Polymers, surface treatment agents and articles containing fluoropolyether groups

Abstract

A surface treatment agent comprising a fluoropolyether group-containing polymer having a hydroxyl-containing silyl group or a hydrolyzable silyl group represented by the following general formula (1) and / or a partial (hydrolyzed) condensate thereof can form a cured film having excellent water and oil repellency, steel wool abrasion resistance, and a small water roll-off angle. α (1) (wherein Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene group, V is independently a monovalent group having a hydroxyl-containing silyl group or a hydrolyzable silyl group at the end, and has no polar group other than the hydroxyl-containing silyl group or the hydrolyzable silyl group. α is 1 or 2).

Description

Technical Field

[0001] The present invention relates to a fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluorooxyalkylene group-containing polymer residue in the molecule), and more specifically, to a fluoropolyether group-containing polymer that forms a film having excellent water- and oil-repellency and abrasion resistance, a surface treatment agent containing the polymer and / or a partial (hydrolysis) condensate thereof, and an article surface-treated with the surface treatment agent. Background Art

[0002] In recent years, led by the display of mobile phone, the touch panelization of screen is accelerating.But the touch panel is the state that screen is exposed, and the chance of direct contact such as finger, cheek is many, and dirt such as sebum easily adheres to and becomes a problem.Therefore, in order to improve appearance, visibility, the requirement of the technology that makes fingerprint difficult to adhere to the surface of display, the technology that makes dirt easily come off is improved year by year, and it is hoped that the material that can meet these requirements is developed.Especially, the surface of touch panel display is easy to adhere to fingerprint dirt, therefore it is hoped that water-repellent and oil-repellent layer is provided.But the water-repellent and oil-repellent of existing water-repellent and oil-repellent layer is high, and dirt wiping property is excellent, but has the problem that antifouling performance deteriorates in use.

[0003] Generally, the compound that contains fluoropolyether group is because its surface free energy is very little, therefore has water and oil repellency, chemical resistance, lubricity, demoulding property, antifouling property etc.Utilize this character, industrially as the water and oil repellent antifouling agent of paper fiber etc., the lubricant of magnetic recording medium, the oil-proof agent of precision equipment, demoulding agent, cosmetics, protective film etc. utilize extensively.But its character means for non-adhesiveness, non-fitting property for other base materials simultaneously, even can be coated on substrate surface, also be difficult to make this tunic close.

[0004] Silane coupling agents, on the other hand, are well-known for bonding organic compounds to the surfaces of substrates such as glass and cloth. They are widely used as coating agents for various substrate surfaces. Silane coupling agents contain an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) within a single molecule. The hydrolyzable silyl group undergoes a self-condensation reaction with moisture in the air, forming a film. This film chemically or physically bonds to the surface of glass, metal, or the like through the hydrolyzable silyl group, creating a durable, strong film.

[0005] Therefore, a composition is disclosed, which uses a fluoropolyether group-containing polymer obtained by introducing a hydrolyzable silyl group into a fluoropolyether group-containing compound, thereby easily adhering to the surface of a substrate and forming a film having water and oil repellency, chemical resistance, lubricity, mold release properties, antifouling properties, etc. on the surface of the substrate (Patent Documents 1 to 6: Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-537557, Japanese Patent Application Laid-Open No. 2012-072272, Japanese Patent Application Laid-Open No. 2012-157856, Japanese Patent Application Laid-Open No. 2013-136833, Japanese Patent Application Laid-Open No. 2015-199906).

[0006] Cured films such as lenses and antireflection films surface-treated with a composition comprising a fluoropolyether-containing polymer having a hydrolyzable silyl group introduced into the fluoropolyether-containing compound exhibit excellent durability against abrasion with steel wool. However, as durability increases, the water roll-off angle increases. Furthermore, when the water roll-off angle is small, the wear durability is poor.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application No. 2008-534696

[0010] Patent Document 2: Japanese Patent Application No. 2008-537557

[0011] Patent Document 3: Japanese Patent Application Laid-Open No. 2012-072272

[0012] Patent Document 4: Japanese Patent Application Laid-Open No. 2012-157856

[0013] Patent Document 5: Japanese Patent Application Laid-Open No. 2013-136833

[0014] Patent Document 6: Japanese Patent Application Laid-Open No. 2015-199906 Summary of the Invention

[0015] Problems to be solved by the invention

[0016] The present invention has been completed in view of the above-mentioned actual situation, and its purpose is to provide a polymer containing a fluoropolyether group that can form a cured film with excellent water and oil repellency and abrasion resistance, a surface treatment agent containing the polymer and / or its partial (hydrolysis) condensate, and an article surface-treated with the surface treatment agent.

[0017] Means for solving problems

[0018] The present inventors have conducted intensive studies to achieve the above-mentioned objectives and have found that, among the above-mentioned fluoropolyether group-containing polymers, by using a fluoropolyether group-containing polymer having a hydroxyl-containing silyl group or a hydrolyzable silyl group represented by the general formula (1) described later, and in particular a fluoropolyether group-containing polymer having a hydroxyl-containing silyl group or a hydrolyzable silyl group represented by the general formula (2) described later, a surface treatment agent containing the polymer and / or its partial (hydrolysis) condensate can form a cured film having excellent water and oil repellency, steel wool abrasion resistance, and a small water roll-off angle, thereby completing the present invention.

[0019] Therefore, the present invention provides the following fluoropolyether group-containing polymer (a compound having a monovalent or divalent fluorooxyalkylene group-containing polymer residue in the molecule), a surface treating agent, and an article.

[0020] [1] A polymer containing a fluoropolyether group, which is represented by the following general formula (1):

[0021] Rf-[CH(V)2] α (1)

[0022] (In the formula, Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene group, V is independently a monovalent group having a hydroxyl-containing silyl group or a hydrolyzable silyl group at a terminal, and the group does not have a polar group other than the hydroxyl-containing silyl group or the hydrolyzable silyl group. α is 1 or 2.)

[0023] express.

[0024] [2] The polymer containing a fluoropolyether group described in [1] is represented by the following general formula (2):

[0025] [Chemistry 1]

[0026]

[0027] (In the formula, Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene group, L is each independently a single bond or a divalent heteroatom, Y is each independently a divalent to hexavalent hydrocarbon group which may have a silicon atom and / or 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 an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.)

[0028] express.

[0029] [3] The fluoropolyether group-containing polymer according to [1] or [2], wherein α in (1) or (2) is 1, and Rf is a group represented by the following general formula (3).

[0030] [Chemistry 2]

[0031]

[0032] (In the formula, A is a fluorine atom, a hydrogen atom, a fluoroalkyl group, or a fluoroalkyl group containing one or more hydrogen atoms; W is a fluoroalkylene group containing one or more hydrogen atoms and having 1 to 6 carbon atoms. d is independently an integer of 1 to 3 in each unit; p, q, r, s, t, u, and v are each an integer of 0 to 200; p+q+r+s+t+u+v=3 to 200; and each of these units may be linear or branched. Furthermore, the repeating units indicated in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)

[0033] [4] The fluoropolyether group-containing polymer according to [1] or [2], wherein α in the formula (1) or (2) is 2, and Rf is a group represented by the following general formula (4).

[0034] [Chemistry 3]

[0035]

[0036] (In the formula, W is a fluoroalkylene group having 1 to 6 carbon atoms containing one or more hydrogen atoms, d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, and p+q+r+s+t+u+v=3 to 200. Each of these units may be linear or branched. Furthermore, the repeating units indicated in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)

[0037] [5] A fluoropolyether group-containing polymer according to any one of [2] to [4], wherein, in the formula (2), when α=1, there are two Ls at one end of the molecular chain, and when α=2, there are two Ls at each end of the molecular chain, and among these Ls, at each end of the molecular chain, one L is an oxygen atom and the other L is a single bond, and Y is independently a group selected from an alkylene group having 3 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the end of a linear or branched or cyclic divalent to tetravalent organopolysiloxane residue having 2 to 10 silicon atoms.

[0038] [6] The fluoropolyether group-containing polymer according to any one of [2] to [5], wherein in the formula (2), X is independently a group selected from 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.

[0039] [7] The fluoropolyether group-containing polymer according to any one of [2] to [6], wherein the polymer represented by formula (2) is selected from polymers represented by the following formula.

[0040] [Chemistry 4]

[0041]

[0042] [Chemistry 5]

[0043]

[0044] [Chemistry 6]

[0045]

[0046] [Chemistry 7]

[0047]

[0048] (In the formula, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, r1 is an integer of 1 to 100, r2 is an integer of 1 to 99, and r3 is an integer of 1 to 99. The total of p1, q1, r1, r2, and r3 is an integer of 10 to 110. The repeating units shown in parentheses with p1, q1, r1, r2, and r3 may be randomly bonded.)

[0049] [8] A surface treatment agent comprising the fluoropolyether group-containing polymer according to any one of [1] to [7] and / or its partial (hydrolysis) condensate.

[0050] [9] The surface treatment agent described in [8], wherein the fluoropolyether group in the fluoropolyether group-containing polymer is a monovalent fluorooxyalkylene-containing polymer residue located at the end of the molecular chain.

[0051]

[10] An article surface-treated with the surface treatment agent described in [8] or [9].

[0052] Effects of the Invention

[0053] The fluoropolyether group-containing polymer of the present invention improves substrate adhesion and wettability, and thus articles surface-treated with a surface treatment agent containing the polymer and / or its partial (hydrolysis) condensate have excellent water and oil repellency, steel wool abrasion resistance, and water roll-off properties. DETAILED DESCRIPTION

[0054] The fluoropolyether group-containing polymer of the present invention has a fluoropolyether group and a reactive functional group in its molecule and is represented by the following general formula (1): The fluoropolyether group-containing polymer of the present invention may be a single species or a mixture of two or more species.

[0055] Rf-[CH(V)2] α (1)

[0056] (In the formula, Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene group, V is independently a monovalent group having a hydroxyl-containing silyl group or a hydrolyzable silyl group at a terminal, and the group does not have a polar group other than the hydroxyl-containing silyl group or the hydrolyzable silyl group. α is 1 or 2.)

[0057] It should be noted that the so-called "about (numerical value)" in this specification is a rounded numerical value (approximate number), and when the lowest digit of the numerical value it represents is not "0", it further includes the numerical range of the numerical value represented by rounding off the next digit. For example, "about 3 equivalents" means more than 2.5 equivalents and less than 3.4 equivalents, and "about 0.02 equivalents" means more than 0.015 equivalents and less than 0.024 equivalents. In addition, when the lowest digit of the numerical value it represents is "0", it includes the numerical range of the numerical value represented by rounding off the lowest digit. For example, "about 50°C" means more than 45°C and less than 54°C, and "about 200 to 350 parts by mass" means more than 195 parts by mass and less than 354 parts by mass.

[0058] The fluoropolyether group-containing polymer of the present invention is characterized by having a structure in which a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group (i.e., a monovalent or divalent fluorooxyalkylene group-containing polymer residue) is bonded to a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group via a linker having no polar group. Since two or more hydrolyzable silyl groups such as an alkoxysilyl group or a hydroxyl group-containing silyl group are present in the molecule and no polar group, specifically no hydroxyl group, is present in the molecule other than the hydrolyzable silyl group or the hydroxyl group-containing silyl group, the polymer exhibits improved substrate adhesion and wettability, and exhibits excellent water and oil repellency, steel wool abrasion resistance, and water roll-off properties.

[0059] In the above formula (1), Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene group. When α is 1 (i.e., when Rf is a monovalent polymer residue containing a fluorooxyalkylene group), it is preferably a monovalent fluoropolyether group represented by the following general formula (3). When α is 2 (i.e., when Rf is a divalent polymer residue containing a fluorooxyalkylene group), it is preferably a divalent fluoropolyether group represented by the following general formula (4).

[0060] [Chemistry 8]

[0061]

[0062] [Chemistry 9]

[0063]

[0064] (In the above formulae, A is a fluorine atom, a hydrogen atom, a fluoroalkyl group, or a fluoroalkyl group containing one or more hydrogen atoms; W is a fluoroalkylene group having 1 to 6 carbon atoms and 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; p+q+r+s+t+u+v=3 to 200; and each of these units may be linear or branched. Furthermore, the repeating units indicated in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)

[0065] In the above formula (3), A is a fluorine atom, a hydrogen atom, a fluoroalkyl group, or a fluoroalkyl group containing one or more hydrogen atoms. The fluoroalkyl group or the fluoroalkyl group containing one or more hydrogen atoms is preferably a group having 1 to 6 carbon atoms, for example, a -CF3 group, a -CF2CF3 group, a -CF2CF2CF3 group, or a group in which one or two fluorine atoms in these groups are replaced by hydrogen atoms. A is preferably a fluorine atom.

[0066] In the above formulae (3) and (4), W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms, and examples thereof include CF2 units, C2F4 units, C3F6 units, C4F8 units, C5F 10 Unit, C6F 12 A group in which one or two fluorine atoms in each perfluoroalkylene unit are replaced by hydrogen atoms, and the like.

[0067] In the above formulae (3) and (4), d is independently an integer of 1 to 3 for each unit, and is preferably 1 or 2.

[0068] Furthermore, p, q, r, s, t, u, and v are each an integer from 0 to 200. Preferably, p is an integer from 5 to 100, q is an integer from 5 to 100, r is an integer from 0 to 100, s is an integer from 0 to 100, t is an integer from 0 to 100, u is an integer from 0 to 100, and v is an integer from 0 to 100. p+q+r+s+t+u+v=3 to 200, preferably 10 to 105, more preferably p+q is an integer from 10 to 105, particularly preferably 15 to 60, and r=s=t=u=v=0. If p+q+r+s+t+u+v is less than the upper limit, adhesion and curability are improved. If it is greater than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferred.

[0069] In the above formulas (3) and (4), each unit may be linear or branched. In addition, each repeating unit represented by a parenthesis containing p, q, r, s, t, u, or v may be randomly bonded. Specifically, the following groups can be exemplified as Rf.

[0070] [Chemical 10]

[0071] CF3O(CF2O) p′ CF2-

[0072] CF3O(CF2O) p′ (CF2CF2O) q′ CF2-

[0073] CF3O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​

[0081] -CF2O(CF2O) p′ CF2-

[0082] -CF2O(CF2O) p′ (CF2CF2O) q′ CF2-

[0083] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2-

[0084] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2CF2O) s′ CF2-

[0085] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ CF2-

[0086] -CF2CF2O(CF2CF2CF2O) r′ CF2CF2-

[0087]

[0088] (In the formula, p', q', r', s', t', and u' are each an integer greater than or equal to 1, and the upper limit thereof is the same as the upper limit of p, q, r, s, t, and u described above. The total of these p', q', r', s', t', and u' is 3 to 200. R2' and R3' are each an integer greater than or equal to 1, and the total of R2' and R3' is 2 to 199. The repeating units shown in parentheses with p', q', r', s', t', and u' may be randomly bonded.)

[0089] In the above formula (1), V is independently a monovalent group having a silyl group or a hydrolyzable silyl group containing a hydroxyl group at the terminal and having no polar group other than the silyl group containing a hydroxyl group or the hydrolyzable silyl group. Preferably, it is a monovalent group consisting of a silyl group or a hydrolyzable silyl group containing a hydroxyl group at the terminal and a linking group having no polar group connecting the silyl group and a CH group. More preferably, it is a monovalent organic group having a plurality of hydroxyl groups or hydrolyzable groups bonded to silicon atoms introduced at the terminal. Examples of such V include groups represented by the following formulae (5a) to (5e).

[0090] [Chemistry 11]

[0091]

[0092] (In the formula, L is a single bond or a divalent heteroatom, D is a divalent organic group having 1 to 20 carbon atoms which may be substituted with fluorine, R is each independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is each independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, a is an integer of 2 to 6, b is independently an integer of 2 to 8, and c is an integer of 1 to 50.)

[0093] In the above formulas (5a) to (5e), ​​L is a single bond or a divalent heteroatom. Examples of the divalent heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom. Preferably, of the two Vs bonded to the carbon atom in formula (1), one L is a single bond and the other L is a divalent heteroatom.

[0094] In the above formulas (5a) to (5e), ​​D is a divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, which may be substituted with fluorine. It is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, which may be substituted with fluorine. Examples of the divalent hydrocarbon group include alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, and octamethylene, arylene groups such as phenylene, combinations of two or more of these groups (alkylene-arylene, etc.), and groups in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms. D is preferably ethylene, propylene, butylene, hexamethylene, or phenylene.

[0095] In the above formulae (5a) to (5e), ​​R is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, or a phenyl group, and among them, a methyl group is preferred.

[0096] X may be different from each other and may be a hydroxyl group or a hydrolyzable group. Examples of such X include hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups, alkoxyalkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy and methoxyethoxy groups, acyloxy groups having 1 to 10 carbon atoms, such as acetoxy groups, alkenyloxy groups having 2 to 10 carbon atoms, such as isopropenyloxy groups, and halogen groups, such as chloro, bromo, and iodo groups. Among these, methoxy, ethoxy, isopropenyloxy, and chloro groups are preferred.

[0097] In the above formulas (5a) to (5e), ​​n is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 from the viewpoint of reactivity and adhesion to the substrate. a is an integer of 2 to 6, preferably an integer of 2 to 4, b is independently an integer of 2 to 8, preferably an integer of 2 to 4, and c is an integer of 1 to 50, preferably an integer of 1 to 9.

[0098] Specific examples of such V include the following groups.

[0099] [Chemistry 12]

[0100] -O-CH2CH2CH2-Si(OCH3)3

[0101] -O-CH2CH2CH2CH2-Si(OCH3)3

[0102] -CH2CH2CH2CH2-Si(OCH3)3

[0103] -CH2CH2CH2CH2CH2-Si(OCH3)3

[0104] -CH2CH2CH2CH2CH2CH2CH2-Si(OCH3)3

[0105] [Chemistry 13]

[0106]

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

[0108] The fluoropolyether group-containing polymer of the present invention is more preferably represented by the following general formula (2).

[0109] [Chemistry 14]

[0110]

[0111] (In the formula, Rf, L, R, X, n, and α are the same as those described above; Y is independently a di- to hexavalent hydrocarbon group, which may have a silicon atom and / or a siloxane bond; and m is an integer from 1 to 5.)

[0112] In the above formula (2), L, like the above-mentioned L, is each independently a single bond or a divalent heteroatom. Examples of the divalent heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom. Preferably, among the Ls present at each end of the molecular chain (i.e., when α=1, there are two at one end of the molecular chain, and when α=2, there are two at each end of the molecular chain (i.e., there are four in the molecule)), it is preferred that at each end of the molecular chain, one L is an oxygen atom and the other L is a single bond.

[0113] In the above formula (2), each Y is independently a hydrocarbon group having a valence of 2 to 6, preferably 2 to 4, more preferably 2, and may have a silicon atom and / or a siloxane bond. By not containing a polar group in Y, a coating film having excellent water roll-off properties can be formed.

[0114] Specific examples of Y include alkylene groups having 3 to 10 carbon atoms, such as propylene, butylene, and hexamethylene; alkylene groups containing arylene groups having 6 to 8 carbon atoms, such as phenylene (e.g., alkylene-arylene groups having 8 to 16 carbon atoms); divalent groups in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure; and divalent organic polysiloxane residues having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, bonded to the ends thereof. The present invention also includes a divalent to hexavalent group containing an alkylene group having 2 to 10 carbon atoms, an alkylene group containing a phenylene group, a divalent group in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the end of a linear or branched or cyclic divalent to tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, and an alkylene group having 3 to 6 carbon atoms is more preferable.

[0115] Among them, the following structures can be exemplified as the silanylene structure and the silanylene structure.

[0116] [Chemistry 15]

[0117]

[0118] (Where R 1 is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, or an aryl group having 6 to 10 carbon atoms, such as phenyl, 1 Can be the same or different. 2 It is an alkylene group having 1 to 4 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), or an arylene group having 6 to 10 carbon atoms, such as phenylene.

[0119] Examples of the linear, branched or cyclic di- to hexavalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, include the following groups.

[0120] [Chemistry 16]

[0121]

[0122] [Chemistry 17]

[0123]

[0124] (Where R 1 Same as above. g is an integer of 1 to 9, preferably an integer of 1 to 4, h is an integer of 2 to 6, preferably an integer of 2 to 4, j is an integer of 0 to 8, preferably 0 or 1, h+j is an integer of 3 to 10, preferably an integer of 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3.

[0125] Examples of Y include groups represented by the following formulae.

[0126] [Chemistry 18]

[0127]

[0128] (In the formula, D, a, and b are the same as above, and c' is an integer from 1 to 9.)

[0129] Specific examples of Y include the following groups.

[0130] [Chemistry 19]

[0131]

[0132] [Chemistry 20]

[0133]

[0134] m is an integer of 1 to 5. If it is less than 1, the adhesion to the substrate decreases. If it is 6 or more, the terminal alkoxy value is too high, which adversely affects the performance. It is preferably an integer of 1 to 3, and particularly preferably 1.

[0135] Examples of the fluoropolyether group-containing polymer represented by the above formula (2) include polymers represented by the following formulas: In each formula, the number of repetitions (or degree of polymerization) of each repeating unit constituting a fluorooxyalkyl group or a fluorooxyalkylene group (a monovalent or divalent fluorooxyalkylene group-containing polymer residue) is as shown below, and may be any number as long as it satisfies the above formulas (3) and (4).

[0136] [Chemistry 21]

[0137]

[0138] [Chemistry 22]

[0139]

[0140] [Chemistry 23]

[0141]

[0142] [Chemistry 24]

[0143]

[0144] (In the formula, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, r1 is an integer of 1 to 100, r2 is an integer of 1 to 99, and r3 is an integer of 1 to 99. The total of p1, q1, r1, r2, and r3 (for example, p1+q1, p1+q1+r1, or p1+q1+r2+r3) is an integer of 10 to 110. The repeating units shown in parentheses with p1, q1, r1, r2, and r3 may be randomly bonded.)

[0145] Examples of methods for producing a fluoropolyether group-containing polymer represented by the above formula (2) where α is 1 (i.e., when Rf is a monovalent fluorooxyalkylene-containing polymer residue) or α is 2 (i.e., when Rf is a divalent fluorooxyalkylene-containing polymer residue) include the following methods.

[0146] First, let the following general formula (6)

[0147] [Chemistry 25]

[0148]

[0149] (In the formula, Rf and α are the same as above, and M is a detachable monovalent group.)

[0150] The fluoropolyether group-containing polymer having a terminal carbonyl group is preferably reacted with an organometallic reagent having a terminal aliphatic unsaturated double bond (olefin moiety) and β-hydrogen (i.e., a hydrogen atom bonded to a carbon atom at the β position of the metal atom) in the presence of a solvent.

[0151] In the above formula (6), M is a detachable monovalent group, examples of which include a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, a thiol group, an alkylthio group, and an acyl group.

[0152] Examples of such M include the following groups.

[0153] [Chemistry 26]

[0154]

[0155] Specific examples of the fluoropolyether group-containing polymer having a terminal carbonyl group represented by formula (6) include the following polymers. In each formula, the number of repetitions (or degree of polymerization) of each repeating unit constituting a fluorooxyalkyl group or a fluorooxyalkylene group (a monovalent or divalent fluorooxyalkylene group-containing polymer residue) is as shown below, and may be any number as long as it satisfies formulas (3) and (4).

[0156] [Chemistry 27]

[0157]

[0158] (In the formula, p1, q1, and r1 are the same as those described above, and the total of each p1, q1, and r1 is an integer from 10 to 110. In addition, the repeating units shown in parentheses with p1, q1, and r1 may be randomly bonded.)

[0159] Specific examples of the organometallic reagent having an aliphatic unsaturated double bond at the terminal and a β-hydrogen group include organolithium reagents, Grignard reagents, organozinc reagents, organoboron reagents, and organotin reagents. Grignard reagents and organozinc reagents are particularly preferred due to their ease of handling. Among these organometallic reagents, the following reagents are particularly preferred.

[0160] [Chemistry 28]

[0161]

[0162] The amount of the organometallic reagent having an aliphatic unsaturated double bond at the terminal and having β-hydrogen used is preferably 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and even more preferably about 3 equivalents, relative to 1 equivalent of the reactive terminal group (detachable monovalent group) of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by the above formula (6).

[0163] In the reaction of the polymer containing a fluoropolyether group having a carbonyl group at the end represented by formula (6) and an organic metal reagent having an aliphatic unsaturated double bond and β hydrogen at the end, a solvent can be used. The solvent used at this time is not particularly limited. Since the reaction compound is a fluorine compound, a fluorine-based solvent is preferably used. As a fluorine-based solvent, 1,3-bis(trifluoromethylbenzene), trifluoromethylbenzene, a perfluoro-based solvent sold by AGC (Asahiklin AC2000, Asahiklin AC6000, etc.), a hydrofluoroether (HFE) solvent sold by 3M (NOVEC7100: C4F9OCH3, NOVEC7200: C4F9OC2H5, NOVEC7300: C2F5-CF(OCH3)-CF(CF3)2, etc.), and a perfluoro-based solvent also sold by 3M (PF5080, PF5070, PF5060, etc.) can be listed. Fluorinated solvents can be used alone or in combination.

[0164] In addition, as a solvent, in addition to the above-mentioned fluorine-based solvents, an organic solvent can be used. As an organic solvent, ether solvents such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used. The organic solvent can be used alone or mixed with a fluorine-based solvent.

[0165] The amount of the solvent used is 10 to 600 parts by mass, preferably 50 to 400 parts by mass, and more preferably about 200 to 350 parts by mass per 100 parts by mass of the fluoropolyether group-containing polymer having a terminal carbonyl group represented by formula (6).

[0166] The reaction conditions of the fluoropolyether group-containing polymer having a carbonyl group at the terminal represented by formula (6) and the organometallic reagent having an aliphatic unsaturated double bond at the terminal and having β-hydrogen can be set to 0 to 80° C., preferably 45 to 70° C., more preferably about 50° C., for 1 to 12 hours, preferably 5 to 7 hours.

[0167] After the reaction is carried out under the above conditions, the reaction is stopped and the aqueous layer and the fluorinated solvent layer are separated by liquid separation. The obtained fluorinated solvent layer is further washed with an organic solvent and the solvent is distilled off to obtain a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal, as represented by the following formula (7).

[0168] [Chemistry 29]

[0169]

[0170] (In the formula, Rf and α are the same as above, and Z is independently a divalent hydrocarbon group, which may contain a silicon atom and / or a siloxane bond.)

[0171] In the above formula (7), Z is a divalent hydrocarbon group, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, particularly 2 to 12 carbon atoms. Specific examples include alkylene groups having 1 to 8 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, and octamethylene; and alkylene groups including arylene groups having 6 to 8 carbon atoms, such as phenylene (e.g., alkylene-arylene groups having 7 to 8 carbon atoms). Z is preferably a straight-chain alkylene group having 1 to 4 carbon atoms.

[0172] Examples of such Z include the following groups.

[0173] [Chemistry 30]

[0174]

[0175] Specific examples of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (7) include the following polymers. In each formula, the number of repetitions (or degree of polymerization) of each repeating unit constituting a fluorooxyalkyl group or a fluorooxyalkylene group (a monovalent or divalent fluorooxyalkylene group-containing polymer residue) is as shown below, and may be any number as long as it satisfies formulas (3) and (4).

[0176] [Chemistry 31]

[0177]

[0178] [Chemistry 32]

[0179]

[0180] [Chemistry 33]

[0181]

[0182] (In the formula, p1, q1, and r1 are the same as those described above, and the total of each p1, q1, and r1 is an integer from 10 to 110. In addition, the repeating units shown in parentheses with p1, q1, and r1 may be randomly bonded.)

[0183] Next, the fluoropolyether group-containing polymer represented by formula (7) obtained above and having a hydroxyl group and an olefin moiety at the end of the molecular chain is aged with an olefin-introducing agent in the presence of a base, using, as needed, an additive or a solvent for improving reactivity, at a temperature of 0 to 90° C., preferably 40 to 60° C., more preferably about 50° C., for 1 to 48 hours, preferably 10 to 40 hours, more preferably about 24 hours.

[0184] Among them, as the olefin-introducing agent that reacts with the fluoropolyether group-containing polymer represented by formula (7) having a hydroxyl group and an olefin moiety at the molecular chain terminal, for example, halides can be used, and specific examples include allyl bromide, allyl chloride, and 3-butenyl bromide.

[0185] The amount of the olefin-introducing agent used is 1 to 15 equivalents, more preferably 3 to 6 equivalents, and even more preferably about 4 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (7).

[0186] As the base used in the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (7) and the olefin-introducing agent, for example, amines and alkali metal bases can be used. Specific examples of amines include triethylamine, diisopropylethylamine, pyridine, DBU, and imidazole. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithiums, potassium tert-butoxide, lithium diisopropylamine, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide.

[0187] The amount of the base used is 1 to 20 equivalents, more preferably 4 to 8 equivalents, and even more preferably about 6 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (7).

[0188] In the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (7) above with an olefin-introducing agent, tetrabutylammonium halide, alkali metal halide, and the like can be used as additives to enhance reactivity. Specific examples of such additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, and crown ethers. These additives enhance reactivity by catalytically exchanging halogens with the olefin-introducing agent in the reaction system. Crown ethers also enhance reactivity by coordinating with metals.

[0189] The amount of the additive used is 0.005 to 0.1 equivalents, more preferably 0.01 to 0.05 equivalents, and even more preferably about 0.02 equivalents, relative to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (7).

[0190] In the reaction of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by formula (7) and the olefin-introducing agent, a solvent may be used. A solvent is not necessarily used, but as a solvent used, examples of fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene, hydrofluoroether (HFE) solvents such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name: Novec series), and perfluorosolvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series) can be listed. Furthermore, as an organic solvent, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, THF, etc. can be used.

[0191] When a solvent is used, the amount used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass, relative to 100 parts by mass of the fluoropolyether group-containing polymer represented by formula (7) having a hydroxyl group and an olefin moiety at the molecular chain terminal.

[0192] By reacting the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the above formula (7) with an olefin-introducing agent, a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminal represented by the following formula (8) is obtained.

[0193] [Chemistry 34]

[0194]

[0195] (Wherein, Rf, Z, and α are the same as above.)

[0196] Preferred examples of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals represented by formula (8) include the following polymers. In each formula, the number of repetitions (or degree of polymerization) of each repeating unit constituting a fluorooxyalkyl group or a fluorooxyalkylene group (a monovalent or divalent fluorooxyalkylene group-containing polymer residue) is as shown below, and may be any number as long as it satisfies formulas (3) and (4).

[0197] [Chemistry 35]

[0198]

[0199] [Chemistry 36]

[0200]

[0201] (In the formula, r1, p1, and q1 are the same as those described above, and the total of p1, q1, and r1 is an integer from 10 to 110. In addition, the repeating units shown in parentheses with p1, q1, and r1 may be randomly bonded.)

[0202] Next, the fluoropolyether group-containing polymer represented by formula (8) obtained above and having two olefin moieties at the ends of the molecular chain is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organic silicon compound having an SiH group and a hydrolyzable terminal group in the molecule such as trimethoxysilane is mixed, and the mixture is aged at a temperature of 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, thereby obtaining the fluoropolyether group-containing polymer represented by formula (2) above.

[0203] In addition, as another method for producing the fluoropolyether group-containing polymer represented by the above formula (2), for example, the following method can be mentioned.

[0204] The fluoropolyether group-containing polymer represented by formula (8) obtained above and having two olefin moieties at the molecular chain terminals is dissolved in a solvent such as a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organosilicon compound having a SiH group and a hydrolyzable terminal group (halogen atom) in the molecule such as trichlorosilane. The mixture is then aged at 40 to 120°C, preferably 60 to 100°C, and more preferably about 80°C, in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours. After aging, the substituent (halogen atom) on the silyl group may be converted to, for example, a methoxy group.

[0205] Furthermore, instead of the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule, an organosilicon compound containing a SiH group but not having a hydrolyzable terminal group can be used. In this case, an organosilicon compound having no hydrolyzable terminal group and having two or more SiH groups in the molecule is used as the organosilicon compound. In this case, the fluoropolyether group-containing polymer represented by formula (8) having two olefin moieties at the molecular chain terminals is reacted with an organosilicon compound having no hydrolyzable terminal group and having two or more SiH groups in the molecule, in the same manner as the above method. The SiH groups at the polymer terminals of the reactant are then mixed with an organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule, such as allyltrimethoxysilane, and the mixture is aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C., for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst, such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex.

[0206] Among them, in the preparation of the fluoropolyether group-containing polymer represented by formula (2), preferred organic silicon compounds having SiH groups and hydrolyzable terminal groups in the molecule are compounds represented by the following general formulae (9a) to (9d).

[0207] [Chemistry 37]

[0208]

[0209] (Where R, X, n, R 1 、R 2 , g, j are the same as above. i is an integer of 1 to 5, preferably an integer of 1 to 3, i+j is an integer of 2 to 9, preferably an integer of 2 to 4, R 3 A divalent hydrocarbon group having 2 to 8 carbon atoms.

[0210] Among them, as R 3The divalent hydrocarbon group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, may include methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), alkylene groups such as hexamethylene and octamethylene, arylene groups such as phenylene, or combinations of two or more of these groups (alkylene-arylene, etc.), among which ethylene and trimethylene are preferred.

[0211] Examples of such organosilicon compounds having a SiH group and a hydrolyzable terminal group in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silane compounds.

[0212] [Chemistry 38]

[0213]

[0214] In the preparation of the fluoropolyether group-containing polymer represented by formula (2), when subjecting the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals to an addition reaction with the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, the amount of the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule can be such that the SiH group in the organosilicon compound becomes 1.5 to 4 equivalents, more preferably 2 to 2.5 equivalents, per 1 equivalent of the reactive terminal group (terminal olefin moiety) of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals.

[0215] In the preparation of the fluoropolyether group-containing polymer represented by formula (2), preferred organic silicon compounds having no hydrolyzable terminal group and two or more SiH groups in the molecule are compounds represented by the following general formulae (10a) to (10c).

[0216] [Chemistry 39]

[0217]

[0218] (Where R 1 、R 2 , g, h, j, and h+j are the same as above.)

[0219] Examples of such an organosilicon compound having no hydrolyzable terminal group and having two or more SiH groups in the molecule include the following compounds.

[0220] [Chemistry 40]

[0221]

[0222] In the preparation of the fluoropolyether group-containing polymer represented by formula (2), when the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals is subjected to an addition reaction with an organosilicon compound having no hydrolyzable terminal group and having two or more SiH groups in the molecule, the amount of the organosilicon compound having no hydrolyzable terminal group and having two or more SiH groups in the molecule can be such that the SiH groups in the organosilicon compound are in an amount of 5 to 30 equivalents, more preferably 7 to 20 equivalents, and even more preferably about 10 equivalents, relative to 1 equivalent of the reactive terminal group (terminal olefin moiety) of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals.

[0223] In the preparation of the fluoropolyether group-containing polymer represented by formula (2), examples of the addition reaction products of a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals and an organosilicon compound having no hydrolyzable terminal groups and having two or more SiH groups in the molecule include the following addition reaction products. In each formula, the number of repetitions (or degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group or fluorooxyalkylene group (monovalent or divalent fluorooxyalkylene group-containing polymer residue) is as shown below and may be any number as long as it satisfies formulas (3) and (4).

[0224] [Chemistry 41]

[0225]

[0226] (In the formula, p1 and q1 are the same as above, and the total of p1 and q1 is an integer from 10 to 110. In addition, the repeating units shown in the parentheses with p1 and q1 may be randomly bonded.)

[0227] In addition, in the preparation of the fluoropolyether group-containing polymer represented by formula (2), the organic silicon compound having an olefin portion and a hydrolyzable terminal group in the molecule to react with the SiH group at the polymer terminal of the above-mentioned addition reaction product is preferably a compound represented by the following general formula (11).

[0228] [Chemistry 42]

[0229]

[0230] (In the formula, R, X, and n are the same as above. U is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms.)

[0231] In the above formula (11), U is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the divalent hydrocarbon group having 1 to 6 carbon atoms include alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), and hexamethylene, and phenylene. U is preferably a single bond or a methylene group.

[0232] Examples of such an organosilicon compound having an olefin moiety and a hydrolyzable terminal group in a molecule include the following compounds.

[0233] [Chemistry 43]

[0234] CH2=CHCH2-Si(OCH3)3

[0235] CH2=CHCH2CH2-Si(OCH3)3

[0236] In the preparation of the fluoropolyether group-containing polymer represented by formula (2), when reacting the addition reaction product of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals and the organosilicon compound having no hydrolyzable terminal group and two or more SiH groups in the molecule with the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule, the amount of the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule can be such that the olefin moiety in the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule is 1.5 to 4 equivalents, more preferably 2 to 2.5 equivalents, per 1 equivalent of the reactive terminal groups (SiH groups at the molecular terminals) of the addition reaction product of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals and the organosilicon compound having no hydrolyzable terminal group and two or more SiH groups in the molecule.

[0237] In the preparation of the polymer containing a fluoropolyether group represented by the above-mentioned formula (2), a fluorine-based solvent is preferably used as the solvent. Examples of the fluorine-based solvent include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), and perfluoro solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series).

[0238] The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals.

[0239] In the preparation of the fluoropolyether group-containing polymer represented by formula (2), examples of hydrosilylation reaction catalysts include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylenic alcohols, and the like, and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinylsiloxane complexes are preferred.

[0240] The amount of the hydrosilylation reaction catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (mass), relative to the mass of the fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminals, or the reaction product of the polymer and an organosilicon compound having no hydrolyzable terminal group and having two or more SiH groups in the molecule.

[0241] Then, the solvent and unreacted products are distilled off under reduced pressure to obtain the target compound.

[0242] For example, as a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain ends, a compound represented by the following formula is used:

[0243] [Chemistry 44]

[0244]

[0245] When trimethoxysilane is used as the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule, a compound represented by the following formula is obtained.

[0246] [Chemistry 45]

[0247]

[0248] For example, as a fluoropolyether group-containing polymer having two olefin moieties at the molecular chain terminal, a compound represented by the following formula is used.

[0249] [Chemistry 46]

[0250]

[0251] When trimethoxysilane is used as the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule, a compound represented by the following formula is obtained.

[0252] [Chemistry 47]

[0253]

[0254] The present invention provides a surface treatment agent containing a fluoropolyether group-containing polymer having a hydroxyl-containing silyl group or a hydrolyzable silyl group represented by the above formula (1), particularly a fluoropolyether group-containing polymer having a hydroxyl-containing silyl group or a hydrolyzable silyl group represented by the above formula (2). The surface treatment agent may comprise a partial (hydrolyzed) condensate obtained by condensing the hydroxyl groups of the fluoropolyether group-containing polymer or the terminal hydrolyzable groups of the fluoropolyether group-containing polymer partially hydrolyzed in advance by a known method.

[0255] If necessary, a hydrolysis condensation catalyst may be added to the surface treatment agent, such as an organotin compound (dibutyl dimethoxytin, dibutyl tin dilaurate, etc.), an organotitanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetra-n-butyl titanate, dibutyl tin dilaurate, and fluorine-modified carboxylic acid are particularly preferred.

[0256] The amount of the hydrolysis-condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer and / or its partial (hydrolysis) condensate.

[0257] The surface treatment agent may contain an appropriate solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferred from the perspectives of solubility and wettability, and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are particularly preferred.

[0258] The above-mentioned solvents may be mixed with two or more thereof, preferably so that the fluoropolyether group-containing polymer and its partial (hydrolysis) condensate are uniformly dissolved. The optimal concentration of the fluoropolyether group-containing polymer and its partial (hydrolysis) condensate dissolved in the solvent varies depending on the treatment method, but any amount that can be easily weighed may be sufficient. In the case of direct coating, the concentration is preferably 0.01 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer (and its partial (hydrolysis) condensate). In the case of vapor deposition, the concentration is preferably 1 to 100 parts by mass, particularly preferably 3 to 30 parts by mass, relative to 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer (and its partial (hydrolysis) condensate).

[0259] The surface treatment agent of the present invention can be applied to the substrate by known methods such as brush coating, dipping, spraying, and vapor deposition. The heating method during vapor deposition can be a resistance heating method or an electron beam heating method, and is not particularly limited. In addition, the curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferably at 25 to 200°C, especially at 25 to 80°C for 30 minutes to 36 hours, especially 1 to 24 hours. In addition, when vapor deposition is used, the range of 20 to 200°C is preferred. In addition, it can be cured under humidification. The film thickness of the cured film is appropriately selected according to the type of substrate, and is generally 0.1 to 100 nm, especially 1 to 20 nm. In addition, for example, in spraying, after dilution and hydrolysis in a fluorine-based solvent to which water has been added in advance, that is, Si-OH is generated, and then spraying is performed, the curing after coating is fast.

[0260] There is no particular limitation on the substrate to be treated with the surface treatment agent of the present invention, and the substrate may be any of various materials, such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc. The surface treatment agent of the present invention can impart water and oil repellency, steel wool abrasion resistance, and water roll-off properties to the substrate. In particular, the surface treatment agent can be suitably used as a surface treatment agent for SiO2-treated glass and membranes.

[0261] As the article processed with the surface treatment agent of the present invention, can enumerate the medical instruments such as car navigation, mobile phone, smart phone, digital camera, digital video camera, PDA, portable audio player, car audio, game console, eyeglass lens, camera lens, lens filter, sunglasses, gastroscope, copy machine, PC, liquid crystal display, organic EL display, plasma display, touch panel display, protective film, anti-reflection film and other optical articles.The surface treatment agent of the present invention can prevent the attachment of fingerprints and sebum to the above-mentioned articles, and then can impart anti-scratch property (wear resistance), therefore particularly can be used as the water-repellent and oil-repellent layer of touch panel display, anti-reflection film etc.

[0262] Furthermore, the surface treatment agent of the present invention can also be used as an antifouling coating for sanitary products such as bathtubs and washbasins, an antifouling coating for window glass or tempered glass of automobiles, trains, aircraft, etc., an antifouling coating for headlight covers, etc., a water- and oil-repellent coating for exterior building materials, an anti-oil coating for kitchen building materials, an antifouling and anti-sticker / graffiti coating for telephone boxes, an anti-fingerprint coating for artworks, an anti-fingerprint coating for CDs, DVDs, etc., a release agent or coating additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, and a lubricity enhancer for tapes, films, etc.

[0263] Example

[0264] The present invention will be described in more detail below with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples.

[0265] [Example 1]

[0266] 272 ml of 3-butenylmagnesium bromide (0.5 M THF solution: 1.4 × 10 -1 mol), and stirred. Then, the following formula (A)

[0267] [Chemistry 48]

[0268]

[0269] The compound represented by 200g (4.5×10 -2 mol), 400g of Asahiklin AC6000 and 200g of PF5060 were dripped into the reaction container and heated at 50°C for 6 hours. After the heating was completed, the mixture was cooled to room temperature and a hydrochloric acid aqueous solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation operation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (B):

[0270] [Chemistry 49]

[0271]

[0272] 193 g of the polymer containing fluoropolyether groups was expressed (number average molecular weight; about 4430).

[0273] 1 H-NMR

[0274] δ1.4-1.7(CC H2 CH2CH=CH2)2H

[0275] δ1.9-2.2(CC H2 CH2CH=CH2、-CF2-CH(O H )-CH2-)3H

[0276] δ3.6-3.8(-CF2-C H (OH)-CH2-)1H

[0277] δ4.8-4.9(-CH2CH=C H2 )2H

[0278] δ5.5-5.6(-CH2C H =CH2)1H

[0279] The above-obtained

[0280] [Chemistry 50]

[0281]

[0282] The compound represented by 100g (2.3×10 -2 mol), allyl bromide 11g (9.2×10 -2 mol), tetrabutylammonium iodide 0.17 g (4.6 × 10 -4 Then, 18 g (1.4 × 10 -1 mol) and heated at 50°C for 24 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (C):

[0283] [Chemistry 51]

[0284]

[0285] The amount of the fluoropolyether group-containing polymer was 97 g.

[0286] 1 H-NMR

[0287] δ1.5-1.7(CC H2 CH2CH=CH2)2H

[0288] δ1.9-2.1(C-CH2C H2 CH=CH2)2H

[0289] δ3.4-3.5(CF2-C H (OCH2CH=CH2))1H

[0290] δ3.8-3.9(CF2-CH(OC H2 CH=CH2))1H

[0291] δ4.1-4.2(CF2-CH(OC H2 CH=CH2))1H

[0292] δ4.8-4.9(CF2-CH(OCH2CH=C H2 ))2H

[0293] δ5.0-5.2(C-CH2CH2CH=C H2 )2H

[0294] δ3.4-3.5(CF2-CH(OCH2C H =CH2))1H

[0295] δ5.7-5.8(C-CH2CH2C H =CH2)1H

[0296] In a reaction container, the above-obtained

[0297] [Chemistry 52]

[0298]

[0299] The compound represented by 80g (1.8×10 -2 mol), 1,3-bis(trifluoromethyl)benzene 80 g, trimethoxysilane 8.8 g (7.2×10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 8.0×10 -2 g (calculated as Pt element, containing 2.4×10 -7 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain 84 g of a liquid product.

[0300] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (D).

[0301] [Chemistry 53]

[0302]

[0303] 1 H-NMR

[0304] δ0.4-0.6(-O-CH2CH2C H2 -Si、C-CH2CH2CH2C H2 -Si)4H

[0305] δ1.2-1.7(-O-CH2C H2 CH2-Si、CC H2 C H2 C H2 CH2-Si)8H

[0306] δ3.4-3.5(CF2-C H (-O-CH2CH2CH2-Si))1H

[0307] δ3.3-3.7(-OC H2 CH2CH2-Si、-Si(OCH3 )3)20H

[0308] [Example 2]

[0309] 272 ml of 5-hexenylmagnesium bromide (0.5 M THF solution: 1.36 × 10 -1 mol), and stirred. Then, the following formula (A)

[0310] [Chemistry 54]

[0311]

[0312] The compound represented by 200g (4.5×10 -2 mol), 400g of Asahiklin AC6000 and 200g of PF5060 were dripped into the reaction container and heated at 50°C for 6 hours. After the heating was completed, the mixture was cooled to room temperature and a hydrochloric acid aqueous solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (E):

[0313] [Chemistry 55]

[0314]

[0315] The amount of the polymer containing fluoropolyether groups was 189 g (number average molecular weight; about 4450).

[0316] 1 H-NMR

[0317] δ1.3-1.8(CC H2 C H2 C H2 CH2CH=CH2)6H

[0318] δ1.9-2.1(C-CH2CH2CH2C H2 CH=CH2)2H

[0319] δ3.3-3.5(-CF2-CH(O H )-CH2-)1H

[0320] δ3.6-3.8(-CF2-C H (OH)-CH2-)1H

[0321] δ4.7-4.9(-CH2CH=C H2 )2H

[0322] δ5.5-5.7(-CH2C H=CH2)1H

[0323] The above-obtained

[0324] [Chemistry 56]

[0325]

[0326] The compound represented by 20g (4.5×10 -3 mol), allyl bromide 2.2g (1.8×10 -2 mol), tetrabutylammonium iodide 0.03 g (9.0 × 10 -5 Then, 3.6 g (2.7 × 10 -2 mol) and heated at 50°C for 24 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (F):

[0327] [Chemistry 57]

[0328]

[0329] 21 g of the fluoropolyether group-containing polymer was expressed.

[0330] 1 H-NMR

[0331] δ1.3-1.8(CC H2 C H2 C H2 CH2CH=CH2)6H

[0332] δ1.9-2.1(C-CH2CH2CH2C H2 CH=CH2)2H

[0333] δ3.4-3.5(CF2-C H (OCH2CH=CH2))1H

[0334] δ3.8-3.9(CF2-CH(OC H2 CH=CH2))1H

[0335] δ4.1-4.2(CF2-CH(OC H2 CH=CH2))1H

[0336] δ4.8-4.9(CF2-CH(OCH2CH=C H2 ))2H

[0337] δ5.0-5.2(C-CH2CH2CH=C H2 )2H

[0338] δ3.4-3.5(CF2-CH(OCH2C H =CH2))1H

[0339] δ5.7-5.8(C-CH2CH2C H =CH2)1H

[0340] The above-obtained

[0341] [Chemistry 58]

[0342]

[0343] The compound represented by 10g (2.2×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 10 g, trimethoxysilane 1.1 g (8.8×10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.0×10 -2 g (calculated as Pt element, containing 3.0×10 -8 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain 9.7 g of a liquid product.

[0344] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (G).

[0345] [Chemistry 59]

[0346]

[0347] 1 H-NMR

[0348] δ0.4-0.6(-O-CH2CH2C H2 -Si、C-CH2CH2CH2C H2 -Si)4H

[0349] δ1.1-1.8(-O-CH2C H2 CH2-Si、CC H2 C H2 C H2 C H2 C H2 CH2-Si)12H

[0350] δ3.6-3.7(CF2-CH (-O-CH2CH2CH2-Si))1H

[0351] δ3.3-3.7(-OC H2 CH2CH2-Si、-Si(OC H3 )3)20H

[0352] [Example 3]

[0353] 126 ml of 3-butenyl magnesium bromide (0.5 M THF solution: 6.3 × 10 -2 mol), and stirred. Then, the following formula (H)

[0354] [Chemistry 60]

[0355]

[0356] The compound represented by 100g (2.1×10 -2 mol), 200g of Asahiklin AC6000 and 100g of PF5060 were dripped into a reaction vessel and heated at 50°C for 6 hours. After the heating was completed, the mixture was cooled to room temperature and a hydrochloric acid aqueous solution was dripped into the reaction vessel. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (I):

[0357] [Chemistry 61]

[0358]

[0359] The amount of the fluoropolyether group-containing polymer represented was 96 g (number average molecular weight; about 4800).

[0360] 1 H-NMR

[0361] δ1.4-1.7(CC H2 CH2CH=CH2)2H

[0362] δ1.9-2.2(CC H2 CH2CH=CH2、-CF(CF3)-CH(O H )-CH2-)3H

[0363] δ3.5-3.7(-CF(CF3)-C H (OH)-CH2-)1H

[0364] δ4.8-4.9(-CH2CH=C H2 )2H

[0365] δ5.5-5.6(-CH2C H =CH2)1H

[0366] In a reaction container, the above-obtained

[0367] [Chemistry 62]

[0368]

[0369] The compound represented by 20g (4.2×10 -3 mol), allyl bromide 2.1g (1.7×10 -2 mol), tetrabutylammonium iodide 0.03 g (8.4 × 10 -5 Then, 3.4 g (2.5 × 10 -2 mol) and heated at 50°C for 24 hours. After heating, the mixture was cooled to room temperature and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again and the residual solvent was distilled off under reduced pressure to obtain the following formula (J):

[0370] [Chemistry 63]

[0371]

[0372] 19 g of the polymer containing fluoropolyether groups was expressed.

[0373] 1 H-NMR

[0374] δ1.5-1.7(CC H2 CH2CH=CH2)2H

[0375] δ2.1-2.3(C-CH2C H2 CH=CH2)2H

[0376] δ3.6-3.7(CF2-C H (OCH2CH=CH2))1H

[0377] δ3.9-4.0(CF2-CH(OC H2 CH=CH2))1H

[0378] δ4.2-4.3(CF2-CH(OC H2 CH=CH2))1H

[0379] δ4.8-4.9(CF2-CH(OCH2CH=C H2 ))2H

[0380] δ5.0-5.2(C-CH2CH2CH=C H2 )2H

[0381] δ3.4-3.5(CF2-CH(OCH2C H =CH2))1H

[0382] δ5.7-5.8(C-CH2CH2C H =CH2)1H

[0383] The above-obtained

[0384] [Chemistry 64]

[0385]

[0386] The compound represented by 10g (2.1×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 10 g, trimethoxysilane 1.0 g (8.2×10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.0×10 -2 g (calculated as Pt element, containing 3.0×10 -8 mol), and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain 9.7 g of a liquid product.

[0387] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (K).

[0388] [Chemistry 65]

[0389]

[0390] 1 H-NMR

[0391] δ0.4-0.6(-O-CH2CH2C H2 -Si、C-CH2CH2CH2C H2 -Si)4H

[0392] δ1.2-1.7(-O-CH2C H2 CH2-Si、CC H2 C H2 C H2 CH2-Si)8H

[0393] δ3.6-3.7(CF2-C H (-O-CH2CH2CH2-Si))1H

[0394] δ3.3-3.7(-OC H2 CH2CH2-Si、-Si(OC H3 )3)20H

[0395] [Example 4]

[0396] The above-obtained

[0397] [Chemistry 66]

[0398]

[0399] The compound represented by 20g (4.5×10 -3 mol) and the following formula (L)

[0400] [Chemistry 67]

[0401]

[0402] The siloxane represented is 6.0 g (4.5 × 10 -2 mol) and 20 g of 1,3-bis(trifluoromethyl)benzene were mixed and heated to 80°C. Then, 2.0×10 mol of a toluene solution of chloroplatinic acid / vinylsiloxane complex was added. -2 g (calculated as Pt element, containing 6.0×10 - 8 mol), and aged at 80°C for 24 hours. Then, the remaining solvent was distilled off under reduced pressure to obtain the following formula (M):

[0403] [Chemistry 68]

[0404]

[0405] 21 g of the fluoropolyether group-containing polymer was expressed.

[0406] 1 H-NMR

[0407] δ0-0.3(-Si-(C H3 )2-)24H

[0408] δ0.4-0.6(-O-CH2CH2C H2 -Si、C-CH2CH2CH2C H2 -Si)4H

[0409] δ1.2-1.7(-O-CH2CH2C H2 -Si、CC H2 C H2 C H 2CH2 -Si)8H

[0410] δ3.4-3.6(CF2-C H (-O-CH2CH2CH2-Si))1H

[0411] δ3.8-4.1(-Si(CH3) H )2H

[0412] In a reaction container, the above-obtained

[0413] [Chemistry 69]

[0414]

[0415] The compound represented by 10g (2.1×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 10 g, allyltrimethoxysilane 1.3 g (8.4×10 -3 mol) and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.0×10 -2 g (calculated as Pt element, containing 3.0×10 -8 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain 10 g of a liquid product.

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

[0417] [Chemistry 70]

[0418]

[0419] 1 H-NMR

[0420] δ0-0.3(-Si-(C H3 )2-)24H

[0421] δ0.4-0.7(-O-CH2CH2C H2 -Si、C-CH2CH2CH2C H2 -Si, Si-C H2 CH2C H2 -Si)12H

[0422] δ1.2-1.8(-O-CH2C H 2CH2-Si、CC H2 C H2 C H2 CH2-SiSi-CH2C H2CH2-Si)12H

[0423] δ3.4-3.5(CF2-C H (-O-CH2CH2CH2-Si))1H

[0424] δ3.3-3.7(-OC H2 CH2CH2-Si、-Si(OC H3 )3)20H

[0425] [Example 5]

[0426] 282 ml of 3-butenyl magnesium bromide (0.5 M THF solution: 1.4 × 10 -1 mol), and stirred. Then, the following formula (O)

[0427] [Chemistry 71]

[0428]

[0429] The compound represented by 100g (2.4×10 -2 mol), 200g of Asahiklin AC6000 and 100g of PF5060 were dripped into the reaction container and heated at 50°C for 6 hours. After the heating was completed, the mixture was cooled to room temperature and a hydrochloric acid aqueous solution was dripped into the reaction container. The fluorine compound layer as the lower layer was recovered by liquid separation and then washed with acetone. The washed fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain the following formula (P)

[0430] [Chemistry 72]

[0431]

[0432] The amount of the fluoropolyether group-containing polymer was 94 g (number average molecular weight: about 4400).

[0433] 1 H-NMR

[0434] δ1.4-1.7(CC H2 CH2CH=CH2)4H

[0435] δ1.9-2.2(CC H2 CH2CH=CH2、-CF2-CH(O H )-CH2-)6H

[0436] δ3.6-3.8(-CF2-C H (OH)-CH2-)2H

[0437] δ4.8-4.9(-CH2CH=C H2 )4H

[0438] δ5.5-5.6(-CH2C H =CH2)2H

[0439] In a reaction vessel, the above-obtained

[0440] [Chemistry 73]

[0441]

[0442] The compound represented by 20g (4.5×10 -3 mol), allyl bromide 4.4g (3.6×10 -2 mol), tetrabutylammonium iodide 0.06 g (1.8 × 10 -4 Then, 7.2 g (5.4 × 10 -2 mol), and then heated at 50°C for 24 hours. After the heating is completed, it is cooled to room temperature and a hydrochloric acid aqueous solution is added dropwise. The fluorine compound layer as the lower layer is recovered by liquid separation operation and then washed with acetone. The washed fluorine compound layer as the lower layer is recovered again, and the residual solvent is distilled off under reduced pressure to obtain the following formula (Q):

[0443] [Chemistry 74]

[0444]

[0445] 21 g of the fluoropolyether group-containing polymer was expressed.

[0446] 1 H-NMR

[0447] δ1.5-1.7(CC H2 CH2CH=CH2)4H

[0448] δ1.9-2.1(C-CH2C H2 CH=CH2)4H

[0449] δ3.4-3.5(CF2-C H (OCH2CH=CH2))2H

[0450] δ3.8-3.9(CF2-CH(OC H2 CH=CH2))2H

[0451] δ4.1-4.2(CF2-CH(OC H2 CH=CH2))2H

[0452] δ4.8-4.9(CF2-CH(OCH2CH=C H2 ))4H

[0453] δ5.0-5.2(C-CH2CH2CH=C H2 )4H

[0454] δ3.4-3.5(CF2-CH(OCH2C H =CH2))2H

[0455] δ5.7-5.8(C-CH2CH2C H =CH2)2H

[0456] The above-obtained

[0457] [Chemistry 75]

[0458]

[0459] The compound represented by 20g (4.5×10 -3 mol), 1,3-bis(trifluoromethyl)benzene 20 g, trimethoxysilane 4.4 g (3.6×10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.8×10 -2 g (calculated as Pt element, containing 1.4×10 -7 mol) were mixed and aged at 80° C. for 24 hours. Then, the solvent and unreacted products were distilled off under reduced pressure to obtain 20 g of a liquid product.

[0460] use 1 H-NMR confirmed that the obtained compound had a structure represented by the following formula (R).

[0461] [Chemistry 76]

[0462]

[0463] 1 H-NMR

[0464] δ0.4-0.6(-O-CH2CH2C H2 -Si、C-CH2CH2CH2C H2 -Si)8H

[0465] δ1.2-1.7(-O-CH2C H2 CH2-Si、CC H2 C H2 C H 2CH2-Si)16H

[0466] δ3.4-3.5(CF2-C H (-O-CH2CH2CH2-Si))2H

[0467] δ3.3-3.7(-OC H2 CH2CH2-Si、-Si(OC H3 )3)40H

[0468] As comparative examples, the following polymers were used.

[0469] [Comparative Example 1]

[0470] [Chemistry 77]

[0471]

[0472] [Comparative Example 2]

[0473] [Chemistry 78]

[0474]

[0475] Preparation of surface treatment agent and formation of cured film

[0476] The fluoropolyether group-containing polymers represented by formulas (D) and (G) obtained in Examples 1 and 2, and the polymers represented by formulas (S) and (T) obtained in Comparative Examples 1 and 2, were dissolved in Novec 7200 (3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare surface treatment agents. 4 μl of each surface treatment agent was vacuum-deposited (treatment conditions: pressure: 3.0×10 -3 Pa, heating temperature: 500° C.), and cured for 12 hours in an atmosphere of 25° C. and 50% humidity to form a cured film with a film thickness of 8 nm.

[0477] Evaluation of water and oil repellency

[0478] [Evaluation of initial water and oil repellency]

[0479] The contact angle (water repellency) of the cured film formed on the glass prepared above with respect to water was measured using a contact angle meter, Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, humidity: 40%). The results (initial water contact angle) are shown in Table 1.

[0480] In the initial stage, both the Examples and Comparative Examples showed good water repellency.

[0481] [Evaluation of wear resistance]

[0482] The glass with the cured film formed thereon was rubbed 10,000 times using a friction tester (manufactured by Shinto Scientific Co., Ltd.) in the same manner as above under the following conditions to measure the contact angle of the cured film with water (water repellency) to evaluate its abrasion resistance. The test environment was 25°C and 40% humidity. The results (water contact angle after abrasion) are shown in Table 1.

[0483] Steel wool abrasion resistance

[0484] Steel wool: BONSTER#0000

[0485] Contact area: 1cm 2

[0486] Travel distance (one way): 40mm

[0487] Moving speed: 4800mm / min

[0488] Load: 1kg / 1cm 2

[0489] [Table 1]

[0490]

[0491] The polymers of Examples 1, 2, and Comparative Example 2 had two or more reactive groups capable of adhering to the substrate, and thus adhered firmly to the substrate, maintaining a water contact angle of 110° or greater even after 10,000 steel wool abrasions. On the other hand, Comparative Example 1, which had only one reactive group, exhibited a water contact angle of less than 100° after 10,000 steel wool abrasions, demonstrating poor durability.

[0492] [Evaluation of water roll-off properties]

[0493] The water roll-off properties of the cured film on the glass formed with the cured film were evaluated using a contact angle meter, Drop Master (manufactured by Kyowa Interface Science Co., Ltd.).

[0494] Water roll-off

[0495] Droplet: 5μl, 10μl, 15μl, 20μl

[0496] Movement determination distance: 0.0536mm

[0497] Tilt mode: Continuous

[0498] Number of tests: 8 times (using the average value)

[0499] [Table 2]

[0500]

[0501] Since the polymers in Examples 1, 2, and Comparative Example 1 lack polar groups, they exhibited water roll-off angles of 20° or less even at a droplet size of 5 μl, and good water roll-off properties of 15° or less at a droplet size of 20 μl. On the other hand, Comparative Example 2, which possesses polar groups, exhibited a large water roll-off angle exceeding 20° even at a droplet size of 20 μl.

Claims

1. A polymer containing a fluoropolyether group, represented by the following general formula (1): Rf-[CH(V)2] α (1) In the formula, Rf is a monovalent fluoropolyether group represented by the following general formula (3) when α=1, and is a divalent fluoropolyether group represented by the following general formula (4) when α=2; V is independently a monovalent group having a hydroxyl-containing silyl group or a hydrolyzable silyl group at the terminal, and having no polar group other than the hydroxyl-containing silyl group or the hydrolyzable silyl group; α is 1 or 2, [Chemistry 2] In the formula, A is a fluorine atom, a hydrogen atom, a fluoroalkyl group, or a fluoroalkyl group containing one or more hydrogen atoms; W is a fluoroalkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms; d is independently an integer of 1 to 3 in each unit; p, q, r, s, t, u, and v are each an integer of 0 to 200, and p+q+r+s+t+u+v=3 to 200. Each of these units may be linear or branched; and the repeating units indicated in parentheses with p, q, r, s, t, u, and v may be randomly combined. [Chemistry 3] In the formula, W is a fluorinated alkylene group having 1 to 6 carbon atoms and containing one or more hydrogen atoms, d is independently an integer of 1 to 3 in each unit, p, q, r, s, t, u, and v are each an integer of 0 to 200, and p+q+r+s+t+u+v=3 to 200. Each of these units can be optionally linear or branched; in addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be optionally randomly combined.

2. The fluoropolyether group-containing polymer according to claim 1, which is represented by the following general formula (2): [Chemistry 1] In the formula, Rf is the same as Rf in claim 1, L is each independently a single bond or a divalent heteroatom, Y is each independently a 2-6 valent hydrocarbon group, optionally having a silicon atom and / or 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 an integer from 1 to 3, m is an integer from 1 to 5, and α is 1 or 2.

3. The fluoropolyether group-containing polymer according to claim 2, wherein In the formula (2), when α=1, there are two Ls at one end of the molecular chain, and when α=2, there are two Ls at each of the two ends of the molecular chain. Among these Ls, at each end of the molecular chain, one L is an oxygen atom and the other L is a single bond. Y is independently a group selected from an alkylene group having 3 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bonding end of a divalent to tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, or a branched or cyclic divalent to tetravalent organopolysiloxane residue having 3 to 10 silicon atoms.

4. The fluoropolyether group-containing polymer according to claim 2, wherein In the formula (2), each X is independently a group selected from 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.

5. The fluoropolyether group-containing polymer according to claim 2, wherein The polymer represented by formula (2) is selected from polymers represented by the following formulae: [Chemistry 4] [Chemistry 5] [Chemistry 6] [Chemistry 7] In the formula, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, r1 is an integer of 1 to 100, r2 is an integer of 1 to 99, r3 is an integer of 1 to 99, the total of p1, q1, r1, r2, and r3 is an integer of 10 to 110, and the repeating units shown in parentheses with p1, q1, r1, r2, and r3 are optionally randomly combined. 6 . A surface treatment agent comprising the fluoropolyether group-containing polymer according to claim 1 and / or its partial condensate or its partial hydrolysis condensate.

7. The surface treatment agent according to claim 6, wherein The fluoropolyether group in the fluoropolyether group-containing polymer is a monovalent fluorooxyalkylene group-containing polymer residue located at the end of the molecular chain.

8. An article surface-treated with the surface treatment agent according to claim 6 or 7.

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