initial water contact angle) are shown in Table 1.

[0453] In the initial stages, both the examples and comparative examples showed good water repellency.

[0454] [Evaluation of abrasion resistance]

[0455] For the glass with a cured coating prepared above, a friction testing machine (manufactured by Shin-Tung Science & Technology Co., Ltd.) was used. After friction under the following conditions, the contact angle (water repellency) of the cured coating to water was measured using the same method as described above, as an evaluation of abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. The results (water contact angle after abrasion) are shown in Table 1.

[0456] Dry eraser abrasion resistance

[0457] Eraser: Raber Eraser (Made by Minoan)

[0458] Contact area: 6mmΦ

[0459] Travel distance (one way): 60mm

[0460] Movement speed: 3,600 mm / min

[0461] Load: 1 kgf / 1 cm 2

[0462] Number of friction cycles: 5,000

[0463] Abrasion resistance of wet erasers

[0464] Eraser: Raber Eraser (Made by Minoan)

[0465] Contact area: 6mmΦ

[0466] Travel distance (one way): 20mm

[0467] Movement speed: 1,600 mm / min

[0468] Load: 1 kgf / 1 cm 2

[0469] Ethanol spray rate: 0.3 ml / min

[0470] Number of friction cycles: 10,000

[0471] The surface treatment agents of Examples 1-9 exhibited improved wettability and high dry eraser abrasion durability due to the presence of polyether groups in the molecules of the compounds used. Furthermore, the presence of urethane bonds in the molecules confirmed high wet eraser abrasion durability. The surface treatment agent of Comparative Example 1, lacking both polyether groups and urethane bonds in its molecules, showed low dry and wet eraser abrasion durability. The surface treatment agent of Comparative Example 2 showed high dry eraser abrasion durability but low wet eraser abrasion durability. As described above, the surface treatment agents of the examples achieved a high level of balance between dry and wet eraser abrasion durability.

[0472] [Table 1]

[0473]

[0474] [Example 10]

[0475] The compound represented by formula (1-D) obtained in Synthesis Example 1 was dissolved in Novec 7200 (3M Corporation, ethyl perfluorobutyl ether) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0476] [Example 11]

[0477] The compound represented by formula (2-D) obtained in Synthesis Example 2 was dissolved in Opteon SF10 (Mitsui-Chemour Fluoride Products Co., Ltd., methyl perfluoroheptene ether) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0478] [Example 12]

[0479] The compound represented by formula (4-D) obtained in Synthesis Example 4 was dissolved in Novec 7300 (3M Corporation, methyl perfluorohexyl ether) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0480] [Example 13]

[0481] The compound represented by formula (6-D) obtained in Synthesis Example 6 was dissolved in Asahiklin AC-6000 (manufactured by AGC, tridecylfluorooctane) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0482] [Comparative Example 3]

[0483] The above compound (Y) was dissolved in Novec 7200 (3M Corporation, ethyl perfluorobutyl ether) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0484] [Comparative Example 4]

[0485] The above compound (Z) was dissolved in Novec 7200 (3M Corporation, ethyl perfluorobutyl ether) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0486] Preparation of surface treatment agent and formation of cured coating

[0487] Surface treatment agents were prepared according to the above examples and comparative examples. Each surface treatment agent was sprayed onto glass (Gorilla, Corning Incorporated), cured at 120°C for 30 minutes, and then cured at 25°C and 50% relative humidity for 12 hours, forming a cured coating with a thickness of 10 nm. Note that the film thickness was measured using a spectroscopic ellipsometer.

[0488] Evaluation of water repellency

[0489] [Evaluation of initial water repellency]

[0490] For the glass with the cured coating prepared above, the contact angle (hydrophobicity) of the cured coating 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%). The results (initial water contact angle) are shown in Table 2.

[0491] In the initial stages, both the examples and comparative examples showed good water repellency.

[0492] [Evaluation of abrasion resistance]

[0493] For the glass with the cured coating prepared above, a friction testing machine (manufactured by Shin-Tung Science & Technology Co., Ltd.) was used. After friction under the following conditions, the contact angle (water repellency) of the cured coating to water was measured using the same method as described above, as an evaluation of abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. The results (water contact angle after abrasion) are shown in Table 2.

[0494] Dry eraser abrasion resistance

[0495] Eraser: Raber Eraser (Made by Minoan)

[0496] Contact area: 6mmΦ

[0497] Travel distance (one way): 60mm

[0498] Movement speed: 3,600 mm / min

[0499] Load: 1 kgf / 1 cm 2

[0500] Number of friction cycles: 5,000

[0501] Abrasion resistance of wet erasers

[0502] Eraser: Raber Eraser (Made by Minoan)

[0503] Contact area: 6mmΦ

[0504] Travel distance (one way): 20mm

[0505] Movement speed: 1,600 mm / min

[0506] Load: 1 kgf / 1 cm 2

[0507] Ethanol spray rate: 0.3 ml / min

[0508] Number of friction cycles: 10,000

[0509] The surface treatment agents of Examples 10-13 exhibited high dry eraser abrasion durability and wet eraser abrasion durability, similar to those used in vapor deposition coating. The surface treatment agent of Comparative Example 3 showed low eraser abrasion durability and low steel wool abrasion durability. The surface treatment agent of Comparative Example 4 showed high dry eraser abrasion durability but low wet eraser abrasion durability. As described above, even with changes in the coating method, the surface treatment agents of the examples can maintain a high level of both dry and wet eraser abrasion durability.

[0510] [Table 2]

[0511]

Claims

1. The polymer containing a fluorinated polyether group represented by the following general formula (1), In the formula, Rf is a monovalent or divalent fluorinated polyether group, B is independently a single bond or a divalent organic group without fluorine atoms, E is independently a monovalent group having a urethane bond and a polyether chain, U is independently a single bond or a divalent organic group, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octvalent organic group, Y is independently a divalent hydrocarbon group that may have at least one of oxygen atoms, sulfur atoms, silicon atoms, and siloxane bonds, R is independently an alkyl or phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl or hydrolyzable group, n is independently an integer of 1 to 3 for each bonded silicon atom, m is independently an integer of 1 to 7, and α is 1 or 2.

2. The polymer containing fluorinated polyether groups according to claim 1, wherein, In formula (1), α is 1, and Rf is a group represented by the following general formula (2). In the formula, A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group with a terminal -CF3 group; W is a fluoroalkylene group containing one or more hydrogen atoms; d is an integer from 1 to 3 for each unit independently; p, q, r, s, t, u, and v are integers from 0 to 200; and the sum of p, q, r, s, t, u, and v is 3 to 200. These units can be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be randomly bonded.

3. The polymer containing fluorinated polyether groups according to claim 1, wherein, In formula (1), α is 2, and Rf is a group represented by the following general formula (3). In the formula, W is a fluorinated alkylene group containing one or more hydrogen atoms, d is an integer from 1 to 3 for each unit independently, p, q, r, s, t, u, and v are integers from 0 to 200, and the sum of p, q, r, s, t, u, and v is 3 to 200. These units can be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be randomly bonded.

4. The polymer containing fluorinated polyether groups according to claim 1, wherein, In the above formula (1), E is a group represented by the following general formula (4). In the formula, W' is a single bond, or X' or a divalent or trivalent group formed by X' and an oxygen atom, X' is a divalent or trivalent group containing a divalent hydrocarbon group with 1 to 20 carbon atoms that may have a carbamate bond, a urea bond, a silicon atom, a siloxane bond, a silanediol structure or a silanediol structure, L is independently an alkylene group with 1 to 4 carbon atoms, k is an integer from 1 to 20, R' is an alkyl or phenyl group with 1 to 4 carbon atoms, and z is 1 or 2.

5. The polymer containing a fluorinated polyether group according to claim 1, wherein, In the formula (1), Y is a group selected from the following: an alkylene group containing 1 to 10 carbon atoms that may contain oxygen or sulfur atoms; an alkylene group containing 6 to 8 arylene atoms that contains 1 to 10 carbon atoms; a divalent group formed by bonding alkylene groups of 1 to 10 carbon atoms to each other via a diorganosilylene, silaneylene, or silaneylene structure; and a divalent group having an alkylene group of 1 to 10 carbon atoms bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue containing 2 to 10 silicon atoms.

6. The polymer containing a fluorinated polyether group according to claim 1, wherein, In the formula (1), B is a single bond or a divalent group that does not contain fluorine atoms and may contain at least one of oxygen atoms, sulfur atoms, secondary amines, tertiary amines, ketones, amides and esters. The divalent group is selected from: alkylene groups with 1 to 10 carbon atoms, alkylene groups with 1 to 10 carbon atoms containing 6 to 8 aryl groups, divalent groups formed by bonding alkylene groups with 1 to 10 carbon atoms to each other via diorganosilyl, silaneylene or silaneylene structures, divalent groups with alkylene groups having 1 to 10 carbon atoms bonded to the bonding ends of linear or branched or cyclic organopolysiloxane residues with 2 to 10 silicon atoms, and carbonyl groups.

7. The polymer containing a fluorinated polyether group according to claim 1, wherein, In the formula (1), U is a single bond or a group selected from the following: an alkylene group containing 1 to 10 carbon atoms that may contain oxygen or sulfur atoms; an alkylene group containing 6 to 8 carbon atoms that contains 1 to 10 carbon atoms; a divalent group formed by bonding alkylene groups of 1 to 10 carbon atoms to each other via a diorganosilyl, silaneylene, or silaneylene structure; and a divalent group having an alkylene group of 1 to 10 carbon atoms bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue containing 2 to 10 silicon atoms.

8. The polymer containing a fluorinated polyether group according to claim 1, wherein, In the formula (1), Z is selected from: single bond, carbon atom, silicon atom, nitrogen atom, -CH=, and 3-6 valent organopolysiloxane residues with 2 to 10 silicon atoms in a straight chain or with 3 to 10 silicon atoms in a branched chain or cyclic structure.

9. The polymer containing a fluorinated polyether group according to claim 1, wherein, In the formula (1), X is selected from: hydroxyl, alkoxy group with 1 to 10 carbon atoms, alkoxy group with 2 to 10 carbon atoms, acyloxy group with 1 to 10 carbon atoms, olefinic group with 2 to 10 carbon atoms and halogen group.

10. The polymer containing a fluorinated polyether group according to claim 1, wherein, The polymer containing fluorinated polyether groups represented by formula (1) can be represented by any of the following formulas. In the formula, p1, q1, r1, and s1 are integers from 1 to 200. The sum of p1, q1, r1, and s1 in each formula is from 3 to 200. The units shown in the parentheses containing p1, q1, r1, and s1 can be randomly bonded. k is an integer from 1 to 20.

11. A surface treatment agent comprising a polymer containing a fluorinated polyether group and / or a portion thereof (hydrolyzed) condensate, characterized in that, It is a surface treatment agent comprising a polymer containing a fluorinated polyether group having two or more hydroxysilyl or hydrolyzable silyl groups and / or a portion thereof (hydrolyzed) condensate, wherein the monovalent or divalent fluorinated polyether group in the polymer containing the fluorinated polyether group is bonded to the hydroxysilyl or hydrolyzable silyl group via a linker, wherein the linker has a tertiary carbon atom bonded with a monovalent group, and the monovalent group has a urethane bond and a polyether chain.

12. A surface treatment agent comprising a polymer containing a fluorinated polyether group according to any one of claims 1 to 10 and / or a portion thereof (hydrolyzed) condensate.

13. An article having been surface-treated with the surface treatment agent according to claim 12.

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