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

Abstract

A surface treatment agent comprising a fluoropolyether group-containing polymer represented by formula (1) and / or a partial (hydrolysis) condensate thereof can form a cured coating film having excellent water and oil repellency, steel wool wear resistance, and rubber wear resistance. (Rf is a monovalent or divalent fluoropolyether group, B is a single bond or a divalent organic group not containing F, E is a monovalent group having an oxyalkylene group, T is a single bond or a divalent organic group, U is a single bond, C, Si, N, or a 3-4-valent organic group, V is a single bond or a divalent organic group, Z is a single bond or a 3-8-valent organic group, Y is a divalent hydrocarbon group optionally having O, S, Si, or a siloxane bond, R is an alkyl group or a phenyl group, and X is a hydrogen atom or a hydrogen atom. X represents a hydroxyl group or a hydrolyzable group, n is 1-3, m is 1-7, beta is 1-3, and alpha 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 that can form films with excellent water and oil repellency and abrasion resistance, and 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 panels in displays, spearheaded by smartphones, has accelerated. However, touch panels expose the screen, leading to frequent direct contact with fingers, cheeks, and other skin types, making them prone to accumulating dirt and sebum. Therefore, the demand for technologies that improve appearance and visibility, making the display surface resistant to fingerprints and easy to remove dirt, has increased year by year, leading to a desire to develop materials that meet these requirements. In particular, the surface of touch panel displays is prone to fingerprints and dirt, thus requiring water- and oil-repellent coatings. However, while existing water- and oil-repellent coatings offer high water and oil repellency and excellent dirt removal, their anti-fouling performance deteriorates during use.

[0003] Generally, compounds containing fluorinated polyether groups possess properties such as water and oil repellency, chemical resistance, lubricity, mold release properties, and stain resistance due to their very low surface free energy. Utilizing these properties, they are widely used in paper industry. Water- and oil-repellent and stain-resistant agents for fibers, lubricants for magnetic recording media, oil-repellent agents for precision equipment, mold release agents, cosmetics, and protective films, etc. However, their properties also mean that they are non-adhesive and non-adhesive to other substrates. Even if they can be coated on the surface of the substrate, it is difficult to make the film adhere tightly.

[0004] On the other hand, silane coupling agents, as substances that bond organic compounds to the surface of substrates such as glass and cloth, are widely used as coating agents for various substrate surfaces. Each silane coupling agent contains an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group). The hydrolyzable silyl group forms a coating film through a self-condensation reaction induced by moisture in the air. This coating film is formed by the chemical bonding between the hydrolyzable silyl group and the surface of glass, metal, etc. They are physically bonded together to form a durable and strong coating.

[0005] Therefore, compositions that readily adhere to a substrate surface and form a coating on the substrate surface with properties such as water and oil repellency, chemical resistance, lubricity, mold release properties, and antifouling properties by using a polymer containing a fluorinated polyether group to introduce a hydrolyzable silyl group into a compound containing a fluorinated polyether group are disclosed (Patent Documents 1-6: Japanese Patent Publication No. 2008-534696, Japanese Patent 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] While cured coatings for lenses, antireflective films, etc., treated with a composition containing a fluorinated polyether group-containing polymer with hydrolyzable silyl groups introduced into the fluorinated polyether group exhibit excellent sliding and release properties and excellent wear resistance against steel wool, their performance is not fully realized, especially in terms of wear resistance against rubber.

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

[0008] While cured coatings for lenses, antireflective films, etc., treated with a composition containing a fluorinated polyether group-introduced polyether group in a fluorinated polyether group-containing polymer exhibit excellent wear durability against rubber, they do not fully demonstrate their performance in terms of wear durability against steel wool, requiring a balance between the wear durability of both rubber and steel wool.

[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: 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-mentioned actual situation, and aims to provide a fluorinated polyether-based polymer capable of forming a cured film with excellent water and oil repellency, resistance to steel wool abrasion and rubber abrasion, a surface treatment agent containing 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 achieve the above objectives, the inventors conducted in-depth research and found that: in the above-mentioned polymers containing fluorinated polyether groups, by using a polymer containing fluorinated polyether groups with hydroxyl or hydrolytic groups and polyether groups represented by general formula (1) as described below, a surface treatment agent containing the polymer and / or a portion thereof (hydrolyzed) condensate can form a cured film with excellent water and oil repellency, resistance to steel wool abrasion and rubber abrasion, thus completing the present invention.

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

[0023] [1] A polymer containing a fluorinated polyether group and having a hydroxyl or hydrolyzable group and a polyether group, 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 with an oxoalkylene group, T is independently a single bond or a divalent organic group, U is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, V is independently a single bond or a divalent organic group, Z is independently a single bond or a trivalent to octvalent organic group, Y is independently a divalent hydrocarbon group that may have at least one selected from oxygen atom, sulfur atom, silicon atom and siloxane bond, R is independently an alkyl or phenyl group with 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, β is independently an integer of 1 to 3, and α is 1 or 2.

[0026] [2] According to [1], the polymer containing fluorinated polyether groups, wherein α in 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 with a terminal -CF3 group; W is a fluoroalkylene group containing one or more hydrogen atoms; d is an integer from 1 to 3 in each unit independently; p, q, r, s, t, u, and v are each 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 containing p, q, r, s, t, u, and v can be randomly combined.

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

[0030]

[0031] In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is an integer from 1 to 3 in each unit independently, p, q, r, s, t, u, and v are each an integer 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 containing p, q, r, s, t, u, and v can be randomly combined.

[0032] [4] The polymer containing a fluorinated polyether group according to any one of [1] to [3], wherein, in the formula (1), Y is a group selected from alkylene groups of 1 to 10 carbon atoms that may contain oxygen atoms or sulfur atoms, alkylene groups of 1 to 10 carbon atoms that contain arylene groups of 6 to 8 carbon atoms, alkylene groups of 1 to 10 carbon atoms that are interposed between two organomymethylene silanes, silane alkylene structures or silane arylene structures, and divalent groups that have alkylene groups of 1 to 10 carbon atoms attached to the binding end of a linear or branched or cyclic organopolysiloxane residue of 2 to 10 silicon atoms.

[0033] [5] A polymer containing a fluorinated polyether group according to any one of [1] to [4], wherein, in the formula (1), B is a single bond, or a divalent group selected from alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing arylene groups having 6 to 8 carbon atoms, alkylene groups having 1 to 10 carbon atoms interposed of two organomycyl groups, silaneylene structures or silaneylene structures, and a divalent group having a alkylene group having 1 to 10 carbon atoms attached to the binding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms, a carbonyl group, and an amide group having at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

[0034] [6] A polymer containing a fluorinated polyether group according to any one of [1] to [5], wherein, in the formula (1), T is a single bond, or a divalent group selected from alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing arylene groups having 6 to 8 carbon atoms, alkylene groups having 1 to 10 carbon atoms interposed of two organomycyl groups, silaneylene structures or silaneylene structures, and a divalent group having alkylene groups having 1 to 10 carbon atoms attached to the binding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms, a carbonyl group, and an amide group having at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

[0035] [7] The polymer containing a fluorinated polyether group according to any one of [1] to [6], wherein, in the formula (1), U is selected from single bond, carbon atom, silicon atom, nitrogen atom, -CH=, and -Si(CH3)=.

[0036] [8] A polymer containing a fluorinated polyether group according to any one of [1] to [7], wherein, in the formula (1), Z is a single bond, or a linear or branched or cyclic organopolysiloxane residue with 2 to 10 silicon atoms in a straight chain or with 3 to 10 silicon atoms in a cyclic manner, in which Z is a single bond or a cyclic organopolysiloxane residue with 3 to 6 valences.

[0037] [9] A polymer containing a fluorinated polyether group according to any one of [1] to [8], wherein, in the formula (1), X is selected from hydroxyl, alkoxy group with 1 to 10 carbon atoms, alkoxy-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.

[0038]

[10] The polymer containing a fluorinated polyether group according to any one of [1] to [9], wherein, in the formula (1), m is an integer from 1 to 3.

[0039]

[11] A polymer containing a fluorinated polyether group according to any one of [1] to

[10] , wherein β is 2 or 3 in the formula (1).

[0040]

[12] The polymer containing a fluorinated polyether group according to any one of [1] to

[11] , 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]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063] In the formula, p1, q1, and s1 are each integers from 1 to 200. However, the sum of p1, q1, and s1 in each formula is 3 to 200. r1 and r2 are each integers from 3 to 200. The repeating units shown in the parentheses containing p1, q1, and s1 can be combined randomly. k is an integer from 1 to 30.

[0064]

[13] A surface treatment agent comprising a polymer containing a fluorinated polyether group and / or a portion thereof having a hydroxyl or hydrolyzable group and a polyether group according to any one of [1] to

[12] .

[0065]

[14] Articles that have been surface-treated with the surface treatment agent according to

[13] .

[0066] The effects of the invention

[0067] The polymer of the present invention, which contains hydroxyl or hydrolyzable groups and polyether groups on secondary carbon, has polyether groups on secondary carbon in a prescribed structure, thereby making the polyether molecules more mobile during wear and improving wear durability. As a result, articles surface-treated with a surface treatment agent containing the polymer and / or a portion thereof (hydrolyzed) condensate have excellent water and oil repellency, resistance to steel wool abrasion and rubber abrasion. Detailed Implementation

[0068] The fluorinated polyether polymer of the present invention having a monovalent or divalent fluorinated polyether group and a reactive functional group in the molecule and having a polyether group on the secondary carbon is a fluorinated polyether polymer having a hydroxyl or hydrolytic group and a polyether group represented by the following general formula (1).

[0069]

[0070] (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 with an oxoalkylene group, T is independently a single bond or a divalent organic group, U is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, V is independently a single bond or a divalent organic group, Z is independently a single bond or a trivalent to octvalent organic group, Y is independently a divalent hydrocarbon group that may have at least one selected from oxygen atom, sulfur atom, silicon atom and siloxane bond, R is independently an alkyl or phenyl group with 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, β is independently an integer of 1 to 3, and α is 1 or 2.)

[0071] The present invention relates to a polymer containing fluorinated polyether groups, having hydroxyl or hydrolyzable groups and polyether groups on a secondary carbon atom, comprising a monovalent fluorooxyalkylene or divalent fluorooxyalkylene (i.e., a monovalent or divalent fluoropolyether group) bonded to a hydrolyzable silylene such as an alkoxysilylene or a hydroxyl-containing silylene via a linker group. The invention is characterized by having polyether groups on the secondary carbon atom in a predetermined structure, thereby facilitating the movement of polyether molecules during wear, improving wear durability, and resulting in a cured film with excellent water and oil repellency, resistance to steel wool abrasion, and resistance to rubber abrasion.

[0072] In the above formula (1), 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).

[0073]

[0074] (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 independently in each unit, p, q, r, s, t, u, and v are each an integer 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 containing p, q, r, s, t, u, and v can be randomly combined.)

[0075] 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.

[0076] In equations (2) and (3) above, W is a fluoroalkyl group containing one or more hydrogen atoms, such as CF2, C2F4, C3F6, C4F8, and C5F6 units. 10 Unit, C6F 12 Groups in which one or two fluorine atoms in each perfluoroalkylene group are replaced by hydrogen atoms, etc.

[0077] In the above equations (2) and (3), d is an integer from 1 to 3 independently in each unit, preferably 1 or 2.

[0078] Furthermore, p, q, r, s, t, u, and v are each integers from 0 to 200, preferably integers from 0 to 100, and the sum of p, q, r, s, t, u, and v is 3 to 200, preferably 10 to 100. If the sum 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; if it is greater than the lower limit mentioned above, the characteristics of the fluoropolyether group can be fully utilized, and therefore this is preferred.

[0079] Furthermore, when r, s, t, u, and v are all 0, it is preferable that p and q are each integers from 5 to 100, and the sum of p and q is from 10 to 105, specifically from 15 to 60.

[0080] In equations (2) and (3) above, each unit can be either a straight chain or a branch. In addition, the repeating units shown in parentheses containing p, q, r, s, t, u, and v can be combined randomly.

[0081] Specifically, Rf can be exemplified by the following groups.

[0082]

[0083]

[0084]

[0085] (In the formula, p', q', r', s', t', and u' are each integers greater than or equal to 1, with the same upper limit as the upper limit of p, q, r, s, t, and u. The sum of these p', q', r', s', t', and u' is 3 to 200. r2' and r3' are each 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 the parentheses containing p', q', r', s', t', and u' can be combined randomly.)

[0086] In the above formula (1), B is independently a single bond or a divalent organic group without fluorine atoms. The divalent organic group is selected from alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing arylene groups having 6 to 8 carbon atoms (e.g., alkylene-arylene groups having 7 to 18 carbon atoms), divalent groups having alkylene groups having 1 to 10 carbon atoms bonded to each other by 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 binding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms, carbonyl groups, and amide groups. The divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

[0087] Among them, the groups bonded to silicon atoms, such as diorganosilyl groups, silanediyl groups, silanediyl groups, and organopolysiloxane residues, are preferably alkyl groups such as methyl, ethyl, propyl, and butyl, or phenyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkyl group in the silanediyl group is preferably ethylene, propylene (trimethylene, methyl ethylene), or butylene (tetramethylene, methyl propyleneene), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0088] Examples of such a B group include the following groups. Furthermore, in the following structures, it is preferable that the left-hand bonding end is bonded to Rf and the right-hand bonding end is bonded to a carbon atom.

[0089]

[0090]

[0091]

[0092] (In the formula, f is an integer from 2 to 4, a, a', and b are each an integer from 1 to 4, c is an integer from 1 to 10, and e is an integer from 1 to 9.)

[0093] In the above formula (1), E is independently a monovalent group having an oxoalkylene group, which can be represented by the following general formula (4).

[0094] -OQ(-(LO)) k -R') g (4)

[0095] In formula (4) above, Q is a single bond, G, or a divalent or trivalent group as a combination of G and an oxygen atom. G is a divalent or trivalent group containing an amide, or a divalent hydrocarbon group with 1 to 20 carbon atoms that may have an amide, silicon atom, siloxane bond, silanediol structure, or 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 have hydroxyl or hydrolyzable groups. In addition, the alkylene group in the silanediol structure preferably has 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as ethylene, propylene (trimethylene, methyl ethylene), butylene (tetramethylene, methyl propyleneene), etc. Furthermore, when Q is a single bond, B or U is preferably a group other than a single bond, and U is particularly preferably a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group.

[0096] Examples of such groups as Q include the following groups.

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103] (In the formula, e is an integer from 1 to 9.)

[0104] In the above formula (4), L is independently an alkylene group having 1 to 4 carbon atoms, such as methylene, ethylene, propylene, or butylene, with ethylene being preferred. These groups may be single groups or a mixture of groups.

[0105] In the above formula (4), k is an integer from 1 to 30, preferably an integer from 1 to 20, and more preferably an integer from 3 to 12.

[0106] In the above formula (4), R' is an alkyl group with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, or phenyl, wherein methyl is preferred.

[0107] In the above formula (4), g is 1 or 2, preferably 1.

[0108] Examples of such groups as E include the following.

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] (In the formula, k is the same as above, k1 and k2 are each integers greater than or equal to 1, k1+k2 is an integer from 2 to 30, and e is an integer from 1 to 9.)

[0118] In the above formula (1), T is independently a single bond or a divalent organic group. The divalent organic group is selected from alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing arylene groups having 6 to 8 carbon atoms (e.g., alkylene-arylene groups having 7 to 18 carbon atoms), divalent groups having alkylene groups having 1 to 10 carbon atoms interposed by diorganosilyl, silaneylene, or silaneylene structures, and divalent groups having alkylene groups having 1 to 10 carbon atoms attached to the binding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms, carbonyl groups, and amide groups. The divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

[0119] Furthermore, T is preferably a single bond when U is a single bond.

[0120] Among them, the groups bonded to silicon atoms, such as diorganosilyl groups, silanediyl groups, silanediyl groups, and organopolysiloxane residues, are preferably alkyl groups such as methyl, ethyl, propyl, and butyl, or phenyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkyl group in the silanediyl group is preferably ethylene, propylene (trimethylene, methyl ethylene), or butylene (tetramethylene, methyl propyleneene), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0121] In addition to single bonds, such T groups can be exemplified by the following groups. Furthermore, in the following structures, it is preferable that the left-hand bonding end is bonded to a carbon atom and the right-hand bonding end is bonded to U.

[0122]

[0123]

[0124]

[0125]

[0126] (In the formula, f is an integer from 2 to 4, a, a', and b are each an integer from 1 to 4, c is an integer from 1 to 10, and e is an integer from 1 to 9.)

[0127] In the above formula (1), U is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group. As a trivalent or tetravalent organic group, it is preferably -CH= or -Si(CH3)=.

[0128] In addition to single bonds, such U can be represented by groups as shown below. Furthermore, in the structure described below, it is preferred that the left-hand binding end is bound to T, and the other binding ends are bound to V.

[0129]

[0130] In the above formula (1), V is independently a single bond or a divalent organic group. The divalent organic group is preferably an alkylene group with 1 to 10 carbon atoms or an alkylene group with 1 to 10 carbon atoms containing an arylene group with 6 to 8 carbon atoms (e.g., an alkylene-arylene group with 7 to 18 carbon atoms). The divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

[0131] Furthermore, V is preferably a single bond when Z is a single bond.

[0132] In addition to single bonds, such a V group can include, for example, the following groups. Furthermore, in the following structure, it is preferred that the left-hand binding end is bound to U and the right-hand binding end is bound to Z.

[0133]

[0134] (In the formula, a, a', and b are each integers from 1 to 4, and c is an integer from 1 to 10.)

[0135] In formula (1) above, Z is independently a single bond or a 3- to 8-valent organic group. Preferably, the 3- to 8-valent organic group is a linear chain with 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic 3- to 6-valent organopolysiloxane residue with 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms. Furthermore, this organopolysiloxane residue may contain a silaneide structure, i.e., Si-(CH2), in which two silicon atoms are bonded by an alkylene group. x -Si (in the above formula, x is an integer from 2 to 6).

[0136] The organopolysiloxane residues preferably have alkyl groups such as methyl, ethyl, propyl, butyl, or phenyl with 1 to 8 carbon atoms, more preferably 1 to 4.

[0137] In addition to single bonds, the following groups can be listed as Z. Furthermore, in the following structures, it is preferred that the left-hand binding end is bonded to V, and the other binding ends are bonded to Y.

[0138]

[0139] In formula (1) above, Y is independently a divalent hydrocarbon group having at least one selected from oxygen atom, sulfur atom, silicon atom, and siloxane bond, preferably having 1 to 20 carbon atoms. Specifically, this divalent hydrocarbon group is selected from 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 having alkylene groups having 1 to 10 carbon atoms bonded to each other by 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 binding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms.

[0140] Among them, the groups bonded to silicon atoms, such as diorganosilyl groups, silanediyl groups, silanediyl groups, and organopolysiloxane residues, are preferably alkyl groups such as methyl, ethyl, propyl, and butyl, or phenyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkyl group in the silanediyl group is preferably ethylene, propylene (trimethylene, methyl ethylene), or butylene (tetramethylene, methyl propyleneene), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0141] Examples of such a Y group include the following groups. Furthermore, in the following structure, it is preferable that the left-hand bonding end is bonded to Z and the right-hand bonding end is bonded to Si.

[0142]

[0143]

[0144]

[0145] (In the formula, f is an integer from 2 to 4, a and b are each integers from 1 to 4, b' and c are each integers from 1 to 10, and e is an integer from 1 to 9.)

[0146] 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., with methyl being preferred.

[0147] In formula (1) above, X is independently a hydroxyl group or a hydrolyzable group. Examples of such X include hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc., which have 1 to 10 carbon atoms; methoxymethoxy, methoxyethoxy, etc., which have 2 to 10 carbon atoms; acetoxy, etc., which have 1 to 10 carbon atoms; alkenoxy, etc., which have 2 to 10 carbon atoms; chloro, bromo, iodo, etc., etc. Among these, methoxy, ethoxy, isopropoxy, and chloro are preferred.

[0148] In the above formula (1), n ​​is an integer from 1 to 3 for each bonded silicon atom, preferably 3. m is an integer from 1 to 7, preferably 1 to 3. β is an integer from 1 to 3, preferably 2 or 3, and α is 1 or 2.

[0149] As for the structure of a fluorinated polyether polymer having hydroxyl or hydrolyzable groups and polyether groups as represented by the above formula (1), the following structures can be listed. By changing the combination of Rf, B, E, T, U, V, Z, Y, R, X, and n in the above formula (1), several fluorinated polyether polymers having hydroxyl or hydrolyzable groups and polyether groups can be obtained.

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171] (In the formula, k is the same as above. p1, q1, and s1 are each integers from 1 to 200, however, the sum of p1, q1, and s1 in each formula is from 3 to 200. r1 and r2 are each integers from 3 to 200. The repeating units shown in parentheses with p1, q1, and s1 can be combined randomly.)

[0172] Methods for preparing a polymer containing a fluoropolyether group having hydroxyl or hydrolyzable groups and a polyether group, as represented by the above formula (1), in the case where α is 1 (i.e., Rf is a 1-valent fluoropolyether group) or in the case where α is 2 (i.e., Rf is a 2-valent fluoropolyether group), can be exemplified by the following methods.

[0173] A polymer containing a fluorinated polyether group, having one or more polyether groups and 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 fluorinated solvent 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 toluene solution of a hydrosilylation catalyst such as a chloroplatinic acid / vinylsiloxane complex. Furthermore, when using a halogenated (organo)silane compound containing a SiH group, such as trichlorosilane, the substituent (halogen atom) on the silyl group can be replaced with other hydrolyzable groups such as alkoxy groups such as methoxy groups. In addition, organosilicon compounds with SiH groups and hydroxyl or hydrolyzable groups in the above molecules can also be produced by using two different compounds, in which case they can be manufactured by staged addition.

[0174] In the preparation of a fluorinated polyether group polymer having hydroxyl or hydrolyzable groups and polyether groups as represented by formula (1), a fluorinated polyether group polymer having one or more polyether groups and olefin sites at one end or both ends of the molecular chain can be exemplified by a polymer containing a fluorinated polyether group represented by the following general formula (5).

[0175]

[0176] (In the formula, Rf, B, E, T, U, V, Z, α, β, m are the same as above, and Y' is independently a single bond, or may have a divalent hydrocarbon group selected from at least one of oxygen atom, sulfur atom, silicon atom and siloxane bond.)

[0177] In formula (5) above, Y' is independently a single bond, or a divalent hydrocarbon group preferably having 1 to 18 carbon atoms, which may have at least one selected from oxygen atom, sulfur atom, silicon atom, and siloxane bond. Specifically, this divalent hydrocarbon group is selected from alkylene groups having 1 to 8 carbon atoms that may contain oxygen or sulfur atoms, alkylene groups having 1 to 8 carbon atoms that contain 6 to 8 carbon atoms (e.g., alkylene-arylene groups having 7 to 16 carbon atoms), divalent groups consisting of alkylene groups having 1 to 10 carbon atoms combined with diorganosilylene, silaneylene structures, or silaneylene structures, and divalent groups consisting of alkylene groups having 1 to 8 carbon atoms bonded to the binding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms. As Y', a linear alkylene group having 1 to 6 carbon atoms is preferred.

[0178] As a method for preparing the polymer containing fluorinated polyether groups represented by the above formula (5), the following methods can be listed as an example.

[0179] For the following general formula (6)

[0180]

[0181] (In the formula, Rf, B, T, U, V, Z, Y', α, β, and m are the same as above.)

[0182] The polymer containing fluorinated polyether groups having hydroxyl and olefin sites at the ends of the molecular chain, and the polyether-based initiator, are cured in the presence of an alkali, with additives and solvents to improve reactivity as needed, at a temperature of 0–90°C, preferably 40–60°C, more preferably 50–60°C, for 1–48 hours, preferably 10–40 hours, more preferably 20–30 hours.

[0183] Among them, the following polymers can be listed as polymers containing fluorinated polyether groups that have hydroxyl and olefin sites at the ends of the molecular chain, as represented by the above formula (6).

[0184]

[0185]

[0186]

[0187] (In the formula, the sums of k, p1, q1, r1, s1, and p1, q1, and s1 in each formula are the same as above. In addition, the repeated units shown in parentheses containing p1, q1, and s1 can be combined randomly.)

[0188] As a polyether-based initiator that reacts with a fluorinated polyether group containing hydroxyl and olefinic sites at the end of the molecular chain, as represented by the above formula (6), the following compounds can be listed as examples.

[0189]

[0190] (In the formula, k, k1, and k2 are the same as above, and R” is an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms, such as a phenyl group, that can be substituted with fluorine.)

[0191] The amount of polyether-based initiator used can be 1 to 15 equivalents, more preferably 3 to 6 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl) of the polymer containing fluorinated polyether groups having hydroxyl and olefinic sites at the end of the molecular chain as represented by formula (6).

[0192] As the base used in the reaction of a polymer containing fluorinated polyether groups with hydroxyl and olefinic sites at the molecular chain ends, as represented by the above formula (6), with a polyether-based initiator, amines, alkali metal bases, etc., can be used, specifically, among amines, triethylamine, diisopropylethylamine, pyridine, DBU, imidazole, etc. Among alkali metal bases, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, potassium tert-butoxy, lithium diisopropylamine, lithium bis(trimethylsilyl)amino, sodium bis(trimethylsilyl)amino, potassium bis(trimethylsilyl)amino, etc.

[0193] The amount of alkali used can be 1 to 20 equivalents relative to 1 equivalent of the reactive terminal group (hydroxyl) of the polymer containing fluorinated polyether groups having hydroxyl and olefinic sites at the end of the molecular chain, as represented by formula (6), more preferably 4 to 8 equivalents, and even more preferably 5 to 7 equivalents.

[0194] In the reaction of a polymer containing fluorinated polyether groups with hydroxyl and olefinic sites at the molecular chain ends, as represented by formula (6) above, with a polyether-based induction agent, tetrabutylammonium halide, alkali metal halides, etc., can be used as additives to improve reactivity. Specifically, examples of additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, crown ethers, etc. These additives improve reactivity by catalytically exchanging halogens with the polyether-based induction agent in the reaction system. Furthermore, crown ethers improve reactivity by coordinating with metals.

[0195] The amount of additive used is 0.005 to 0.1 equivalents relative to the reactive terminal group (hydroxyl) of the polymer containing fluorinated polyether groups having hydroxyl and olefinic sites at the end of the molecular chain, as represented by formula (6), more preferably 0.01 to 0.05 equivalents, and even more preferably 0.015 to 0.03 equivalents.

[0196] In the reaction of a polymer containing fluorinated polyether groups with hydroxyl and olefinic sites at the ends of the molecular chain, as represented by the above formula (6), with a polyether-based introducing agent, a solvent can be used. The use of a solvent is not necessarily required. 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 Corporation, trade name: Novec series), and perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M Corporation, trade name: Fluorine series). Furthermore, as organic solvents, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, THF, etc., can be used.

[0197] When using solvent, the amount used is 10 to 300 parts by mass relative to 100 parts by mass of the fluorinated polyether group-containing polymer having hydroxyl and olefinic sites at the molecular chain end as represented by formula (6), preferably 30 to 150 parts by mass, more preferably 50 to 100 parts by mass.

[0198] 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 to remove the solvent, thereby obtaining the polymer containing fluorinated polyether groups represented by the above formula (5).

[0199] In addition, as another method for preparing the polymer containing fluorinated polyether groups represented by the above formula (5), for example, for the polymer containing fluorinated polyether groups with hydroxyl and olefin sites at the end of the molecular chain represented by the above formula (6) and the organosilicon compound having two or more SiH groups without hydrolyzable end groups in the molecule, in the presence of a dehydrogenation catalyst, a solvent is used as needed, and a dehydrogenation reaction is carried out at a temperature of 0 to 60°C, preferably 15 to 35°C, more preferably 20 to 30°C, for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably 1 to 1.5 hours, to obtain the polymer containing fluorinated polyether groups with SiH groups and olefin sites at the end of the molecular chain.

[0200] Next, the polymers containing fluorinated polyether groups with SiH groups and olefin sites at the ends of the molecular chains and the polyether compounds with olefin sites in the molecules (such as polyoxyethylene compounds with single-terminal olefin oxides at the ends of the molecular chains) are dissolved in a solvent such as 1,3-bis(trifluoromethyl)benzene and a fluorinated solvent. In the presence of a toluene solution of a hydrogenation silylation catalyst such as chloroplatinic acid / vinylsiloxane complex, the mixture is 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.

[0201] Among them, the organosilicon compound having no hydrolytic end groups and having two or more SiH groups in the molecule, which is the polymer containing fluorinated polyether groups with hydroxyl and olefin sites at the end of the molecular chain obtained by formula (6) above, is preferably represented by the following formula when reacting with an organosilicon compound having two or more SiH groups without hydrolytic end groups in the molecule.

[0202]

[0203] (In the formula, f and e are the same as above.)

[0204] Examples of organosilicon compounds that do not have hydrolyzable end groups in their molecules and have two or more SiH groups include the organosilicon compounds shown below.

[0205]

[0206] When the polymer containing fluorinated polyether groups with hydroxyl and olefinic sites at the end of the molecular chain shown in formula (6) reacts with an organosilicon compound having two or more SiH groups but no hydrolyzable end groups in the molecule, the amount of the organosilicon compound having two or more SiH groups but no hydrolyzable end 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 1 equivalent of the reactive end group (hydroxyl) of the polymer containing fluorinated polyether groups with hydroxyl and olefinic sites at the end of the molecular chain.

[0207] As a dehydrogenation catalyst used in the reaction of a polymer containing fluorinated polyether groups with hydroxyl and olefinic sites at the ends of the molecular chain as shown in formula (6) above with an organosilicon compound having two or more SiH groups but no hydrolyzable end groups in the molecule, for example, platinum group metal catalysts such as rhodium, palladium, and ruthenium, and boron catalysts can be used. Specifically, platinum group metal catalysts such as tetra(triphenylphosphine)palladium and trichloro(triphenylphosphine)rhodium, and boron catalysts such as tri(pentafluorophenyl)borane can be listed.

[0208] The amount of dehydrogenation catalyst used is 0.0005 to 0.01 equivalents relative to the reactive terminal group (hydroxyl) of the polymer containing fluorinated polyether groups with hydroxyl and olefin sites at the molecular chain end as shown in formula (6) above, more preferably 0.001 to 0.007 equivalents, and even more preferably 0.004 to 0.006 equivalents.

[0209] In another method of preparing the polymer containing fluorinated polyether groups as shown in formula (5) above, a solvent may be used. It is not necessary to use a solvent, and the same solvent as that shown in the method of preparing the polymer containing fluorinated polyether groups as shown in formula (5) above can be used.

[0210] When using solvent, the amount used is 10 to 300 parts by mass relative to 100 parts by mass of the fluorinated polyether group-containing polymer having hydroxyl and olefinic sites at the molecular chain end as represented by formula (6), preferably 30 to 150 parts by mass, more preferably 50 to 100 parts by mass.

[0211] After reacting the polymer containing fluorinated polyether groups with hydroxyl and olefinic sites at the molecular chain ends, as shown in formula (6), with an organosilicon compound having two or more SiH groups but no hydrolyzable terminal groups in the molecule, the aqueous layer and the fluorinated solvent layer are separated by a liquid-liquid separation operation. The obtained fluorinated solvent layer is further washed with an organic solvent to remove the solvent by distillation, thereby obtaining the polymer containing fluorinated polyether groups with SiH and olefinic sites at the molecular chain ends.

[0212] As a polyether compound having an olefinic site in its molecule, which is used to react the polymer containing fluorinated polyether groups with SiH groups and olefinic sites at the ends of the molecular chains obtained above with a polyether compound having an olefinic site in its molecule, examples of polyether compounds represented by the following formulas can be listed.

[0213]

[0214] (In the formula, L, R', and k are the same as above, and e' is an integer from 0 to 2.)

[0215] Specifically, examples include polyoxyethylene compounds with one end of the molecular chain capped with an allyloxy group and the other end capped with a methoxy group, such as polyoxyethylene.

[0216]

[0217] (In the formula, k is the same as above.)

[0218] Polyether compounds that have an olefin site in their molecules, such as polyoxyalkylene oxide-terminated polyoxyalkylene compounds with single-terminal olefin groups in their molecular chains, can be specifically exemplified by Uniox MA-200, Uniox MA-300, Uniox MA-350S, and Uniox MA-500 manufactured by Nippon Oil Company.

[0219] The amount of polyether compound having an olefin site in the molecule used is 1 to 10 equivalents relative to 1 equivalent of the reactive terminal group (SiH group) of the polymer containing fluorinated polyether group having SiH group and olefin site at the end of the molecular chain. More preferably, it is 2 to 5 equivalents, and even more preferably, it is 2.5 to 3.5 equivalents.

[0220] As catalysts for the hydrosilylation reaction of the polymer containing fluorinated polyether groups with SiH groups and olefin sites at the molecular chain ends obtained above, and the polyether compound with olefin sites in the molecule, examples include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, alkynyl 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.

[0221] The amount of the hydrogenation silylation catalyst used, relative to the mass of the polymer containing fluorinated polyether groups having SiH groups and olefin sites at the ends of the molecular chain, can be 0.1 to 100 ppm, more preferably 1 to 50 ppm, in transition metal conversion (mass).

[0222] 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 to remove the solvent by distillation, thereby obtaining the polymer containing fluorinated polyether groups represented by the above formula (5).

[0223] Furthermore, as another method for preparing the polymer containing fluorinated polyether groups represented by the above formula (5), for example, for the polymer containing fluorinated polyether groups with hydroxyl and olefin sites at the ends of the molecular chain represented by the above formula (6) and the polyether-based initiator containing isocyanate groups, in the presence of a catalyst, a solvent is used as needed to mature it 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.

[0224] Among them, the following compounds can be listed as polyether-based initiators containing isocyanate groups that react with polymers containing fluorinated polyether groups having hydroxyl and olefinic sites at the ends of the molecular chains represented by the above formula (6).

[0225]

[0226]

[0227]

[0228]

[0229] (In the formula, k and e are the same as above.)

[0230] The amount of the polyether-based initiator containing isocyanate groups used is 1 to 15 equivalents relative to the reactive terminal group (hydroxyl) of the fluorinated polyether-based polymer having hydroxyl and olefin sites at the end of the molecular chain as represented by formula (6), and more preferably 3 to 6 equivalents.

[0231] As catalysts used in the reaction of a polymer containing a fluorinated polyether group having hydroxyl and olefinic sites at the end of the molecular chain, as represented by the above formula (6), with a polyether-based initiator containing an isocyanate group, examples include 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 dimethoxydibutyltin and dibutyltin dilaurate; bismuth compounds such as tris(2-ethylhexanoate)bismuth; and amine catalysts such as diazabicycloundecene.

[0232] The amount of catalyst used is 0.01 to 100 parts by mass relative to 100 parts by mass of the polymer containing fluorinated polyether groups having hydroxyl and olefin sites at the molecular chain end as represented by the above formula (6), preferably 0.05 to 20 parts by mass.

[0233] In another method for preparing the polymer containing fluorinated polyether groups represented by formula (5) above, a solvent may be used. It is not necessary to use a solvent, but the same solvent as that exemplified in the method for preparing the polymer containing fluorinated polyether groups represented by formula (5) above can be used.

[0234] When using solvent, the amount used is 10 to 300 parts by mass relative to 100 parts by mass of the fluorinated polyether group-containing polymer having hydroxyl and olefinic sites at the molecular chain end as represented by formula (6), preferably 30 to 150 parts by mass, more preferably 50 to 100 parts by mass.

[0235] After the reaction is complete, the aqueous layer and the fluorinated solvent layer are separated by a liquid-liquid separation process. The obtained fluorinated solvent layer is further washed with an organic solvent to remove the solvent by distillation, thereby obtaining the polymer containing fluorinated polyether groups represented by the above formula (5).

[0236] As a polymer containing a fluorinated polyether group as represented by the above formula (5), the following polymers can be listed as examples.

[0237]

[0238]

[0239]

[0240] (In the formula, the sums of k, p1, q1, r1, s1, and p1, q1, and s1 in each formula are the same as above. In addition, the repeated units shown in parentheses containing p1, q1, and s1 can be combined randomly.)

[0241] In the preparation of a fluorinated polyether group polymer having hydroxyl or hydrolyzable groups and polyether groups as represented by formula (1), the organosilicon compound having SiH groups and hydrolyzable groups in the molecule is preferably a compound represented by the following general formulas (7) to (10).

[0242]

[0243] (In the formula, R, X, n, and e are the same as above. R) 1 R is independently an alkyl or phenyl group having 1 to 8 carbon atoms. 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 combined.

[0244] Among them, R1 It is an alkyl group such as methyl, ethyl, propyl, butyl, or phenyl, having 1 to 8 carbon atoms, preferably 1 to 4, among which methyl is preferred. R 1 They can be the same or different.

[0245] R 2 It is an alkylene group having 2 to 6 carbons, preferably 2 to 4 carbons, such as ethylene, propylene (trimethylene, methyl ethylene), butylene (tetramethylene, methyl propyleneene), or an arylene group having 6 to 8 carbons, such as phenylene. Among these, ethylene, trimethylene, and phenylene are preferred.

[0246] As R 3 The group has 2 to 8 carbon atoms, preferably 2 or 3 divalent hydrocarbon groups, and examples include methylene, ethylene, propylene (trimethylene, methyl ethylene), butylene (tetramethylene, methyl propyleneene), hexamethylene, octamethylene and other alkylene, phenylene and other arylene groups, or combinations of two or more of these groups (alkylene-arylene, etc.), among which ethylene and trimethylene are preferred.

[0247] Organosilicon compounds having SiH groups and hydroxyl or hydrolyzable groups in their molecules include, for example, the following organosilicon compounds: trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silane or siloxane compounds, and their (partial) hydrolysates.

[0248]

[0249]

[0250]

[0251] In the preparation of a fluorinated polyether group polymer having hydroxyl or hydrolyzable groups and polyether groups as represented by formula (1), when the fluorinated polyether group polymer having one or more polyether groups and olefin sites at one or both ends of the molecular chain reacts with an organosilicon compound having SiH groups and hydroxyl or hydrolyzable groups in the molecule, the amount of the organosilicon compound having SiH groups and hydroxyl or hydrolyzable groups in the molecule relative to 1 equivalent of the olefin site of the fluorinated polyether group polymer can be used in a manner that is 1 to 4 equivalents, more preferably 1.5 to 3 equivalents.

[0252] In the preparation of polymers containing fluorinated polyether groups, represented by formula (1), having hydroxyl or hydrolyzable groups and polyether groups, the following catalysts can be listed as catalysts for the hydrosilylation reaction: Platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, alkynyl 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.

[0253] The amount of the hydrogenation silanization catalyst used is 0.1 to 100 ppm, more preferably 1 to 50 ppm, relative to the mass of the fluorinated polyether polymer having one or more polyether groups and olefin sites at one or both ends of the molecular chain.

[0254] In the preparation of a fluorinated polyether polymer represented by formula (1) having hydroxyl or hydrolyzable groups and a polyether group, fluorinated solvents can be listed as solvents, for example. 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 Corporation, trade name: Novec series), and perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M Corporation, trade name: Florinator series), etc.

[0255] The amount of solvent used is 10 to 300 parts by weight, preferably 50 to 150 parts by weight, and more preferably 50 to 100 parts by weight, relative to 100 parts by weight of a fluorinated polyether polymer having one or more polyether groups and olefin sites at one or both ends of the molecular chain.

[0256] Furthermore, when using organosilicon compounds containing SiH groups and hydroxyl or hydrolyzable groups in the molecule, such as trichlorosilane, a halogenated (organosilicon) compound containing SiH groups can be used. Subsequently, the substituent (halogen atom) on the silane group can be replaced with other hydrolyzable groups such as alkoxy groups such as methoxy groups. As reagents that can be used to replace the substituent (halogen atom) on the silane group with other hydrolyzable groups, examples include alcohols with 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.

[0257] The amount used is 10 to 200 parts by mass relative to 100 parts by mass of the addition reaction product of a fluorinated polyether polymer having one or more polyether groups and an olefinic site at one or both ends of the molecular chain, and a halogenated (organo)silicon compound containing SiH groups. More preferably, it is 40 to 100 parts by mass, and even more preferably, it is 50 to 70 parts by mass.

[0258] After the reaction is complete, the solvent and unreacted substances are removed by vacuum distillation to obtain a fluorinated polyether polymer represented by the above formula (1) having hydroxyl or hydrolyzable groups and polyether groups.

[0259] As another method for preparing a polymer containing a fluoropolyether group having hydroxyl or hydrolyzable groups and a polyether group, represented by the above formula (1) in the case of α being 1 (i.e., Rf being a 1-valent fluoropolyether group) or α being 2 (i.e., Rf being a 2-valent fluoropolyether group), the following methods can be listed as an example.

[0260] A polymer containing fluorinated polyether groups (e.g., a polymer containing fluorinated polyether groups with one or more polyether groups and SiH groups at one or both ends of the molecular chain, or a polymer containing three polyether groups and SiH groups at one or both ends of the molecular chain), an organosilicon compound having an olefinic site and hydroxyl or hydrolyzable groups in the molecule, and a solvent such as a fluorinated solvent like 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 hydrosilylation catalyst, such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, for 1–72 hours, preferably 20–36 hours, more preferably 22–30 hours. Furthermore, two different compounds can be used to produce the organosilicon compound having an olefinic site and hydroxyl or hydrolyzable groups in the molecule; in this case, it can be manufactured by staged addition.

[0261] In another method of preparing a fluorinated polyether-based polymer having hydroxyl or hydrolyzable groups and polyether groups as represented by formula (1), a polymer containing fluorinated polyether groups represented by the following general formula (11) can be exemplified as a polymer having one or more polyether groups and SiH groups at one end or both ends of the molecular chain.

[0262]

[0263] (In the formula, Rf, B, E, T, U, V, Z, α, β, and m are the same as above.)

[0264] As a method for preparing the polymer containing fluorinated polyether groups represented by the above formula (11), the following methods can be listed as an example.

[0265] A polymer containing a fluorinated polyether group having one or more polyether groups and an olefinic site at one or both ends of the molecular chain, an organosilicon compound having two or more SiH groups without hydrolyzable end groups in the molecule, and a fluorinated solvent 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 toluene solution of a hydrogenation silylation catalyst such as a chloroplatinic acid / vinylsiloxane complex.

[0266] In the preparation of a polymer containing a fluorinated polyether group as represented by the above formula (11), the following polymers can be listed as examples of polymers containing a fluorinated polyether group that have one or more polyether groups and olefin sites at one end or both ends of the molecular chain.

[0267]

[0268] (In the formulas, k, p1, q1, and the sum of p1 and q1 in each formula are the same as above. In addition, the repeated units shown in parentheses with p1 and q1 can be combined randomly.)

[0269] In the preparation of the polymer containing fluorinated polyether groups represented by the above formula (11), the preferred organosilicon compound is one that does not have hydrolyzable end groups in the molecule and has two or more SiH groups.

[0270]

[0271] (In the formula, f and e are the same as above.)

[0272] Examples of organosilicon compounds that do not have hydrolyzable end groups in their molecules and have two or more SiH groups include the organosilicon compounds shown below.

[0273]

[0274] In the preparation of the polymer containing a fluorinated polyether group represented by the above formula (11), the amount of the organosilicon compound having two or more SiH groups in the molecule that does not have hydrolyzable end groups can be 7 to 30 equivalents relative to 1 equivalent of the olefin portion of the polymer containing a fluorinated polyether group having one or more polyether groups and olefin portions at one or both ends of the molecular chain. More preferably, it can be 5 to 20 equivalents, and even more preferably 8 to 12 equivalents.

[0275] In the preparation of the polymer containing a fluorinated polyether group represented by the above formula (11), the following catalysts can be listed as catalysts for the hydrosilylation reaction: Platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, alkynyl 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.

[0276] The amount of the hydrogenation silanization catalyst used is 0.1 to 100 ppm, more preferably 1 to 50 ppm, relative to the mass of the fluorinated polyether polymer having one or more polyether groups and olefin sites at one or both ends of the molecular chain.

[0277] In the preparation of the polymer containing fluorinated polyether groups represented by the above formula (11), fluorinated solvents can be listed 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 Corporation, trade name: Novec series), and perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M Corporation, trade name: Florinator series), etc.

[0278] The amount of solvent used is 10 to 300 parts by mass relative to 100 parts by mass of a fluorinated polyether polymer having one or more polyether groups and olefin sites at one or both ends of the molecular chain, preferably 50 to 150 parts by mass, and more preferably 50 to 100 parts by mass.

[0279] After the reaction is complete, the solvent and unreacted substances are removed by vacuum distillation, thereby obtaining the polymer containing fluorinated polyether groups represented by the above formula (11).

[0280] As a polymer containing a fluorinated polyether group represented by the above formula (11), the following polymers can be listed as examples.

[0281]

[0282]

[0283]

[0284]

[0285] (In the formulas, the sums of k, p1, q1, r1, and p1 and q1 in each formula are the same as above. Furthermore, the repeating units shown within parentheses containing p1 and q1 can be combined randomly.)

[0286] In another method for preparing a fluorinated polyether group polymer having hydroxyl or hydrolyzable groups and polyether groups as represented by formula (1), the organosilicon compound having olefin sites and hydroxyl or hydrolyzable groups in the molecule, which reacts with a fluorinated polyether group polymer having one or more polyether groups and SiH groups at one or both ends of the molecular chain, is preferably a compound represented by the following general formula (12).

[0287]

[0288] (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 at least one of oxygen, sulfur, silicon, and siloxane bonds.)

[0289] In formula (12) above, Y” is a single bond, or a divalent hydrocarbon group preferably having 1 to 18 carbon atoms, which may have at least one selected from oxygen atom, sulfur atom, silicon atom and siloxane bond. Specifically, this divalent hydrocarbon group is selected from alkylene groups having 1 to 8 carbon atoms that may contain oxygen or sulfur atoms, alkylene groups having 1 to 8 carbon atoms that contain 6 to 8 carbon atoms (e.g., alkylene-arylene groups having 7 to 18 carbon atoms), divalent groups consisting of alkylene groups having 1 to 10 carbon atoms combined with diorganosilylene, silaneylene structures or silaneylene structures, and divalent groups consisting of alkylene groups having 1 to 10 carbon atoms attached to the binding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms. Y” is preferably a single bond or a linear alkylene group having 1 to 6 carbon atoms.

[0290] Examples of organosilicon compounds that have olefinic sites 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 the following silane or siloxane compounds, their (partial) hydrolysates, etc.

[0291]

[0292] In another method for preparing a fluorinated polyether polymer having hydroxyl or hydrolyzable groups and polyether groups as represented by formula (1), the amount of organosilicon compound having olefin sites and hydroxyl or hydrolyzable groups in the molecule can be used in an amount of 1 to 4 equivalents, more preferably 1.5 to 2.5 equivalents, and even more preferably 1.8 to 2.2 equivalents, relative to the amount of SiH groups in the fluorinated polyether polymer having one or more polyether groups and SiH groups at one or both ends of the molecular chain.

[0293] As a hydrogen silanization catalyst used in another method for preparing a fluorinated polyether-containing polymer having hydroxyl or hydrolyzable groups and polyether groups as represented by formula (1), the same hydrogen silanization catalyst as the hydrogen silanization catalyst exemplified in the above-described preparation method can be used in an amount of 0.1 to 100 ppm, more preferably 0.3 to 50 ppm, relative to the mass of the fluorinated polyether-containing polymer having one or more polyether groups and SiH groups at one or both ends of the molecular chain.

[0294] As another method for preparing a fluorinated polyether polymer having hydroxyl or hydrolyzable groups and polyether groups as represented by formula (1), the solvent used can be the same as the solvent exemplified in the above preparation method. As the amount of the mixture, 10 to 300 parts by mass can be used relative to 100 parts by mass of a fluorinated polyether polymer having one or more polyether groups and 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.

[0295] After the reaction is complete, the solvent and unreacted substances are removed by vacuum distillation to obtain a fluorinated polyether polymer represented by the above formula (1) having hydroxyl or hydrolyzable groups and polyether groups.

[0296] The present invention also provides a surface treatment agent containing a polymer and / or a portion thereof (hydrolyzed) condensate of a fluorinated polyether group having hydroxyl or hydrolyzable groups and a polyether group, as represented by formula (1) above. This surface treatment agent only needs to contain a polymer and / or a portion thereof (hydrolyzed) condensate of a fluorinated polyether group having hydroxyl or hydrolyzable groups and a polyether group, as represented by formula (1) above, as the main agent, and may contain unreacted raw materials, reaction intermediates, etc., preceding the terminal hydroxyl or hydrolyzable groups of the polymer containing the fluorinated polyether group having hydroxyl or hydrolyzable groups and a polyether group.

[0297] Furthermore, in this invention, the term "partial (hydrolyzed) condensate" refers to a partial condensate or a partially hydrolyzed condensate, which is obtained by condensing the hydroxyl groups of a fluorinated polyether group polymer having hydroxyl or hydrolyzable groups and polyether groups represented by the above formula (1) in advance by partially hydrolyzing the hydroxyl groups or the terminal hydrolyzable groups of the fluorinated polyether group polymer in advance using a known method.

[0298] The surface treatment agent may contain hydrolysis-condensation catalysts, such as organotin compounds (dimethoxydibutyltin, 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 preferred.

[0299] The amount of hydrolysis condensation catalyst added is the amount of catalyst, 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 having hydroxyl or hydrolytic groups and polyether groups as represented by the above formula (1).

[0300] 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 spirits, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferred in terms of solubility and wettability, especially 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, methyl perfluorohexyl ether, methyl perfluoroheptenyl ether, ethyl perfluorobutyl ether, tridecylfluorooctane, and tetrafluoroethyltrifluoroethyl ether.

[0301] Regarding the solvents mentioned above, two or more can be mixed, preferably to uniformly dissolve the fluorinated polyether polymer and its partial (hydrolyzed) condensate (hereinafter referred to as the fluorinated polyether polymer) having hydroxyl or hydrolyzable groups and polyether groups as represented by the above formula (1). Furthermore, the optimal concentration of the fluorinated polyether polymer dissolved in the solvent varies depending on the processing method, and only an easily weighable amount is required. In the case of direct coating, it is preferably 0.01 to 10 parts by mass relative to the total of 100 parts by mass of the solvent and the fluorinated polyether polymer, and particularly preferably 0.05 to 5 parts by mass. In the case of 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 fluorinated polyether polymer, and particularly preferably 3 to 30 parts by mass.

[0302] The surface treatment agent of the present invention can be applied to a substrate using known methods such as brush coating, dipping, spraying, and vapor deposition. The heating method during vapor deposition can be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferable to perform the process at 25–200°C, particularly 25–150°C, for 30 minutes to 36 hours, particularly 1–24 hours. In the case of application via vapor deposition, it is preferable to perform the process at 20–200°C for 1–24 hours. Furthermore, it can be cured under humidification. Additionally, for example, in the case of spraying, dilution and hydrolysis in a fluorinated solvent with pre-added water to generate Si-OH before spraying results in faster curing after coating.

[0303] The thickness of the cured film is appropriately selected according to the type of substrate, typically ranging from 0.1 to 100 nm, particularly 1 to 20 nm. It should be noted that the film thickness can be measured using methods such as spectrophotometry, X-ray reflectance measurement, spectrophotometric ellipsography, and fluorescence X-ray measurement.

[0304] There are no particular limitations on the substrates treated with the surface treatment agent of the present invention; they can be various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. The surface treatment agent of the present invention can impart water and oil repellency to the above-mentioned substrates. In particular, it is preferably used as a surface treatment agent for SiO2-treated glass and films.

[0305] Articles treated with the surface treatment agent of the present invention include, but are not limited to, car navigation systems, mobile phones, smartphones, digital cameras, digital camcorders, PDAs, portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, endoscopes and other medical devices, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch screen displays, protective films, anti-reflective films and other optical articles and electronic components. The surface treatment agent of the present invention prevents fingerprints and sebum from adhering to the aforementioned articles, thereby imparting scratch resistance, and is therefore particularly suitable as a water- and oil-repellent layer for touch screen displays, anti-reflective films, etc.

[0306] In addition, the surface treatment agent of the present invention can also be used as a stain-resistant coating for sanitary products such as bathtubs and washbasins, a stain-resistant coating for window glass or tempered glass of automobiles, trains, aircraft, etc., a stain-resistant coating for headlight covers, a water- and oil-repellent coating for exterior wall building materials, an oil-resistant coating for kitchen building materials, a stain-resistant and anti-sticker / graffiti coating for telephone boxes, a coating that prevents fingerprint adhesion to artworks, a fingerprint-resistant coating for CDs, DVDs, etc., a mold release agent or coating additive, a resin modifier, a flow modifier or dispersant modifier for inorganic fillers, and a lubricity improver for tapes, films, etc.

[0307] Example

[0308] The following examples, embodiments, and comparative examples illustrate the invention in more detail, but the invention is not limited to the following examples. It should be noted that in the examples below, molar amounts are... 19 F-NMR, 1 The values ​​were calculated from the results of analyses such as H-NMR.

[0309] [Synthesis Example 1]

[0310] In the reaction vessel, it will be produced by the following formula (A)

[0311]

[0312] The compound represented is 100g (2.35 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (B)

[0313]

[0314] The compound represented is 42.0 g (9.41 × 10⁻⁶). -2 mol), tetrabutylammonium iodide 0.174 g (4.71 × 10⁻⁶ mol), 0.174 g (4.71 × 10⁻⁶ mol) -4The mixture was then stirred with 7.90 g (0.141 mol) of potassium hydroxide. The mixture was then heated at 60 °C for 24 hours. After heating, the mixture was cooled to room temperature, and hydrochloric acid solution was added dropwise. The lower fluoride layer was recovered by separation and washed with acetone. The washed lower layer, i.e., the fluoride layer, was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the product according to the following formula (C).

[0315]

[0316] The indicated amount is 89g of polymer containing fluorinated polyether groups.

[0317] 50 g (1.06 × 10⁻⁶) of the compound obtained above, represented by formula (C), was added to a reaction vessel. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 5.19g of trimethoxysilane (4.25×10 -2 A toluene solution of 3.94 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (as elemental Pt, containing 1.03 × 10⁻⁶) -6 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 50 g of the liquid product.

[0318] use 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (D).

[0319]

[0320] [Synthesis Example 2]

[0321] In the reaction vessel, it will be produced by the following formula (E).

[0322]

[0323] The compound represented is 100g (1.51 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (F)

[0324]

[0325] The compound represented is 20.3 g (6.34 × 10⁻⁶). -2 0.447 g (7.92 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium (7.92 × 10⁻⁶ mol) - 4After mixing (mol), the mixture was heated at 90°C for 24 hours. After heating, it was cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluoride layer was recovered by separation and washed with acetone. The washed lower layer, i.e., the fluoride layer, was recovered again, and the residual solvent was distilled off under reduced pressure, thus obtaining the product according to the following formula (G).

[0326]

[0327] This indicates 95g of polymer containing fluorinated polyether groups.

[0328] 50 g (7.54 × 10⁻⁶) of the compound obtained above, represented by formula (G), was added to a reaction vessel. -3 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 3.68g of trimethoxysilane (3.01×10⁻⁶ mol), -2 A toluene solution of 2.79 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (as elemental Pt, containing 7.32 × 10⁻⁶) -7 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 49 g of the liquid product.

[0329] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (H).

[0330]

[0331] [Synthesis Example 3]

[0332] In the reaction vessel, it will be composed of the following formula (I)

[0333]

[0334] The compound represented is 100g (2.35 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (J)

[0335]

[0336] The compound represented is 25.1 g (9.31 × 10⁻⁶). -2 mol), tetrabutylammonium iodide 0.172 g (4.66 × 10⁻⁶) -4The mixture was then stirred with 7.86 g (0.140 mol) of potassium hydroxide. The mixture was then heated at 60 °C for 24 hours. After heating, the mixture was cooled to room temperature, and hydrochloric acid solution was added dropwise. The lower fluoride layer was recovered by separation and washed with acetone. The washed lower layer, i.e., the fluoride layer, was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the product according to the following formula (K).

[0337]

[0338] The indicated amount is 93g of polymer containing fluorinated polyether groups.

[0339] 50 g (1.11 × 10⁻⁶) of the compound obtained above, represented by formula (K), was added to a reaction vessel. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 5.44g of trimethoxysilane (4.45×10 -2 A toluene solution of 4.13 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (as elemental Pt, containing 1.08 × 10⁻⁶) -6 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 48 g of the liquid product.

[0340] use 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (L).

[0341]

[0342] [Synthesis Example 4]

[0343] In the reaction vessel, it will be composed of the following formula (M)

[0344]

[0345] The compound represented is 100g (2.33 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (B)

[0346]

[0347] The compound represented is 41.6 g (9.32 × 10⁻⁶). -2 mol), tetrabutylammonium iodide 0.172 g (4.66 × 10⁻⁶) -4The mixture was then stirred with 7.83 g (0.140 mol) of potassium hydroxide. The mixture was then heated at 60 °C for 24 hours. After heating, the mixture was cooled to room temperature, and hydrochloric acid solution was added dropwise. The lower fluoride layer was recovered by separation and washed with acetone. The washed lower layer, i.e., the fluoride layer, was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the product according to the following formula (N).

[0348]

[0349] The indicated amount is 94g of polymer containing fluorinated polyether groups.

[0350] 50 g (1.07 × 10⁻⁶) of the compound obtained above, represented by the above formula (N), was added to a reaction vessel. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 7.86g of trimethoxysilane (6.44×10 -2 A toluene solution of 3.98 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (as elemental Pt, containing 1.04 × 10⁻⁶) -6 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 50 g of the liquid product.

[0351] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (O).

[0352]

[0353] [Synthesis Example 5]

[0354] In the reaction vessel, it will be produced by the following formula (P)

[0355]

[0356] The compound represented is 100g (2.35 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (Q)

[0357]

[0358] The compound represented is 17.8 g (9.43 × 10⁻⁶). -2 0.666 g (1.18 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium - 3After mixing (mol), the mixture was heated at 90°C for 24 hours. After heating, it was cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluoride layer was recovered by separation and washed with acetone. The washed lower layer, i.e., the fluoride layer, was recovered again, and the residual solvent was distilled off under reduced pressure, thus obtaining the product according to the following formula (R).

[0359]

[0360] The indicated amount is 90g of a polymer containing fluorinated polyether groups.

[0361] 50 g (1.13 × 10⁻⁶) of the compound obtained above, represented by the above formula (R), was added to a reaction vessel. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 5.51g of trimethoxysilane (4.51×10 -2 A toluene solution of 4.18 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (as elemental Pt, containing 1.10 × 10⁻⁶) -6 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 51 g of the liquid product.

[0362] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (S).

[0363]

[0364] [Synthesis Example 6]

[0365] In the reaction vessel, it will be produced by the following formula (T)

[0366]

[0367] The compound represented is 100g (2.11 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (J)

[0368]

[0369] The compound represented is 22.8 g (8.43 × 10⁻⁶). -2 mol), tetrabutylammonium iodide 0.156 g (4.22 × 10⁻⁶ mol), 0.156 g (4.22 × 10⁻⁶ mol) -4The mixture was then stirred with 7.08 g (0.126 mol) of potassium hydroxide. The mixture was then heated at 60 °C for 24 hours. After heating, the mixture was cooled to room temperature, and hydrochloric acid solution was added dropwise. The lower fluoride layer was recovered by separation and washed with acetone. The washed lower layer, i.e., the fluoride layer, was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the product according to the following formula (U).

[0370]

[0371] The indicated amount is 97g of polymer containing fluorinated polyether groups.

[0372] 50 g (1.01 × 10⁻⁶) of the compound obtained above, represented by the above formula (U), was added to a reaction vessel. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 7.42g of trimethoxysilane (6.08×10⁻⁶ mol), -2 A toluene solution of 3.76 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (as elemental Pt, containing 9.84 × 10⁻⁶) -7 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 47 g of the liquid product.

[0373] use 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (V).

[0374]

[0375] [Synthesis Example 7]

[0376] In the reaction vessel, it will be produced by the following formula (W)

[0377]

[0378] The compound represented is 100g (2.30 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (B)

[0379]

[0380] The compound represented is 41.0 g (9.20 × 10⁻⁶). -2 mol), tetrabutylammonium iodide 0.170 g (4.60 × 10⁻⁶) -4The mixture was then stirred with 7.72 g (0.138 mol) of potassium hydroxide. The mixture was then heated at 60 °C for 24 hours. After heating, the mixture was cooled to room temperature, and hydrochloric acid solution was added dropwise. The lower fluoride layer was recovered by separation and washed with acetone. The washed lower layer, i.e., the fluoride layer, was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the product according to the following formula (X).

[0381]

[0382] The indicated amount is 94g of polymer containing fluorinated polyether groups.

[0383] 50 g (1.06 × 10⁻⁶) of the compound obtained above, represented by formula (X), was added to a reaction vessel. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, 7.76g of trimethoxysilane (6.36×10 -2 A toluene solution of 3.93 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (as elemental Pt, containing 1.03 × 10⁻⁶) -6 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 50 g of the liquid product.

[0384] use 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (Y).

[0385]

[0386] [Synthesis Example 8]

[0387] In the reaction vessel, it will be produced by the following formula (A)

[0388]

[0389] The compound represented is 100g (2.35 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (AA)

[0390]

[0391] The compound represented is 55.1 g (9.41 × 10⁻⁶). -2 0.664 g (1.18 × 10⁻⁶ mol) of tetra-2-ethylhexyloxytitanium - 3After mixing (mol), the mixture was heated at 90°C for 24 hours. After heating, it was cooled to room temperature, and hydrochloric acid aqueous solution was added dropwise. The lower fluoride layer was recovered by separation and washed with acetone. The washed lower layer, i.e., the fluoride layer, was recovered again, and the residual solvent was distilled off under reduced pressure, thus obtaining the product according to the following formula (AB).

[0392]

[0393] The indicated amount is 90g of a polymer containing fluorinated polyether groups.

[0394] 50 g (1.03 × 10⁻⁶) of the compound represented by the above formula (AB) was added to the reaction vessel. -2 mol), 25g of 1,3-bis(trifluoromethyl)benzene, from the following formula (AC)

[0395]

[0396] The compound represented is 14.7 g (4.13 × 10⁻⁶). -2 A toluene solution of 3.83 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (as elemental Pt, containing 1.00 × 10⁻⁶) -6 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 52 g of the liquid product.

[0397] use 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (AD).

[0398]

[0399] [Synthesis Example 9]

[0400] In the reaction vessel, the following formula (AE) will be used.

[0401]

[0402] The compound represented is 100g (2.44 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (AF)

[0403]

[0404] The indicated compound was 78.4 g (0.195 mol), and tetrabutylammonium iodide was 0.360 g (9.75 × 10⁻⁶ mol). -4The mixture was then stirred with 16.4 g (0.292 mol) of potassium hydroxide. The mixture was then heated at 60 °C for 24 hours. After heating, the mixture was cooled to room temperature, and hydrochloric acid solution was added dropwise. The lower fluoride layer was recovered by separation and washed with acetone. The washed lower layer, i.e., the fluoride layer, was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the product according to the following formula (AG).

[0405]

[0406] The indicated amount is 87g of polymer containing fluorinated polyether groups.

[0407] 30 g (6.31 × 10⁻⁶) of the compound obtained above, represented by the above formula (AG), was added to a reaction vessel. -3 1,3-bis(trifluoromethyl)benzene 15g, trimethoxysilane 6.17g (5.05×10 mol), 1,3-bis(trifluoromethyl)benzene 15g, trimethoxysilane 6.17g (5.05×10 mol) -2 A toluene solution of 2.34 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (as elemental Pt, containing 6.13 × 10⁻⁶) -7 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 51 g of the liquid product.

[0408] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (AH).

[0409]

[0410] [Synthesis Example 10]

[0411] In the reaction vessel, the same material obtained as in Synthesis Example 1, derived from the following formula (C), is...

[0412]

[0413] The compound represented is 50g (1.06 × 10⁻⁶). -2 mol), 50g of 1,3-bis(trifluoromethyl)benzene, from the following formula (AI)

[0414]

[0415] The compound represented was 51.0 g (0.213 mol), and a toluene solution of the chloroplatinic acid / vinylsiloxane complex was 3.94 × 10⁻⁶. -2 g (as elemental Pt, containing 1.03 × 10⁻⁶) -6 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 52 g of the liquid product.

[0416] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (AJ).

[0417]

[0418] 50 g (9.81 × 10⁻⁶) of the compound represented by the above formula (AJ) obtained above was added to a reaction vessel. -3 A toluene solution of 1,3-bis(trifluoromethyl)benzene 25 g, octenyltrimethoxysilane 27.4 g (0.118 mol), and chloroplatinic acid / vinylsiloxane complex 3.64 × 10⁻⁶ -2 g (as elemental Pt, containing 9.52 × 10⁻⁶) -7 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 53 g of the liquid product.

[0419] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (AK).

[0420]

[0421] [Example 1]

[0422] The compound obtained in Synthesis Example 1 was dissolved in Opteon SF10 (Mitsui). A surface treatment agent was prepared by Kemaz Froro Produktsu Co., Ltd. (methyl perfluoroheptene ether) to a concentration of 20% by mass.

[0423] [Example 2]

[0424] The compound obtained in Synthesis Example 2 was dissolved in Asahiclin AC-6000 (manufactured by AGC Corporation, tridecylfluorooctane) to a concentration of 20% by mass to prepare a surface treatment agent.

[0425] [Example 3]

[0426] The compound obtained in Synthesis Example 3 was dissolved in Novec 7300 (3M Corporation, methyl perfluorohexyl ether) to a concentration of 20% by mass to prepare a surface treatment agent.

[0427] [Example 4]

[0428] The compound obtained in Synthesis Example 4 was dissolved in AE3000 (1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether manufactured by AGC) to a concentration of 20% by mass, thus preparing a surface treatment agent.

[0429] [Example 5]

[0430] The compound obtained in Synthesis Example 6 was dissolved in a mixture of Novec 7200 (3M, ethyl perfluorobutyl ether) / AE3000 at a mass ratio of 50:50 to obtain a concentration of 20% by mass, thus preparing a surface treatment agent.

[0431] [Example 6]

[0432] The compound obtained in Synthesis Example 7 was dissolved in a Novec 7300 / AE3000 mixture at a mass ratio of 50:50 to obtain a concentration of 20% by mass, thus preparing a surface treatment agent.

[0433] [Example 7]

[0434] The compound obtained in Synthesis Example 10 was dissolved in Novec 7200 to a concentration of 20% by mass to prepare a surface treatment agent.

[0435] [Comparative Example 1]

[0436] Make the following formula (AL)

[0437]

[0438] The compound was dissolved in Novec 7200 to a concentration of 20% by mass, and a surface treatment agent was prepared.

[0439] [Comparative Example 2]

[0440] Make the following formula (AM)

[0441]

[0442] The compound was dissolved in Novec 7200 to a concentration of 20% by mass, and a surface treatment agent was prepared.

[0443] [Comparative Example 3]

[0444] Make the following formula (AN)

[0445]

[0446] The compound was dissolved in Novec 7200 to a concentration of 20% by mass, and a surface treatment agent was prepared.

[0447] Preparation of surface treatment agents and formation of cured films

[0448] As described in the above examples and comparative examples, surface treatment agents were prepared. For glass (Gorilla glass manufactured by Corning Incorporated) with a 10 nm thick SiO2 coating on the outermost surface, each surface treatment agent was vacuum-deposited (treatment conditions: pressure: 2.0 × 10⁻⁶). -2 The film was cured for 12 hours at 25°C and 50% relative humidity (Pa, heating temperature: 700°C) to form a cured film with a thickness of 10 nm. It should be noted that the film thickness was measured using spectroscopic ellipsography with a spectrophotometer.

[0449] Evaluation of water and oil repellency

[0450] [Evaluation of initial water and oil repellency]

[0451] For the glass with the cured film formed as described above, the contact angle (hydrophobicity) of the cured film to water was measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25 °C, relative humidity: 40%). The results (initial water contact angle) are shown in Table 1.

[0452] In the initial stages, both the examples and comparative examples showed good water repellency.

[0453] [Evaluation of Abrasion Resistance]

[0454] For the glass with a cured coating formed as described above, the contact angle (water repellency) of the cured coating with water after rubbing was measured using a friction tester (manufactured by Shin-To Science Co., Ltd.) under the same conditions as above, and the abrasion resistance was evaluated. The test environment conditions were 25°C and 40% relative humidity. The results (water contact angle after steel wool abrasion and water contact angle after rubber abrasion) are shown in Table 1.

[0455] Resistance to steel wool abrasion

[0456] Steel wool: Bonster #0000

[0457] Contact area: 1cm 2

[0458] Travel distance (one way): 40mm

[0459] Movement speed: 4800 mm / min

[0460] Load: 1 kgf / 1 cm 2

[0461] Wear cycles: 10,000 times

[0462] Rubber abrasion resistance

[0463] Eraser: Raber Eraser (Made by Minoan)

[0464] Contact area: 6mm

[0465] Travel distance (one way): 40mm

[0466] Movement speed: 3600 mm / min

[0467] Load: 1kgf / 6mm

[0468] Wear cycles: 10,000 times

[0469] The surface treatment agents of Examples 1-7 showed that, because the polyether groups of the compounds used were located on secondary carbon atoms, the molecular mobility of the polyether groups was ensured, resulting in both steel wool abrasion durability and high rubber abrasion durability. The surface treatment agent of Comparative Example 1 exhibited low rubber abrasion durability and steel wool abrasion durability. While the surface treatment agent of Comparative Example 2 showed high steel wool abrasion durability, its rubber abrasion durability was low. Furthermore, the surface treatment agent of Comparative Example 3, due to the polyether groups of the compounds used being located on tertiary carbon atoms, had restricted molecular mobility, resulting in poor rubber abrasion durability compared to the examples. As described above, the surface treatment agents of the examples can achieve a high level of both rubber abrasion durability and steel wool abrasion durability.

[0470] [Table 1]

[0471]

[0472] [Example 8]

[0473] The compound obtained in Synthesis Example 1 was dissolved in Opteon SF10 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0474] [Example 9]

[0475] The compound obtained in Synthesis Example 2 was dissolved in AE3000 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0476] [Example 10]

[0477] The compound obtained in Synthesis Example 4 was dissolved in Novec 7200 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0478] [Comparative Example 4]

[0479] The above compound (AL) was dissolved in Novec 7300 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0480] [Comparative Example 5]

[0481] The above compound (AM) was dissolved in Novec 7300 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0482] [Comparative Example 6]

[0483] The above compound (AN) was dissolved in Novec 7300 to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0484] Preparation of surface treatment agents and formation of cured films

[0485] As described in the above examples and comparative examples, surface treatment agents were prepared. For glass (Gorilla glass manufactured by Corning Incorporated), each surface treatment agent was sprayed onto the glass and cured at 120°C for 30 minutes, then cured at 25°C and 50% relative humidity for 12 hours, forming a cured film with a thickness of 10 nm. It should be noted that the film thickness was measured using spectroscopic ellipsography with a spectroscopic ellipsometer.

[0486] Evaluation of water and oil repellency

[0487] [Evaluation of initial water and oil repellency]

[0488] For the glass with the cured film formed as described above, the contact angle (hydrophobicity) of the cured film to water was measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25 °C, relative humidity: 40%). The results (initial water contact angle) are shown in Table 2.

[0489] In the initial stages, both the examples and comparative examples showed good water repellency.

[0490] [Evaluation of Abrasion Resistance]

[0491] For the glass with a cured coating formed as described above, the contact angle (water repellency) of the cured coating with water after rubbing was measured using a friction tester (manufactured by Shin-To Science Co., Ltd.) under the same conditions as above, and the abrasion resistance was evaluated. The test environment conditions were 25°C and 40% relative humidity. The results (water contact angle after steel wool abrasion and water contact angle after rubber abrasion) are shown in Table 2.

[0492] Resistance to steel wool abrasion

[0493] Steel wool: Bonster #0000

[0494] Contact area: 1cm 2

[0495] Travel distance (one way): 40mm

[0496] Movement speed: 4800 mm / min

[0497] Load: 1 kgf / 1 cm 2

[0498] Wear cycles: 10,000 times

[0499] Rubber abrasion resistance

[0500] Eraser: Raber Eraser (Made by Minoan)

[0501] Contact area: 6mm

[0502] Travel distance (one way): 40mm

[0503] Movement speed: 3600 mm / min

[0504] Load: 1kgf / 6mm

[0505] Wear cycles: 10,000 times

[0506] The surface treatment agents of Examples 8-10 exhibited the same high rubber wear durability and high steel wool durability as those used in vapor deposition coating. The surface treatment agent of Comparative Example 4 showed low rubber wear durability and steel wool durability, while the surface treatment agent of Comparative Example 5, although exhibiting high steel wool durability, had low rubber wear durability. Furthermore, the surface treatment agent of Comparative Example 6, due to the polyether group of the compound being located on a tertiary carbon atom, had restricted molecular movement, resulting in poor rubber wear durability compared to the examples. As shown above, even with changes in the coating method, the surface treatment agents of the examples can still achieve a high level of both rubber wear durability and steel wool durability.

[0507] [Table 2]

[0508]

Claims

1. A fluoropolyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group represented by the following general formula (1), ###0001### wherein Rf is a monovalent or divalent fluoropolyether group, B is independently a single bond or a divalent organic group not containing a fluorine atom, E is independently a monovalent group having an oxyalkylene group, T is independently a single bond or a divalent organic group, U is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, V is independently a single bond or a divalent organic group, Z is independently a single bond, or a trivalent to octavalent organic group, Y is independently a divalent hydrocarbon group which can have at least one selected from the group consisting of an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each combined silicon atom, m is independently an integer of 1 to 7, β is independently an integer of 1 to 3, and α is 1 or 2. In the formula (1), α is 1, and Rf is a group represented by the following general formula (2), ###0002### wherein A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group having a terminal -CF3 group, W is a fluoroalkylene group containing one or more hydrogen atoms, d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, the total of p, q, r, s, t, u, and v is 3 to 200, each of the units can be linear or branched, and each of the repeating units shown within the parentheses having p, q, r, s, t, u, and v can be combined randomly.

2. The fluorine-polyether group-containing polymer according to claim 1, wherein, In the formula (1), α is 2, and Rf is a group represented by the following general formula (3), ###0003### wherein W is a fluoroalkylene group containing one or more hydrogen atoms, d is independently an integer of 1 to 3 for each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, the total of p, q, r, s, t, u, and v is 3 to 200, each of the units can be linear or branched, and each of the repeating units shown within the parentheses having p, q, r, s, t, u, and v can be combined randomly. In the formula (1), Y is a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms which can contain an oxygen atom or a sulfur atom, an alkylene group having 1 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups having 1 to 10 carbon atoms are combined with each other via a diorganodisilyl group, a silylalkylene structure, or a silylarylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is combined with a terminal of an organic polysiloxane residue having 2 to 10 silicon atoms in a linear form or 3 to 10 silicon atoms in a branched or cyclic form.

3. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, ​ ​ 4. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, ​ 5. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, In the formula (1), B is a single bond, or a 2-valent group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms, a 2-valent group in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganodisilyl group, a silylalkylene structure or a silylarylene structure, and a 2-valent group in which an alkylene group having 1 to 10 carbon atoms is bonded to a bonding end of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl group, and an amido group, and can contain at least any one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide and an ester group.

6. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, In the formula (1), T is a single bond, or a 2-valent group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms, a 2-valent group in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a diorganodisilyl group, a silylalkylene structure or a silylarylene structure, and a 2-valent group in which an alkylene group having 1 to 10 carbon atoms is bonded to a bonding end of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl group, and an amido group, and can contain at least any one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide and an ester group.

7. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, In the formula (1), U is selected from the group consisting of a single bond, a carbon atom, a silicon atom, a nitrogen atom, -CH=, and -Si(CH3)=.

8. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, In the formula (1), Z is a single bond, or a 3- to 6-valent organopolysiloxane residue having 2 to 10 silicon atoms or 3 to 10 silicon atoms.

9. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, In the formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.

10. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, In the formula (1), m is an integer of 1 to 3.

11. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, In the formula (1), β is 2 or 3.

12. The fluorine-containing polyether group-containing polymer according to claim 1, wherein, The fluorine-containing polyether group-containing polymer represented by the formula (1) is represented by any one of the following formulas, in the formula, each of p1, q1, s1 is an integer of 1 to 200, wherein the total of p1, q1, s1 in each formula is 3 to 200, each of r1, r2 is an integer of 3 to 200, each of the repeating units shown within the parentheses with p1, q1, s1 can be randomly bonded, and k is an integer of 1 to 30.

13. A surface treatment agent comprising the fluorine-containing polyether group-containing polymer having a hydroxyl group or a hydrolyzable group and a polyether group and / or a partial (hydrolytic) condensate thereof according to any one of claims 1 to 12.

14. An article surface-treated with the surface treatment agent according to claim 13.

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