Fluorine-containing ether composition, surface treatment agent, and article

Abstract

Provided is a fluorine-containing ether composition which contains: a fluoropolyether group-containing polymer that contains a hydrolyzable silyl group or a silanol group having a specific structure that includes CF3O- or CF3CF2O- at a terminal; and / or a partial (hydrolysis) condensation product of the polymer. The fluoropolyether group-containing polymer and / or the partial (hydrolysis) condensation product of the polymer are contained at a quantity whereby the molar ratio of CF3O- and CF3CF2O- (CF3CF2O- / CF3O-) is 0.01-0.17. The fluorine-containing ether composition can form a cured film that exhibits water-and oil-repellency and excellent anti-fouling properties, heat resistance, surface release properties and durability against eraser abrasion.

Description

Fluorine-containing ether composition, surface treatment agent and article

[0001] The present invention relates to a fluorine-containing ether composition containing a fluoropolyether group-containing polymer (a compound having a fluoropolyether group in the molecule), and more particularly to a fluorine-containing ether composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, which is capable of forming a cured coating having water and oil repellency, as well as excellent stain resistance, heat resistance, surface release property and eraser abrasion resistance; a surface treatment agent containing the fluorine-containing ether composition; and an article surface-treated with the surface treatment agent.

[0002] In recent years, the use of touch panels in displays, including smartphones, has accelerated. However, touch panels have exposed screens, which are often directly touched by fingers or cheeks, making them susceptible to sebum and other contaminants. Therefore, there is an increasing demand for technologies that make display surfaces less susceptible to fingerprints and easier to clean, thereby improving appearance and visibility. The development of materials that can meet these demands is highly desirable. Touch panel display surfaces are particularly susceptible to fingerprints, making them ideal for providing a water- and oil-repellent layer. However, while conventional water- and oil-repellent layers offer high water- and oil-repellent properties and excellent wipeability, they suffer from the problem of degradation of their anti-fouling properties during use.

[0003] In general, fluoropolyether group-containing compounds have very low surface free energy and therefore have water and oil repellency, chemical resistance, lubricity, release properties, antifouling properties, etc. Utilizing these properties, they are widely used industrially as water and oil repellent and antifouling agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, etc. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and even if they can be applied to the surface of a substrate, it has been difficult to adhere the coating to it.

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

[0005] Thus, compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, which can form coatings that easily adhere to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, and the like on the substrate surfaces (Patent Documents 1 to 6: JP-T-2008-534696, JP-T-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, and JP-A-2015-199906).

[0006] In particular, as a method for forming a coating with improved heat resistance, it has been reported that an organic group containing an alicyclic structure having 3 to 13 carbon atoms has a thermally stable structure, and that a fluorine-containing ether compound containing this organic group improves heat resistance (Patent Document 7: International Publication No. 2021 / 054202). However, since a specific organic group must be introduced, it becomes difficult to achieve both of these improvements even if other performances are also improved. In addition to the above-mentioned documents, the following documents can be cited as prior art related to the present invention.

[0007] Japanese Patent Publication No. 2008-534696 Japanese Patent Publication No. 2008-537557 Japanese Patent Application Laid-Open No. 2012-072272 Japanese Patent Application Laid-Open No. 2012-157856 Japanese Patent Application Laid-Open No. 2013-136833 Japanese Patent Application Laid-Open No. 2015-199906 International Publication No. 2021 / 054202 Japanese Patent No. 6451279 Japanese Patent No. 6119656 Japanese Patent No. 6828744 Japanese Patent No. 6524955 Japanese Patent No. 6521091

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorine-containing ether composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, which is capable of forming a cured coating having water and oil repellency, as well as excellent stain resistance, heat resistance, surface release property and eraser abrasion resistance; a surface treatment agent containing the fluorine-containing ether composition; and an article surface-treated with the surface treatment agent.

[0009] In order to achieve the above object, the present inventors have newly discovered that, by taking into consideration the molar ratio in the composition of the fluoropolyether groups contained in a fluoropolyether group-containing compound, particularly the fluorooxymethylene group and the fluorooxyethylene group adjacent to the terminal fluorooxyalkyl group, a surface treatment agent containing a fluorine-containing composition containing a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, in which a hydrolyzable silyl group has been introduced into the fluoropolyether group-containing compound, can form a cured coating that has high performance in terms of water and oil repellency, heat resistance, and abrasion resistance.

[0010] As a result of further investigations, the present inventors have found that a surface treatment agent containing a fluorine-containing ether composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and / or a partial (hydrolyzed) condensate thereof, which is represented by the average composition formula (1) described below, in which the molar ratio of the terminal groups fluorooxymethyl group and fluorooxyethyl group is within a specific range, can form a cured coating that has water and oil repellency, as well as excellent stain resistance, heat resistance, surface peeling property and eraser abrasion resistance, and has thereby completed the present invention.

[0011] Accordingly, the present invention provides the following fluorinated ether composition, surface treatment agent, and article: [1] A fluorinated ether composition comprising a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one terminal, represented by the following average composition formula (1), and / or a partial (hydrolyzed) condensate thereof: [wherein, RF 1is CF3O- or CF3CF2O-, and the molar ratio of CF3O- to CF3CF2O- (CF3CF2O- / CF3O-) is 0.01 or more and 0.17 or less. 2 is —CF2O— or —CF2CF2O—, and Rf is represented by the following formula (2): (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer of 1 to 6. p, q, r, s, t, u, and v are each an integer of 0 to 450, such that p+q+r+s+t+u+v=10 to 450, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.) wherein U is a single bond or a divalent to pentavalent organic group, Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, -SiR'= (R' is an alkyl group having 1 to 4 carbon atoms) or a trivalent to nonavalent organic group, Y is independently a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is independently 2 or 3 for each unit bonded to a silicon atom, b is independently an integer of 1 to 8, and c is an integer of 1 to 4.] [2] RF of the formula (1) 2 The fluorine-containing ether composition according to [1], wherein the molar ratio of -CF2O- to -CF2CF2O- (-CF2CF2O- / -CF2O-) is 1.05 or more and 1.2 or less. [3] The fluorine-containing ether composition according to [1] or [2], wherein, in formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group. [4] The fluorine-containing ether composition according to [1], wherein, in formula (1), U is a single bond, a carbonyl group, an amide group, a group represented by the following formula: (wherein B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms), or a divalent to pentavalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom, a hydroxyl group, a polyether group, a diorganosilylene group, a linear divalent organopolysiloxane residue having 2 to 100 silicon atoms, a silalkylene group, a silarylene group, a secondary amino group, a tertiary amino group, an ether group, a carbonyl group, an amide group, and an ester group. [5] The fluorinated ether composition according to any one of [1] to [4], wherein, in formula (1), Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a linear, branched or cyclic organopolysiloxane residue having 3 to 13 silicon atoms and having a valence of 3 to 8, a trivalent isocyanuric group, or a trivalent triazine ring-containing group. [6] The fluorine-containing ether composition according to any one of [1] to [5], wherein in the formula (1), Y is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms and containing a fluorine atom, alkylene groups having 1 to 10 carbon atoms and containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a divalent organopolysiloxane residue that is linear having 2 to 10 silicon atoms or branched or cyclic having 3 to 10 silicon atoms. [7] The fluorine-containing ether composition according to any one of [1] to [6], further comprising 25 mass% or less of a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the following general formula (3), and / or a partial (hydrolyzed) condensate thereof: [In the formula, U, Z, Y, R, X, a, b, and c are independently the same as above, and Rf′ is a group represented by the following formula (4): (wherein W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as defined above. d' is an integer of 1 to 6. These units may be linear or branched. Furthermore, the repeating units shown in parentheses followed by p, q, r, s, t, u, and v may be bonded randomly.) [8] The fluorine-containing ether composition according to any one of [1] to [7], further comprising 30 mass% or less of a fluoropolyether group-containing polymer represented by the following general formula (5): A-Rf'-A (5) [wherein A independently represents a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group which is terminally CF3-, CF2H-, CF3CF2-, or CF3CFH- and which may contain an oxygen atom. Rf' is a divalent fluoropolyether group represented by the following formula (4): (wherein W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above, and d' is an integer of 1 to 6. Each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses followed by p, q, r, s, t, u, or v may be randomly bonded.) [9] The fluorine-containing ether composition according to any of [1] to [8], wherein the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one terminal, represented by formula (1), is at least one selected from those represented by the following formulas: (In the formula, RF 1 , RF 2 are the same as above, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 20 to 450, and the repeating units shown in parentheses after p1 and q1 may be bonded randomly.)

[10] A surface treatment agent comprising the fluorinated ether composition according to any one of [1] to [9].

[11] An article surface-treated with the surface treatment agent according to

[10] .

[0012] The fluorine-containing ether composition of the present invention contains a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, and which is represented by the above average composition formula (1) taking into consideration the molar ratio of the terminal groups fluorooxymethyl and fluorooxyethyl, and / or a partial (hydrolyzed) condensate thereof. An article surface-treated with a surface treatment agent containing the fluorine-containing ether composition has improved properties in terms of stain resistance, heat resistance, surface peeling property and eraser abrasion resistance, in addition to water and oil repellency.

[0013] In the present invention, the number average molecular weight (Mn) of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or its partial (hydrolyzed) condensate, or the fluorinated ether composition is 19 It can be calculated from the characteristic peak intensity ratio in F-NMR analysis.

[0014] In the present invention, the "partial (hydrolyzed) condensate" of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group is obtained by partially condensing the hydroxyl groups of the fluoropolyether group-containing polymer having a silanol group, or the hydroxyl groups of the fluoropolyether group-containing polymer having a hydrolyzable silyl group, which have been partially hydrolyzed in advance by a known method.

[0015] The fluorine-containing ether composition (fluoropolyether group-containing polymer composition) of the present invention contains a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one terminal, represented by the following average composition formula (1), and / or a partial (hydrolyzed) condensate thereof: [wherein, RF 1 is CF3O- or CF3CF2O-, and the molar ratio of CF3O- to CF3CF2O- (CF3CF2O- / CF3O-) is 0.01 or more and 0.17 or less. 2 is —CF2O— or —CF2CF2O—, and Rf is represented by the following formula (2): (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer of 1 to 6. p, q, r, s, t, u, and v are each an integer of 0 to 450, such that p+q+r+s+t+u+v=10 to 450, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.) wherein U is a single bond or a divalent to pentavalent organic group; Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, -SiR'= (R' is an alkyl group having 1 to 4 carbon atoms) or a trivalent to nonavalent organic group; Y is independently a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond; R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group; X is independently a hydroxyl group or a hydrolyzable group; a is independently 2 or 3 for each unit bonded to a silicon atom; b is independently an integer of 1 to 8; and c is an integer of 1 to 4.

[0016] In the above formula (1), RF 1 is CF3O- or CF3CF2O-, and the molar ratio of CF3O- to CF3CF2O- (CF3CF2O- / CF3O-) is 0.01 or more and 0.17 or less, more preferably 0.04 or more and 0.16 or less. If the molar ratio is less than 0.01, the resulting cured coating cannot maintain high heat resistance. If it exceeds 0.17, the resulting cured coating will have reduced stain resistance and eraser abrasion resistance. If the molar ratio is in the range of 0.01 or more and 0.17 or less, the resulting cured coating will be able to simultaneously exhibit all the required properties of stain resistance, heat resistance, surface peelability, and eraser abrasion resistance. The molar ratio is 19 It can be calculated from the characteristic peak intensity ratio in F-NMR analysis.

[0017] In the above formula (1), RF 2is -CF2O- or -CF2CF2O-, and the molar ratio of -CF2O- to -CF2CF2O- (-CF2CF2O- / -CF2CF2O-) is preferably 1.05 or more and 1.2 or less, and more preferably 1.1 or more and less than 1.2. If the molar ratio is less than 1.05, the heat resistance of the resulting cured coating may decrease, and if it exceeds 1.2, the release properties of the surface of the resulting cured coating may decrease. 19 It can be calculated from the characteristic peak intensity ratio in F-NMR analysis.

[0018] In the above formula (1), Rf is a divalent fluoropolyether group represented by the following formula (2). (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer of 1 to 6. p, q, r, s, t, u, and v are each an integer of 0 to 450, such that p+q+r+s+t+u+v=10 to 450, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.)

[0019] In the above formula (2), W is a fluoroalkylene group containing one or more hydrogen atoms, such as CF, CF, CF, CF, CF 10 , C6F 12 and the like, in which one or two fluorine atoms are substituted with hydrogen atoms.

[0020] In the above formula (2), d is an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2. Furthermore, p, q, r, s, t, u, and v are each integers of 0 to 450, preferably p is an integer of 5 to 440, q is an integer of 5 to 250, r is an integer of 0 to 180, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, and v is an integer of 0 to 100; p+q+r+s+t+u+v is 10 to 450, preferably 20 to 200, and p+q is 20 to 450, particularly preferably 20 to 200. When p+q+r+s+t+u+v is smaller than the upper limit, adhesion and curability are good; when it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferred. Each unit may be linear or branched. Furthermore, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.

[0021] Specific examples of Rf include the following: (In the formula, p', q', and r' are each an integer of 1 or greater, the upper limit of which is the same as the upper limit of p, q, and r above, and the total of p', q', and r' is 20 to 450. In addition, each repeating unit shown in parentheses followed by p', q', and r' may be bonded randomly.)

[0022] In the above formula (1), RF 1 -RF 2 The number average molecular weight of the fluoropolyether group represented by -Rf- is preferably 1,000 to 50,000, more preferably 2,000 to 20,000. If the number average molecular weight is less than 1,000, the amount of fluorine is insufficient, and the antifouling properties of the resulting cured coating may be reduced, while if it exceeds 50,000, the surface properties of the resulting cured coating may become unstable. In the present invention, the number average molecular weight (Mn) can be determined by gel permeation chromatography (GPC) analysis using a fluorinated solvent as a developing solvent, 19 It can be calculated by means of F-NMR or the like.

[0023] In the above formula (1), U is a single bond or a divalent to pentavalent organic group, and is preferably a single bond, a carbonyl group, an amide group, or a group represented by the following formula: (In the formula, B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms), or a di- to pentavalent, preferably di- to tetravalent, hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom, a hydroxyl group, a polyether group, a diorganosilylene group such as a dimethylsilylene group, a linear divalent organopolysiloxane residue having 2 to 100 silicon atoms, preferably 2 to 50 silicon atoms, a silalkylene group, a silarylene group, a secondary amino group, a tertiary amino group, an ether group, a carbonyl group, an amide group, and an ester group.

[0024] In the above formula, examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms for B and B' include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, neopentyl, and thexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, and propenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups. Furthermore, examples of the monovalent polyether group for B include -(C e1 H 2e1 O) e Those represented by -CH3 (e1 is an integer of 1 to 6, and e is an integer of 1 to 30) are preferred.

[0025] Examples of the linear divalent organopolysiloxane residue having 2 to 100, preferably 2 to 50 silicon atoms that may be contained in the divalent to pentavalent hydrocarbon group include those shown below. (In the formula, R 1 is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group, and R 1may be the same or different, and g is an integer of 1 to 99, preferably an integer of 1 to 49.

[0026] Examples of the silalkylene group and silarylene group include those shown below. (In the formula, R 1 is the same as above, and R 2 is an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or a butylene group, or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.

[0027] Examples of U include the following groups in addition to a single bond: It is preferable that the left bond is bonded to Rf and the other bond is bonded to Z. (In the formula, f is independently an integer of 1 to 4, l1 and l2 are integers of 1 to 4, n is an integer of 1 to 100, and e is an integer of 1 to 30.)

[0028] In the above formula (1), Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, -SiR'= (R' represents an alkyl group having 1 to 4 carbon atoms, such as a methyl group or an ethyl group), or a trivalent to nonavalent, preferably trivalent to heptavalent, organic group, and is preferably a single bond, a carbon atom, a silicon atom, a nitrogen atom, a linear, branched, or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms, a trivalent isocyanuric group, or a trivalent triazine ring-containing group.

[0029] Examples of the linear, branched or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms, include those represented by the following general formula: [In the formula, R 1 , R 2 is the same as above, and R 1 , R 2 may be the same or different. 3 are independently R 1 Or the following general formula (6) (In the formula, R1 is the same as above, and R 1 may be the same or different. m8 is an integer of 1 to 6, preferably 1, and the left bond is bonded to Si. 3 At least one of R is formula (6). 4 are independently a single bond or a group represented by the following general formula (7): (In the formula, R 2 , R 3 is the same as above, and R 2 , R 3 may be the same or different. m9 is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 1, m10 is an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and m9 + m10 ≠ 0. Each repeating unit shown in parentheses may be randomly bonded. The bond on the left is bonded to Si. m1 is an integer of 1 to 9, preferably an integer of 1 to 4, m2 is an integer of 0 to 9, preferably an integer of 0 to 3, m3 is an integer of 2 to 6, preferably an integer of 3 to 5, m4 is an integer of 0 to 8, preferably 0 or 1, m3 + m4 is an integer of 3 to 10, preferably an integer of 3 to 5, m5 is 2 or 3, m6 is an integer of 3 to 9, preferably an integer of 3 to 7, and m7 is an integer of 0 to 9, preferably an integer of 0 to 3, and each repeating unit shown in parentheses may be randomly bonded. However, the number of silicon atoms in each organopolysiloxane residue is 3 to 13.]

[0030] Examples of Z include the following groups in addition to a single bond: It is preferable that the left bond is bonded to U, and the other bond is bonded to Y.

[0031] In the above formula (1), b is independently an integer of 1 to 8, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and c is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2.

[0032] In the above formula (1), Y is independently a divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond. Examples of the divalent hydrocarbon group which may have one or more selected from a fluorine atom, a silicon atom, and a siloxane bond include alkylene groups having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group; alkylene groups having 1 to 10 carbon atoms and containing a fluorine atom; The group is selected from the group consisting of alkylene groups having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (alkylene-arylene groups having 7 to 18 carbon atoms), divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms. Among these, alkylene groups having 1 to 10 carbon atoms, preferably 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms are preferred.

[0033] Here, examples of the silalkylene group and silarylene group include the same groups as those shown for U. Furthermore, examples of the divalent organopolysiloxane residue that is linear having 2 to 10 silicon atoms or branched or cyclic having 3 to 10 silicon atoms include those shown below. (In the formula, R 1 is the same as above, and R 1 may be the same or different. g1 is an integer of 1 to 9, preferably an integer of 1 to 3, and g2 is an integer of 1 to 8, preferably an integer of 1 to 3.

[0034] Specific examples of Y include the following: In the following structure, it is preferable that the left bond is bonded to Z and the right bond is bonded to Si.

[0035] In the above formula (1), X's are hydroxyl groups or hydrolyzable groups, which may be different from one another. Examples of such X's include hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy groups, alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy groups, acyloxy groups having 2 to 10 carbon atoms such as acetoxy and propionoxy groups, alkenyloxy groups having 2 to 10 carbon atoms such as vinyloxy, allyloxy, propenoxy, and isopropenoxy groups, and halogen groups such as chlorine, bromo, and iodo groups. Among these, methoxy, ethoxy, isopropenoxy, and chlorine groups are preferred.

[0036] In the above formula (1), R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, with a methyl group and an ethyl group being preferred.

[0037] In the above formula (1), a is independently 2 or 3 for each unit bonded to a silicon atom, and is preferably 3 from the viewpoints of reactivity and adhesion to a substrate.

[0038] Examples of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), include the following structures. By changing the combination of Rf, U, Z, Y, R, X, and a in the above formula (1), several types of fluoropolyether group-containing polymers having a silanol group or a hydrolyzable silyl group at one end can be obtained. In the following formula, RF 1 , RF 2 is the same as above, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 20 to 450, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.

[0039]

[0040] Examples of methods for preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), include those disclosed in Japanese Patent Nos. 6451279, 6119656, 6828744, 6524955, and 6521091, and further include the following methods. [Preparation Method 1] A fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) is dissolved in a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having SiH groups and silanol groups or hydrolyzable silyl groups (halogenated silyl groups, alkoxysilyl groups, etc.) is mixed with the resulting mixture. The resulting mixture is aged for 1 to 72 hours, preferably 10 to 36 hours, more preferably about 12 hours, in the presence of a hydrosilylation catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex at 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C. Note that when an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used in the organosilicon compound having SiH groups and silanol groups or hydrolyzable silyl groups, the substituent (halogen atom) on the silyl group may be subsequently converted to another hydrolyzable group, such as an alkoxy group, e.g., a methoxy group.

[0041] Here, in preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the above average composition formula (1), examples of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) include fluoropolyether group-containing polymers having an olefin moiety (alkenyl group) represented by the following average composition formula (8) or (9). [wherein, RF 1 , RF 2 , Rf, U, Z, b, and c are the same as above, and U' is a divalent to pentavalent, preferably divalent or trivalent hydrocarbon group having 1 to 18 carbon atoms which may contain an ether group.

[0042] In the above average composition formula (9), U' is a divalent to pentavalent, preferably divalent or trivalent hydrocarbon group having 1 to 18 carbon atoms, which may contain an ether group. Specific examples include those shown below. (In the formula, l1 is an integer of 1 to 4, l2' is an integer of 0 to 2, and f' is independently an integer of 0 to 2.)

[0043] Examples of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the above average composition formula (8) include the following. (In the formula, RF 1 , RF 2 , p1, q1, and p1+q1 are the same as above, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.)

[0044] Examples of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the above average composition formula (9) include the following. (In the formula, RF 1 , RF 2 , p1, q1, and p1+q1 are the same as above, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.)

[0045] In preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, which is represented by the above average composition formula (1), examples of the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group include compounds represented by the following general formula (10) or (11): (wherein Z, Y, R, X, a, b, and c are the same as above. Y 1 is a hydrogen atom, or a monovalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.

[0046] In the above formula (10), Y 1is a hydrogen atom, or a monovalent hydrocarbon group which may have one or more bonds selected from silicon atoms and siloxane bonds, and is preferably a hydrogen atom, a monovalent group in which a hydrogen atom and an alkylene group having 1 to 10 carbon atoms are bonded via a silalkylene structure or a silarylene structure, or a monovalent group in which a hydrogen atom and an alkylene group having 2 to 10 carbon atoms are bonded to a bond of a divalent organopolysiloxane residue which is linear having 2 to 10 silicon atoms or branched or cyclic having 3 to 10 silicon atoms.

[0047] Y 1 Specific examples of the group include the following groups.

[0048] Examples of the compound represented by the general formula (10) include the following.

[0049] Examples of the compound represented by the general formula (11) include the following:

[0050] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the above average composition formula (1), when reacting the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) with an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, the amount of the organosilicon compound used is such that the SiH group in the organosilicon compound is 1 to 4 equivalents, more preferably 1 to 2.5 equivalents, and even more preferably about 1.2 equivalents per equivalent of the olefin moiety (alkenyl group) in the fluoropolyether group-containing polymer.

[0051] In addition, when using the fluoropolyether group-containing polymer that has olefin moiety (alkenyl group) and has the fluoropolyether group-containing polymer that has the olefin moiety (alkenyl group) represented by the average composition formula (8) as the fluoropolyether group-containing polymer that has the olefin moiety (alkenyl group), use the compound that is represented by the general formula (10) as the organosilicon compound that has SiH group and silanol group or hydrolyzable silyl group; when using the fluoropolyether group-containing polymer that has the olefin moiety (alkenyl group) and has the fluoropolyether group-containing polymer that has the olefin moiety (alkenyl group) represented by the average composition formula (9) as the fluoropolyether group-containing polymer that has the olefin moiety (alkenyl group), use the compound that is represented by the general formula (11) as the organosilicon compound that has SiH group and silanol group or hydrolyzable silyl group.

[0052] In preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the average composition formula (1), examples of the solvent include fluorine-based solvents. Examples of fluorine-based solvents include hydrofluoroether (HFE) solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name: Novec series), and perfluorosolvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series). The amount of solvent used is 10 to 300 parts by weight, preferably 30 to 150 parts by weight, and more preferably about 50 parts by weight, per 100 parts by weight of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group).

[0053] In preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), examples of hydrosilylation reaction catalysts include the following: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The amount of hydrosilylation reaction catalyst used is 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (by mass), relative to the mass of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group).

[0054] In addition, when an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used in an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group. Examples of reagents that can be used when converting the substituent (halogen atom) on the silyl group to another hydrolyzable group include alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol. The amount used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, per 100 parts by mass of the addition reaction product of a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) and an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group (such as a halogenated silyl group or an alkoxysilyl group) in the molecule.

[0055] For example, as a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group), a compound represented by the following formula: When trimethoxysilane is used as the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, a compound represented by the following formula is obtained.

[0056] Other methods for preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, as represented by the above average composition formula (1), include the following: [Preparation Method 2] A fluoropolyether group-containing polymer having SiH groups is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having, for example, an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group (halogenated silyl group, alkoxysilyl group, etc.) is mixed, and the mixture is aged in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C, for 1 to 72 hours, preferably 10 to 36 hours, more preferably about 12 hours. In addition, when an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used in an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group may be subsequently converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.

[0057] An example of the fluoropolyether group-containing polymer having SiH groups is a compound represented by the following average composition formula (12). (In the formula, RF 1 , RF 2 , Rf, U, Z, b, and c are the same as above.)

[0058] Examples of the compound represented by the above average composition formula (12) include the following. (In the formula, RF 1 , RF 2 , p1, q1, and p1+q1 are the same as above, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.)

[0059] An example of an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group is a compound represented by the following general formula (13). (wherein R, X, and a are the same as above. Y 2 is a monovalent hydrocarbon group having an alkenyl group at its terminal and optionally having one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.

[0060] In the above formula (13), Y 2 is a monovalent hydrocarbon group which has an alkenyl group at the terminal and which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond, and examples thereof include those represented by the following formula:

[0061] Examples of the compound represented by the general formula (13) include the following.

[0062] In the preparation method 2 of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the above average composition formula (1), when the fluoropolyether group-containing polymer having a SiH group is reacted with an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group, the amount of the organosilicon compound used can be such that the olefin moiety (alkenyl group) in the organosilicon compound is 1 to 4 equivalents, more preferably 1 to 2.5 equivalents, and even more preferably about 1.2 equivalents per equivalent of the SiH group in the fluoropolyether group-containing polymer.

[0063] In the preparation [Preparation Method 2] of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), the solvent can be, for example, a fluorine-based solvent. Examples of the fluorine-based solvent include those similar to those exemplified in Preparation Method 1. The amount of the solvent used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having a SiH group.

[0064] In the preparation method 2 of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and represented by the average composition formula (1), examples of the hydrosilylation reaction catalyst include those exemplified in the preparation method 1. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The amount of the hydrosilylation reaction catalyst used is 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (by mass), relative to the mass of the fluoropolyether group-containing polymer having SiH groups.

[0065] In addition, when an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used in an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group, and examples of reagents that can be used to convert the substituent (halogen atom) on this silyl group to another hydrolyzable group include those similar to those exemplified in Preparation Method 1. The amount used can also be the same as in Preparation Method 1.

[0066] For example, as a fluoropolyether group-containing polymer having a SiH group, a compound represented by the following formula: is used, and KBM-1083 (7-octenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group, a compound represented by the following formula is obtained:

[0067] In addition, the following method can also be mentioned. For example, a compound represented by the following formula is used and cohydrolyzed with 1,1,3,3-tetramethyldisiloxane to give a compound of the formula:

[0068] When the compound represented by the above formula is used as the fluoropolyether group-containing polymer having SiH groups, and KBM-1083 (7-octenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group, the compound represented by the following formula is obtained.

[0069] The number average molecular weight of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and / or its partial (hydrolyzed) condensate, represented by the above average composition formula (1), is preferably 1,000 to 53,000, more preferably 2,000 to 23,000, even more preferably 2,500 to 13,000, and particularly preferably 3,000 to 8,300. If the number average molecular weight is less than 1,000, the antifouling properties of the resulting cured coating may be reduced, while if it exceeds 53,000, the surface properties of the resulting cured coating may become unstable. To achieve the above number average molecular weight, the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and / or its partial (hydrolyzed) condensate, represented by the above average composition formula (1), may be obtained by rectification or molecular distillation.

[0070] In the fluorine-containing ether composition (fluoropolyether group-containing polymer composition) of the present invention, the blending amount of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above-mentioned average composition formula (1), and / or its partial (hydrolyzed) condensate, in the fluorine-containing ether composition (particularly the total amount of the fluoropolyether group-containing polymer) is preferably 70 to 100 mass%, more preferably 80 to 100 mass%. If it is less than 70 mass%, heat resistance will decrease, and it may not be possible to obtain a cured coating that combines stain resistance, heat resistance, surface peelability, and eraser abrasion resistance.

[0071] The fluorine-containing ether composition of the present invention may further contain, if necessary, a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the following general formula (3), and / or a partial (hydrolyzed) condensate thereof (a polymer containing functional fluoropolyether groups at both ends), which has the effect of further improving heat resistance. [In the formula, U, Z, Y, R, X, a, b, and c are independently the same as above, and Rf′ is a group represented by the following formula (4): (wherein W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above; and d' is an integer of 1 to 6. Each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.)

[0072] In the above formula (3), Rf' is a divalent fluoropolyether group represented by the above formula (4), and W, d, p, q, r, s, t, u, v, p+q+r+s+t+u+v in formula (4) can be exemplified as those exemplified for Rf in the above formula (1).

[0073] In the above formula (4), d' is an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0074] Specific examples of Rf' include the following. (In the formula, p', q', and r' each represent an integer of 1 or greater, the upper limit of which is the same as the upper limit of p, q, and r above, and the sum of p', q', and r' is 20 to 450. r2' and r3' each represent an integer of 1 or greater, and the sum of r2' and r3' is 35 to 180. In addition, the repeating units shown in parentheses followed by p', q', and r' may be bonded randomly.)

[0075] In the above formula (4), the number average molecular weight of the fluoropolyether group represented by Rf' is preferably 1,000 to 50,000, and more preferably 2,000 to 20,000. If the number average molecular weight is less than 1,000, the amount of fluorine will be insufficient, and the antifouling properties of the resulting cured coating may be reduced, whereas if it exceeds 50,000, the surface properties of the resulting cured coating may be unstable.

[0076] In addition, the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the general formula (3), may be the same or different in U, Z, Y, R, X, a, b, c, and W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v in the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above-mentioned average composition formula (1).

[0077] Examples of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends (double-end functional fluoropolyether group-containing polymer) represented by the general formula (3) include the following. (In the formula, p2 is an integer of 5 to 440, q2 is an integer of 5 to 250, p2+q2 is an integer of 20 to 450, and the repeating units shown in parentheses with p2 and q2 may be bonded randomly.)

[0078] The number average molecular weight of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the general formula (3), and / or its partial (hydrolyzed) condensate, is preferably 1,000 to 56,000, more preferably 2,000 to 26,000, even more preferably 2,600 to 16,000, and particularly preferably 3,100 to 14,000. If the number average molecular weight is less than 1,000, the antifouling properties of the resulting cured coating may be reduced, while if it exceeds 56,000, the surface properties of the resulting cured coating may become unstable. To achieve the above number average molecular weight, the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the general formula (3), and / or its partial (hydrolyzed) condensate, can be obtained by rectification or molecular distillation.

[0079] In the fluorine-containing ether composition (fluoropolyether group-containing polymer composition) of the present invention, the amount of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends represented by the general formula (3) and / or its partial (hydrolysis) condensate (both-terminally functional fluoropolyether group-containing polymer) blended is preferably 0 to 25% by mass, particularly 0 to 15% by mass, in the fluorine-containing ether composition (particularly the total amount of fluoropolyether group-containing polymers). If it exceeds 25% by mass, the surface release properties will decrease, and it may not be possible to obtain a cured coating that combines antifouling properties, heat resistance, surface release properties, and eraser abrasion durability. When blended, it is preferably 5% by mass or more, particularly 8% by mass or more, in the fluorine-containing ether composition (particularly the total amount of fluoropolyether group-containing polymers).

[0080] If necessary, the fluorine-containing ether composition of the present invention can further contain a fluoropolyether group-containing polymer (non-functional fluoropolyether polymer) represented by the following general formula (5). This can further improve surface releasability. A-Rf'-A (5) (wherein Rf' is the same as above, and A independently represents a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3-, CF2H-, CF3CF2-, or CF3CFH- and which may contain an oxygen atom.)

[0081] In the above formula (5), Rf' is the same as Rf' in the above formula (3), and examples thereof include those exemplified for Rf' (the divalent fluoropolyether group represented by formula (4)). Rf' may be the same as or different from Rf' in formula (3).

[0082] In the above formula (5), A independently represents a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3-, CF2H-, CF3CF2-, or CF3CFH- and which may contain an oxygen atom; specific examples include a fluorine atom, a hydrogen atom, CF3-, CF2H-, CF2CF3-, CF3CFH-, CF3O-, and CF3CF2O-.

[0083] Examples of the fluoropolyether group-containing polymer (non-functional fluoropolyether polymer) represented by the general formula (5) include the following. (In the formula, p3, q3, and r3 each independently represent an integer of 0 to 450, the sum of p3, q3, and r3 is 20 to 450, and r4 and r5 each represent an integer of 20 to 450. The repeating units shown in parentheses with p3, q3, and r3 may be bonded randomly.)

[0084] The number average molecular weight of the fluoropolyether group-containing polymer represented by the general formula (5) is preferably 1,000 to 50,000, more preferably 2,000 to 20,000, even more preferably 2,500 to 10,000, and particularly preferably 3,000 to 8,000. If the number average molecular weight is less than 1,000, the fluoropolyether group-containing polymer represented by the formula (5) in the resulting cured coating may volatilize in a heated environment, while if it exceeds 50,000, the surface properties of the resulting cured coating may become unstable. The above number average molecular weight can be achieved by rectification or molecular distillation of the fluoropolyether group-containing polymer represented by the general formula (5).

[0085] In the fluorine-containing ether composition (fluoropolyether group-containing polymer composition) of the present invention, the blending amount of the fluoropolyether group-containing polymer (non-functional fluoropolyether group-containing polymer) represented by general formula (5) is desirably 0 to 30% by mass, particularly 0 to 20% by mass, based on the fluorine-containing ether composition (particularly the total amount of fluoropolyether group-containing polymers). If it exceeds 30% by mass, eraser abrasion durability will decrease, and it may not be possible to obtain a cured coating that combines stain resistance, heat resistance, surface release properties, and eraser abrasion durability. When blended, it is preferably 0.1% by mass or more, particularly 1% by mass or more, based on the fluorine-containing ether composition (particularly the total amount of fluoropolyether group-containing polymers).

[0086] The fluorine-containing ether composition of the present invention can be prepared by uniformly mixing predetermined amounts of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above-mentioned average composition formula (1), and / or a partial (hydrolyzed) condensate thereof, and, if necessary, the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the general formula (3), and / or a partial (hydrolyzed) condensate thereof, or the fluoropolyether group-containing polymer represented by the general formula (5), in accordance with a conventional method.

[0087] The fluorine-containing ether composition of the present invention preferably has a number average molecular weight of 1,000 to 56,000, more preferably 2,000 to 26,000, even more preferably 2,500 to 16,000, and particularly preferably 3,000 to 8,600. If the number average molecular weight is less than 1,000, the stain resistance and heat resistance of the resulting cured coating may decrease, while if it exceeds 56,000, the surface properties of the resulting cured coating may become unstable. The above number average molecular weight can be achieved by rectifying or molecular distilling the fluorine-containing ether composition.

[0088] The present invention further provides a surface treatment agent containing the above-mentioned fluorinated ether composition. If necessary, the surface treatment agent may contain a hydrolysis condensation catalyst, such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Of these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is typically 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluorinated ether composition (particularly the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups in the composition and / or its partial (hydrolysis) condensate).

[0089] The surface treatment agent may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, tridecafluorooctane, hexafluoropropene trimer, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptenyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, hexafluoroisopropyl methyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are desirable in terms of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, tridecafluorooctane, and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether are particularly preferred.

[0090] Two or more of the above solvents may be mixed, and it is preferable to dissolve the fluorinated ether composition uniformly in the solvent. The optimum concentration of the fluorinated ether composition to be dissolved in the solvent varies depending on the treatment method, and may be any amount that is easy to weigh, but in the case of direct coating, it is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of the total of the solvent and the fluorinated ether composition, and in the case of vapor deposition treatment, it is preferably 1 to 100 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the total of the solvent and the fluorinated ether composition.

[0091] The surface treatment agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition. The heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferably 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, particularly 1 to 18 hours. Furthermore, when applied by vapor deposition, it is desirable to use a temperature in the range of 20 to 200°C for 1 to 24 hours. Curing may also be performed under humidified conditions. For example, in the case of spray coating, dilution with a fluorine-based solvent containing added water and subsequent hydrolysis, i.e., generation of Si—OH, can be achieved, resulting in rapid curing after coating.

[0092] The thickness of the cured coating is determined appropriately depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. The thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, X-ray fluorescence measurement, etc.

[0093] The substrate to be treated with the surface treatment agent of the present invention is not particularly limited and may be made of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, and quartz. The surface treatment agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO-treated glass or film.

[0094] Examples of articles that can be treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, and other optical articles. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the articles and further impart scratch resistance, and is therefore particularly useful as a water- and oil-repellent layer for lenses, touch panel displays, anti-reflection films, and the like.

[0095] The surface treatment agent of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins; an anti-fouling coating for window glass or tempered glass for automobiles, trains, aircraft, etc., and headlamp covers; a water- and oil-repellent coating for exterior wall building materials; an anti-grease stain coating for kitchen building materials; an anti-fouling and anti-poster / anti-graffiti coating for telephone booths; a coating for imparting fingerprint resistance to artworks, etc.; a fingerprint-resistant coating for compact discs, DVDs, etc.; a release agent or paint additive for molds; a resin modifier; a flowability modifier or dispersibility modifier for inorganic fillers; and a lubricity improver for tapes, films, etc.

[0096] In particular, the surface treatment agent of the present invention can provide a cured coating that is excellent in water and oil repellency, stain resistance, heat resistance, surface peeling properties, and eraser abrasion resistance.

[0097] The present invention will be described in more detail below with reference to synthesis examples, working examples, and comparative examples, but the present invention is not limited to these examples. In the following formulas, the repeating units indicated in parentheses with p1 and q1, p2 and q2, and p3 and q3 are randomly bonded. Furthermore, the film thicknesses are values ​​measured by spectroscopic ellipsometry using a spectroscopic ellipsometer.

[0098] The number average molecular weight (Mn) of the fluoropolyether group-containing polymer and the fluorinated ether composition is 1 H-NMR analysis and19 It is a value calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether group-containing polymer based on F-NMR analysis. 1 Molar ratio (CF3CF2O- / CF3O-) and RF 2 In the molar ratio (-CFCFO- / -CFO-), p1, q1, p2, q2, p3, and q3, 19 It was calculated from the characteristic peak intensity ratio of F-NMR analysis.

[0099] Raw material polymers A to G represented by the following average composition formula (I) having the compositions shown in Table 1 below were prepared.

[0100]

[0101] [Synthesis Example 1] With reference to Japanese Patent No. 6451279, polymers containing a functional fluoropolyether group at one end and represented by the following average composition formula (II) and having the compositions shown in Table 2 below (A-II, B-II, C-II, and G-II in Table 2) were synthesized using raw material polymers A, B, C, and G represented by the average composition formula (I) and having the compositions shown in Table 1 as starting materials.

[0102] [Synthesis Example 2] With reference to Japanese Patent No. 6,119,656 and Japanese Patent No. 6,828,744, starting materials C and F represented by average composition formula (I) and having the compositions shown in Table 1 were used to synthesize polymers containing a functional fluoropolyether group at one end (C-III and F-III in Table 2) represented by the following average composition formula (III) and having the compositions shown in Table 2 below.

[0103] [Synthesis Example 3] With reference to Japanese Patent No. 6,119,656 and Japanese Patent No. 6,524,955, a polymer containing a functional fluoropolyether group at one end and represented by the following average composition formula (IV) and having the composition shown in Table 2 below (B-IV in Table 2) was synthesized using raw material polymer B represented by average composition formula (I) and having the composition shown in Table 1 as a starting material.

[0104] [Synthesis Example 4] With reference to Japanese Patent No. 6,119,656 and Japanese Patent No. 6,524,955, starting materials were polymers E and F represented by average composition formula (I) and having the compositions shown in Table 1, and polymers containing a functional fluoropolyether group at one end represented by average composition formula (V) (EV and FV in Table 2) having the compositions shown in Table 2 were synthesized using a compound represented by formula (a) below as an organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule.

[0105] Synthesis Example 5 30 g of raw material polymer A represented by average composition formula (I) having the composition shown in Table 1, 30 g of 1,3-trifluoromethylbenzene, and 6.0 g of 2,2-diallyl-4-penten-1-amine were stirred at 50° C. for 5 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure, yielding 25 g of a liquid product. The resulting product was 1 It was confirmed by H-NMR that the compound was represented by the following average composition formula (VI-a): 1 Molar ratio and RF 2 The molar ratio is the RF 1 Molar ratio and RF 2 The molar ratio was the same.

[0106] 25 g of the compound represented by the average composition formula (VI-a) above, 10 g of 1,3-trifluoromethylbenzene, 2.0 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt simple substance), -8 The mixture was mixed with the above-mentioned components (containing 1 mole of methylcellulose) and aged at 80° C. for 3 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by H-NMR that the polymer was a one-terminal functional fluoropolyether group-containing polymer represented by the following average composition formula (VI): 1 Molar ratio and RF 2 The molar ratio is the RF 1 Molar ratio and RF 2The molar ratio was the same as that of the copolymer, and the number average molecular weight was 5,071.

[0107] Synthesis Example 6 A mixture of 100 g of raw material polymer D represented by average composition formula (I) having the composition shown in Table 1, 130 ml of 3-butenyl magnesium bromide, 200 g of Asahiklin AC6000, and 100 g of PF5060 was stirred at 50° C. for 6 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure, yielding 93 g of a liquid product. The resulting product was 1 It was confirmed by H-NMR that the compound was represented by the following average composition formula (VII-a): 1 Molar ratio and RF 2 The molar ratio is RF in raw polymer D. 1 Molar ratio and RF 2 The molar ratio was the same.

[0108] 80 g of the compound represented by the average composition formula (VII-a), 8.8 g of allyl bromide, and 0.14 g of tetrabutylammonium iodide were mixed, and 14.4 g of a 30% by mass aqueous solution of sodium hydroxide was added, followed by heating at 50° C. for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure, yielding 75 g of a liquid product. The resulting product was 1 It was confirmed by H-NMR that the compound was represented by the following average composition formula (VII-b): 1 Molar ratio and RF 2 The molar ratio is RF in raw polymer D. 1 Molar ratio and RF 2 The molar ratio was the same.

[0109] 70 g of the compound represented by the average composition formula (VII-b), 100 g of 1,3-bis(trifluoromethyl)benzene, 37 g of 2,4,6,8-tetramethylcyclotetrasiloxane, and 8.0 × 10 toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) -2 g (2.4 x 10 as Pt alone) -7The mixture was stirred at 80° C. for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 65 g of a liquid product. 1 It was confirmed by H-NMR that the compound was represented by the following average composition formula (VII-c): 1 Molar ratio and RF 2 The molar ratio is RF in raw polymer D. 1 Molar ratio and RF 2 The molar ratio was the same.

[0110] 50 g of the compound represented by the average composition formula (VII-c), 100 g of 1,3-bis(trifluoromethyl)benzene, 17.5 g of 7-octenyltrimethoxysilane, and 8.0 × 10 toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) -2 g (2.4 x 10 as Pt alone) -7 The mixture was stirred at 80° C. for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 30 g of a liquid product. 1 It was confirmed by H-NMR that the polymer was a one-terminal functional fluoropolyether group-containing polymer represented by the following average composition formula (VII): 1 Molar ratio and RF 2 The molar ratio is RF in raw polymer D. 1 Molar ratio and RF 2 The molar ratio was the same as that of the copolymer, and the number average molecular weight was 6,490.

[0111] Synthesis Example 7 100 g of a compound represented by the following general formula (H′), 50 g of 1,3-bis(trifluoromethyl)benzene, 7.0 g of trimethoxysilane, and 8.0×10 toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex) were mixed. -2 g (2.4 x 10 as Pt alone) -7The mixture was stirred at 80° C. for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 90 g of a liquid product. 1 By H-NMR, it was confirmed that the polymer was polymer H having functional fluoropolyether groups at both ends, represented by the following general formula (H). The number average molecular weight was 4,720.

[0112] [Synthesis Example 8] A polymer J having functional fluoropolyether groups at both ends and represented by the following general formula (J) was synthesized using a compound represented by the following general formula (J') as a starting material, with reference to Japanese Patent No. 6451279. The number average molecular weight was 4,510.

[0113] [Synthesis Example 9] With reference to Japanese Patent No. 6524955, a compound represented by the following general formula (K') was used as a starting material, and a compound represented by the following formula (a) was used as an organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, to synthesize a polymer K having functional fluoropolyether groups at both ends represented by the following general formula (K). The number average molecular weight was 4,630.

[0114] As a non-functional fluoropolyether polymer, a non-functional fluoropolyether group-containing polymer L (number average molecular weight 4,300) represented by the following general formula (L) was prepared.

[0115] Polymers containing a functional fluoropolyether group at one end The polymers containing a functional fluoropolyether group at one end obtained in Synthesis Examples 1-6 are listed in Table 2. For example, polymer A-II containing a functional fluoropolyether group at one end is a polymer containing a functional fluoropolyether group at one end and has a structure represented by the average composition formula (II) above, which was obtained using raw material polymer A represented by average composition formula (I) having the composition in Table 1 as a starting material.

[0116]

[0117] The following solvents were used for dilution: Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether), Novec 7300 (manufactured by 3M, methyl perfluorohexyl ether), Asahiklin AC-6000 (manufactured by AGC Inc., tridecafluorooctane), Opteon SF10 (manufactured by Mitsui-Chemours Fluoroproducts Co., Ltd., methyl perfluoroheptenyl ether), hexafluoropropene trimer (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), and hexafluoroisopropyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0118] [Examples 1 to 19, Comparative Examples 1 to 4] The polymers obtained in the above synthesis examples were diluted with a solvent to a concentration of 20 mass% of a fluorine-containing ether composition, which was a mixture of a polymer having a functional fluoropolyether group at one end, a polymer having functional fluoropolyether groups at both ends, and a polymer having a non-functional fluoropolyether group, in the composition shown in Table 3, to prepare surface treatment agents.

[0119]

[0120] Preparation of Surface Treatment Agents and Formation of Cured Coatings Cured coatings were produced using the surface treatment agents prepared in Examples 1 to 19 and Comparative Examples 1 to 4. Each surface treatment agent was vacuum-deposited (treatment conditions: pressure: 3.0 × 10 -2 The coating was cured for 12 hours in an atmosphere of 25°C and 50% relative humidity (700°C, 700 Pa).

[0121] Evaluation of Water and Oil Repellency [Measurement of Initial Water Contact Angle] For the glass on which the cured coating film prepared above was formed, the contact angle (water repellency) of the cured coating film with water was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The results (initial water contact angle) are shown in Table 4.

[0122] Evaluation of stain resistance [Evaluation of marker ink wiping ability] On the glass on which the cured coating prepared above was formed, a 1 cm x 1 cm square was drawn with a Pentel Pen 50 (manufactured by Pentel Co., Ltd.), filled in, the ink was allowed to dry, and the ink was wiped off with tissue paper (manufactured by Kami Shoji Co., Ltd.). The number of rubs required until the ink was wiped off was evaluated. (Evaluation criteria) A: 4 or fewer rubs B: 5 or more rubs The results of evaluation based on the above evaluation criteria are shown in Table 4.

[0123] Evaluation of Heat Resistance [Measurement of Water Contact Angle After Heating] The glass having the cured coating formed thereon was heated at 250°C for 24 hours, then washed with the neutral detergent Mama Lemon (manufactured by Lion Corporation). The contact angle with water was measured under the conditions described in the "Measurement of Initial Water Contact Angle" above (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The test environmental conditions were 25°C and relative humidity 40%. (Evaluation Criteria) A: The difference in contact angle between the "initial water contact angle measurement" and the "water contact angle after heating" was less than 6°. B: The difference in contact angle between the "initial water contact angle measurement" and the "water contact angle after heating" was 6° or more but less than 10°. C: The difference in contact angle between the "initial water contact angle measurement" and the "water contact angle after heating" was 10° or more. The results of evaluation using the above evaluation criteria are shown in Table 4.

[0124] Evaluation of Peelability: A polyester adhesive tape No. 31B (manufactured by Nitto Denko Corporation) was applied to the glass on which the cured coating was formed, and the glass was left standing for 3 days in a pressure-bonded state under a load of 1 kgf. The peel strength was then evaluated using an autograph AGS-X10N (manufactured by Shimadzu Corporation). The test environment conditions were a temperature of 25°C, a relative humidity of 50%, a crosshead speed of 300 mm / min, and a test piece width of 19 mm. (Evaluation Criteria) A: Peel strength less than 0.08 N B: Peel strength of 0.08 N or more but less than 0.11 N C: Peel strength of 0.11 N or more The results evaluated using the above evaluation criteria are shown in Table 4.

[0125] Evaluation of Eraser Abrasion Resistance The glass on which the cured coating prepared above was formed was rubbed 3,000 times under the following conditions using a reciprocating abrasion tester (Tribogear, manufactured by Shinto Scientific Co., Ltd.), and the contact angle of the cured coating with water was measured in the same manner as above to evaluate abrasion resistance. The test environmental conditions were 25°C and a relative humidity of 40%. (Abrasion conditions) Eraser: Rubber eraser (manufactured by Minoan Co., Ltd.) Travel distance (one way): 40 mm Travel speed: 2,400 mm / min Load: 1 kgf / 6 mm 2 Φ (Evaluation criteria) A: The difference in contact angle between [measurement of initial water contact angle] and [water contact angle after abrasion] is less than 6° B: The difference in contact angle between [measurement of initial water contact angle] and [water contact angle after abrasion] is 6° or more and less than 11° C: The difference in contact angle between [measurement of initial water contact angle] and [water contact angle after abrasion] is 11° or more The results of evaluation based on the above evaluation criteria are shown in Table 4.

[0126]

[0127] [Examples 20 to 25, Comparative Examples 5 and 6] The polymers obtained in the above Synthesis Examples were diluted with a solvent so that the fluorine-containing ether composition, which was a mixture of a polymer having a functional fluoropolyether group at one end, a polymer having functional fluoropolyether groups at both ends, and a polymer having a non-functional fluoropolyether group, had a composition shown in Table 5, was 0.1 mass % to prepare surface treatment agents.

[0128]

[0129] Preparation of Surface Treatment Agent and Formation of Cured Coating Cured coatings were prepared using the surface treatment agents prepared in Examples 20 to 25 and Comparative Examples 5 and 6. The surface of plasma-treated and cleaned chemically strengthened glass (Corning Gorilla V) was spray coated using a spray coating device (T&K Corporation, NST-51). The coating was then cured for 12 hours in an atmosphere of 25°C and 50% relative humidity to form a cured coating with a film thickness of 10 nm, and a test specimen was obtained.

[0130] The evaluation methods for Examples 20 to 25 and Comparative Examples 5 and 6 were the same as those for Examples 1 to 19 and Comparative Examples 1 to 4. The results (initial contact angle, number of rubs required until the ink was wiped off, water contact angle after heating, and peel value) are shown in Table 6.

[0131]

[0132] From the above results, in Comparative Examples 1 to 3, and 5, the decrease in water contact angle after heating compared to the initial water contact angle remained less than 6° (i.e., the water contact angle remained 100° or more), but the number of rubs required to wipe the ink off increased, and the water contact angle after eraser abrasion also decreased significantly. In Comparative Examples 4 and 6, the ink could be wiped off quickly, and the decrease in water contact angle after eraser abrasion remained less than 6° (i.e., the water contact angle remained 100° or more), but the heat resistance was poor and the release value was high. On the other hand, in Examples 1 to 25, by adjusting the molar ratio of CF3CF2O- and CFO-, which are the terminal groups of the polymer containing a single-terminal functional fluoropolyether group, to a range of 0.01 to 0.17, good results were obtained in four properties: water and oil repellency, stain resistance, heat resistance, surface release property, and eraser abrasion resistance.

Claims

1. A fluorine-containing ether composition comprising a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the following average composition formula (1), and / or a partial (hydrolyzed) condensate thereof: [In the formula, RF 1 is CF3O- or CF3CF2O-, and the molar ratio of CF3O- to CF3CF2O- (CF3CF2O- / CF3O-) is 0.01 or more and 0.17 or less. 2 is -CF2O- or -CF2CF2O-, and Rf is represented by the following formula (2): (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer of 1 to 6. p, q, r, s, t, u, and v are each an integer of 0 to 450, where p+q+r+s+t+u+v=10 to 450, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.) wherein U is a single bond or a divalent to pentavalent organic group, Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, -SiR'= (R' is an alkyl group having 1 to 4 carbon atoms) or a trivalent to nonavalent organic group, Y is independently a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is independently 2 or 3 for each unit bonded to a silicon atom, b is independently an integer of 1 to 8, and c is an integer of 1 to 4.] 2. RF of the above formula (1) 2 2. The fluorine-containing ether composition according to claim 1, wherein the molar ratio of --CF2O-- to --CF2CF2O-- (-CF2CF2O- / -CF2O--) is 1.05 or more and 1.2 or less.

3. The fluorine-containing ether composition according to claim 1, wherein in said formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.

4. In the formula (1), U is a single bond, a carbonyl group, an amide group, or a group represented by the following formula: (In the formula, B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms), or a di- to pentavalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom, a hydroxyl group, a polyether group, a diorganosilylene group, a linear divalent organopolysiloxane residue having 2 to 100 silicon atoms, a silalkylene group, a silarylene group, a secondary amino group, a tertiary amino group, an ether group, a carbonyl group, an amide group, and an ester group.

5. The fluorine-containing ether composition according to claim 1, wherein, in said formula (1), Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a linear, branched or cyclic tri- to octa-valent organopolysiloxane residue having 3 to 13 silicon atoms, a trivalent isocyanuric group, or a trivalent triazine ring-containing group.

6. The fluorine-containing ether composition according to claim 1, wherein in said formula (1), Y is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms and containing a fluorine atom, alkylene groups having 1 to 10 carbon atoms and containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a divalent organopolysiloxane residue which is linear having 2 to 10 silicon atoms, or branched or cyclic having 3 to 10 silicon atoms.

7. The fluorine-containing ether composition according to claim 1, further comprising 25 mass% or less of a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the following general formula (3), and / or a partial (hydrolyzed) condensate thereof: [In the formula, U, Z, Y, R, X, a, b, and c are independently the same as above, and Rf′ is a compound represented by the following formula (4): (wherein W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above; and d' is an integer of 1 to 6. Each of these units may be linear or branched. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.) 8. The fluorine-containing ether composition according to claim 1, further comprising 30 mass% or less of a fluoropolyether group-containing polymer represented by the following general formula (5): A-Rf'-A (5) [wherein A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group whose terminal is CF3-, CF2H-, CF3CF2-, or CF3CFH- and which may contain an oxygen atom. Rf' is a group represented by the following formula (4): (wherein W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above; and d' is an integer of 1 to 6. Each of these units may be linear or branched. In addition, each of the repeating units shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.) is a divalent fluoropolyether group represented by the following formula.

9. The fluorine-containing ether composition according to claim 1, wherein the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end thereof, represented by formula (1), is at least one type selected from those represented by the following formula: (In the formula, RF 1 , R.F. 2 is the same as above, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 20 to 450, and each repeat unit shown in parentheses with p1 and q1 may be randomly bonded.

10. A surface treatment agent comprising the fluorine-containing ether composition according to any one of claims 1 to 9.

11. An article whose surface has been treated with the surface treatment agent according to claim 10.

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