Fluoropolyether group-containing polymer, surface treatment agent and articles

Abstract

A polymer containing fluoropolyether groups, comprising a hydroxyl group or hydrolyzable group and a polyether group, having the general formula (1): where Rf represents a mono- or bivalent polymer residue containing a fluorooxyalkylene group, B independently represents a bivalent organic group, V independently represents a carbon atom, silicon atom, nitrogen atom, or a tri- to octavalent organic group, E independently represents a monovalent group with an oxyalkylene group, R' independently represents a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, a phenyl group, a C1-C4 alkoxy group, or a halogen group, U independently represents a single bond or a bivalent organic group, Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a tri- to octavalent organic group, and Y independently represents a bivalent hydrocarbon group that may contain at least one selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond.R independently represents a C1-C4 alkyl group or a phenyl group, X independently represents a hydroxyl group or a hydrolyzable group, n independently represents an integer from 1 to 3 for each silicon atom to be bound, m independently represents an integer from 1 to 7, α represents 1 or 2, β independently represents an integer from 1 to 6, γ independently represents 0 or 1, δ independently represents 1 or 2, and the sum of β, γ and δ independently represents an integer from 2 to 7 for each V to be bound.

Description

TECHNICAL AREA

[0001] This invention relates to a polymer containing fluoropolyether groups (or a compound with a mono- or bivalent fluoroxyalkylene group-containing polymer residue in the molecule), and in particular to a polymer containing fluoropolyether groups that can form a coating with improved water / oil repellency and improved abrasion resistance, a surface treatment agent comprising the polymer and / or a partial (hydrolytic) condensate thereof, and an article having a surface treated with the surface treatment agent. STATE OF THE ART

[0002] Recently, there has been an increasing demand for the use of touch panels as displays in smartphones and other devices. Since touch panels have an unprotected screen, direct contact between fingers or cheeks and the display is common. It is undesirable for touch panels to become easily soiled with smudges such as sebum. There is a growing need for technologies that offer fingerprint resistance or easy smudge removal from display surfaces to improve appearance or visibility. Accordingly, it is desirable to have a material available that can meet these requirements. In particular, for touch panel displays that are easily soiled with fingerprints, it is desirable to have a water- and oil-repellent coating on their surface.Previous water / oil repellent coatings have a high water / oil repellency and easy stain removal, but have the problem that their anti-rot properties deteriorate during use.

[0003] In general, compounds containing fluoropolyether groups exhibit water / oil repellency, chemical resistance, lubricity, release properties, anti-rot properties, and other characteristics due to their extremely low surface free energy. Because of these properties, they are used in a wide variety of industries, for example, as water / oil repellents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetic ingredients, protective films, and the like. Conversely, these same properties also correlate with a lack of stickiness or adhesion to other substrates. Even if they can be applied to the substrate surface, ensuring a strong bond between the coating and the substrate can be challenging.

[0004] On the other hand, silane coupling agents are known for bonding organic compounds to the surfaces of glass or fabric substrates. They are widely used as surface coating agents for numerous substrates. The silane coupling agent contains an organic functional group and a reactive silyl group (typically hydrolyzable silyl such as alkoxysilyl) in its molecule. In the presence of atmospheric moisture or similar substances, the hydrolyzable silyl groups undergo a self-condensation reaction, forming a coating. The hydrolyzable silyl groups form chemical and physical bonds with the surface of the glass or metal, resulting in a durable and resilient coating.

[0005] Patent documents 1 to 6 (JP-A 2008-534696, JP-A 2008-537557, JP-A 2012-072272, JP-A 2012-157856, JP-A 2013-136833, JP-A 2015-199906) disclose a composition comprising a fluoropolyether group-containing polymer obtained by introducing a hydrolyzable silyl group into a fluoropolyether group-containing compound, wherein the composition adheres firmly to the substrate surface and is able to form a coating on the substrate surface with water / oil repellency, chemical resistance, lubricity, separability, anti-rotting properties and other properties.

[0006] When lenses and antireflective coatings are surface-treated with a composition comprising the fluoropolyether-containing polymer obtained by introducing a hydrolyzable silyl group into a fluoropolyether-containing compound, the hardened films exhibit improved lubricity, separability, and abrasion resistance to steel wool, but cannot achieve sufficient performance, particularly with regard to abrasion resistance to erasers.

[0007] A composition which can form a coating with excellent lubricity and separability and has abrasion resistance to erasers, by utilizing a fluoropolyether group-containing polymer in which a polyether group has been introduced into a fluoropolyether group-containing compound, is disclosed (Patent document 7: WO 2017 / 212850).

[0008] When lenses and antireflective coatings are surface-treated with a composition comprising the fluoropolyether-containing polymer, in which a polyether group has been introduced into a fluoropolyether-containing compound, the hardened films exhibit improved abrasion resistance against erasers, but cannot achieve sufficient performance in terms of abrasion resistance against steel wool. However, abrasion resistance against both erasers and steel wool is required. STATE OF TECHNOLOGY PATENT DOCUMENTS Patent Document 1: JP-A 2008-534696 Patent Document 2: JP-A 2008-537557 Patent Document 3: JP-A 2012-072272 Patent Document 4: JP-A 2012-157856 Patent Document 5: JP-A 2013-136833 Patent Document 6: JP-A 2015-199906 Patent document 7: WO 2017 / 212850 SUMMARY OF THE INVENTIONAL PROBLEM

[0009] An objective of the invention made under the aforementioned circumstances is to provide a fluoropolyether group-containing polymer that can form a hardened film with improved water / oil repellency properties and improved abrasion resistance, a surface treatment agent comprising the polymer and / or a partial (hydrolytic) condensate thereof, and an article having a surface treated with the surface treatment agent. SOLUTION TO THE PROBLEM

[0010] In the course of extensive investigations to achieve the above objective, the inventor has found that among the aforementioned fluoropolyether-containing polymers, a fluoropolyether-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group, represented by the general formula (1), is effective in that a surface treatment agent comprising the polymer and / or a partial (hydrolytic) condensate thereof is able to form a hardened film with improved water / oil repellency, improved abrasion resistance to erasers, and improved abrasion resistance to steel wool. The present invention is based on this finding.

[0011] Accordingly, the invention provides a polymer containing fluoropolyether groups (or a compound with a mono- or bivalent fluoroxyalkylene group-containing polymer residue in the molecule), a surface treatment agent and an article as defined below.

[0012] [1] A fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group having the general formula (1): where Rf represents a mono- or bivalent polymer residue containing a fluorooxyalkylene group, B independently represents a bivalent organic group, V independently represents a carbon atom, silicon atom, nitrogen atom, or a tri- to octavalent organic group, E independently represents a monovalent group with an oxyalkylene group, R' independently represents a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, a phenyl group, a C1-C4 alkoxy group, or a halogen group, U independently represents a single bond or a bivalent organic group, Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a tri- to octavalent organic group, and Y independently represents a bivalent hydrocarbon group that may contain at least one selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond.R independently represents a C1-C4 alkyl group or a phenyl group, X independently represents a hydroxyl group or a hydrolyzable group, n independently represents an integer from 1 to 3 for each silicon atom to be bound, m independently represents an integer from 1 to 7, α represents 1 or 2, β independently represents an integer from 1 to 6, γ independently represents 0 or 1, δ independently represents 1 or 2, and the sum of β, γ and δ independently represents an integer from 2 to 7 for each V to be bound.

[0013] [2] The fluoropolyether group-containing polymer according to [1], where in formula (1) α stands for 1 and Rf stands for a group of the general formula (2): where A represents a fluorine atom, a hydrogen atom, or a fluoroalkyl group ending with a -CF3 group; W represents a fluoroalkyl group containing at least one hydrogen atom; d independently represents an integer from 1 to 3 for each unit; p, q, r, s, t, u, and v each represent an integer from 0 to 200; p + q + r + s + t + u + v is a number from 3 to 200; and each of the units can be linear or branched. and individual repetition units within the brackets can be randomly bound to p, q, r, s, t, u and v.

[0014] [3] The fluoropolyether group-containing polymer according to [1], where in formula (1) α stands for 2 and Rf stands for a group of the general formula (3): where W represents a fluoroalkylene group containing at least one hydrogen atom, d independently represents an integer from 1 to 3 for each unit, p, q, r, s, t, u and v each represent an integer from 0 to 200, p + q + r + s + t + u + v is a number from 3 to 200, each of the units can be linear or branched, and individual repeating units within the brackets can be randomly linked with p, q, r, s, t, u and v.

[0015] [4] The fluoropolyether group-containing polymer according to one of [1] to [3], wherein in formula (1) B is selected for a bivalent group from the group consisting of a C1-C 10 -alkylene group, an alkylene group containing a C6-C8 arylene residue, a bivalent group with alkylene residues bonded via a diorganosilylene residue, a silalkylene structure or a silarylene group, and a bivalent group with a C1-C 10-Alkylene residue, which is bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms, a carbonyl group and an amide group, and may contain at least one selected from an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide and an ester group.

[0016] [5] The fluoropolyether group-containing polymer according to one of [1] to [4], wherein in formula (1) V represents a carbon atom, a silicon atom, a nitrogen atom, a linear tri- to hexavalent organopolysiloxane residue with 2 to 10 silicon atoms, a branched or cyclic tri- to hexavalent organopolysiloxane residue with 3 to 10 silicon atoms, a trivalent isocyanur group or a trivalent triazine ring-containing group.

[0017] [6] The fluoropolyether group-containing polymer according to one of [1] to [5], wherein in formula (1) Y is selected for a group from the group consisting of a C1-C 10 -Alkylene group which may contain an oxygen atom or a sulfur atom, an alkylene group which contains a C6-C8 arylene group, a bivalent group with alkylene residues which are bonded via a diorganosilylene residue, a silalkylene structure or a silarylene structure, and a bivalent group with a C1-C 10 -Alkylene group, which is bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms.

[0018] [7] The fluoropolyether group-containing polymer according to one of [1] to [6], wherein in formula (1) U is selected for a group from the group consisting of a single bond, a C1-C 10-Alkylene group which may contain an oxygen atom and a sulfur atom, an alkylene group which contains a C6-C8 arylene residue, a bivalent group with alkylene residues which are bonded via a diorganosilylene residue, a silalkylene structure or a silarylene structure, and a bivalent group with a C1-C 10 -Alkylene residue, which is bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms.

[0019] [8] The fluoropolyether group-containing polymer according to one of [1] to [7], wherein in formula (1) Z represents any element selected from the group consisting of a single bond, a carbon atom, a silicon atom, a nitrogen atom, -CH=, a linear tri- to hexavalent organopolysiloxane residue with 2 to 10 silicon atoms, and a branched or cyclic tri- to hexavalent organopolysiloxane residue with 3 to 10 silicon atoms.

[0020] [9] The fluoropolyether group-containing polymer according to one of [1] to [8], wherein in formula (1) X is from the group consisting of a hydroxyl group, a C1-C 10 -Alkoxy group, a C2-C 10 -Alkoxyalkoxy group, a C1-C 10 -Acyloxy group, a C2-C 10 -Alkenyloxy group and a halogen group is selected.

[0021]

[10] The fluoropolyether group-containing polymer according to one of [1] to [9], wherein the fluoropolyether group-containing polymer of formula (1) has one of the following formulas: where p1, q1, r1 and s1 each represent an integer from 1 to 200, with the stipulation that the sum of p1, q1, r1 and s1 in each formula is 3 to 200, r2 and r3 each represent an integer of at least 1, the sum of r2 and r3 is 2 to 199, individual units within the parentheses may be randomly bound to p1, q1, r1, r2, r3 and s1, and k represents an integer from 1 to 20.

[0022]

[11] A surface treatment agent comprising a fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group and / or a partial (hydrolytic) condensate thereof.

[0023]

[12] The surface treatment agent according to

[11] , wherein the polyether group in the fluoropolyether group-containing polymer with a hydroxyl group or a hydrolyzable group and a polyether group is a group with a monovalent oxyalkylene residue at a molecular chain branch.

[0024]

[13] The surface treatment agent according to

[11] or

[12] , wherein the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group is the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group according to one of [1] to

[10] .

[0025]

[14] An article with a surface that has been treated with the surface treatment agent according to one of

[11] to

[13] . ADVANTAGEOUS EFFECTS OF THE INVENTION

[0026] The fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of the present invention has a polyether group in a predetermined structure in the molecule, thereby improving substrate adhesion and wettability, whereby an article whose surface has been treated with a surface treatment agent comprising the polymer and / or a partial (hydrolytic) condensate thereof has excellent water / oil repellency properties, excellent abrasion resistance to erasers and excellent abrasion resistance to steel wool. DESCRIPTION OF EXECUTION FORMS

[0027] As used herein, the term "about (a value)" is a numerical value (approximate value) obtained by counting fractions greater than 1 / 2 as one and neglecting the remainder, where, if the lowest digit of the described numerical value is not "0", it encompasses a range of numerical values ​​within which the described numerical value is achieved by counting fractions of the digit below the lowest digit greater than 1 / 2 as one and neglecting the remainder. For example, "about 3 equivalents" denotes a range from 2.5 equivalents to 3.4 equivalents, and "about 0.02 equivalents" denotes a range from 0.015 equivalents to 0.024 equivalents. If the lowest digit of the numerical value is "0", the term "approximately (a value)" encompasses a range of numerical values ​​in which the described numerical value is achieved by counting fractions of the lowest digit above 1 / 2 as one and neglecting the remainder.For example, “about 80°C” refers to a range of 75°C to 84°C. In the present invention, the term “partial (hydrolytic) condensate” refers to a partial condensate or a partial hydrolytic condensate.

[0028] The fluoropolyether group-containing polymer with a fluoropolyether group (mono- or bivalent fluoroxyalkylene group-containing polymer residue) and a reactive functional group and with a polyether group in the molecule of the present invention is a fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group and has the general formula (1): where Rf represents a mono- or bivalent polymer residue containing a fluorooxyalkylene group, B independently represents a bivalent organic group, V independently represents a carbon atom, silicon atom, nitrogen atom, or a tri- to octavalent organic group, E independently represents a monovalent group with an oxyalkylene group, R' independently represents a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, a phenyl group, a C1-C4 alkoxy group, or a halogen group, U independently represents a single bond or a bivalent organic group, Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a tri- to octavalent organic group, and Y independently represents a bivalent hydrocarbon group that may contain at least one selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond.R independently represents a C1-C4 alkyl group or a phenyl group, X independently represents a hydroxyl group or a hydrolyzable group, n independently represents an integer from 1 to 3 for each silicon atom to be bound, m independently represents an integer from 1 to 7, α represents 1 or 2, β independently represents an integer from 1 to 6, γ independently represents 0 or 1, δ independently represents 1 or 2, and the sum of β, γ and δ independently represents an integer from 2 to 7 for each V to be bound.

[0029] The fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of the present invention has a structure in which a fluorooxyalkyl group or fluorooxyalkylene group (i.e., a mono- or bivalent fluoroxyalkylene group-containing polymer residue) and a hydrolyzable silyl group, such as an alkoxysilyl group or a hydroxyl group-containing silyl group, are linked to each other via a linker group, a polyether group is present in the molecule, and a long molecular chain is also present between a fluoroxyalkylene group-containing polymer residue and a polyether group, thereby improving substrate adhesion and wettability and achieving excellent water / oil repellency properties, excellent abrasion resistance against erasers, and excellent abrasion resistance against steel wool.

[0030] In formula (1), Rf represents a mono- or bivalent fluoroxyalkylene group-containing polymer residue, preferably, if α represents 1 (i.e., if Rf is a monovalent fluoroxyalkylene group-containing polymer residue), a monovalent fluoropolyether group of the following general formula (2), or, if α represents 2 (i.e., if Rf is a bivalent fluoroxyalkylene group-containing polymer residue), a bivalent fluoropolyether group of the following general formula (3). where A represents a fluorine atom, a hydrogen atom, or a fluoroalkyl group ending with a -CF3 group, W represents a fluoroalkyl group containing at least one hydrogen atom, d independently represents an integer from 1 to 3 for each unit, p, q, r, s, t, u, and v each represent an integer from 0 to 200, p + q + r + s + t + u + v is a number from 3 to 200, each of the units may be linear or branched, and individual repeating units within the brackets may be randomly linked with p, q, r, s, t, u, and v.

[0031] In formula (2) A represents a fluorine atom, a hydrogen atom or a fluoroalkyl group ending with a -CF3 group, and preferably represents a fluorine atom.

[0032] In formulas (2) and (3), W represents a fluoroalkylene group containing at least one hydrogen atom, where examples include perfluoroalkylene groups such as CF2-, C2F4-, C3F6-, C4F8-, C5F 10 - and C6F 12-units comprise in which one or two fluorine atoms are substituted by hydrogen.

[0033] In formulas (2) and (3) d independently represents an integer from 1 to 3 for each unit, preferably 1 or 2.

[0034] Furthermore, p, q, r, s, t, u, and v each represent an integer from 0 to 200; p represents an integer from 0 to 100, in particular from 5 to 100; q represents an integer from 0 to 100, in particular from 5 to 100; r represents an integer from 0 to 100; s represents an integer from 0 to 100; t represents an integer from 0 to 100; u represents an integer from 0 to 100; v represents an integer from 0 to 100; p + q + r + s + t + u + v is a number from 3 to 200, preferably from 10 to 100; p + q is preferably a number from 10 to 105, in particular from 15 to 60; and r = s = t = u = v = 0. If p + q + r + s + t + u + v is not above the upper limit, the adhesion and curability are satisfactory, while if p + q + r + s + t + u + v is not below the lower limit, the properties of the fluoropolyether group are fully developed.

[0035] In formulas (2) and (3), each unit can be linear or branched. Furthermore, individual repeating units within the parentheses can be randomly linked to p, q, r, s, t, u, and v.

[0036] Examples of Rf are shown below. where p', q', r', s', t', and u' each represent an integer of at least 1, their upper bounds being the same as the upper bounds of p, q, r, s, t, and u, and where the sum of p', q', r', s', t', and u' is 3 to 200, r2' and r3' each represent an integer of at least 1, and the sum of r2' and r3' is 2 to 199. Furthermore, individual repetition units within the parentheses may be randomly bound to p', q', r', s', t', and u'.

[0037] In formula (1), B independently represents a bivalent organic group and is a linker group that connects an Rf group and a V group. The bivalent organic group is a group selected from the group consisting of a C1-C 10 -alkylene group, an alkylene group containing a C6-C8 arylene residue, a bivalent group with alkylene residues bonded via a diorganosilylene residue, a silalkylene structure or a silarylene group, and a bivalent group with a C1-C 10-Alkylene residue bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms, a carbonyl group, and an amide group, wherein the bivalent organic group may contain at least one selected from an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group. If B is a bivalent organic group, flexibility between the Rf group and the branched V group containing a polyether residue can be ensured, and the mobility of the molecule can be increased, thus improving abrasion resistance.

[0038] The residue bonded to a silicon atom of the diorganosilylene residue, the silalkylene structure, the silarylene structure, or the organopolysiloxane residue is preferably an alkyl group with 1 to 8, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, or phenyl. The alkylene residue of the silalkylene structure preferably has 2 to 6, preferably 2 to 4 carbon atoms, such as ethylene, propylene (trimethylene, methylethylene), or butylene (tetramethylene, methylpropylene).

[0039] Examples of such a B include the following groups. In these structures, the left-hand valence bond is attached to Rf and the right-hand valence bond is attached to V. where f represents an integer from 2 to 4, a, a' and b each represent an integer from 1 to 4, c represents an integer from 1 to 10, and e represents an integer from 1 to 9.

[0040] In formula (1), V independently represents a carbon atom, a silicon atom, a nitrogen atom, or a tri- to octavalent organic group, and preferably a carbon atom, a silicon atom, a nitrogen atom, a linear tri- to hexavalent organopolysiloxane residue with 2 to 10 silicon atoms, in particular with 2 to 5 silicon atoms, a branched or cyclic tri- to hexavalent organopolysiloxane residue with 3 to 10 silicon atoms, in particular with 3 to 5 silicon atoms, a trivalent isocyanuric group, or a trivalent triazine ring-containing group. The organopolysiloxane residue may contain a silalkylene structure in which two silicon atoms are linked to each other via an alkylene residue, i.e., Si-(CH2) x -Si (in the formula x represents an integer from 2 to 6).

[0041] The organopolysiloxane residue preferably contains an alkyl group with 1 to 8, preferably with 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group or butyl group, or a phenyl group.

[0042] Examples of such a V include the structures shown below.

[0043] In formula (1), E independently represents a monovalent group with an oxyalkylene group, and can be replaced by -W'(-(LO) k -R") f' be displayed.

[0044] W' represents a single bond, an oxygen atom, X', or a bivalent or trivalent group that is a combination of X' and an oxygen atom; X' represents a bivalent or trivalent group with a bivalent C1-C 20-A hydrocarbon group, which may contain a nitrogen atom, a silicon atom, a siloxane bond, a silalkylene bond, or a silarylene bond, or an amide group, wherein the silicon atom preferably comprises an alkyl group with 1 to 8, more preferably with 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, and may contain a hydroxyl group or a hydrolyzable group. The alkylene residue in the silalkylene bond is preferably a C1-C6 alkylene residue, particularly preferably a C2-C4 alkylene residue, and is, for example, preferably methylene, ethylene, propylene (trimethylene, methylethylene), or butylene (tetramethylene, methylpropylene).

[0045] L independently represents a C1-C4 alkylene group, such as a methylene group, ethylene group, propylene group, or butylene group, where the number of carbon atoms may be the same or different. k represents an integer from 1 to 20, preferably an integer from 1 to 10. R" represents a C1-C4 alkyl group, such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group. A methyl group is preferred, among others. f' represents 1 or 2.

[0046] Examples of such an E include the following groups: where k is the same as described above.

[0047] In formula (1) R' independently represents a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, such as a methyl group, ethyl group, propyl group or butyl group, a phenyl group, a C1-C4 alkoxy group, such as a methoxy group, ethoxy group, propoxy group or butoxy group, or a halogen group such as fluorine, chlorine, bromine or iodine.

[0048] In formula (1), U independently represents either a single bond or a bivalent organic group and is a linker group that connects a V group and a Z group. The bivalent organic group is a group selected from the group consisting of a C1-C 10 -alkylene group, an alkylene group containing a C6-C8 arylene residue, a bivalent group with alkylene residues bonded via a diorganosilylene residue, a silalkylene structure or a silarylene group, and a bivalent group with a C1-C 10-Alkylene residue bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms, wherein the bivalent organic group may contain an oxygen atom and a sulfur atom.

[0049] The residue bonded to a silicon atom of the diorganosilylene residue, the silalkylene structure, the silarylene structure, or the organopolysiloxane residue is preferably an alkyl group with 1 to 8, preferably 1 to 4, carbon atoms, such as methyl, ethyl, propyl, or butyl, or phenyl. The alkylene residue of the silalkylene structure is preferably a C1-C6 alkylene, particularly preferably a C2-C4 alkylene, and is, for example, preferably methylene, ethylene, propylene (trimethylene, methylethylene), or butylene (tetramethylene, methylpropylene).

[0050] Examples of such a U-shape include, besides a single bond, the following groups. In these structures, the left-hand valence bond is attached to V and the right-hand valence bond is attached to Z, where f1 represents an integer from 1 to 4, a and b each represent an integer from 1 to 4, c represents an integer from 1 to 10, and e represents an integer from 1 to 9.

[0051] In formula (1), Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a tri- to octavalent organic group, wherein the tri- to octavalent organic group is preferably -CH=, a linear tri- to octavalent organopolysiloxane residue with 2 to 10 silicon atoms, in particular with 2 to 8 silicon atoms, or a branched or cyclic tri- to hexavalent organopolysiloxane residue with 3 to 10 silicon atoms, in particular with 3 to 8 silicon atoms. The organopolysiloxane residue may contain a silalkylene structure in which two silicon atoms are linked to each other via an alkylene residue, i.e., Si-(CH2) x -Si (in the formula x represents an integer from 2 to 6).

[0052] The organopolysiloxane residue preferably contains an alkyl group with 1 to 8, more preferably with 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, or phenyl.

[0053] Examples of such a Z include, besides a single bond, the structures shown below.

[0054] In formula (1), Y independently represents a bivalent hydrocarbon group, which may contain at least one selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond, preferably 1 to 20 carbon atoms, and more preferably 2 to 20 carbon atoms, and is a linker group that connects the Z residue (or the V residue) and the Si residue. In particular, the bivalent hydrocarbon group is preferably a group selected from the group consisting of a C1-C 10 -alkylene group, an alkylene group containing a C6-C8 arylene residue, a bivalent group with alkylene residues bonded via a diorganosilylene residue, a silalkylene structure or a silarylene group, and a bivalent group with a C1-C 10-Alkylene residue bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms, which may contain an oxygen atom or a sulfur atom.

[0055] The residue bonded to the silicon atom of the diorganosilylene residue, the silalkylene group, the silarylene structure, or the organopolysiloxane residue is preferably an alkyl group with 1 to 8, preferably 1 to 4, carbon atoms, such as methyl, ethyl, propyl, butyl, or phenyl. The alkylene residue of the silalkylene structure is preferably a C1-C6 alkylene, particularly preferably a C2-C4 alkylene, and is, for example, preferably methylene, ethylene, propylene (trimethylene, methylethylene), or butylene (tetramethylene, methylpropylene).

[0056] Examples of such a Y include the following groups. In these structures, the left-hand valence bond is attached to Z (or V) and the right-hand valence bond is attached to Si. where f1 represents an integer from 1 to 4, a and b each represent an integer from 1 to 4, b' and c each represent an integer from 1 to 10, and e represents an integer from 1 to 9.

[0057] In formula (1), R independently represents a C1-C4 alkyl group, such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group. A methyl group is among the preferred options.

[0058] X independently represents a hydroxyl group or hydrolyzable group, where examples of such an X are a hydroxyl group, a C1-C 10 -Alkoxy group, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group and a butoxy group, a C2-C 10-Alkoxyalkoxy group, such as a methoxymethoxy group and a methoxyethoxy group, a C1-C 10 -Acyloxy group, such as an acetoxy group, a C2-C 10 The group comprises an alkenyloxy group, such as an isopropenoxy group, and a halogen group, such as a chlorine group, a bromine group, and an iodine group. Among others, a methoxy group, an ethoxy group, an isopropenoxy group, and a chlorine group are preferred.

[0059] In formula (1) α represents 1 or 2, β independently represents an integer from 1 to 6, preferably 1 or 2, γ independently represents 0 or 1, preferably 0, and δ independently represents 1 or 2, preferably 1. The sum of β, γ and δ for each V to be bound is independently an integer from 2 to 7 (i.e. the valence of V is -1). n represents each silicon atom to be bonded independently for an integer from 1 to 3, preferably 3, and m represents independently for an integer from 1 to 7, preferably 1 or 3.

[0060] Examples of the process for preparing the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), where α stands for 1 (i.e., where Rf is a monovalent fluoroxyalkylene group-containing polymer residue) or where α stands for 2 (i.e., where Rf is a bivalent fluoroxyalkylene group-containing polymer residue), include the following processes.

[0061] A polymer containing fluoropolyether groups, with one or more polyether groups and one or more olefin sites at one or both ends of the molecular chain, is dissolved in a solvent, for example in a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene. An organosilicon compound with a SiH group and a hydroxyl group or hydrolyzable end group (a halogen atom, an alkoxy group, or the like) in one molecule, such as trichlorosilane or trialkoxysilane, is added. The mixture is then 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 catalyst, for example a chloroplatinic acid / vinylsiloxane complex in toluene. If a silicon group-containing, halogenated (organic) silicon compound such as e.g.When trichlorosilane is used as an organosilicon compound with a SiH group and a hydroxyl group or hydrolyzable end group in the molecule, the substituent (halogen atom) of the silyl group can subsequently be converted, for example, into an alkoxy group, such as a methoxy group, as another hydrolyzable group. Two different compounds can be used as organosilicon compounds with a SiH group and a hydroxyl group or hydrolyzable end group in the molecule, in which case compounds with different Y groups in formula (1) can be prepared by stepwise addition.

[0062] In the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), examples of the fluoropolyether group-containing polymer with one or more polyether groups and one or more olefin sites at one or both ends of the molecular chain may include a fluoropolyether group-containing polymer of the general formula (4): where Rf, B, V, R', E, U, Z, α, β, γ, δ and m are defined as described above and Y' independently represents a single bond or a bivalent hydrocarbon group which may contain at least one selected from an oxygen atom, a sulfur atom, a silicon atom and a siloxane bond.

[0063] In formula (4), Y' independently represents a single bond or a bivalent hydrocarbon group, which may contain at least one selected from an oxygen atom, a sulfur atom, a silicon atom and a siloxane bond, and preferably has 1 to 18 carbon atoms; in particular, the bivalent hydrocarbon group is preferably a group selected from the group consisting of a C1-C8 alkylene group, an alkylene group containing a C6-C8 arylene residue, a bivalent group with alkylene residues bonded to a diorganosilylene residue, a silalkylene structure or a silarylene group, and a bivalent group with a C1-C8 alkylene residue bonded to the valence bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, which may contain an oxygen atom or a sulfur atom.Preferably, Y' represents a linear C1-C6 alkylene group.

[0064] Examples of the fluoropolyether group-containing polymer of the formula include the following structures. where k is defined as described above, p1, q1 and r1 each represent an integer of at least 1 whose upper bounds are the same as the upper bounds of p, q and r described above, and the sum of p1, q1 and r1 in each formula is 3 to 200, and individual repetition units within the parentheses may be randomly bound to p1 and q1.

[0065] For example, a process for producing the fluoropolyether group-containing polymer of formula (4) includes a fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain and a polyether group-introducing agent, wherein the aging is carried out at a temperature of 0 to 90°C, preferably 50 to 80°C, more preferably about 60°C, for 1 to 48 hours, preferably 10 to 40 hours, more preferably about 24 hours, in the presence of a base and, if necessary, an additive or solvent is used to improve the reactivity.

[0066] Specific examples of the fluoropolyether group-containing polymer used to prepare the polymer of formula (4) with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain include the polymers shown below. where the sum of p1, q1, r1, p1 and q1 is defined as described above, and individual repetition units within the parentheses may be randomly bound to p1 and q1.

[0067] For example, a polyether halide can be used as a polyether group introductory agent for the preparation of the fluoropolyether group-containing polymer of formula (4), with specific examples including 2-bromomethyl methyl ether, ethylene glycol 2-bromomethyl methyl ether, diethylene glycol 2-bromomethyl methyl ether and triethylene glycol 2-bromomethyl methyl ether.

[0068] The amount of polyether group introducing agent used can be 1 to 15 equivalents, preferably 3 to 9 equivalents, and even more preferably about 6 equivalents per 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain.

[0069] Examples of the base used to prepare the fluoropolyether-containing polymer of formula (4) include an amine and an alkali metal base. Specific examples of the amine include triethylamine, diisopropylethylamine, pyridine, DBU, and imidazole. Examples of the alkali metal base include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, t-butoxypotassium, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide.

[0070] The amount of base used can be 1 to 15 equivalents, more preferably 3 to 9 equivalents, and even more preferably about 6 equivalents per 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain.

[0071] In the preparation of the fluoropolyether-containing polymer of formula (4), a tetrabutylammonium halide, an alkali metal halide, or the like may be used as an additive to improve the reactivity of the reaction between the fluoropolyether-containing polymer, which has one or more hydroxyl or amino groups and one or more olefin sites at one or both ends of the molecular chain, and the polyether group-introducing agent. Specific examples of the additive include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, and crown ethers. With these additives, a catalytic halogen exchange with the olefin-introducing agent takes place in the reaction system to improve reactivity, while the crown ether coordinates to the metal to enhance reactivity.

[0072] The amount of the additive used can be 0.005 to 0.1 equivalents, more preferably 0.01 to 0.05 equivalents, and even more preferably about 0.02 equivalents per 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain.

[0073] In the preparation of the fluoropolyether-containing polymer of formula (4), a solvent may be used for the reaction between the fluoropolyether-containing polymer, which has one or more hydroxyl or amino groups and one or more olefin sites at one or both ends of the molecular chain, and the polyether-introducing agent. The use of a solvent is not mandatory, and examples of solvents that may be used include a fluorinated aromatic hydrocarbon solvent, such as 1,3-bis(trifluoromethyl)benzene or trifluoromethylbenzene; a hydrofluoroether (HFE) solvent (manufactured by 3M, trade name: Novec series), such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane; and a perfluorinated solvent consisting of a fully fluorinated compound (manufactured by 3M, trade name: Fluorinert series).Furthermore, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, THF and the like can also be used as organic solvents.

[0074] If a solvent is used, the amount of solvent used can be 10 to 300 parts by weight, preferably 30 to 150 parts by weight, and even more preferably about 50 parts by weight per 100 parts by weight of the fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain.

[0075] In a further process for the preparation of a fluoropolyether group-containing polymer of formula (4) (process 2), for example, a fluoropolyether group-containing polymer having one or more hydroxyl or amino groups and one or more olefin sites at one or both ends of the molecular chain and an organosilicon compound having two or more SiH groups in the molecule are used, and dehydrogenation is carried out at 0 to 60°C, preferably 15 to 35°C, more preferably about 25°C for 10 minutes to 24 hours, more preferably 30 minutes to 2 hours, more preferably about 1 hour in the presence of a dehydrogenation catalyst and, if necessary, using a solvent, wherein a fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin sites at one or both ends of the molecular chain is obtained.

[0076] Subsequently, the fluoropolyether group-containing polymer with one or more SiH groups and one or more olefin sites at one or both ends of the molecular chain and a polyether compound with one olefin site in the molecule (for example, a polyalkylene oxide compound blocked at one end of the molecular chain by an alkenyloxy group or the like) are dissolved in a solvent, for example, in a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene, 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 catalyst, for example, a chloroplatinic acid / vinylsiloxane complex in toluene.

[0077] Examples of the fluoropolyether group-containing polymer used to produce the polymer of formula (4) (production method 2) with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain include the same polymers as the fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain mentioned above as an example.

[0078] Organosilicon compounds with two or more SiH groups in the molecule, which are used to prepare the fluoropolyether group-containing polymer of formula (4) (preparation method 2), compounds of the general formulas (5) to (7) are preferred. where R 1R represents an alkyl group with 1 to 8, preferably 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group or butyl group, or a phenyl group. 1 may be the same or different, R 2 for an alkylene group with 2 to 6, preferably 2 to 4 carbon atoms, such as an ethylene group, propylene group (trimethylene group, methylethylene group) or butylene group (tetramethylene group, methylpropylene group), or a C6-C8 arylene group, such as a phenyl group, g represents an integer from 1 to 9, preferably 1 to 4, i represents 2 or 3, j represents an integer from 0 to 7, preferably 0 or 1, i + j is an integer from 2 to 9, and in formula (7) individual repetition units within the parentheses may be randomly bound.

[0079] Examples of such organosilicon compounds with two or more SiH groups in the molecule include the compounds shown below.

[0080] In the preparation of the fluoropolyether group-containing polymer of formula (4) (preparation process 2), the amount of organosilicon compound used with two or more SiH groups in the molecule can be 5 to 30 equivalents, more preferably 7 to 20 equivalents, and even more preferably about 8 to 12 equivalents per 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain.

[0081] For example, a platinum group metal-based catalyst such as rhodium, palladium or ruthenium, a boron catalyst and the like may be used as a dehydrogenation catalyst for the preparation of the fluoropolyether group-containing polymer of formula (4) (production process 2), with specific examples being a platinum group metal catalyst such as tetrakis(triphenylphosphine)palladium or chlorotris(triphenylphosphine)rhodium and a boron catalyst such as tris(pentafluorophenyl)borane.

[0082] The amount of dehydrogenation catalyst used can be 0.0005 to 0.01 equivalents, more preferably 0.001 to 0.007 equivalents per 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain.

[0083] In the preparation of the fluoropolyether group-containing polymer of formula (4) (preparation process 2), examples of the polyether compound having an olefin site in the molecule, which is reacted with the obtained fluoropolyether group-containing polymer having one or more SiH groups and one or more olefin sites at one or both ends of the molecular chain, include a polyalkylene oxide compound blocked at one end of the molecular chain by an alkenyloxy group, such as the polyethylene oxide shown below, which is blocked at one end of the molecular chain by an allyloxy group and at the other end of the molecular chain by a methoxy group. where k is defined as described above.

[0084] Specific examples of the polyether compound with an olefin site in the molecule, such as a polyalkylene oxide compound blocked at one end of the molecular chain with an alkenyloxy group, include UNIOX MA-200, UNIOX MA-300, UNIOX MA-350S and UNIOX MA-500, manufactured by NOF CORPORATION.

[0085] The amount of polyether compound used with an olefin site in the molecule can be 1 to 10 equivalents, more preferably 2 to 5 equivalents, and even more preferably about 3 equivalents per 1 equivalent of the SiH group of the fluoropolyether group-containing polymer with one or more SiH groups and one or more olefin sites at one or both ends of the molecular chain.

[0086] In the preparation of the fluoropolyether group-containing polymer of formula (4) (preparation process 2), examples of the hydrosilylation catalyst in the reaction between the fluoropolyether group-containing polymer with one or more SiH groups and one or more olefin sites at one or both ends of the molecular chain and the polyether compound with one olefin site in the molecule include a platinum group metal-based catalyst such as platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and olefin, aldehyde, vinylsiloxane or acetylene alcohol, tetrakis(triphenylphosphine)palladium or chlorotris(triphenylphosphine)rhodium. Among others, a platinum compound such as a vinylsiloxane coordination compound is preferred.

[0087] The amount of hydrosilylation catalyst used is 0.1 to 100 ppm, more preferably 0.5 to 50 ppm based on the transition metal (weight) per weight of the fluoropolyether group-containing polymer with one or more SiH groups and one or more olefin sites at one or both ends of the molecular chain.

[0088] In the preparation of the fluoropolyether group-containing polymer of formula (4) (preparation process 2), a fluorine solvent is preferred as the solvent, wherein examples of the fluorine solvent include a hydrofluoroether (HFE) solvent (manufactured by 3M, trade name: Novec series), such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether or 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, and a perfluorine solvent consisting of an all-fluorinated compound (manufactured by 3M, trade name: Fluorinert series).

[0089] The amount of solvent used can be 10 to 300 parts by weight, preferably 50 to 150 parts by weight, and even more preferably about 100 parts by weight per 100 parts by weight of a fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain, or of a fluoropolyether group-containing polymer with one or more SiH groups and one or more olefin sites at one or both ends of the molecular chain.

[0090] In yet another process for the preparation of a fluoropolyether group-containing polymer of formula (4) (process 3), for example, a fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain and an organosilicon compound with a SiH group and a polyether group in the molecule are used, and dehydrogenation is carried out at 0 to 60°C, preferably 15 to 35°C, more preferably about 25°C for 10 minutes to 24 hours, more preferably 30 minutes to 2 hours, more preferably about 1 hour in the presence of a dehydrogenation catalyst and, if necessary, using a solvent.

[0091] Examples of the fluoropolyether group-containing polymer used to produce the polymer of formula (4) (production method 3) with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain include the same polymers as the fluoropolyether group-containing polymer with one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain mentioned above as an example.

[0092] Examples of the organosilicon compound having a SiH group and a polyether group in the molecule, which is used to prepare the fluoropolyether group-containing polymer of formula (4) (preparation method 3), include the following compounds. where k is defined as described above.

[0093] In the preparation of the fluoropolyether group-containing polymer of formula (4) (preparation method 3), the amount of the organosilicon compound used, having a SiH group and a polyether group in the molecule, can be 1 to 5 equivalents, more preferably 1 to 3 equivalents, per 1 equivalent of the hydroxyl group of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain.

[0094] Examples of the dehydrogenation catalyst used for the preparation of the fluoropolyether group-containing polymer of formula (4) (production process 3) include the same catalysts as the dehydrogenation catalyst mentioned by way of example in the preceding process (production process 2), wherein the amounts of these catalysts may be 0.0005 to 0.01 equivalents, more preferably 0.001 to 0.007 equivalents per 1 equivalent of the hydroxyl group of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain.

[0095] Examples of the solvent used for the preparation of the fluoropolyether group-containing polymer of formula (4) (preparation process 3) include the same solvents as the solvents mentioned by way of example in the preceding process (preparation process 2), wherein the amounts of these solvents may be 10 to 300 parts by weight, preferably 50 to 150 parts by weight, and even more preferably about 100 parts by weight per 100 parts by weight of the fluoropolyether group-containing polymer having one or more hydroxyl groups or amino groups and one or more olefin sites at one or both ends of the molecular chain.

[0096] In yet another process for the preparation of a fluoropolyether group-containing polymer of formula (4) (production process 4), a fluoropolyether group-containing polymer with two or more olefin sites at one or both ends of the molecular chain is used as a starting material. For example, a fluoropolyether group-containing polymer with three olefin sites at one or both ends of the molecular chain is dissolved in a solvent, for example, in a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene. First, an organosilicon compound with a SiH group and a polyether group in the molecule is added, for example, in an amount of 1 / 3 equivalent per 1 equivalent of the reactive end group (olefin sites) of the fluoropolyether group-containing polymer with three olefin sites at one or both ends of the molecular chain.To react some of the olefin sites of the fluoropolyether group-containing polymer with the SiH group of the SiH group-containing organosilicon compound, in the presence of a hydrosilylation catalyst, for example a chloroplatinic acid / vinylsiloxane complex in toluene, 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, an aging process is carried out.

[0097] Specific examples of the fluoropolyether group-containing polymer with two or more olefin sites at one or both ends of the molecular chain used to produce the polymer of formula (4) (production method 4) include the polymers shown below. where the sum of p1, q1, r1, p1 and q1 is defined as described above, and individual repetition units within the parentheses may be randomly bound to p1 and q1.

[0098] Examples of the organosilicon compound containing a SiH group and a polyether group in the molecule used to prepare the polymer of formula (4) (preparation method 4) include the following compounds. where k is defined as described above.

[0099] The amount of the organosilicon compound having a SiH group and a polyether group in the molecule used to prepare the fluoropolyether group-containing polymer of formula (4) (preparation method 4) may be 1 equivalent if n = 2, and may be 1 / n to 2 / n equivalents per n equivalents of the olefin sites of the fluoropolyether group-containing polymer having two or more olefin sites at one or both ends of the molecular chain if n < 2.

[0100] Examples of the hydrosilylation catalyst used for the preparation of the fluoropolyether group-containing polymer of formula (4) (preparation process 4) include the same catalysts as the hydrosilylation catalyst mentioned by way of example in the preceding process (preparation process 2), wherein the hydrosilylation catalyst, with respect to the amount added, can be used in an amount of 0.1 to 100 ppm, more preferably 0.5 to 50 ppm based on the transition metal (weight) per weight of the fluoropolyether group-containing polymer having two or more olefin sites at one or both ends of the molecular chain.

[0101] Examples of the solvent used for the preparation of the fluoropolyether group-containing polymer of formula (4) (preparation process 4) include the same solvents as the solvents mentioned by way of example in the preceding process (preparation process 2), wherein the amount of admixture may be 10 to 300 parts by weight, preferably 50 to 150 parts by weight and even more preferably about 100 parts by weight of the fluoropolyether group-containing polymer having two or more olefin sites at one end of the molecular chain or at both ends of the molecular chain.

[0102] In yet another process for the preparation of a fluoropolyether group-containing polymer of formula (4) (production process 5), for example, a fluoropolyether group-containing polymer is dissolved with an acid halide or the like at one or both ends of the molecular chain in a solvent, for example a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene, and is aged using an organic nitrogen compound having a polyether group and an olefin site in the molecule at a temperature of 0 to 90°C, preferably 60 to 90°C, for 1 to 48 hours, preferably 10 to 40 hours, even more preferably 15 to 24 hours, in the presence of a base and, if necessary, using a solvent.

[0103] As a group at one molecular chain end of the fluoropolyether group-containing polymer with an acid halide or the like at one molecular chain end or both molecular chain ends, which is used to prepare the fluoropolyether group-containing polymer of formula (4) (preparation process 5), in addition to the acid halide described above, an acid anhydride, an ester, a carboxylic acid, an amide, a sulfonic acid ester and the like may also be used.

[0104] Specific examples of the fluoropolyether group-containing polymer with these groups at one or both ends of the molecular chain include the polymers shown below. where the sum of p1, q1, r1, p1 and q1 is defined as described above, and individual repetition units within the parentheses may be randomly bound to p1 and q1.

[0105] Examples of the organic nitrogen compound containing a polyether group and an olefin site in the molecule used to prepare the polymer of formula (4) (preparation method 5) include the following compounds. where k is defined as described above.

[0106] The amount of the organic nitrogen compound with a polyether group and an olefin site in the molecule used to prepare the fluoropolyether group-containing polymer of formula (4) (preparation process 5) can be 1 to 15 equivalents, more preferably 2 to 6 equivalents, and even more preferably about 4 equivalents per 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer with an acid halide or the like at one or both ends of the molecular chain.

[0107] Examples of the base used to prepare the fluoropolyether group-containing polymer of formula (4) (preparation method 5) include an amine and an alkali metal base. Specific examples of the amine include triethylamine, diisopropylethylamine, pyridine, DBU, and imidazole. Examples of the alkali metal base include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, t-butoxypotassium, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide.

[0108] The amount of base used can be 1 to 15 equivalents, more preferably 2 to 6 equivalents, and even more preferably about 4 equivalents per 1 equivalent of the reactive end group of the fluoropolyether group-containing polymer with an acid halide or the like at one or both ends of the molecular chain.

[0109] A solvent may be used in the preparation of the fluoropolyether-containing polymer of formula (4) (preparation process 5). The use of a solvent is not mandatory, and examples of solvents that may be used include a fluorinated aromatic hydrocarbon solvent, such as 1,3-bis(trifluoromethyl)benzene or trifluoromethylbenzene; a hydrofluoroether (HFE) solvent (manufactured by 3M, trade name: Novec series), such as 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane; and a perfluorinated solvent consisting of a fully fluorinated compound (manufactured by 3M, trade name: Fluorinert series). In addition, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, THF, and the like may also be used as organic solvents.

[0110] If a solvent is used, the amount of solvent used can be 10 to 300 parts by weight, preferably 30 to 150 parts by weight, and even more preferably about 50 to 100 parts by weight per 100 parts by weight of the fluoropolyether group-containing polymer with an acid halide or the like at one or both ends of the molecular chain.

[0111] In the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), the organosilicon compound with a SiH group and a hydroxyl group or hydrolyzable end group in the molecule is preferably compounds of the general formulas (8) to (11). where R, X, n, R 1 , R 2 , e and j are defined as described above, R 3for a bivalent C2-C8 hydrocarbon group, h stands for 1, j' stands for an integer from 1 to 8, h + j' is an integer from 2 to 9, and in formula (11) individual repeating units within the parentheses may be randomly bound.

[0112] Examples of the bivalent hydrocarbon group with 2 to 8, preferably 2 to 3 carbon atoms of R 3 These groups include an alkylene group, such as a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), a hexamethylene group, and an octamethylene group; an arylene group, such as a phenylene group; and a combination of two or more of these groups (an alkylenarylene group). Among others, an ethylene group and a trimethylene group are preferred.

[0113] Examples of organosilicon compounds with a SiH group and a hydroxyl group or hydrolyzable end group in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, the following silane or siloxane compounds, and (partial) hydrolysates thereof.

[0114] In the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), the amount of the organosilicon compound with a SiH group and a hydroxyl group or hydrolyzable end group in the molecule, which is used in the reaction between the fluoropolyether group-containing polymer with one or more polyether groups and one or more olefin sites at one or both ends of the molecular chain and the organosilicon compound with a SiH group and a hydroxyl group or hydrolyzable end group in the molecule, can be 1 to 4 equivalents, more preferably 1.5 to 4 equivalents per 1 equivalent of the olefin site of the fluoropolyether group-containing polymer.

[0115] When a SiH-containing, halogenated (organic) silicon compound, such as trichlorosilane, is used as an organosilicon compound with a SiH group and a hydroxyl group or a hydrolyzable end group in the molecule, the substituent (halogen atom) of the silyl group can then be converted, for example, into an alkoxy group, such as a methoxy group, as another hydrolyzable group. Examples of the reagent that can be used to convert the substituent (halogen atom) of the silyl group into another hydrolyzable group include a C1-C 10 -Includes alcohols such as methanol, ethanol, propanol, isopropanol or butanol.

[0116] The amount used can be 10 to 200 parts by weight, more preferably 40 to 100 parts by weight, and even more preferably about 65 parts by weight per 100 parts by weight of an addition reaction product of the fluoropolyether group-containing polymer with one or more polyether groups and one or more olefin sites at one or both ends of the molecular chain and the SiH group-containing, halogenated (organic) silicon compound.

[0117] In the preparation of the fluoropolyether-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), examples of the solvent include a fluorinated solvent. Examples of the fluorinated solvent include a hydrofluoroether (HFE) solvent (manufactured by 3M, trade name: Novec series), such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, or 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, and a perfluorinated solvent consisting of a fully fluorinated compound (manufactured by 3M, trade name: Fluorinert series).

[0118] The amount of solvent used can be 10 to 300 parts by weight, preferably 50 to 150 parts by weight, more preferably 50 to 100 parts by weight per 100 parts by weight of the fluoropolyether group-containing polymer with one or more polyether groups and one or more olefin sites at one or both ends of the molecular chain.

[0119] In the preparation of the fluoropolyether-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), examples of the hydrosilylation catalyst include the following catalysts. Examples include platinum group metal-based catalysts such as platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and olefin, aldehyde, vinylsiloxane or acetylene alcohol, tetrakis(triphenylphosphine)palladium or chlorotris(triphenylphosphine)rhodium, and the like. Among others, a platinum compound such as a vinylsiloxane coordination compound is preferred.

[0120] The amount of hydrosilylation catalyst used is 0.1 to 100 ppm, more preferably 1 to 50 ppm based on the transition metal (weight) per weight of the fluoropolyether group-containing polymer with one or more polyether groups and one or more olefin sites at one or both ends of the molecular chain.

[0121] Examples of another process for the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), where α stands for 1 (i.e., where Rf is a monovalent fluoroxyalkylene group-containing polymer residue) or where α stands for 2 (i.e., where Rf is a bivalent fluoroxyalkylene group-containing polymer residue), include the following processes.

[0122] In this process, a fluoropolyether-containing polymer with two or more SiH groups at one or both ends of the molecular chain is used as a starting material. For example, a fluoropolyether-containing polymer with three SiH groups at one or both ends of the molecular chain is dissolved in a solvent, such as a fluorinated solvent like 1,3-bis(trifluoromethyl)benzene. First, a polyether compound with an olefin site in the molecule (for example, a polyalkylene oxide compound blocked at one end of the molecular chain by an alkenyloxy group or the like) is added, for example, in an amount of 1 / 3 equivalent per 1 equivalent of the reactive end group (SiH group) of the fluoropolyether-containing polymer with three SiH groups at one or both ends of the molecular chain.To react some of the SiH groups of the fluoropolyether-containing polymer with the olefin site of the polyether compound with an olefin site in the molecule, in the presence of a hydrosilylation catalyst, for example a chloroplatinic acid / vinylsiloxane complex in toluene, 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, an aging process is carried out to obtain a fluoropolyether-containing polymer with a SiH group and a polyether group at one or both ends of the molecular chain.

[0123] Subsequently, the fluoropolyether group-containing polymer with a SiH group and a polyether group at one or both ends of the molecular chain and an organosilicon compound with an olefin site and a hydroxyl group or hydrolyzable end group in the molecule are dissolved in a solvent, for example a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene, 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 catalyst, for example a chloroplatinic acid / vinylsiloxane complex in toluene.Two different compounds can be used as organosilicon compounds with an olefin site and a hydroxyl group or hydrolyzable end group in the molecule, in which case compounds with different Y residues in formula (1) can be prepared by stepwise addition.

[0124] In another process for the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), examples of the fluoropolyether group-containing polymer with two or more SiH groups at one or both ends of the molecular chain include the following polymers. where the sum of p1, q1, r1, p1 and q1 is as described above, and individual repetition units within the brackets may be randomly linked to p1 and q1.

[0125] In another process for the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), examples of the polyether compound with an olefin site in the molecule include a polyalkylene oxide compound blocked at one end of the molecular chain by an alkenyloxy group, such as the polyethylene oxide shown below, which is blocked at one end of the molecular chain by an allyloxy group and at the other end of the molecular chain by a methoxy group. where k is defined as described above.

[0126] Specific examples of the polyether compound with an olefin site in the molecule, such as a polyalkylene oxide compound blocked at one end of the molecular chain with an alkenyloxy group, include UNIOX MA-200, UNIOX MA-300, UNIOX MA-350S and UNIOX MA-500, manufactured by NOF CORPORATION.

[0127] In another process for the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), the amount of the polyether compound used with an olefin site in the molecule can be 1 equivalent when n = 2, and the amount can be 1 / n to 2 / n equivalents per n equivalents of the reactive end group (SiH group) of the fluoropolyether group-containing polymer with two or more SiH groups at one or both ends of the molecular chain when n < 2.

[0128] In a further process for the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), an organosilicon compound with an olefin site and a hydroxyl group or hydrolyzable end group in the molecule, which is to be reacted with the obtained fluoropolyether group-containing polymer with a SiH group and a polyether group at one or both ends of the molecular chain, is preferred, a compound of the general formula (12). where R, X and n are defined as described above and Y" represents a single bond or a bivalent hydrocarbon group which may contain at least one selected from an oxygen atom, a sulfur atom, a silicon atom and a siloxane bond.

[0129] In formula (12), Y' represents a single bond or a bivalent hydrocarbon group, which may contain at least one selected from an oxygen atom, a sulfur atom, a silicon atom and a siloxane bond, and which preferably has 1 to 18 carbon atoms; in particular, the bivalent hydrocarbon group is preferably a group selected from the group consisting of a C1-C8 alkylene group, an alkylene group containing a C6-C8 arylene residue, a bivalent group with alkylene residues bonded to a diorganosilylene residue, a silalkylene structure or a silarylene group, and a bivalent group with a C1-C8 alkylene residue bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms, which may contain an oxygen atom or a sulfur atom.Preferably, "Y" represents a single bond or a linear C1-C6 alkylene group.

[0130] Examples of such organosilicon compounds with an olefin site and a hydroxyl group or hydrolyzable end group in the molecule include the following compounds. These include vinyltrimethoxysilane, allyltrimethoxysilane, hexenyltrimethoxysilane, octenyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, hexenyltriethoxysilane, octenyltriethoxysilane, vinyltriisopropoxysilane, allyltriisopropoxysilane, vinyltributoxysilane, allyltributoxysilane, vinyltriacetoxysilane, allyltriacetoxysilane, vinyltrichlorosilane, vinyltribromosilane, vinyltriiodosilane, the following silane or siloxane compounds, and (partial) hydrolysates thereof.

[0131] In a further process for the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1), the amount of the organosilicon compound used with an olefin site and a hydroxyl group or hydrolyzable end group in the molecule can be 1 to 4 equivalents, more preferably 1.5 to 2.5 equivalents, and even more preferably about 2 equivalents per 1 equivalent of the unreacted SiH group in the reactive end group of the fluoropolyether group-containing polymer with two or more SiH groups at one or both ends of the molecular chain (i.e.,the SiH group of the fluoropolyether group-containing polymer with a SiH group and a polyether group at one or both ends of the molecular chain, which is a reaction product of a fluoropolyether group-containing polymer with two or more SiH groups at one or both ends of the molecular chain and a polyether compound with an olefin site in the molecule).

[0132] Examples of the hydrosilylation catalyst used in another process for the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1) include the same catalysts as the hydrosilylation catalyst mentioned as an example in the preparation process, wherein the admixture amount is 0.1 to 100 ppm, more preferably 0.3 to 50 ppm, based on the transition metal (weight) per weight of the fluoropolyether group-containing polymer with a SiH group and a polyether group at one or both ends of the molecular chain, which is a reaction product of a fluoropolyether group-containing polymer with two or more SiH groups at one or both ends of the molecular chain or a fluoropolyether group-containing polymer with two or more SiH groups at one or both ends of the molecular chain and a polyether compound with an olefin site in the molecule.

[0133] Examples of the solvent used in another process for the preparation of the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1) include the same solvents as the solvent mentioned by way of example in the preparation process, wherein the admixture amount is 10 to 300 parts by weight, preferably 50 to 150 parts by weight, and even more preferably about 100 parts by weight per 100 parts by weight of the fluoropolyether group-containing polymer with a SiH group and a polyether group at one or both ends of the molecular chain.which may be a reaction product of a fluoropolyether-containing polymer with two or more SiH groups at one or both ends of the molecular chain, or of a fluoropolyether-containing polymer with two or more SiH groups at one or both ends of the molecular chain and a polyether compound with an olefin site in the molecule.

[0134] Examples of the structure of the fluoropolyether-containing polymer with a hydroxyl or hydrolyzable group and a polyether group of formula (1) include the following structures. By changing the combination of Rf, B, V, E, R, U, Z, Y, R, X, α, β, γ, δ, m and n in formula (1), several types of a fluoropolyether-containing polymer with a hydroxyl or hydrolyzable group and a polyether group are obtained. where p1, q1, r1 and k are as described above, s1 represents an integer of at least 1 whose upper limit is the same as the upper limit of s mentioned above, with the proviso that the sum of p1, q1, r1 and s1 in each formula is 3 to 200, r2 and r3 each represent an integer of at least 1, the sum of r2 and r3 is 2 to 199, and individual units within the parentheses may be randomly bound to p1, q1, r1, r2, r3 and s1.

[0135] For example, if a combination of the formula: where the sum of p1, q1, p1 and q1 is as described above, and individual repetition units within the brackets may be randomly linked to p1 and q1, When used as a fluoropolyether group-containing polymer with two olefin sites at one end of the molecular chain, and when trimethoxysilane is used as an organosilicon compound with a SiH group and a hydroxyl group or hydrolyzable end group in the molecule, a compound of the formula is obtained: where the sum of p1, q1, p1 and q1 is as described above, and individual repetition units within the brackets may be randomly linked to p1 and q1.

[0136] For example, if a combination of the formula: where the sum of p1, q1, p1 and q1 is as described above, and individual repetition units within the brackets may be randomly linked to p1 and q1, When used as a fluoroxyalkylene-containing polymer with two olefin sites at each end of the molecular chain, and when trimethoxysilane is used as an organosilicon compound with a SiH group and a hydroxyl group or hydrolyzable end group in the molecule, a compound of the formula is obtained: where the sum of p1, q1, p1 and q1 is as described above, and individual repetition units within the brackets may be randomly linked to p1 and q1.

[0137] The present invention further provides a surface treatment agent comprising as its main component a fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group, preferably a polymer in which a polyether group of the polymer is a monovalent oxyalkylene group-containing polymer residue located at a molecular chain branch, and in particular the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group of formula (1).The surface treatment agent need only comprise a fluoropolyether-containing polymer with a hydroxyl or hydrolyzable group and a polyether group as its main component, and may include an unreacted starting material or a reaction intermediate prior to the introduction of a terminal hydroxyl or hydrolyzable group of a fluoropolyether-containing polymer with a hydroxyl or hydrolyzable group and a polyether group. The surface treatment agent may also comprise a partial (hydrolytic) condensate obtained by condensing the hydroxyl group of the fluoropolyether-containing polymer or a hydroxyl group resulting from partial hydrolysis of the hydrolyzable group of the fluoropolyether-containing polymer in a known manner.

[0138] A hydrolytic condensation catalyst can be added to the surface treatment agent if required. Suitable hydrolytic condensation catalysts include organotin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate, organotitanium compounds such as tetra-n-butyl titanate, organic acids such as acetic acid, methanesulfonic acid, and fluorinated carboxylic acids, as well as inorganic acids such as hydrochloric acid and sulfuric acid. Of these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, and fluorinated carboxylic acids are preferred.

[0139] The hydrolytic condensation catalyst can be added in a catalytic amount, typically in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight per 100 parts by weight of the fluoropolyether group-containing polymer and / or its partial (hydrolytic) condensate.

[0140] The surface treatment agent may also include a solvent. Suitable solvents include fluoromodified aliphatic hydrocarbon solvents such as perfluoroheptane, perfluorooctane, and tridecafluorooctane; fluoromodified aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene; fluoromodified ether solvents such as methyl perfluorobutyl ether, ethyl perfluorobutyl ether, and perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptenyl ether, and tetrafluoroethyltrifluoroethyl ether; fluoromodified alkylamine solvents such as perfluorotributylamine and perfluorotripentylamine; hydrocarbon solvents such as gasoline, toluene, and xylene; and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.Of these, fluorine-modified solvents are preferred due to their solubility and wettability, with 1,3-bis(trifluoromethyl)benzene, perfluoro-(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether, tridecafluorooctane and tetrafluoroethyltrifluoroethyl ether being particularly preferred.

[0141] The solvents can be used as a mixture of two or more of them, preferably in which the fluoropolyether-containing polymer and its partial (hydrolytic) condensate are uniformly dissolved. The optimal concentration of the fluoropolyether-containing polymer and its partial (hydrolytic) condensate in the solvent varies depending on the specific treatment method. The quantity chosen should be easily weighed. In the case of direct coating, the concentration can preferably be 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight per 100 parts by weight of the sum of the solvent and the fluoropolyether-containing polymer (and its partial (hydrolytic) condensate).In the case of an evaporation treatment, the concentration can preferably be 1 to 100 parts by weight, more preferably 3 to 30 parts by weight per 100 parts by weight of the sum of solvent and the fluoropolyether group-containing polymer (and its partial (hydrolytic) condensate).

[0142] The surface treatment agent of the present invention can be applied to a substrate by any known technique, such as brush application, dipping, spraying, and evaporation. In the case of evaporation, the heating mode can be either resistance heating or electrical conductivity (EB) heating and is not specifically limited. The curing temperature varies depending on the curing method. In the case of direct coating (brush application, dipping, or spraying), suitable curing conditions include, for example, a temperature of 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, and more specifically, 1 to 24 hours. When the agent is applied by evaporation, the curing temperature is preferably in the range of 20 to 200°C for 1 to 24 hours. Humid curing conditions are also advantageous. The cured film typically has a thickness of 0.1 to 100 nm, preferably 1 to 20 nm, although the thickness depends on the type of substrate. In the case of a spray coating, for example, a method is recommended which includes diluting the agent with a fluorine-containing solvent that has been previously mixed with water to induce hydrolysis and generate Si-OH, and then spraying on the dilute to achieve rapid coating hardening.

[0143] The substrate to be treated with the surface treatment agent of the present invention is not limited in any particular way and can consist of any material, including paper, fabrics, metals, metal oxides, glass, plastics, ceramics, and quartz. The surface treatment agent of the present invention is effective in imparting water / oil-repellent properties to the substrate. In particular, the surface treatment agent is advantageously used for the treatment of SiO2-coated glasses and films.

[0144] Preferred articles that can be treated with the surface treatment agent of the present invention include automotive navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, automotive audio players, game consoles, spectacle lenses, camera lenses, lens filters, sunglasses, medical instruments (e.g., gastroscopes), copiers, personal computers, LCDs, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, and other optical articles. The surface treatment agent of the present invention is effective in preventing fingerprints and skin oils from adhering to the articles and in imparting scratch resistance. Therefore, it is particularly useful as a water- and oil-repellent layer on touch panel displays and anti-reflective films.

[0145] The surface treatment agent of the present invention is also used for dirt-repellent coatings on sanitary ware such as bathtubs and washbasins, dirt-repellent coatings on glazing or reinforced glass and headlight covers in transport vehicles such as cars, trains and airplanes, water / oil-repellent coatings on building exteriors, coatings to prevent oil contamination on kitchenware, dirt-, adhesion- and graffiti-repellent coatings in telephone booths, fingerprint-repellent coatings on works of art, fingerprint-repellent coatings on CDs and DVDs, mold release agents, paint additives and resin modifiers. The agent is also effective for modifying the flow and dispersion behavior of inorganic fillers and for improving the lubricity of tapes and films. EXAMPLES

[0146] The present invention is described in more detail below with reference to synthesis examples, examples, and comparative examples, the present invention being not limited to the following examples. In the following examples, the molar quantity of the compound is a value calculated by dividing the measured weight of the target compound by the molecular weight of the polymer, which was calculated from the p1 and q1 values ​​obtained by analysis. [Synthesis example 1]

[0147] In a reactor, 100 g (2.4×10 -2 mol) of a compound according to the following formula (A):33 g (1.4×10 -1 mol) Diethylene glycol-2-bromomethyl methyl ether and 0.17 g (4.8×10 -4 mol) Tetrabutylammonium iodide mixed together. Then 7.8 g (1.4×10 -1mol) potassium hydroxide was added and the mixture was heated to 60°C for 24 hours. After heating, the solution was cooled to room temperature and aqueous hydrochloric acid was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 89 g of a fluoropolyether group-containing polymer according to the following formula (B):

[0148] In a reactor, 50 g (1.1×10 -2 mol) of a compound obtained as above according to the following formula (B): 25 g 1,3-bis(trifluoromethyl)benzene, 5.4 g (4.4×10 -2 mol) Trimethoxysilane and 4.2×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.1×10 -6The two components (mol of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 51 g of a liquid product.

[0149] At the 1 -H-NMR analysis revealed that the compound has a structure according to the following formula (C): [Synthesis example 2]

[0150] In a reactor, 50 g (1.2×10 -2 mol) of a compound according to the following formula (D):

[0151] 19.4 g (7.2×10 -2 mol) Triethylene glycol-2-bromomethyl methyl ether and 0.09 g (2.4×10 -4 mol) Tetrabutylammonium iodide were mixed together. Then 4.0 g (7.2×10 -2mol) potassium hydroxide was added and the mixture was heated to 60°C for 24 hours. After heating, the solution was cooled to room temperature and aqueous hydrochloric acid was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 47 g of a fluoropolyether group-containing polymer according to the following formula (E):

[0152] In a reactor, 25 g (5.7×10 -3 mol) of a compound obtained as above according to the following formula (E):

[0153] 13 g 1,3-bis(trifluoromethyl)benzene, 2.8 g (2.3×10 -2 mol) Trimethoxysilane and 2.2×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 5.6×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 47 g of a liquid product.

[0154] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (F): [Synthesis example 3]

[0155] In a reactor, 50 g of 1,3-bis(trifluoromethyl)benzene, 0.014 g (2.6×10 -5 mol) Tris(pentafluorophenyl)borane and 50 g (1.3×10 -2 mol) of a compound according to the following formula (A): Mixed together, 25 g (1.3×10) were slowly added drop by drop. -1mol) of a siloxane according to the following formula (G): was added, and the mixture was then heated to 25°C for 1 hour. Water was then added dropwise, and the lower layer or fluorine compound layer was recovered by separation treatment and washed with acetone. The lower layer or fluorine compound layer was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 46 g of a fluoropolyether group-containing polymer according to the following formula (H):

[0156] In a reactor, 20 g (4.5×10 -3 mol) of a compound obtained as above according to the following formula (H): 20 g 1,3-bis(trifluoromethyl)benzene, 2.8 g (1.4×10 -2 mol) of a polyether compound according to the following formula (I): and 2.0×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 5.1×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80 °C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 21 g of a fluoropolyether group-containing polymer according to the following formula (J):

[0157] In a reactor, 20 g (4.3×10 -3 mol) of a compound obtained as above with according to the following formula (J): 10 g 1,3-bis(trifluoromethyl)benzene, 2.1 g (1.7×10 -2 mol) Trimethoxysilane and 1.9×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 4.9×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 19 g of a liquid product.

[0158] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (K): [Synthesis example 4]

[0159] In a reactor, 50 g of 1,3-bis(trifluoromethyl)benzene, 0.014 g (2.6×10 -5 mol) Tris(pentafluorophenyl)borane and 50 g (1.3×10 -2 mol) of a compound according to the following formula (A): Mixed together, 10 g (2.6×10) were slowly added drop by drop. -2 mol) of a polyethersilane according to the following formula (L):

[0160] The mixture was added and then heated to 25°C for 1 hour. Water was then added dropwise, and the lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 52 g of a fluoropolyether group-containing polymer according to the following formula (J):

[0161] The compound is the same as the intermediate from synthesis example 3.

[0162] Using 20 g (4.3×10 -3 From mol) of the above obtained fluoropolyether group-containing polymer of formula (J) 19 g of a liquid product with a structure of formula (K) were obtained in the same way as in synthesis example 3. [Synthesis example 5]

[0163] In a reactor, 25 g (1.2×10 -2mol) of a compound according to the following formula (M): 17 g (7.4×10 -2 mol) Diethylene glycol-2-bromomethyl methyl ether and 0.09 g (2.4×10 -4 mol) Tetrabutylammonium iodide were mixed together. Then 4.1 g (7.4×10 -2 mol) potassium hydroxide was added and the mixture was heated to 60°C for 24 hours. After heating, the solution was cooled to room temperature and aqueous hydrochloric acid was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 21 g of a fluoropolyether group-containing polymer according to the following formula (N):

[0164] In a reactor, 20 g (9.2×10 -3mol) of a compound obtained as above according to the following formula (N): 20 g 1,3-bis(trifluoromethyl)benzene, 4.5 g (3.7×10 -2 mol) Trimethoxysilane and 3.7×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 9.5×10 -7 Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 21 g of a liquid product.

[0165] At the 1 -H-NMR analysis revealed that the compound has a structure according to the following formula (O): [Synthesis example 6]

[0166] In a reactor, 50 g (9.5×10 -3 mol) of a compound according to the following formula (P): 50 g 1,3-bis(trifluoromethyl)benzene, 5.1 g (9.5×10 -3 mol) of a polyethersilane according to the following formula (Q): and 4.2×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.1×10 -6 Moles of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 48 g of a fluoropolyether group-containing polymer according to the following formula (R):

[0167] In a reactor, 40 g (7.1×10 -3 mol) of a compound obtained as above according to the following formula (R): 20 g 1,3-bis(trifluoromethyl)benzene, 3.4 g (2.8×10 -2 mol) Trimethoxysilane and 3.2×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 8.2×10-7 Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 41 g of a liquid product.

[0168] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (S): [Synthesis example 7]

[0169] In a reactor, 50 g (7.7×10 -3 mol) of a compound according to the following formula (T): 50 g 1,3-bis(trifluoromethyl)benzene, 5.1 g (7.7×10 -3 mol) of a polyether compound according to the following formula (U): and 3.4×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 8.7×10 -7The two components (mol Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Dibutyl ether was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 45 g of a fluoropolyether-containing polymer according to the following formula (V):

[0170] In a reactor, 30 g (4.3×10 -3 mol) of a compound obtained as above according to the following formula (V): 30 g 1,3-bis(trifluoromethyl)benzene, 2.6 g (1.7×10 -2 mol) Vinyltrimethoxysilane and 1.9×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 4.8×10 -7The two components (mol of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 29 g of a liquid product.

[0171] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (W): [Synthesis example 8]

[0172] In a reactor, 50 g (1.1×10 -2 mol) of a compound according to the following formula (X): 50 g 1,3-bis(trifluoromethyl)benzene, 4.8 g (1.1×10 -2 mol) of a polyether compound according to the following formula (Y): and 4.8×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.2×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Dibutyl ether was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 47 g of a fluoropolyether-containing polymer according to the following formula (Z):

[0173] In a reactor, 40 g (8.3×10 -3 mol) of a compound obtained as above according to the following formula (Z): 40 g 1,3-bis(trifluoromethyl)benzene, 7.7 g (3.3×10 -2 mol) Octenyltrimethoxysilantrimethoxysilane and 3.7×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 9.5×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 41 g of a liquid product.

[0174] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (AA): [Synthesis example 9]

[0175] In a reactor, 50 g (1.1×10 -2 mol) of a compound according to the following formula (AB): 50 g 1,3-bis(trifluoromethyl)benzene, 8.7 g (2.2×10 -2 mol) of a polyethersilane according to the following formula (AC): and 4.9×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.3×10 -6Mole of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 53 g of a fluoropolyether group-containing polymer according to the following formula (AD):

[0176] In a reactor, 50 g (9.9×10 -3 mol) of a compound obtained as above according to the following formula (AD): 50 g 1,3-bis(trifluoromethyl)benzene, 2.4 g (2.8×10 -2 mol) Trimethoxysilane and 4.4×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.1×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 50 g of a liquid product.

[0177] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (AE): [Synthesis example 10]

[0178] In a reactor, 50 g (1.2×10 -2 mol) of a compound according to the following formula (AF): 50 g 1,3-bis(trifluoromethyl)benzene, 3.3 g (1.2×10 -2 mol) of a polyethersilane according to the following formula (AG): and 5.3×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.4×10 -6Mole of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 51 g of a fluoropolyether group-containing polymer according to the following formula (AH):

[0179] In a reactor, 40 g (8.7×10 -3 mol) of a compound obtained as above according to the following formula (AH): 40 g 1,3-bis(trifluoromethyl)benzene, 10 g (3.5×10 -2 mol) of a siloxane compound with a trimethoxysilyl group according to the following formula (10A): and 3.9×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.0×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 41 g of a liquid product.

[0180] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (AI): [Synthesis example 11]

[0181] In a reactor, 100 g (4.3×10 -2 mol) of a compound according to the following formula (AJ): 100 g 1,3-bis(trifluoromethyl)benzene, 14 g (4.3×10 -2 mol) of a polyethersilane according to the following formula (Q): and 2.6×10 -1 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 2.1×10 -6Mole of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 104 g of a fluoropolyether group-containing polymer according to the following formula (AK):

[0182] In a reactor, 50 g (1.9×10 -2 mol) of a compound obtained as above according to the following formula (AK): 25 g 1,3-bis(trifluoromethyl)benzene, 4.6 g (3.7×10 -2 mol) Trimethoxysilane and 4.2×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.1×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 50 g of a liquid product.

[0183] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (AL): [Synthesis example 12]

[0184] In a reactor, 50 g (1.0×10 -2 mol) of a compound according to the following formula (AM): 14 g (6.2×10 -2 mol) Diethylene glycol-2-bromomethyl methyl ether and 0.08 g (2.1×10 -4 mol) Tetrabutylammonium iodide were mixed together. Then 3.4 g (6.2 × 10 -2Potassium hydroxide (mol) was added and the mixture was heated to 60°C for 24 hours. After heating, the solution was cooled to room temperature and aqueous hydrochloric acid was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 48 g of a fluoropolyether group-containing polymer according to the following formula (AN):

[0185] In a reactor, 40 g (8.0×10 -3 mol) of a compound obtained as above according to the following formula (AN): 20 g 1,3-bis(trifluoromethyl)benzene, 2.0 g (1.6×10 -2 mol) Trimethoxysilane and 3.1×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 7.9×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 40 g of a liquid product.

[0186] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (AO): [Synthesis example 13]

[0187] In a reactor, 100 g (2.4×10 -2 mol) of a compound according to the following formula (AP): 100 g 1,3-bis(trifluoromethyl)benzene, 8.1 g (2.4×10 -2 mol) of a polyethersilane according to the following formula (Q): and 4.0×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.0×10 -6Mole of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 96 g of a fluoropolyether group-containing polymer according to the following formula (AQ):

[0188] In a reactor, 50 g (1.1×10 -2 mol) of a compound obtained as above according to the following formula (AQ): 25 g 1,3-bis(trifluoromethyl)benzene, 3.4 g (4.4×10 -2 mol) Trimethoxysilane and 1.9×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 4.8×10 -7The two components (mol of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 49 g of a liquid product.

[0189] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (AR): [Synthesis example 14]

[0190] In a reactor, 50 g (1.1×10 -2 mol) of a compound according to the following formula (B): 25 g 1,3-bis(trifluoromethyl)benzene, 2.6 g (2.1×10 -2 mol) Trimethoxysilane and 4.2×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.1×10 -6 The two components (mol of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 51 g of a liquid product.

[0191] At the 1 H-NMR analysis identified the compound as a mixture of structures according to the following formula (C) and formula (AS): The mixing ratio was (C) : (AS) = 96 : 4. [Synthesis example 15]

[0192] In a reactor, 50 g (7.7×10 -3 mol) of a compound according to the following formula (AT): 50 g 1,3-bis(trifluoromethyl)benzene, 3.0 g (7.7×10 -3 mol) of a polyethersilane according to the following formula (L): and 4.7×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.2×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 49 g of a fluoropolyether group-containing polymer according to the following formula (AU):

[0193] In a reactor, 40 g (5.8×10 -3 mol) of a compound obtained as above according to the following formula (AU): 20 g 1,3-bis(trifluoromethyl)benzene, 1.4 g (1.2×10 -2 mol) Trimethoxysilane and 3.3×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 8.5×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 39 g of a liquid product.

[0194] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (AV): [Synthesis example 16]

[0195] In a reactor, 50 g (1.2×10 -2 mol) of a compound according to the following formula (AW): 50 g 1,3-bis(trifluoromethyl)benzene, 3.1 g (1.2×10 -2 mol) of a polyethersilane according to the following formula (AG): and 5.1×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.3×10 -6Mol of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 48 g of a fluoropolyether group-containing polymer according to the following formula (AX):

[0196] In a reactor, 40 g (8.7×10 -3 mol) of a compound obtained as above according to the following formula (AX): 20 g 1,3-bis(trifluoromethyl)benzene, 4.3 g (3.5×10 -2 mol) Trimethoxysilane and 3.9×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.0×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 40 g of a liquid product.

[0197] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (AY): [Synthesis example 17]

[0198] In a reactor, 50 g (9.5×10 -3 mol) of a compound according to the following formula (AZ): 50 g 1,3-bis(trifluoromethyl)benzene, 3.2 g (9.5×10 -3 mol) of a polyethersilane according to the following formula (Q): and 5.8×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.5×10 -6Mole of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 51 g of a fluoropolyether group-containing polymer according to the following formula (BA):

[0199] In a reactor, 50 g (8.9×10 -3 mol) of a compound obtained as above according to the following formula (BA): 25 g 1,3-bis(trifluoromethyl)benzene, 2.2 g (1.7×10 -2 mol) Trimethoxysilane and 5.4×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.4×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 50 g of a liquid product.

[0200] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (BB): [Synthesis example 18]

[0201] In a reactor, 30 g (7.0×10 -3 mol) of a compound according to the following formula (BC): 30 g 1,3-bis(trifluoromethyl)benzene, 2.8 g (7.0×10 -3 mol) of a polyethersilane according to the following formula (L): and 4.3×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.1×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 29 g of a fluoropolyether group-containing polymer according to the following formula (BD):

[0202] In a reactor, 25 g (5.3×10 -3 mol) of a compound obtained as above according to the following formula (BD): 13 g 1,3-bis(trifluoromethyl)benzene, 1.3 g (1.0×10 -2 mol) Trimethoxysilane and 3.0×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 7.7×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 24 g of a liquid product.

[0203] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (BE): [Synthesis example 19]

[0204] In a reactor, 20 g (5.2×10 -3 mol) of a compound according to the following formula (BF): 20 g 1,3-bis(trifluoromethyl)benzene, 3.7 g (5.2×10 -3 mol) of a polyethersilane according to the following formula (BG): and 2.0×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 5.1×10 -7Mole of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 17 g of a fluoropolyether group-containing polymer according to the following formula (BH):

[0205] In a reactor, 15 g (3.3×10 -3 mol) of a compound obtained as above according to the following formula (BH): 8 g 1,3-Bis(trifluoromethyl)benzene, 0.81 g (6.6×10 -3 mol) Trimethoxysilane and 1.3×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 3.3×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 15 g of a liquid product.

[0206] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (BI): [Synthesis example 20]

[0207] In a reactor, 100 g (2.4×10 -2 mol) of a compound according to the following formula (BJ): 100 g 1,3-bis(trifluoromethyl)benzene, 14 g (2.4×10 -2 mol) of a polyethersilane according to the following formula (BK): and 9.0×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 2.3×10 -6Mole of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum. Acetone was added, and the fluorine compound was washed by separation treatment. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 106 g of a fluoropolyether group-containing polymer according to the following formula (BL):

[0208] In a reactor, 100 g (2.1×10 -2 mol) of a compound obtained as above according to the following formula (BL): 50 g 1,3-bis(trifluoromethyl)benzene, 14 g (4.2×10 -2 mol) of a silane compound with a trimethoxysilyl group according to the following formula (BM): and 7.9×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 2.0×10 -6The mixture (mol of Pt) was mixed together and aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 105 g of liquid product.

[0209] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (BN): [Synthesis example 21]

[0210] In a reactor, 50 g (1.1×10 -2 mol) of a compound according to the following formula (BO): 15 g (6.5×10 -2 mol) Diethylene glycol-2-bromomethyl methyl ether and 0.08 g (2.2×10 -4 mol) Tetrabutylammonium iodide were mixed together. Then 3.6 g (6.5×10 -2Potassium hydroxide (mol) was added and the mixture was heated to 60°C for 24 hours. After heating, the solution was cooled to room temperature and aqueous hydrochloric acid was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 48 g of a fluoropolyether group-containing polymer according to the following formula (BP):

[0211] In a reactor, 45 g (9.5×10 -3 mol) of a compound obtained as above according to the following formula (BP): 23 g 1,3-bis(trifluoromethyl)benzene, 5.6 g (1.9×10 -2 mol) of a silane compound with a trimethoxysilyl group according to the following formula (BQ): and 3.6×10 -2g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 9.2×10 -7 Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 45 g of a liquid product.

[0212] At the 1 -H-NMR analysis revealed that the compound has a structure according to the following formula (BR): [Synthesis example 22]

[0213] In a reactor, 100 g (1.5×10 -2 mol) of a compound according to the following formula (BS): 100 g 1,3-bis(trifluoromethyl)benzene, 12 g (6.0×10 -2 mol) of a polyether compound according to the following formula (BT): and 6.1 g (6.0×10 -2mol) triethylamine was mixed together, whereupon the mixture was heated at 90°C for 18 hours. After heating, the solution was cooled to room temperature and water was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 101 g of a fluoropolyether group-containing polymer according to the following formula (BU):

[0214] In a reactor, 80 g (1.2×10 -2 mol) of a compound obtained as above according to the following formula (BU): 40 g 1,3-bis(trifluoromethyl)benzene, 5.7 g (4.7×10 -2 mol) Trimethoxysilane and 4.5×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.2×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 79 g of a liquid product.

[0215] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (BV): [Synthesis example 23]

[0216] In a reactor, 50 g (1.6×10 -2 mol) of a compound according to the following formula (BW): 25 g 1,3-bis(trifluoromethyl)benzene, 13 g (6.4×10 -2 mol) of a polyether compound according to the following formula (BT): and 6.5 g (6.4×10 -2mol) triethylamine was mixed together, whereupon the mixture was heated at 60°C for 15 hours. After heating, the solution was cooled to room temperature and water was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 47 g of a fluoropolyether group-containing polymer according to the following formula (BX):

[0217] In a reactor, 40 g (1.3×10 -2 mol) of a compound obtained as above according to the following formula (BX): 20 g 1,3-bis(trifluoromethyl)benzene, 3.1 g (2.5×10 -2 mol) Trimethoxysilane and 4.8×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.2×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 41 g of a liquid product.

[0218] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (BY): [Synthesis example 24]

[0219] In a reactor, 100 g (2.4×10 -2 mol) of a compound according to the following formula (BZ): 50 g 1,3-bis(trifluoromethyl)benzene, 30 g (9.6×10 -2 mol) of a polyether compound according to the following formula (CA): and 6.5 g (9.6×10 -2mol) Triethylamine was mixed together, whereupon the mixture was heated at 60°C for 15 hours. After heating, the solution was cooled to room temperature and water was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 96 g of a fluoropolyether group-containing polymer according to the following formula (CB):

[0220] In a reactor, 50 g (1.1×10 -2 mol) of a compound obtained as above according to the following formula (CB): 25 g 1,3-bis(trifluoromethyl)benzene, 8.2 g (6.7×10 -2 mol) Trimethoxysilane and 4.2×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.1×10 -6Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 50 g of a liquid product.

[0221] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (CC): [Synthesis example 25]

[0222] In a reactor, 40 g (9.0×10 -3 mol) of a compound according to the following formula (CB), which was obtained in the same way as in Synthesis Example 24: 40 g 1,3-bis(trifluoromethyl)benzene, 15 g (5.4×10 -2 mol) of a silane compound with a trimethoxysilyl group according to the following formula (CD): and 3.4×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 8.7×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 44 g of a liquid product.

[0223] At the 1 -H-NMR analysis revealed that the compound has a structure according to the following formula (CE): [Synthesis example 26]

[0224] In a reactor, 50 g (9.8×10 -3 mol) of a compound according to the following formula (CF): 25 g 1,3-bis(trifluoromethyl)benzene, 12 g (3.9×10 -2 mol) of a polyether compound according to the following formula (CA): and 4.0 g (3.9×10 -2mol) Triethylamine was mixed together, whereupon the mixture was heated at 60°C for 15 hours. After heating, the solution was cooled to room temperature and water was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 51 g of a fluoropolyether group-containing polymer according to the following formula (CG):

[0225] In a reactor, 50 g (9.3×10 -3 mol) of a compound obtained as above according to the following formula (CG): 25 g 1,3-bis(trifluoromethyl)benzene, 6.8 g (5.5×10 -2 mol) Trimethoxysilane and 3.6×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 9.2×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 50 g of a liquid product.

[0226] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (CH): [Synthesis example 27]

[0227] In a reactor, 50 g (1.4×10 -2 mol) of a compound according to the following formula (CI): 50 g 1,3-bis(trifluoromethyl)benzene, 20 g (5.5×10 -2 mol) of a polyether compound according to the following formula (CJ): and 5.6 g (5.5×10 -2mol) triethylamine was mixed together, whereupon the mixture was heated at 60°C for 15 hours. After heating, the solution was cooled to room temperature and water was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 52 g of a fluoropolyether group-containing polymer according to the following formula (CK):

[0228] In a reactor, 50 g (1.3×10 -2 mol) of a compound obtained as above according to the following formula (CK): 25 g 1,3-bis(trifluoromethyl)benzene, 9.2 g (7.5×10 -2 mol) Trimethoxysilane and 5.0×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 1.3×10 -6The two components (mol of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 51 g of a liquid product.

[0229] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (CL): [Synthesis example 28]

[0230] In a reactor, 50 g (1.2×10 -2 mol) of a compound according to the following formula (CM): 25 g 1,3-bis(trifluoromethyl)benzene, 9.8 g (4.8×10 -2 mol) of a polyether compound according to the following formula (BT): and 4.9 g (4.8×10 -2mol) triethylamine was mixed together, whereupon the mixture was heated at 80°C for 24 hours. After heating, the solution was cooled to room temperature and water was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 49 g of a fluoropolyether group-containing polymer according to the following formula (CN):

[0231] In a reactor, 40 g (9.3×10 -3 mol) of a compound obtained as above according to the following formula (CN): 20 g 1,3-bis(trifluoromethyl)benzene, 7.1 g (1.9×10 -2 mol) of a silane compound with a trimethoxysilyl group according to the following formula (CO): and 3.5×10 -2g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 9.0×10 -7 The two components (mol of Pt) were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 53 g of a liquid product.

[0232] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (CP): [Synthesis example 29]

[0233] In a reactor, 50 g (9.7×10 -3 mol) of a compound according to the following formula (CQ): 25 g 1,3-bis(trifluoromethyl)benzene, 19 g (3.9×10 -2 mol) of a polyether compound according to the following formula (CR): and 3.9 g (3.9×10 -2mol) triethylamine was mixed together, whereupon the mixture was heated at 60°C for 15 hours. After heating, the solution was cooled to room temperature and water was added dropwise. The lower layer, or fluorine compound layer, was recovered by separation treatment and washed with acetone. The lower layer, or fluorine compound layer, was recovered after washing. The remaining solvent was distilled off under vacuum, yielding 48 g of a fluoropolyether group-containing polymer according to the following formula (CS):

[0234] In a reactor, 40 g (7.2×10 -3 mol) of a compound obtained as above according to the following formula (CS): 20 g 1,3-bis(trifluoromethyl)benzene, 4.7 g (2.9×10 -2 mol) Triethoxysilane and 2.7×10 -2 g Chloroplatinic acid / vinylsiloxane complex in toluene (containing 6.9×10 -7Moles of Pt were mixed together and the mixture was aged for 24 hours at 80°C. The solvent and unreacted reactants were then distilled off under vacuum, yielding 41 g of a liquid product.

[0235] At the 1 H-NMR analysis revealed that the compound has a structure according to the following formula (CT): [Example 1]

[0236] The final compound obtained in Synthesis Example 1 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 2]

[0237] The final compound obtained in Synthesis Example 2 was dissolved in Opteon SF 10 (methyl perfluoroheptenyl ether, manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd.) at a concentration of 20 wt% to produce a surface treatment agent. [Example 3]

[0238] The final compound obtained in Synthesis Example 3 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 4]

[0239] The final compound obtained in Synthesis Example 6 was dissolved in ASAHIKLIN AC-6000 (tridecafluorooctane, manufactured by AGC Inc.) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 5]

[0240] The final compound obtained in Synthesis Example 7 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 6]

[0241] The final compound obtained in Synthesis Example 10 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 7]

[0242] The final compound obtained in Synthesis Example 11 was dissolved in ASAHIKLIN AE-3000 (tetrafluoroethyl trifluoroethyl ether, manufactured by AGC Inc.) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 8]

[0243] The final compound obtained in Synthesis Example 13 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 9]

[0244] The final compound obtained in Synthesis Example 14 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 10]

[0245] The final compound obtained in Synthesis Example 15 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 11]

[0246] The final compound obtained in Synthesis Example 16 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 12]

[0247] The final compound obtained in Synthesis Example 18 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 13]

[0248] The final compound obtained in Synthesis Example 25 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Example 14]

[0249] The final compound obtained in Synthesis Example 26 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Comparison example 1]

[0250] A compound according to the following formula (CU) was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt% to produce a surface treatment agent. [Comparative example 2]

[0251] A compound according to the following formula (CV) was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt%, thereby producing a surface treatment agent. [Comparative example 3]

[0252] A compound according to the following formula (CW) was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 20 wt% to produce a surface treatment agent. Production of the surface treatment agent and formation of a hardened film

[0253] Surface treatment compounds were produced according to the examples and comparative examples. Each surface treatment compound was produced under vacuum (treatment conditions were as follows: pressure: 2.0 × 10⁻⁶). -2 Pa, heating temperature: 700°C) onto glass (Gorilla, manufactured by Corning Incorporated), the outermost surface of which was coated with SiO2 to a thickness of 10 nm, and was then cured for 12 hours under an atmosphere of 25°C and a relative humidity of 50% to form a hardened film with a film thickness of 10 nm. Evaluation of water / oil repellency [Evaluation of initial water / oil repellency]

[0254] Using a Drop Master contact angle measuring device (Kyowa Interface Science Co., Ltd.), the contact angle with water (2 µl drop, 25°C temperature, 40% relative humidity) of the glass-tempered film was measured as an index of water repellency. The results (initial contact angle with water) are shown in Table 1.

[0255] Initially, all the slides in the examples and comparison examples exhibited excellent water repellency. [Evaluation of abrasion resistance]

[0256] Using a friction tester (Shinto Scientific Co., Ltd.), the glass-tempered film was subjected to a friction test under the conditions specified below. Subsequently, the tempered film was measured in a similar manner with respect to the contact angle with water (water repellency) as an index of abrasion resistance. The test environment conditions included a temperature of 25°C and a relative humidity of 40%. The results (contact angle with water after abrasion) are shown in Table 1. Abrasion resistance compared to steel wool Steel wool: Bonster # 0000 Contact area: 1 cm 2 Movement path (simple): 40 mm Speed ​​of movement: 4,800 mm / min Burden: 1 kg / 1 cm 2 Number of steel wool abrasions: 15,000 cycles Abrasion resistance compared to erasers Eraser: Raber eraser (manufactured by Minoan) Contact area: 6 mmφ Movement path (simple): 60 mm Speed ​​of movement: 3,600 mm / min Burden: 1 kg / 6 mmφ Number of steel wool abrasions: 5,000 cycles

[0257] In the surface treatment compounds of Examples 1 to 14, the presence of a polyether group in the molecule of the compound used improved substrate adhesion and wettability and exhibited high abrasion resistance against erasers. Because the bonding region between the fluorine chain and the branch point of the terminal adhesive group was long, molecular mobility was ensured, and high abrasion resistance against steel wool was confirmed. The surface treatment compound from Comparative Example 1 exhibits low abrasion resistance against erasers and low abrasion resistance against steel wool, while the surface treatment compound from Comparative Example 2 exhibits high abrasion resistance against steel wool but low abrasion resistance against erasers.The surface treatment agent from comparative example 3 exhibits high abrasion resistance against erasers, but low abrasion resistance against steel wool. As described above, the surface treatment agents in the examples achieved both high abrasion resistance against erasers and high abrasion resistance against steel wool. [Table 1] Connection Initial contact angle with water (°) Contact angle with water after abrasion with steel wool (°) Contact angle with water after abrasion with eraser (°) Example 1 Synthesis example 1 118 109 106 Example 2 Synthesis example 2 117 108 108 Example 3 Synthesis example 3 116 107 104 Example 4 Synthesis example 6 115 109 104 Example 5 Synthesis example 7 113 108 107 Example 6 Synthesis example 10 112 106 105 Example 7 Synthesis example 11 117 103 101 Example 8 Synthesis example 13 118 104 104 Example 9 Synthesis example 14 116 108 104 Example 10 Synthesis example 15 116 103 101 Example 11 Synthesis example 16 117 105 106 Example 12 Synthesis example 18 114 102 101 Example 13 Synthesis example 25 117 109 107 Example 14 Synthesis example 26 118 110 106 Comparative example 1 Formula (CU) 118 91 71 Comparative example 2 Formula (CV) 116 110 86 Comparative example 3 Formula (CW) 115 99 96 [Example 15]

[0258] The compound obtained in Synthesis Example 1 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 0.1 wt% to produce a surface treatment agent. [Example 16]

[0259] The compound obtained in Synthesis Example 2 was dissolved in Opteon SF 10 (methyl perfluoroheptenyl ether, manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd.) at a concentration of 0.1 wt% to produce a surface treatment agent. [Example 17]

[0260] The compound obtained in Synthesis Example 3 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 0.1 wt% to produce a surface treatment agent. [Example 18]

[0261] The compound obtained in Synthesis Example 6 was dissolved in ASAHIKLIN AC-6000 (tridecafluorooctane, manufactured by AGC Inc.) at a concentration of 0.1 wt% to produce a surface treatment agent. [Example 19]

[0262] The compound obtained in Synthesis Example 10 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 0.1 wt% to produce a surface treatment agent. [Example 20]

[0263] The compound obtained in Synthesis Example 16 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 0.1 wt% to produce a surface treatment agent. [Example 21]

[0264] The compound obtained in Synthesis Example 25 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 0.1 wt% to produce a surface treatment agent. [Example 22]

[0265] The compound obtained in Synthesis Example 26 was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 0.1 wt% to produce a surface treatment agent. [Comparative example 4]

[0266] The compound (CU) was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 0.1 wt% to produce a surface treatment agent. [Comparative example 5]

[0267] The compound (CV) was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 0.1 wt% to produce a surface treatment agent. [Comparative example 6]

[0268] The compound (CW) was dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) at a concentration of 0.1 wt% to produce a surface treatment agent. Production of the surface treatment agent and formation of a hardened film

[0269] Surface treatment compounds were prepared according to the examples and comparative examples. Each surface treatment compound was sprayed onto glass (Gorilla, manufactured by Corning Incorporated) and cured for 30 minutes under an atmosphere of 120°C and then for 12 hours under an atmosphere of 25°C and 50% relative humidity to form a cured film with a film thickness of 10 nm. Evaluation of water / oil repellency [Evaluation of initial water / oil repellency]

[0270] Using a Drop Master contact angle measuring device (Kyowa Interface Science Co., Ltd.), the contact angle with water (2 µl drop, 25°C temperature, 40% relative humidity) of the glass-tempered film was measured as an index of water repellency. The results (initial contact angle with water) are shown in Table 2.

[0271] Initially, all the slides in the examples and comparison examples exhibited excellent water repellency. [Evaluation of abrasion resistance]

[0272] Using a friction tester (Shinto Scientific Co., Ltd.), the glass-tempered film was subjected to a friction test under the conditions specified below. Subsequently, the tempered film was measured in a similar manner with respect to the contact angle with water (water repellency) as an index of abrasion resistance. The test environment conditions included a temperature of 25°C and a relative humidity of 40%. The results (contact angle with water after abrasion) are shown in Table 2. Abrasion resistance compared to steel wool Steel wool: Bonster # 0000 Contact area: 1 cm 2 Movement path (simple): 40 mm Speed ​​of movement: 4,800 mm / min Burden: 1 kg / 1 cm 2 Number of steel wool abrasions: 10,000 cycles Abrasion resistance compared to erasers Eraser: Raber eraser (manufactured by Minoan) Contact area: 6 mmφ Movement path (simple): 30 mm Speed ​​of movement: 3,600 mm / min Burden: 1 kg / 6 mmφ Number of steel wool abrasions: 5,000 cycles

[0273] The surface treatments of Examples 15 to 22, like the vapor deposition coating, exhibited high abrasion resistance to erasers and high resistance to steel wool. The surface treatment of Comparative Example 4 exhibits low abrasion resistance to erasers and low abrasion resistance to steel wool, while the surface treatment of Comparative Example 5 exhibits high abrasion resistance to steel wool but low abrasion resistance to erasers. The surface treatment of Comparative Example 6 exhibits high abrasion resistance to erasers but low abrasion resistance to steel wool.As described above, the surface treatment agents in the examples achieved both high abrasion resistance against erasers and high abrasion resistance against steel wool, even when the coating process was changed. [Table 2] Connection Initial contact angle with water (°) Contact angle with water after abrasion with steel wool (°) Contact angle with water after abrasion with eraser (°) Example 15 Synthesis example 1 118 107 108 Example 16 Synthesis example 2 117 107 106 Example 17 Synthesis example 3 116 105 105 Example 18 Synthesis example 6 115 110 103 Example 19 Synthesis example 10 112 104 105 Example 20 Synthesis example 16 117 106 107 Example 21 Synthesis example 25 117 109 105 Example 22 Synthesis example 26 118 107 106 Comparative example 4 Formula (CU) 118 89 64 Comparative example 5 Formula (CV) 116 109 82 Comparative example 6 Formula (CW) 115 96 97 QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP-A 2008-534696 [0005, 0008] JP-A 2008-537557 [0005, 0008] JP-A 2012-072272 [0005, 0008] JP-A 2012-157856

[0005] JP-A 2013-136833 [0005, 0008] JP-A 2015-199906 [0005, 0008] WO 2017 / 212850 [0007, 0008]

Claims

[1] A polymer containing fluoropolyether groups, comprising a hydroxyl group or hydrolyzable group and a polyether group, having the general formula (1): where Rf represents a mono- or bivalent polymer residue containing a fluorooxyalkylene group, B independently represents a bivalent organic group, V independently represents a carbon atom, silicon atom, nitrogen atom, or a tri- to octavalent organic group, E independently represents a monovalent group with an oxyalkylene group, R' independently represents a hydrogen atom, a hydroxyl group, a C1-C4 alkyl group, a phenyl group, a C1-C4 alkoxy group, or a halogen group, U independently represents a single bond or a bivalent organic group, Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a tri- to octavalent organic group, and Y independently represents a bivalent hydrocarbon group that may contain at least one selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond.R independently represents a C1-C4 alkyl group or a phenyl group, X independently represents a hydroxyl group or a hydrolyzable group, n independently represents an integer from 1 to 3 for each silicon atom to be bound, m independently represents an integer from 1 to 7, α represents 1 or 2, β independently represents an integer from 1 to 6, γ independently represents 0 or 1, δ independently represents 1 or 2, and the sum of β, γ and δ independently represents an integer from 2 to 7 for each V to be bound. [2] Polymer containing fluoropolyether groups according to claim 1, wherein in formula (1) α represents 1 and Rf represents a group of the general formula (2): where A represents a fluorine atom, a hydrogen atom, or a fluoroalkyl group ending with a -CF3 group, W represents a fluoroalkyl group containing at least one hydrogen atom, d independently represents an integer from 1 to 3 for each unit, p, q, r, s, t, u, and v each represent an integer from 0 to 200, p + q + r + s + t + u + v is a number from 3 to 200, each of the units can be linear or branched, and individual repeating units within the brackets can be randomly linked with p, q, r, s, t, u, and v. [3] Polymer containing fluoropolyether groups according to claim 1, wherein in formula (1) α represents 2 and Rf represents a group of the general formula (3): where W represents a fluoroalkylene group containing at least one hydrogen atom, d independently represents an integer from 1 to 3 for each unit, p, q, r, s, t, u and v each represent an integer from 0 to 200, p + q + r + s + t + u + v is a number from 3 to 200, each of the units can be linear or branched, and individual repeating units within the brackets can be randomly linked with p, q, r, s, t, u and v. [4] A polymer containing fluoropolyether groups according to any one of claims 1 to 3, wherein in formula (1) B is selected for a bivalent group from the group consisting of a C1-C 10 -alkylene group, an alkylene group containing a C6-C8 arylene residue, a bivalent group with alkylene residues bonded via a diorganosilylene residue, a silalkylene structure or a silarylene group, and a bivalent group with a C1-C 10-Alkylene residue, which is bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms, a carbonyl group and an amide group, and may contain at least one selected from an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide and an ester group. [5] A polymer containing fluoropolyether groups according to any one of claims 1 to 4, wherein in formula (1) V represents a carbon atom, a silicon atom, a nitrogen atom, a linear tri- to hexavalent organopolysiloxane residue with 2 to 10 silicon atoms, a branched or cyclic tri- to hexavalent organopolysiloxane residue with 3 to 10 silicon atoms, a trivalent isocyanur group or a trivalent triazine ring-containing group. [6] A polymer containing fluoropolyether groups according to any one of claims 1 to 5, wherein in formula (1) Y is selected for a group consisting of a C1-C 10 -Alkylene group which may contain an oxygen atom or a sulfur atom, an alkylene group which contains a C6-C8 arylene group, a bivalent group with alkylene residues which are bonded via a diorganosilylene residue, a silalkylene structure or a silarylene structure, and a bivalent group with a C1-C 10 -Alkylene group, which is bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms. [7] A polymer containing fluoropolyether groups according to any one of claims 1 to 6, wherein in formula (1) U is selected for a group consisting of a single bond, a C1-C 10-Alkylene group which may contain an oxygen atom and a sulfur atom, an alkylene group which contains a C6-C8 arylene residue, a bivalent group with alkylene residues which are bonded via a diorganosilylene residue, a silalkylene structure or a silarylene structure, and a bivalent group with a C1-C 10 -Alkylene residue, which is bonded to the valence bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms or to the valence bond of a branched or cyclic organopolysiloxane residue with 3 to 10 silicon atoms. [8] A polymer containing fluoropolyether groups according to any one of claims 1 to 7, wherein in formula (1) Z represents any element selected from the group consisting of a single bond, a carbon atom, a silicon atom, a nitrogen atom, -CH=, a linear tri- to hexavalent organopolysiloxane residue with 2 to 10 silicon atoms, and a branched or cyclic tri- to hexavalent organopolysiloxane residue with 3 to 10 silicon atoms. [9] A polymer containing fluoropolyether groups according to any one of claims 1 to 8, wherein in formula (1) X is composed of the group consisting of a hydroxyl group, a C1-C 10 -Alkoxy group, a C2-C 10 -Alkoxyalkoxy group, a C1-C 10 -Acyloxy group, a C2-C 10 -Alkenyloxy group and a halogen group is selected. [10] The fluoropolyether group-containing polymer according to any one of claims 1 to 9, wherein the fluoropolyether group-containing polymer of formula (1) has one of the following formulas: where p1, q1, r1 and s1 each represent an integer from 1 to 200, with the stipulation that the sum of p1, q1, r1 and s1 in each formula is 3 to 200, r2 and r3 each represent an integer of at least 1, the sum of r2 and r3 is 2 to 199, individual units within the parentheses may be randomly bound to p1, q1, r1, r2, r3 and s1, and k represents an integer from 1 to 20. [11] Surface treatment composition comprising a fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group and / or a partial (hydrolytic) condensate thereof. [12] Surface treatment composition according to claim 11, wherein the polyether group in the fluoropolyether group-containing polymer with a hydroxyl group or a hydrolyzable group and a polyether group is a group with a monovalent oxyalkylene residue at a molecular chain branch. [13] Surface treatment composition according to claim 11 or 12, wherein the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group is the fluoropolyether group-containing polymer with a hydroxyl group or hydrolyzable group and a polyether group according to any one of claims 1 to 10. [14] Articles with a surface that has been treated with the surface treatment agent according to any one of claims 11 to 13.

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