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

Abstract

A fluorine-containing ether composition containing a fluoropolyether group-containing polymer containing a silanol group or a hydrolyzable silyl group having a specific structure having CF3O-or CF3CF2O-at the terminal and / or a partial (hydrolyzed) condensate thereof in an amount such that the molar ratio of CF3O-to CF3CF2O-(CF3CF2O- / CF3O-) is 0.01-0.17, can form a fluorine-containing ether composition having water and oil repellency, excellent antifouling properties, heat resistance, and excellent heat resistance, and can be used in the fields of water and oil repellency, water and oil repellency, water and oil repellency, water and oil repellency, water and oil repellency, water and oil repellency, water and oil repellency, water and oil repellency, water and oil repellency, and water and oil repellency. And a cured coating film having surface peelability and rubber wear durability.

Description

Technical Field

[0001] This invention relates to fluorinated ether compositions comprising polymers containing fluorinated polyether groups (compounds having fluorinated polyether groups in the molecule), and more specifically, to fluorinated ether compositions comprising polymers containing fluorinated polyether groups having silanol groups or hydrolyzable silyl groups and / or portions thereof (hydrolyzed) condensates having water and oil repellency and excellent antifouling, heat resistance, surface peeling and rubber abrasion durability, surface treatment agents comprising the fluorinated ether compositions, and articles surface-treated with the surface treatment agents. Background Technology

[0002] In recent years, the trend of touch panels in displays, spearheaded by smartphones, has accelerated. However, touch panels expose the screen, leading to frequent direct contact with fingers, cheeks, and other skin types, making them prone to accumulating dirt and grime. Therefore, the demand for technologies that improve appearance and visibility, making the display surface resistant to fingerprints and easy to remove dirt, has increased year by year, leading to a desire to develop materials that meet these requirements. In particular, the surface of touch panel displays is prone to fingerprints and grime, thus requiring water- and oil-repellent coatings. However, while existing water- and oil-repellent coatings offer high water and oil repellency and excellent dirt removal, their anti-fouling performance deteriorates during use.

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

[0004] On the other hand, silane coupling agents are well known as substances that bond organic compounds to the surface of substrates such as glass and cloth, and are widely used as coating agents for various substrate surfaces. A silane coupling agent has 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 forms a coating film by inducing a self-condensation reaction using moisture in the air, etc. This coating film is formed by the chemical bonding between the hydrolyzable silyl group and the surface of glass, metal, etc. They are physically bonded together to form a durable and strong coating.

[0005] Therefore, compositions that readily adhere to a substrate surface and form a coating on the substrate surface with properties such as water and oil repellency, chemical resistance, lubricity, mold release properties, and antifouling properties by using a polymer containing a fluorinated polyether group in which hydrolyzable silyl groups are introduced into a compound containing a fluorinated polyether group are disclosed (Patent Documents 1-6: Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-537557, Japanese Patent Application Publication No. 2012-072272, Japanese Patent Application Publication No. 2012-157856, Japanese Patent Application Publication No. 2013-136833, Japanese Patent Application Publication No. 2015-199906).

[0006] In particular, as a method for forming a coating that improves heat resistance, it has been reported that an organic group containing an alicyclic structure with 3 to 13 carbon atoms is a thermally stable structure, and the heat resistance of fluorinated ether compounds containing this organic group is improved (Patent Document 7: International Publication No. 2021 / 054202). However, since a specific organic group must be introduced, it is difficult to achieve both improvements in other properties.

[0007] Furthermore, as prior art related to this invention, the following documents can be listed together with the above-mentioned documents.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Publication No. 2008-534696

[0011] Patent Document 2: Japanese Patent Publication No. 2008-537557

[0012] Patent Document 3: Japanese Patent Application Publication No. 2012-072272

[0013] Patent Document 4: Japanese Patent Application Publication No. 2012-157856

[0014] Patent Document 5: Japanese Patent Application Publication No. 2013-136833

[0015] Patent Document 6: Japanese Patent Application Publication No. 2015-199906

[0016] Patent Document 7: International Publication No. 2021 / 054202

[0017] Patent Document 8: Japanese Patent No. 6451279

[0018] Patent Document 9: Japanese Patent No. 6119656

[0019] Patent Document 10: Japanese Patent No. 6828744

[0020] Patent Document 11: Japanese Patent No. 6524955

[0021] Patent Document 12: Japanese Patent No. 6521091 Summary of the Invention

[0022] The problem that the invention aims to solve

[0023] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a fluorinated ether composition comprising a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group and / or a portion thereof (hydrolyzed) condensate of a polymer having a silanol group or a hydrolyzable silyl group, capable of forming a cured film having water and oil repellency, and excellent antifouling, heat resistance, surface peeling and rubber wear durability; a surface treatment agent comprising the fluorinated ether composition; and articles surface-treated with the surface treatment agent.

[0024] Methods for solving problems

[0025] In order to achieve the above-mentioned objective, the inventors have newly discovered that by considering the molar ratio of fluorinated polyether groups contained in a compound containing fluorinated polyether groups, particularly fluorinated oxymethylene and fluorinated oxyethylene adjacent to the terminal fluorinated oxyalkyl group, a surface treatment agent comprising a polymer containing a fluorinated polyether group and / or a portion thereof (hydrolyzed) condensate of the polymer containing the fluorinated polyether group in which hydrolyzable silyl groups are introduced, can form a cured film with high performance in terms of water and oil repellency, heat resistance, and wear durability.

[0026] Through further repeated research, the inventors discovered that a surface treatment agent comprising a polymer and / or a portion thereof (hydrolyzed) condensate of a fluorinated polyether group having a silanol group or a hydrolyzable silane group at a single end, and having a molar ratio of fluorinated oxymethyl and fluorinated oxyethyl groups (described later as terminal groups) within a specific range, represented by the average composition formula (1), can form a cured film with water and oil repellency, and excellent antifouling properties, heat resistance, surface peeling properties, and rubber wear durability, thus completing the present invention.

[0027] Therefore, the present invention provides the following fluorinated ether compositions, surface treatment agents and articles.

[0028] [1] A fluorinated ether composition comprising a polymer and / or a portion thereof having a fluorinated polyether group having a silanol group or a hydrolyzable silane group at a single end, represented by the following average compositional formula (1).

[0029]

[0030] In the formula, RF 1It is CF3O- or CF3CF2O-, and the molar ratio of CF3O- to CF3CF2O- (CF3CF2O- / CF3O-) is greater than 0.01 and less than 0.17. RF 2 The form is -CF2O- or -CF2CF2O-, Rf is a divalent fluorinated polyether group represented by the following formula (2), U is a single bond or an organogroup with 2 to 5 valences, Z is independently a single bond, or an organogroup with carbon, silicon, nitrogen, -SiR' (R' is an alkyl group with 1 to 4 carbon atoms) or 3 to 9 valences, Y is independently a divalent hydrocarbon group that may have one or more divalent hydrocarbon groups selected from fluorine, silicon and siloxane bonds, R is independently an alkyl or phenyl group with 1 to 4 carbon atoms, X is independently a hydroxyl or hydrolyzable group, a is independently 2 or 3 in each unit bonded to a silicon atom, b is independently an integer from 1 to 8, and c is an integer from 1 to 4.

[0031]

[0032] In the formula, W is a fluorinated alkylene group containing one or more hydrogen atoms, d is an integer from 1 to 6, p, q, r, s, t, u, and v are each an integer from 0 to 450, and p+q+r+s+t+u+v = 10 to 450. These units can be linear or branched. In addition, the repeating units shown in parentheses containing p, q, r, s, t, u, and v can be randomly combined.

[0033] [2] According to the fluorinated ether composition of [1], wherein, in the RF of formula (1) 2 In this context, the molar ratio of -CF2O- to -CF2CF2O- (-CF2CF2O- / -CF2O-) is greater than 1.05 and less than 1.2.

[0034] [3] The fluorinated ether composition according to [1] or [2], wherein, in the formula (1), X is selected from hydroxyl, alkoxy with 1 to 10 carbon atoms, alkoxy-substituted alkoxy with 2 to 10 carbon atoms, acyloxy with 2 to 10 carbon atoms, olefinic group with 2 to 10 carbon atoms and halogen group.

[0035] [4] A fluorinated ether composition according to any one of [1] to [3], wherein, in the formula (1), U is a single bond, carbonyl, amide, a group represented by the following formula, or may contain one or more atoms or groups selected from oxygen atom, sulfur atom, hydroxyl, polyether group, diorganosilyl group, linear divalent organopolysiloxane residue with 2 to 100 silicon atoms, silane, silane, secondary amino, tertiary amino, ether group, carbonyl, amide, and ester group with a carbon number of 1 to 20 and a 2 to 5 valent hydrocarbon group.

[0036]

[0037] In the formula, B is a hydrogen atom, a monovalent hydrocarbon group with 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms.

[0038] [5] A fluorinated ether composition according to any one of [1] to [4], wherein, in the formula (1), Z is a single bond, a straight-chain, branched or cyclic organopolysiloxane residue with 3 to 13 silicon atoms, a trivalent isocyanurate group or a trivalent group containing a triazine ring.

[0039] [6] The fluorinated ether composition according to any one of [1] to [5], wherein, in the formula (1), Y is selected from alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing fluorine atoms, alkylene groups having 1 to 10 carbon atoms containing aryl groups having 6 to 8 carbon atoms, divalent groups having 1 to 10 carbon atoms bonded to each other by a silanealkylene structure or a silanearyl structure, and divalent groups having alkylene groups having 2 to 10 carbon atoms bonded to the binding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms.

[0040] [7] A fluorinated ether composition according to any one of [1] to [6], wherein the composition further comprises 25% by mass or less of a polymer and / or a portion thereof having a silanol group or a hydrolyzable silyl group at both ends, represented by the following general formula (3).

[0041]

[0042] In the formula, U, Z, Y, R, X, a, b, and c are independently the same as those above, and Rf' is a divalent fluorinated polyether group represented by the following formula (4).

[0043]

[0044] In the formula, W, d, p, q, r, s, t, u, v, p+q+r+s+t+u+v are the same as above, and d' is an integer from 1 to 6. These units can be linear or branched. In addition, the repeating units shown in the parentheses containing p, q, r, s, t, u, v can be combined randomly.

[0045] [8] A fluorinated ether composition according to any one of [1] to [7], wherein the composition further contains 30% by mass or less of a polymer containing a fluorinated polyether group represented by the following general formula (5),

[0046] A-Rf'-A (5)

[0047] In the formula, A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorinated hydrocarbon group with a terminal CF3-, CF2H-, CF3CF2-, or CF3CFH-, which may contain an oxygen atom, and Rf' is a divalent fluorinated polyether group represented by the following formula (4).

[0048]

[0049] In the formula, W, d, p, q, r, s, t, u, v, p+q+r+s+t+u+v are the same as above, and d' is an integer from 1 to 6. These units can be linear or branched. In addition, the repeating units shown in the parentheses containing p, q, r, s, t, u, v can be combined randomly.

[0050] [9] The fluorinated ether composition according to any one of [1] to [8], wherein the polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, represented by formula (1), is selected from at least one polymer represented by the following formula.

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] In the formula, RF 1 RF 2 As above, p1 is an integer from 5 to 440, q1 is an integer from 5 to 250, p1+q1 is an integer from 20 to 450, and the repeating units shown in parentheses with p1 and q1 can be combined randomly.

[0060]

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

[0061]

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

[10] .

[0062] The effects of the invention

[0063] The fluorinated ether composition of the present invention comprises a polymer and / or a portion thereof (hydrolyzed) condensate of a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, as shown in the above average compositional formula (1) taking into account the molar ratio of fluorinated oxymethyl and fluorinated oxyethyl groups as terminal groups. Articles surface-treated with a surface treatment agent containing the fluorinated ether composition have improved properties of stain resistance, heat resistance, surface peel resistance, and rubber wear durability in addition to water and oil repellency. Detailed Implementation

[0064] In this invention, the number average molecular weight (Mn) of polymers containing fluorinated polyether groups having silanol groups or hydrolyzable silyl groups and / or their partial (hydrolyzed) condensates, or fluorinated ether compositions, can be determined by... 19 The intensity ratio of the characteristic peaks was calculated from the F-NMR analysis.

[0065] Furthermore, in this invention, the "partial (hydrolyzed) condensate" of a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group is obtained by partially condensing the hydroxyl group of the polymer containing a fluorinated polyether group having a silanol group, or the hydroxyl group of the polymer containing a fluorinated polyether group having a hydrolyzable silyl group that has been partially hydrolyzed in advance using a known method.

[0066] The fluorinated ether composition of the present invention (polymer composition containing fluorinated polyether group) comprises a polymer containing fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, and / or a portion thereof (hydrolyzed) condensate, represented by the following average compositional formula (1).

[0067]

[0068] [In the formula, RF] 1 It is CF3O- or CF3CF2O-, and the molar ratio of CF3O- to CF3CF2O- (CF3CF2O- / CF3O-) is greater than 0.01 and less than 0.17. RF 2 For -CF2O- or -CF2CF2O-, Rf is determined by the following equation (2).

[0069]

[0070] (In the formula, W is a fluorinated alkylene group containing one or more hydrogen atoms. d is an integer from 1 to 6, p, q, r, s, t, u, and v are each an integer from 0 to 450, and p+q+r+s+t+u+v = 10 to 450. These units can be linear or branched. In addition, the repeating units shown in parentheses containing p, q, r, s, t, u, and v can be randomly combined.)

[0071] The term represents a divalent fluorinated polyether group, where U is a single bond or an organogroup with 2 to 5 valences, Z is independently a single bond, or an organogroup with carbon, silicon, nitrogen, -SiR' (R' being an alkyl group with 1 to 4 carbon atoms) or 3 to 9 valences, Y is independently a divalent hydrocarbon group that may have one or more divalent hydrocarbon groups selected from fluorine, silicon, and siloxane bonds, R is independently an alkyl or phenyl group with 1 to 4 carbon atoms, X is independently a hydroxyl or hydrolyzable group, a is independently 2 or 3 in each unit bonded to a silicon atom, b is independently an integer from 1 to 8, and c is an integer from 1 to 4.

[0072] In equation (1) above, RF 1 The material is either 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 above molar ratio is less than 0.01, the resulting cured film cannot maintain high heat resistance. Furthermore, if it exceeds 0.17, the antifouling properties and rubber wear durability of the resulting cured film decrease. If the above molar ratio is in the range of 0.01 or more and 0.17 or less, the resulting cured film can simultaneously exhibit all the required characteristics of antifouling, heat resistance, surface peel resistance, and rubber wear durability. It should be noted that the above molar ratio can be determined by... 19 The intensity ratio of the characteristic peaks was calculated from the F-NMR analysis.

[0073] In the above formula (1), RF 2 The molar ratio of -CF2O- to -CF2CF2O- (-CF2CF2O- / -CF2O-) is preferably 1.05 or more and 1.2 or less, more preferably 1.1 or more and less than 1.2. If the above molar ratio is less than 1.05, the heat resistance of the resulting cured film may decrease; if it exceeds 1.2, the peelability of the surface of the resulting cured film may decrease. The above molar ratio can be determined by... 19 The intensity ratio of the characteristic peaks was calculated from the F-NMR analysis.

[0074] In the above formula (1), Rf is a divalent fluorinated polyether group represented by the following formula (2).

[0075]

[0076] (In the formula, W is a fluorinated alkylene group containing one or more hydrogen atoms. d is an integer from 1 to 6, p, q, r, s, t, u, and v are each an integer from 0 to 450, and p+q+r+s+t+u+v = 10 to 450. These units can be linear or branched. In addition, the repeating units shown in parentheses containing p, q, r, s, t, u, and v can be randomly combined.)

[0077] In the above formula (2), W is a fluorinated alkylene group containing one or more hydrogen atoms, for example, it can be exemplified by CF2, C2F4, C3F6, C4F8, C5F4, etc. 10 C6F 12 Groups in perfluoroalkylene groups in which one or two fluorine atoms are replaced by hydrogen atoms, etc.

[0078] In the above formula (2), d is an integer from 1 to 6, preferably an integer from 1 to 3, and more preferably 1 or 2.

[0079] Furthermore, p, q, r, s, t, u, and v are each integers from 0 to 450. Preferably, p is an integer from 5 to 440, q is an integer from 5 to 250, r is an integer from 0 to 180, s is an integer from 0 to 100, t is an integer from 0 to 100, u is an integer from 0 to 100, v is an integer from 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. If p+q+r+s+t+u+v is smaller than the above upper limit, the adhesion and curing properties are good; if it is larger than the above lower limit, the characteristics of the fluoropolyether group can be fully utilized, which is therefore preferred. Each unit can be linear or branched. In addition, the repeating units shown in parentheses containing p, q, r, s, t, u, and v can be randomly combined.

[0080] Specifically, Rf can be exemplified by the following groups.

[0081]

[0082]

[0083] (In the formula, p', q', and r' are each integers greater than or equal to 1, with the same upper limit as the upper limit of p, q, and r mentioned above. The total of these p', q', and r' is 20 to 450. In addition, the repeating units shown in the parentheses containing p', q', and r' can be combined randomly.)

[0084] In the above equation (1), RF 1 -RF 2 The number-average molecular weight of the fluorinated polyether group represented by -Rf- is preferably 1000 to 50000, more preferably 2000 to 20000. If the number-average molecular weight is less than 1000, the fluorine content is insufficient, and sometimes the antifouling properties of the cured film are reduced. If it exceeds 50000, sometimes the surface properties of the cured film become unstable. It should be noted that in this invention, the number-average molecular weight (Mn) can be analyzed by gel permeation chromatography (GPC) using a fluorinated solvent as the developing solvent. 19 Calculated using methods such as F-NMR.

[0085] In formula (1) above, U is a single bond or a 2- to 5-valent organic group, preferably a single bond, carbonyl group, amide group, or a group represented by the following formula.

[0086]

[0087] (In the formula, B is a hydrogen atom, a monovalent hydrocarbon group with 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms.)

[0088] It may contain one or more of the following: diorganosilyl groups selected from oxygen atoms, sulfur atoms, hydroxyl groups, polyether groups, dimethylmethylenesilyl groups, linear divalent organopolysiloxane residues with 2 to 100 silicon atoms, preferably 2 to 50; silanediol groups, silanearyl groups, secondary amino groups, tertiary amino groups, ether groups, carbonyl groups, amide groups, and ester groups; and hydrocarbon groups with 1 to 20 carbon atoms, having a 2 to 5 valent, preferably 2 to 4 valent, hydrocarbon group.

[0089] In the above formula, the monovalent hydrocarbon groups with 1 to 20 carbon atoms of B and B' can be exemplified by straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, neopentyl, and tert-hexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, and propenyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl.

[0090] Furthermore, the monovalent polyether group of B is preferably composed of -(C e1 H 2e1 O) e -CH3 (e1 is an integer from 1 to 6, and e is an integer from 1 to 30.) represents this.

[0091] As a linear divalent organopolysiloxane residue containing 2 to 100, preferably 2 to 50, silicon atoms in a 2 to 5 valent hydrocarbon group, examples of which are shown below are possible.

[0092]

[0093] (where R) 1 R is an alkyl group having 1 to 4 carbons, such as methyl, ethyl, propyl, or butyl, or an aryl group having 6 to 10 carbons, such as phenyl. 1 They can be the same or different. g is an integer from 1 to 99, preferably an integer from 1 to 49.

[0094] In addition, the following groups can be exemplified as silanediol or silanearyl groups.

[0095]

[0096] (where R)1 Similar to the above, R 2 It can be an alkylene group with 1 to 4 carbon atoms, such as methylene, ethylene, propylene, or butylene, or an aryl group with 6 to 10 carbon atoms, such as phenylene.

[0097] In addition to single bonds, such U can be represented by groups such as those listed below. Furthermore, it is preferred that the left-hand binding end is bonded to Rf, and the other binding ends are bonded to Z.

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] (In the formula, f is an integer from 1 to 4, l1 and l2 are integers from 1 to 4, n is an integer from 1 to 100, and e is an integer from 1 to 30.)

[0105] In the above formula (1), Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, -SiR' (R' is an alkyl group such as methyl or ethyl with 1 to 4 carbon atoms), or a 3 to 9 valent, preferably a 3 to 7 valent organic group, preferably a straight-chain, branched or cyclic 3 to 8 valent organopolysiloxane residue with a single bond or carbon atom, silicon atom, nitrogen atom, 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms, a trivalent isocyanurate group or a trivalent group containing a triazine ring.

[0106] Among them, the groups represented by the following general formulas can be exemplified as straight-chain, branched or cyclic organopolysiloxane residues with 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms.

[0107]

[0108] [In the formula, R] 1 R 2 Similar to the above, R 1 R 2 They can be the same or different. R 3 Independently for R 1 Or by the following general formula (6)

[0109]

[0110] (where R)1 Similar to the above, R 1 They can be the same or different. m8 is an integer from 1 to 6, preferably 1, and the left-side bonding end is bonded to Si.

[0111] The group represented by R 3 At least one of them is equation (6). R 4 It can be a single bond independently or by the following general formula (7).

[0112]

[0113] (where R) 2 R 3 Similar to the above, R 2 R 3 They can be the same or different. m9 is an integer from 0 to 6, preferably an integer from 0 to 3, more preferably 0 or 1; m10 is an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1; m9 + m10 ≠ 0. The repeating units shown in parentheses can be randomly combined. The left-hand connecting end is combined with Si.

[0114] The groups indicated are as follows: m1 is an integer from 1 to 9, preferably an integer from 1 to 4; m2 is an integer from 0 to 9, preferably an integer from 0 to 3; m3 is an integer from 2 to 6, preferably an integer from 3 to 5; m4 is an integer from 0 to 8, preferably 0 or 1; m3+m4 is an integer from 3 to 10, preferably an integer from 3 to 5; m5 is 2 or 3; m6 is an integer from 3 to 9, preferably an integer from 3 to 7; m7 is an integer from 0 to 9, preferably an integer from 0 to 3. The repeating units shown in parentheses can be randomly combined. However, the number of silicon atoms in each organopolysiloxane residue is 3 to 13.

[0115] In addition to single bonds, such a Z group can include, for example, the following groups. Furthermore, it is preferred that the left-hand binding end is bound to U, and the other binding ends are bound to Y.

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] In the above formula (1), b is independently an integer from 1 to 8, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and c is an integer from 1 to 4, preferably an integer from 1 to 3, more preferably 1 or 2.

[0122] In the above formula (1), Y is independently a divalent hydrocarbon group that may have one or more of the following selected from fluorine atoms, silicon atoms and siloxane bonds. As a divalent hydrocarbon group that may have one or more of the following selected from fluorine atoms, silicon atoms and siloxane bonds, it is a group selected from alkylene groups with carbon numbers of 1 to 10, such as methylene, ethylene, propylene, butylene, hexene, octylene, etc.; alkylene groups with carbon numbers of 1 to 10 containing fluorine atoms; alkylene groups with carbon numbers of 1 to 10 containing aryl groups with carbon numbers of 6 to 8 (alkylene-arylene with carbon numbers of 7 to 18); divalent groups with carbon numbers of 1 to 10 alkylene groups bonded to each other by a silane-alkylene structure or a silane-aryl structure; and divalent groups with carbon numbers of 2 to 10 alkylene groups bonded to the binding end of a divalent organopolysiloxane residue with carbon numbers of 2 to 10, which is either a straight chain with 2 to 10 silicon atoms or a branched or cyclic structure with 3 to 10 silicon atoms. Among these, alkylene groups with 1 to 10 carbon atoms are preferred, 2 to 5 are preferred, and 2 or 3 are more preferred.

[0123] Among them, silanediol and silanearyl can be exemplified as the same groups as those shown in U.

[0124] In addition, the following groups can be exemplified as linear or branched or cyclic divalent organopolysiloxane residues with 2 to 10 silicon atoms.

[0125]

[0126] (where R) 1 Similar to the above, R 1 They can be the same or different. g1 is an integer from 1 to 9, preferably an integer from 1 to 3, and g2 is an integer from 1 to 8, preferably an integer from 1 to 3.

[0127] Specifically, Y can be exemplified by the groups shown below. Furthermore, in the structure described below, it is preferable that the left-hand bonding end is bonded to Z and the right-hand bonding end is bonded to Si.

[0128]

[0129]

[0130] In formula (1) above, X is a hydroxyl group or a hydrolyzable group that may be different from each other. Examples of such X include hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc., alkoxy groups with 1 to 10 carbon atoms; methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, etc., alkoxy-substituted alkoxy groups with 2 to 10 carbon atoms; acetoxy, propionyloxy, etc., acyloxy groups with 2 to 10 carbon atoms; vinyloxy, allyloxy, propionyloxy, isopropionyloxy, etc., alkenyloxy groups with 2 to 10 carbon atoms; chloro, bromo, iodo, etc., halogen groups. Among these, methoxy, ethoxy, isopropionyloxy, and chloro are preferred.

[0131] In the above formula (1), R is independently an alkyl or phenyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc., wherein methyl or ethyl is preferred.

[0132] In the above formula (1), a is independently 2 or 3 in each unit bonded to silicon atoms, and 3 is preferred from the viewpoint of reactivity and adhesion to the substrate.

[0133] As a polymer containing a fluorinated polyether group with a silanol group or a hydrolyzable silyl group at a single end, as represented by the above average composition formula (1), the following structures can be listed. By changing the combination of Rf, U, Z, Y, R, X, and a in the above formula (1), several polymers containing a fluorinated polyether group with a silanol group or a hydrolyzable silyl group at a single end can be obtained. Furthermore, in the following formula, RF 1 RF 2 As above, p1 is an integer from 5 to 440, q1 is an integer from 5 to 250, p1+q1 is an integer from 20 to 450, and the repeating units shown in parentheses with p1 and q1 can be combined randomly.

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142] As a method for preparing a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, as represented by the above average composition formula (1), examples include Japanese Patent No. 6451279, Japanese Patent No. 6119656, Japanese Patent No. 6828744, Japanese Patent No. 6524955, Japanese Patent No. 6521091, etc., and the following methods can be further listed.

[0143] [Preparation Method 1]

[0144] A polymer containing a fluorinated polyether group and having an olefinic site (alkenyl group) is dissolved in a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene. An organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group (halosilyl, alkoxysilyl, etc.) is mixed and aged at a temperature of 40–120°C, preferably 60–100°C, more preferably about 80°C, for 1–72 hours, preferably 10–36 hours, more preferably about 12 hours, in the presence of a toluene solution of a chloroplatinic acid / vinylsiloxane complex catalyst. Furthermore, if an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group is used as the hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can subsequently be replaced with other hydrolyzable groups such as alkoxy groups such as methoxy groups.

[0145] In the preparation of a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, represented by the above average composition formula (1), a polymer containing a fluorinated polyether group having an olefinic site (alkenyl group) can be exemplified as a polymer containing a fluorinated polyether group having an olefinic site (alkenyl group) represented by the following average composition formula (8) or (9).

[0146]

[0147] [In the formula, RF] 1 RF 2 Rf, U, Z, b, and c are the same as above, where U' is a hydrocarbon group with 1 to 18 carbon atoms, having a 2 to 5 valence, preferably 2 or 3 valence, and may contain an ether group.

[0148] In the above average composition formula (9), U' is a hydrocarbon group with 1 to 18 carbon atoms that may contain an ether group and has a 2 to 5 valence, preferably a 2 or 3 valence. Specifically, the group shown below can be exemplified.

[0149]

[0150] (In the formula, l1 is an integer from 1 to 4, l2' is an integer from 0 to 2, and f' is an integer from 0 to 2 independently.)

[0151] As a polymer containing a fluoropolyether group having an olefinic site (alkenyl group) as represented by the above average composition formula (8), the following polymers can be listed as examples.

[0152]

[0153]

[0154]

[0155]

[0156] (where RF) 1 RF 2 p1, q1, and p1+q1 are the same as above; the repeating units shown within parentheses containing p1 and q1 can be randomly combined.

[0157] In addition, the following polymers can be listed as polymers containing fluoropolyether groups having an olefinic site (alkenyl group) as represented by the above average composition formula (9).

[0158]

[0159] (where RF) 1 RF 2 p1, q1, and p1+q1 are the same as above; the repeating units shown in parentheses containing p1 and q1 can be randomly combined.

[0160] In the preparation of a fluorinated polyether group containing a silanol group or a hydrolyzable silyl group at a single end, represented by the above average composition formula (1), compounds represented by the following general formula (10) or (11) can be exemplified as organosilicon compounds having a SiH group and a silanol group or a hydrolyzable silyl group.

[0161]

[0162] (In the formula, Z, Y, R, X, a, b, and c are the same as above. Y) 1 It is a hydrogen atom, or may have one or more monovalent hydrocarbon groups selected from fluorine atoms, silicon atoms, and siloxane bonds.

[0163] In the above equation (10), Y 1It is a hydrogen atom, or may have one or more monovalent hydrocarbon groups selected from silicon atoms and siloxane bonds, preferably a hydrogen atom, a monovalent group in which a hydrogen atom and an alkylene group having 1 to 10 carbon atoms are bonded by a silaneylene structure or a silanearyl structure, and a monovalent group in which a hydrogen atom and an alkylene group having 2 to 10 carbon atoms are bonded to the binding end of a divalent organopolysiloxane residue having a straight chain having 2 to 10 silicon atoms or a branched or cyclic structure having 3 to 10 silicon atoms.

[0164] As Y 1 Specifically, the following groups can be exemplified.

[0165]

[0166] As compounds represented by the above general formula (10), the following compounds can be listed as examples.

[0167]

[0168]

[0169] In addition, the following compounds can be listed as examples of compounds represented by the above general formula (11).

[0170]

[0171] In the preparation of a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, as represented by the above average composition formula (1), when the polymer containing a fluorinated polyether group having an olefinic site (alkenyl group) reacts with an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, the amount of the organosilicon compound used relative to 1 equivalent of the olefinic site (alkenyl group) in the polymer containing the fluorinated polyether group can be 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.

[0172] Furthermore, when using a fluorinated polyether group containing an olefinic site (alkenyl) as a polymer containing a fluorinated polyether group containing an olefinic site (alkenyl) as represented by the above average composition formula (8), when using an organosilicon compound containing SiH group and silanol group or hydrolyzable silyl group, when using a compound represented by the above general formula (10), when using a fluorinated polyether group containing an olefinic site (alkenyl) as a polymer containing a fluorinated polyether group containing an olefinic site (alkenyl) as represented by the above average composition formula (9), when using an organosilicon compound containing SiH group and silanol group or hydrolyzable silyl group, when using a compound represented by the above general formula (11).

[0173] In the preparation of polymers containing fluorinated polyether groups with a silanol group or a hydrolyzable silane group at a single end, as represented by the above average composition formula (1), fluorinated solvents can be listed as examples. Examples of fluorinated solvents include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M Corporation, trade name: Novec series), and perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M Corporation, trade name: Florinator series), etc.

[0174] Regarding the amount of solvent used, 10 to 300 parts by weight, preferably 30 to 150 parts by weight, and more preferably about 50 parts by weight, can be used relative to 100 parts by weight of the fluorinated polyether group having an olefinic site (alkenyl group).

[0175] In the preparation of polymers containing fluorinated polyether groups with a silanol group or a hydrolyzable silane group at a single end, as represented by the above average composition formula (1), the following catalysts can be listed as catalysts for the hydrosilylation reaction: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, alkynyl alcohols, etc., and platinum group metal catalysts such as tetra(triphenylphosphine)palladium and trichloro(triphenylphosphine)rhodium. Platinum group compounds such as vinylsiloxane coordination compounds are preferred.

[0176] The amount of the hydrogenation silanization reaction catalyst used, relative to the mass of the fluorinated polyether group containing the olefinic site (alkenyl group), is 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in transition metal conversion (mass).

[0177] Furthermore, in organosilicon compounds having SiH groups and silanol groups or hydrolyzable silyl groups in the molecule, if an organosilicon compound having halogen atoms is used as the hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can then be replaced with other hydrolyzable groups such as alkoxy groups such as methoxy groups. As reagents that can be used to replace the substituent (halogen atom) on the silyl group with other hydrolyzable groups, examples include alcohols with 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.

[0178] The amount used is 10 to 200 parts by mass relative to 100 parts by mass of the polymer containing fluorinated polyether groups having an olefinic site (alkenyl group) and the addition reaction product of organosilicon compounds having SiH groups and silanol groups or hydrolyzable silyl groups (halosilyl, alkoxysilyl, etc.) in the molecule, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass.

[0179] For example, as a polymer containing a fluorinated polyether group having an olefinic site (alkenyl group), a compound represented by the following formula is used.

[0180]

[0181] As organosilicon compounds having SiH groups and silanol groups or hydrolyzable silyl groups, when using trimethoxysilanes, compounds represented by the following formulas can be listed.

[0182]

[0183] As a method for preparing a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, as represented by the above average composition formula (1), the following methods may also be listed.

[0184] [Preparation Method 2]

[0185] A polymer containing a fluorinated polyether group and having a SiH group is dissolved in a fluorinated solvent such as 1,3-bis(trifluoromethyl)benzene. For example, an organosilicon compound having an olefinic site (alkenyl group) and a silanol group or a hydrolyzable silyl group (halosilyl, alkoxysilyl, etc.) is mixed and aged at a temperature of 40–120°C, preferably 60–100°C, more preferably about 80°C, for 1–72 hours, preferably 10–36 hours, more preferably about 12 hours, in the presence of a toluene solution of a hydrosilylation catalyst such as a chloroplatinic acid / vinylsiloxane complex. Furthermore, in organosilicon compounds having a SiH group and a silanol group or a hydrolyzable silyl group, if an organosilicon compound with a halogen atom is used as the hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can subsequently be replaced with other hydrolyzable groups such as alkoxy groups such as methoxy groups.

[0186] As a polymer containing a fluorinated polyether group with a SiH group, a compound represented by the following average compositional formula (12) can be exemplified.

[0187]

[0188] (where RF) 1 RF 2 Rf, U, Z, b, and c are the same as above.

[0189] Examples of compounds represented by the above average composition formula (12) include the following compounds.

[0190]

[0191]

[0192] (where RF) 1 RF 2 p1, q1, and p1+q1 are the same as above; the repeating units shown in parentheses containing p1 and q1 can be randomly combined.

[0193] As organosilicon compounds having an olefinic site (alkenyl) and a silanol group or a hydrolyzable silyl group, compounds represented by the following general formula (13) can be exemplified.

[0194]

[0195] (In the formula, R, X, and a are the same as above. Y) 2 (This refers to a compound having an alkenyl group at the end, which may have one or more monovalent hydrocarbon groups selected from fluorine atoms, silicon atoms, and siloxane bonds.)

[0196] In the above equation (13), Y 2 For a group to have an alkenyl group at the end, and may have one or more monovalent hydrocarbon groups selected from fluorine atoms, silicon atoms and siloxane bonds, the following formula can be used as an example.

[0197]

[0198]

[0199] As compounds represented by the above general formula (13), the following compounds can be listed as examples.

[0200]

[0201]

[0202] In the preparation of the fluorinated polyether group having a silanol group or hydrolyzable silyl group at a single end as shown in the above average composition formula (1) [Preparation Method 2], when the polymer containing the fluorinated polyether group having a SiH group reacts with an organosilicon compound having an olefinic site (alkenyl group) and a silanol group or hydrolyzable silyl group, the amount of organosilicon compound used relative to the SiH group in the fluorinated polyether group is 1 equivalent, such that the olefinic site (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.

[0203] In the preparation of the polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, as shown in the above average composition formula (1) [Preparation Method 2], fluorinated solvents can be listed as examples. As a fluorinated solvent, the same solvents as those listed in Preparation Method 1 can be used as examples.

[0204] The amount of solvent used is 10 to 300 parts by weight relative to 100 parts by weight of the fluorinated polyether polymer with SiH groups, preferably 30 to 150 parts by weight, and more preferably about 50 parts by weight.

[0205] In the preparation of the polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silane group at a single end, as shown in the above average composition formula (1) [Preparation Method 2], the same reaction catalyst as that shown in Preparation Method 1 can be used as the catalyst for the hydrosilylation reaction. Platinum group compounds such as vinylsiloxane coordination compounds are preferred.

[0206] The amount of the hydrogenation silylation reaction catalyst used, relative to the mass of the fluorinated polyether polymer having SiH groups, is expressed as transition metal (mass) at 0.01 to 100 ppm, more preferably 0.1 to 50 ppm.

[0207] Furthermore, in organosilicon compounds having an olefinic site (alkenyl group) and a silanol group or a hydrolyzable silyl group, if an organosilicon compound having a halogen atom is used as the hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can be replaced with other hydrolyzable groups such as alkoxy groups such as methoxy groups. The same reagent as that illustrated in preparation method 1 can be used as the reagent that can be used when replacing the substituent (halogen atom) on the silyl group with other hydrolyzable groups. Additionally, the amount used can also be the same as in preparation method 1.

[0208] For example, as a polymer containing fluorinated polyether groups and having SiH groups, a compound represented by the following formula is used.

[0209]

[0210] When using KBM-1083 (7-octenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), as an organosilicon compound having an olefinic site (alkenyl group) and a silanol group or a hydrolyzable silyl group, a compound represented by the following formula is obtained.

[0211]

[0212] Alternatively, the following methods can also be listed. For example, using a compound represented by the following formula.

[0213]

[0214] When co-hydrolyzed with 1,1,3,3-tetramethyldisiloxane, a compound represented by the following formula is obtained.

[0215]

[0216] When using a compound represented by the above formula as a polymer containing a fluorinated polyether group with a SiH group, and using an organosilicon compound having an olefinic site (alkenyl group) and a silanol group or a hydrolyzable silyl group, and using KBM-1083 (7-octenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), a compound represented by the following formula is obtained.

[0217]

[0218] The number-average molecular weight of the polymer and / or its partial (hydrolyzed) condensate containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, represented by the above average composition formula (1), is preferably 1,000 to 53,000, more preferably 2,000 to 23,000, further 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 film may decrease; if it exceeds 53,000, the surface properties of the resulting cured film may become unstable. To achieve the above-mentioned number-average molecular weight, it can be obtained by distillation or molecular distillation of the polymer and / or its partial (hydrolyzed) condensate containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, represented by the above average composition formula (1).

[0219] In the fluorinated ether composition (polymer composition containing fluorinated polyether groups) of the present invention, the amount of the polymer containing fluorinated polyether groups with silanol groups or hydrolyzable silyl groups at a single end, as shown in the above-mentioned average compositional formula (1), and / or a portion thereof (hydrolyzed) condensate, in the fluorinated ether composition (especially the total amount of polymers containing fluorinated polyether groups) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass. If it is less than 70% by mass, the heat resistance decreases, and sometimes a cured film that balances antifouling properties, heat resistance, surface peelability, and rubber wear durability cannot be obtained.

[0220] In the fluorinated ether composition of the present invention, furthermore, as needed, it is possible to combine a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at both ends, represented by the following general formula (3), and / or a partial (hydrolyzed) condensate thereof (a polymer with a fluorinated polyether group at both ends). This results in a further improvement in heat resistance.

[0221]

[0222] [In the formula, U, Z, Y, R, X, a, b, c are independently the same as above, and Rf' is derived from the following formula (4)]

[0223]

[0224] (In the formula, W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above. d' is an integer from 1 to 6. These units can be linear or branched. In addition, the repeating units shown in parentheses containing p, q, r, s, t, u, and v can be combined randomly.)

[0225] This indicates a divalent fluorinated polyether group.

[0226] In the above formula (3), Rf' is a divalent fluorinated polyether group represented by the above formula (4). W, d, p, q, r, s, t, u, v, p+q+r+s+t+u+v in formula (4) can represent the same content as that represented in Rf in the above formula (1).

[0227] In the above formula (4), d' is an integer from 1 to 6, preferably an integer from 1 to 3, and more preferably 1 or 2.

[0228] Specifically, Rf' can be exemplified by the following groups.

[0229]

[0230]

[0231]

[0232] (In the formula, p', q', and r' are each integers greater than or equal to 1, with the same upper limit as the upper limit of p, q, and r mentioned above. The sum of these p', q', and r' is 20 to 450. r2' and r3' are each integers greater than or equal to 1, and the sum of r2' and r3' is 35 to 180. In addition, the repeating units shown in the parentheses containing p', q', and r' can be combined randomly.)

[0233] In the above formula (4), the number average molecular weight of the fluorinated polyether 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 sometimes the antifouling properties of the cured film are reduced. If it exceeds 50,000, sometimes the surface properties of the cured film become unstable.

[0234] It should be noted that the W, d, p, q, r, s, t, u, v, p+q+r+s+t+u+v of the polymers containing fluorinated polyether groups with silanol groups or hydrolyzable silyl groups at both ends, represented by general formula (3), and the polymers containing fluorinated polyether groups with silanol groups or hydrolyzable silyl groups at one end, represented by average formula (1), may be the same or different.

[0235] As polymers containing fluorinated polyether groups with silanol groups or hydrolyzable silyl groups at both ends, represented by general formula (3), the following polymers can be listed.

[0236]

[0237]

[0238] (In the formula, p2 is an integer from 5 to 440, q2 is an integer from 5 to 250, p2+q2 is an integer from 20 to 450, and the repeating units shown in the parentheses with p2 and q2 can be combined randomly.)

[0239] The number-average molecular weight of the polymer and / or its partial (hydrolyzed) condensate containing fluorinated polyether groups with silanol groups or hydrolyzable silyl groups at both ends, represented by the above general formula (3), is preferably 1,000 to 56,000, more preferably 2,000 to 26,000, further 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 film may decrease; if it exceeds 56,000, the surface properties of the resulting cured film may become unstable. To achieve the above-mentioned number-average molecular weight, it can be obtained by distillation or molecular distillation of the polymer and / or its partial (hydrolyzed) condensate containing fluorinated polyether groups with silanol groups or hydrolyzable silyl groups at both ends, represented by the above general formula (3).

[0240] In the fluorinated ether composition (polymer composition containing fluorinated polyether groups) of the present invention, the amount of the polymer containing fluorinated polyether groups with silanol groups or hydrolyzable silyl groups at both ends, represented by general formula (3), and / or its partial (hydrolyzed) condensates (polymers with fluorinated polyether groups at both ends functionalized), in the fluorinated ether composition (particularly the total amount of polymers containing fluorinated polyether groups) is preferably 0 to 25% by mass, and particularly preferably 0 to 15% by mass. If it exceeds 25% by mass, the surface peelability decreases, and sometimes it is not possible to obtain a cured film that simultaneously achieves antifouling properties, heat resistance, surface peelability, and rubber wear durability. Furthermore, in the case of formulation, it is preferably 5% by mass or more, and particularly preferably 8% by mass or more, in the fluorinated ether composition (particularly the total amount of polymers containing fluorinated polyether groups).

[0241] In the fluorinated ether composition of the present invention, furthermore, as needed, a polymer containing a fluorinated polyether group (a nonfunctional fluorinated polyether polymer) represented by the following general formula (5) can be incorporated. As a result, surface peelability can be further improved.

[0242] A-Rf'-A (5)

[0243] (In the formula, Rf' is the same as above. A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorinated hydrocarbon group with the terminal CF3-, CF2H-, CF3CF2-, or CF3CFH-, which may contain an oxygen atom.)

[0244] In the above formula (5), Rf' is the same as Rf' in the above formula (3), and can represent the same group as the group represented in Rf' (the divalent fluoropolyether group represented by formula (4)). Furthermore, Rf' can be the same as or different from Rf' in formula (3).

[0245] In the above formula (5), A is independently a fluorine atom, a hydrogen atom, or a fluorinated hydrocarbon group with a terminal of CF3-, CF2H-, CF3CF2-, or CF3CFH-, which may contain an oxygen atom. Specifically, examples include fluorine atom, hydrogen atom, CF3-, CF2H-, CF2CF3-, CF3CFH-, CF3O-, CF3CF2O-, etc.

[0246] The following polymers can be listed as polymers containing fluorinated polyether groups (non-functional fluorinated polyether polymers) represented by general formula (5).

[0247]

[0248] (In the formula, p3, q3, and r3 are each independent integers from 0 to 450, and the sum of p3, q3, and r3 is from 20 to 450. r4 and r5 are each integers from 20 to 450. The repeating units shown in parentheses containing p3, q3, and r3 can be combined randomly.)

[0249] The number-average molecular weight of the polymer containing fluorinated polyether groups represented by the above 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 polymer containing fluorinated polyether groups represented by the above formula (5) in the obtained cured film may sometimes volatilize under heating conditions; if it exceeds 50,000, the surface properties of the obtained cured film may sometimes become unstable. In order to make it reach the above-mentioned number-average molecular weight, it can be obtained by distillation or molecular distillation of the polymer containing fluorinated polyether groups represented by the above general formula (5).

[0250] In the fluorinated ether composition (polymer composition containing fluorinated polyether groups) of the present invention, the amount of the polymer containing fluorinated polyether groups (non-functional polymer containing fluorinated polyether groups) represented by general formula (5) in the fluorinated ether composition (especially the total amount of polymers containing fluorinated polyether groups) is preferably 0 to 30% by mass, and particularly preferably 0 to 20% by mass. If it exceeds 30% by mass, the rubber wear durability decreases, and sometimes it is not possible to obtain a cured film that combines antifouling properties, heat resistance, surface peelability, and rubber wear durability. Furthermore, in the case of formulation, it is preferably 0.1% by mass or more, and particularly preferably 1% by mass or more, in the fluorinated ether composition (especially the total amount of polymers containing fluorinated polyether groups).

[0251] The fluorinated ether composition of the present invention can be prepared by uniformly mixing a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at one end, as shown in the above-mentioned average composition formula (1), and a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at both ends, as shown in general formula (3), and a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at both ends, as shown in general formula (5), in a specified amount by conventional methods.

[0252] The fluorinated 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 antifouling and heat resistance of the cured film may decrease; if it exceeds 56,000, the surface properties of the cured film may become unstable. To achieve the above-mentioned number average molecular weight, it can be obtained by distillation or molecular distillation of the fluorinated ether composition.

[0253] The present invention also provides a surface treatment agent comprising the above-described fluorinated ether composition.

[0254] The surface treatment agent may contain hydrolysis-condensation catalysts, such as organotin compounds (dimethoxydibutyltin, dibutyltin dilaurate, etc.), organotitanium compounds (tetrabutyl titanate, etc.), organic acids (acetic acid, methanesulfonic acid, fluorinated carboxylic acids, etc.), and inorganic acids (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetrabutyl titanate, dibutyltin dilaurate, and fluorinated carboxylic acids are particularly preferred.

[0255] The amount of hydrolysis condensation catalyst added is the catalyst amount, which is generally 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, relative to 100 parts by mass of the fluorinated ether composition (especially the polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group in the composition and / or a portion thereof (hydrolysis) condensate).

[0256] The surface treatment agent may contain a suitable solvent. Examples of such solvents include fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, tridecafluorooctane, hexafluoropropylene trimer, etc.), fluorinated aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorinated ether solvents (methyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptene ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, hexafluoroisopropyl methyl ether, etc.), fluorinated alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum ether, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferred in terms of solubility and wettability, especially 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, tridecafluorooctane, and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether.

[0257] Regarding the aforementioned solvents, two or more can be mixed, preferably to ensure uniform dissolution of the fluorinated ether composition. Furthermore, the optimal concentration of the fluorinated ether composition dissolved in the solvent varies depending on the processing method; any easily weighable amount is acceptable. In the case of direct coating, it is preferably 0.01 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass, relative to a total of 100 parts by mass of the solvent and the fluorinated ether composition. In the case of vapor deposition, it is preferably 1 to 100 parts by mass, particularly preferably 3 to 30 parts by mass, relative to a total of 100 parts by mass of the solvent and the fluorinated ether composition.

[0258] The surface treatment agent of the present invention can be applied to a substrate using known methods such as brush coating, dipping, spraying, and vapor deposition. The heating method during vapor deposition can be either resistance heating or electron beam heating, and is not particularly limited. Furthermore, the curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferable to perform the process at 25–200°C, particularly 25–150°C, for 30 minutes to 36 hours, particularly 1 to 18 hours. Furthermore, when applied via vapor deposition, it is preferable to perform the process at 20–200°C for 1 to 24 hours. Additionally, it can be cured under humidification. Moreover, for example, in the case of spraying, diluting and hydrolyzing the agent in a fluorine-based solvent with pre-added water to generate Si-OH before spraying results in faster curing after coating.

[0259] The thickness of the cured film is appropriately selected according to the type of substrate, typically ranging from 0.1 to 100 nm, particularly 1 to 20 nm. It should be noted that the film thickness can be measured using methods such as spectrophotometry, X-ray reflectance measurement, spectrophotometric ellipsography, and fluorescence X-ray measurement.

[0260] There are no particular limitations on the substrates treated with the surface treatment agent of the present invention; they can be various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. The surface treatment agent of the present invention can impart water and oil repellency to the above-mentioned substrates. In particular, it is preferably used as a surface treatment agent for SiO2-treated glass and films.

[0261] Articles treated with the surface treatment agent of the present invention include, but are not limited to, car navigation systems, mobile phones, smartphones, digital cameras, digital camcorders, PDAs, portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, endoscopes and other medical devices, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch screen displays, protective films, anti-reflective films and other optical articles. The surface treatment agent of the present invention prevents fingerprints and sebum from adhering to the aforementioned articles, thereby imparting scratch resistance, and is therefore particularly suitable as a water- and oil-repellent layer for lenses, touch screen displays, anti-reflective films, etc.

[0262] In addition, the surface treatment agent of the present invention can also be used as a stain-resistant coating for sanitary products such as bathtubs and washbasins, a stain-resistant coating for window glass or tempered glass of automobiles, trains, aircraft, etc., a stain-resistant coating for headlight covers, a water- and oil-repellent coating for exterior wall building materials, an oil-resistant coating for kitchen building materials, a stain-resistant and anti-sticker / graffiti coating for telephone boxes, a coating that prevents fingerprint adhesion to artworks, a fingerprint-resistant coating for CDs, DVDs, etc., a mold release agent or coating additive, a resin modifier, a flow modifier or dispersant modifier for inorganic fillers, and a lubricity improver for tapes, films, etc.

[0263] In particular, the surface treatment agent of the present invention can impart a cured film with excellent water and oil repellency, and thus stain resistance, heat resistance, surface peelability, and rubber wear durability.

[0264] Example

[0265] The following examples, embodiments, and comparative examples illustrate the invention in more detail, but the invention is not limited to the following embodiments. Furthermore, in the following formulas, the repeating units shown within parentheses containing p1 and q1, p2 and q2, and p3 and q3 are randomly combined. Moreover, the film thickness is a value measured using spectroscopic ellipsography with a spectroscopic ellipsometer.

[0266] The number-average molecular weight (Mn) of polymers containing fluorinated polyether groups and fluorinated ether compositions is based on 1 H-NMR analysis and 19 The value is calculated from the ratio of the characteristic peak intensities of the end structure and main chain structure of polymers containing fluorinated polyether groups analyzed by RF-NMR. Additionally, RF... 1 Molar ratio (CF3CF2O- / CF3O-) and RF 2 The molar ratio (-CF₂CF₂O⁻ / -CF₂O⁻), p₁, q₁, p₂, q₂, p₃, q₃ are determined by... 19 The intensity ratio of the characteristic peaks was calculated from the F-NMR analysis.

[0267] Raw material polymers A to G, having the compositions shown in Table 1 below, were prepared and represented by the average composition formula (I) below.

[0268]

[0269] [Table 1]

[0270]

[0271] [Synthesis example 1]

[0272] Referring to Japanese Patent No. 6451279, using raw material polymers A, B, C, and G with compositions as shown in Table 1 and represented by the average composition formula (I) as initial raw materials, single-terminal functional polymers containing fluorinated polyether groups with compositions as shown in Table 2 and represented by the average composition formula (II) below were synthesized (A-II, B-II, C-II, G-II in Table 2).

[0273]

[0274] [Synthesis example 2]

[0275] Referring to Japanese Patent No. 6119656 and Japanese Patent No. 6828744, using raw material polymers C and F, which have the composition shown in Table 1 and are represented by the average composition formula (I), as initial raw materials, single-terminal functional polymers containing fluorinated polyether groups (C-III and F-III in Table 2) with the composition shown in Table 2 and represented by the average composition formula (III) are synthesized respectively.

[0276]

[0277] [Synthesis example 3]

[0278] Referring to Japanese Patent No. 6119656 and Japanese Patent No. 6524955, using raw material polymer B having the composition shown in Table 1 and represented by the average composition formula (I) as the starting material, a single-terminal functional polymer containing a fluorinated polyether group having the composition shown in Table 2 and represented by the average composition formula (IV) was synthesized (B-IV in Table 2).

[0279]

[0280] [Synthesis Example 4]

[0281] Referring to Japanese Patent No. 6119656 and Japanese Patent No. 6524955, using raw material polymers E and F with compositions as shown in Table 1 and represented by the average composition formula (I) as initial raw materials, and using organosilicon compounds having SiH groups and hydrolyzable terminal groups in the molecule, polymers with single-terminal functionalities containing fluorinated polyether groups (EV and FV in Table 2) with compositions as shown in Table 2 and represented by the average composition formula (V) as shown in Table 2 were synthesized.

[0282]

[0283]

[0284] [Synthesis Example 5]

[0285] 30 g of raw material polymer A, 30 g of 1,3-trifluoromethylbenzene, and 6.0 g of 2,2-diallyl-4-penten-1-amine, having the composition shown in Table 1 and represented by the average formula (I), were stirred at 50 °C for 5 hours. Then, the solvent and unreacted matter were removed by vacuum distillation, resulting in 25 g of a liquid product. 1 1H-NMR confirmed that the obtained product was a compound represented by the following average composition formula (VI-a). Furthermore, RF in formula (VI-a) 1 molar ratio and RF 2 Molar ratio and RF in raw material polymer A 1 molar ratio and RF 2 The molar ratio is the same.

[0286]

[0287] 25 g of the compound shown in the average composition formula (VI-a), 10 g of 1,3-trifluoromethylbenzene, 2.0 g of trimethoxysilane, and 0.015 g of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (as elemental Pt, containing 4.5 × 10⁻⁶ Pt) were mixed. -8 The mixture (in moles) was aged at 80°C for 3 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 25 g of the liquid product. 1 H-NMR confirmed that the obtained product was a single-terminal functional polymer containing fluorinated polyether groups, represented by the following average composition formula (VI). Furthermore, RF in formula (VI) 1 molar ratio and RF 2 Molar ratio and RF in raw material polymer A 1 molar ratio and RF 2 The molar ratio is the same. Additionally, the number-average molecular weight is 5071.

[0288]

[0289] [Synthesis example 6]

[0290] A mixture of 100 g of raw material polymer D (represented by the average composition formula (I) with the composition shown in Table 1), 130 ml of 3-butenyl magnesium bromide, 200 g of Asahiiclein AC6000, and 100 g of PF5060 was stirred at 50 °C for 6 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 93 g of the liquid product. 1 1H-NMR confirmed that the product obtained was a compound represented by the following average composition formula (VII-a). Furthermore, RF in formula (VII-a) 1 molar ratio and RF 2 Molar ratio and RF in raw material polymer D 1 molar ratio and RF2 The molar ratio is the same.

[0291]

[0292] 80 g of the compound represented by the above average 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% (w / w) sodium hydroxide aqueous solution was added. The mixture was then heated at 50 °C for 24 hours. The solvent and unreacted substances were then removed by vacuum distillation, yielding 75 g of a liquid product. 1 1H-NMR confirmed that the product obtained was a compound represented by the following average composition formula (VII-b). Furthermore, RF in formula (VII-b) 1 molar ratio and RF 2 Molar ratio and RF in raw material polymer D 1 molar ratio and RF 2 The molar ratio is the same.

[0293]

[0294] 70 g of the compound represented by the above average composition formula (VII-b), 100 g of 1,3-bis(trifluoromethyl)benzene, 37 g of 2,4,6,8-tetramethylcyclotetrasiloxane, and 8.0 × 10⁸ g of a toluene solution of a platinum-1,3-divinyltetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex). -2 g (as elemental Pt, containing 2.4 × 10⁻⁶) -7 The mixture (mol) was stirred at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 65 g of the liquid product. 1 1H-NMR confirmed that the product obtained was a compound represented by the following average composition formula (VII-c). Furthermore, RF in formula (VII-c) 1 molar ratio and RF 2 Molar ratio and RF in raw material polymer D 1 molar ratio and RF 2 The molar ratio is the same.

[0295]

[0296] 50 g of the compound represented by the above average composition formula (VII-c), 100 g of 1,3-bis(trifluoromethyl)benzene, 17.5 g of 7-octenyltrimethoxysilane, and 8.0 × 10⁸ g of a toluene solution of a platinum-1,3-divinyltetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex). -2 g (as elemental Pt, containing 2.4 × 10⁻⁶) -7The mixture (mol) was stirred at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 30 g of the liquid product. 1 H-NMR confirmed that the obtained product was a single-terminal functional polymer containing fluorinated polyether groups, represented by the following average composition formula (VII). Furthermore, RF in formula (VII) 1 molar ratio and RF 2 Molar ratio and RF in raw material polymer D 1 molar ratio and RF 2 The molar ratios are the same. Additionally, the number-average molecular weight is 6490.

[0297]

[0298] [Synthesis Example 7]

[0299] 100 g of the compound represented by the following general formula (H'), 50 g of 1,3-bis(trifluoromethyl)benzene, 7.0 g of trimethoxysilane, and 8.0 × 10⁸ g of a toluene solution of a platinum-1,3-divinyltetramethyldisiloxane complex (chloroplatinic acid / vinylsiloxane complex). -2 g (as elemental Pt, containing 2.4 × 10⁻⁶) -7 The mixture (mol) was stirred at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation, yielding 90 g of the liquid product. 1 1H-NMR confirmed that the product was a polymer H containing fluorinated polyether groups at both ends, represented by the following general formula (H). Furthermore, the number-average molecular weight was 4720.

[0300]

[0301] [Synthesis example 8]

[0302] Referring to Japanese Patent No. 6451279, a polymer J containing fluorinated polyether groups at both ends, represented by the following general formula (J'), was synthesized using a compound represented by the following general formula (J') as the starting material. Furthermore, the number average molecular weight is 4510.

[0303]

[0304] [Synthesis Example 9]

[0305] Referring to Japanese Patent No. 6524955, using a compound represented by the following general formula (K') as the starting material, and an organosilicon compound having SiH groups and hydrolyzable terminal groups in the molecule, a polymer K containing fluorinated polyether groups with two terminal functionalities represented by the following general formula (K) was synthesized using a compound represented by the following formula (a). Furthermore, the number average molecular weight is 4630.

[0306]

[0307]

[0308]

[0309] As a nonfunctional fluorinated polyether polymer, a nonfunctional polymer L containing fluorinated polyether groups (number average molecular weight 4300) represented by the following general formula (L) was prepared.

[0310]

[0311] Polymers with single-terminal functional groups containing fluorinated polyether groups

[0312] Table 2 shows a list of the single-terminal functional polymers containing fluorinated polyether groups obtained in Synthetic Examples 1-6. For example, polymers A-II containing fluorinated polyether groups with single-terminal functional groups are polymers with single-terminal functional groups containing fluorinated polyether groups that have a structure represented by the above average composition formula (II) obtained by using polymer A, which has the composition shown in Table 1, as the starting material.

[0313] [Table 2]

[0314]

[0315] The following solvents were used during dilution.

[0316] Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether)

[0317] Novec 7300 (manufactured by 3M, methyl perfluorohexyl ether)

[0318] アサヒクリンAC-6000 (manufactured by AGC Co., Ltd., tridecafluorooctane),

[0319] Opteon SF10 (Mitsui Methyl perfluoroheptenyl ether (manufactured by Kemage Fiber Co., Ltd.),

[0320] Hexafluoropropylene trimer (manufactured by Fujifilm and Kazumitsu Chemical Co., Ltd.)

[0321] Hexafluoroisopropyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0322] [Examples 1-19, Comparative Examples 1-4]

[0323] In the polymers obtained in the above synthesis examples, a surface treatment agent was prepared by diluting a fluorinated ether composition, which is a mixture of a polymer with single-terminal functional fluorinated polyether groups, a polymer with two-terminal functional fluorinated polyether groups, and a polymer without functional fluorinated polyether groups, with a solvent to a concentration of 20% by mass, as shown in Table 3.

[0324] [Table 3]

[0325]

[0326] Preparation of surface treatment agents and formation of cured films

[0327] Cured films were fabricated using the surface treatment agents prepared in Examples 1-19 and Comparative Examples 1-4. For glass (Corning Gorilla V) with a 10 nm thick SiO2 coating on the outermost surface, each surface treatment agent was vacuum-deposited (treatment conditions: pressure: 3.0 × 10⁻⁶). -2 (Pa, heating temperature: 700℃), and cured for 12 hours in an atmosphere of 25℃ and 50% relative humidity, forming a cured film with a thickness of 10nm.

[0328] Evaluation of water and oil repellency

[0329] [Determination of initial water contact angle]

[0330] For the glass with the cured film formed as described above, the contact angle (hydrophobicity) of the cured film to water was measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The results (initial water contact angle) are shown in Table 4.

[0331] Evaluation of stain resistance

[0332] [Erasability Evaluation of All-Purpose Ink]

[0333] For the glass with the cured film formed as described above, a 1cm x 1cm square was drawn using Penteru Pen 50 (manufactured by Penteru Co., Ltd.). After the ink dried, it was wiped off with a paper towel (manufactured by Kamishō Co., Ltd.). The number of wipings required until the ink was completely removed was evaluated.

[0334] (Evaluation criteria)

[0335] A: Wiping 4 times or less

[0336] B: Wipe more than 5 times

[0337] The results of the evaluation using the above evaluation criteria are shown in Table 4.

[0338] Evaluation of heat resistance

[0339] [Determination of the contact angle of heated water]

[0340] The glass with the cured film formed as described above was heated at 250°C for 24 hours, then cleaned with the neutral detergent Mamaremon (manufactured by Lion Co., Ltd.), and the contact angle with water was measured under the conditions described above in [Determination of Initial Water Contact Angle] (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The test environment conditions were 25°C and 40% relative humidity.

[0341] (Evaluation criteria)

[0342] A: The difference between the contact angle measured at the initial stage and the contact angle measured after heating is less than 6°.

[0343] B: The difference between the contact angle of the initial water contact angle and the contact angle of the heated water is greater than 6° but less than 10°.

[0344] C: The difference between the contact angle of the initial water contact angle and the contact angle of the heated water contact angle is greater than 10°.

[0345] The results of the evaluation using the above evaluation criteria are shown in Table 4.

[0346] Evaluation of peelability

[0347] For the glass with the cured film formed as described above, polyester adhesive tape No. 31B (manufactured by Nitto Denko Corporation) was applied and left to stand for 3 days under a 1 kgf load. Then, the peel strength was evaluated using Autograph AGS-X10N (manufactured by Shimadzu Corporation). The test conditions were: temperature 25°C, relative humidity 50%, crosshead speed 300 mm / min, and test piece width 19 mm.

[0348] (Evaluation criteria)

[0349] A: Peel force is less than 0.08N

[0350] B: Peel force is greater than 0.08N but less than 0.11N

[0351] C: Peel force is above 0.11N

[0352] The results of the evaluation using the above evaluation criteria are shown in Table 4.

[0353] Evaluation of rubber wear durability

[0354] For the glass with a cured coating formed as described above, the contact angle of the cured coating with water after 3000 rubs under the following conditions was measured using a reciprocating abrasion tester (Traybogia, manufactured by Shin-To Science Co., Ltd.), in the same manner as above, to evaluate its abrasion resistance. The test environment conditions were 25°C and 40% relative humidity.

[0355] (Wear conditions)

[0356] Eraser: rubber eraser (manufactured by Minoan)

[0357] Travel distance (one way): 40mm

[0358] Movement speed: 2400 mm / min

[0359] Load: 1 kgf / 6 mm 2 Φ

[0360] (Evaluation criteria)

[0361] A: The difference between the contact angle measured at the initial stage and the contact angle measured after wear is less than 6°.

[0362] B: The difference between the contact angle of the initial water contact angle and the water contact angle after wear is greater than 6° but less than 11°.

[0363] C: The difference between the contact angle of the initial water contact angle and the water contact angle after wear is greater than 11°.

[0364] The results of the evaluation using the above evaluation criteria are shown in Table 4.

[0365] [Table 4]

[0366]

[0367] [Examples 20-25, Comparative Examples 5 and 6]

[0368] For the polymers obtained in the above synthesis examples, a surface treatment agent was prepared by diluting a fluorinated ether composition, which is a mixture of a polymer with single-terminal functional fluorinated polyether groups, a polymer with two-terminal functional fluorinated polyether groups, and a polymer without functional fluorinated polyether groups, with a solvent to a concentration of 0.1% by mass, using the composition shown in Table 5.

[0369] [Table 5]

[0370]

[0371] Preparation of surface treatment agents and formation of cured films

[0372] Using the surface treatment agents prepared in Examples 20-25 and Comparative Examples 5 and 6, cured films were fabricated. The films were sprayed onto the surface of plasma-treated chemically strengthened glass (Corning Gorilla V) using a spraying apparatus (T&K NST-51). The films were then cured for 12 hours at 25°C and 50% relative humidity, resulting in a 10 nm thick cured film, thus obtaining the test specimen.

[0373] For the evaluation methods of Examples 20-25 and Comparative Examples 5 and 6, the same evaluation items as those of Examples 1-19 and Comparative Examples 1-4 were performed. The results (initial contact angle, number of wipes until ink removal, water contact angle after heating, and peel value) are shown in Table 6.

[0374] [Table 6]

[0375]

[0376] Based on the above results, in Comparative Examples 1-3 and 5, compared with the initial water contact angle, the decrease in water contact angle after heating remained less than 6° (i.e., the water contact angle remained above 100°), until the number of wipings to remove ink increased, and subsequently, the water contact angle after rubber wear decreased significantly. In Comparative Examples 4 and 6, ink could be wiped off immediately, and the decrease in water contact angle after rubber wear remained less than 6° (i.e., the water contact angle remained above 100°), but the heat resistance was weak and the peel value was high. On the other hand, in Examples 1-25, by adjusting the molar ratio of the terminal groups of the polymer containing fluorinated polyether groups at the single end to a range of 0.01 or more and 0.17 or less, good results were obtained in the four properties of water and oil repellency, stain resistance, heat resistance, surface peeling, and rubber wear durability.

Claims

1. A fluorinated ether composition comprising a polymer and / or a portion thereof containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group at a single end, as represented by the following average compositional formula (1). In the formula, RF 1 It is CF3O- or CF3CF2O-, and the molar ratio of CF3O- to CF3CF2O- (CF3CF2O- / CF3O-) is greater than 0.01 and less than 0.

17. RF 2 The form is -CF2O- or -CF2CF2O-, Rf is a divalent fluorinated polyether group represented by the following formula (2), U is a single bond or an organic group with 2 to 5 valences, Z is independently a single bond, or a carbon atom, silicon atom, nitrogen atom, R' is an alkyl group with 1 to 4 carbon atoms, -SiR' = or an organic group with 3 to 9 valences, Y is independently a divalent hydrocarbon group that may have one or more divalent hydrocarbon groups selected from fluorine atoms, silicon atoms and siloxane bonds, R is independently an alkyl or phenyl group with 1 to 4 carbon atoms, X is independently a hydroxyl or hydrolyzable group, a is independently 2 or 3 in each unit bonded to a silicon atom, b is independently an integer from 1 to 8, and c is an integer from 1 to 4. In the formula, W is a fluorinated alkylene group containing one or more hydrogen atoms, d is an integer from 1 to 6, p, q, r, s, t, u, and v are each an integer from 0 to 450, and p+q+r+s+t+u+v = 10 to 450. These units can be linear or branched. In addition, the repeating units shown in parentheses containing p, q, r, s, t, u, and v can be randomly combined.

2. The fluorinated ether composition according to claim 1, wherein, RF in equation (1) 2 In this context, the molar ratio of -CF2O- to -CF2CF2O- (-CF2CF2O- / -CF2O-) is greater than 1.05 and less than 1.

2.

3. The fluorinated ether composition according to claim 1, wherein, In the formula (1), X is selected from hydroxyl, alkoxy with 1 to 10 carbon atoms, alkoxy-substituted alkoxy with 2 to 10 carbon atoms, acyloxy with 2 to 10 carbon atoms, olefinic group with 2 to 10 carbon atoms, and halogen group.

4. The fluorinated ether composition according to claim 1, wherein, In formula (1), U is a single bond, carbonyl, amide, a group represented by the following formula, or may contain one or more atoms or groups selected from oxygen atom, sulfur atom, hydroxyl, polyether group, diorganomymethylene silyl, linear divalent organopolysiloxane residue with 2 to 100 silicon atoms, silane, silane, secondary amino, tertiary amino, ether group, carbonyl, amide, and ester group, with a carbon number of 1 to 20 and a 2 to 5 valent hydrocarbon group. In the formula, B is a hydrogen atom, a monovalent hydrocarbon group with 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms.

5. The fluorinated ether composition according to claim 1, wherein, In the formula (1), Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a straight-chain, branched or cyclic 3-8 valent organopolysiloxane residue with 3 to 13 silicon atoms, a 3 valent isocyanurate group, or a 3 valent group containing a triazine ring.

6. The fluorinated ether composition according to claim 1, wherein, In the formula (1), Y is a group selected from alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing fluorine atoms, alkylene groups having 1 to 10 carbon atoms containing aryl groups having 6 to 8 carbon atoms, divalent groups having 1 to 10 carbon atoms bonded to each other by a silanealkylene structure or a silanearyl structure, and divalent groups having alkylene groups having 2 to 10 carbon atoms bonded to the binding end of a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms.

7. The fluorinated ether composition according to claim 1, wherein, The composition also contains less than 25% by mass of a polymer and / or a portion thereof (hydrolyzed) condensate of a fluorinated polyether group having silanol or hydrolyzable silane groups at both ends, represented by the following general formula (3). In the formula, U, Z, Y, R, X, a, b, and c are independently the same as those above, and Rf' is a divalent fluorinated polyether group represented by the following formula (4). In the formula, W, d, p, q, r, s, t, u, v, p+q+r+s+t+u+v are the same as above, and d' is an integer from 1 to 6. These units can be linear or branched. In addition, the repeating units shown in the parentheses containing p, q, r, s, t, u, v can be combined randomly.

8. The fluorinated ether composition according to claim 1, wherein, The composition also contains less than 30% by mass of a polymer containing a fluorinated polyether group, represented by the following general formula (5). A-Rf'-A (5) In the formula, A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorinated hydrocarbon group with a terminal CF3-, CF2H-, CF3CF2-, or CF3CFH- and may contain an oxygen atom, and Rf' is a divalent fluorinated polyether group represented by the following formula (4). In the formula, W, d, p, q, r, s, t, u, v, p+q+r+s+t+u+v are the same as above, and d' is an integer from 1 to 6. These units can be linear or branched. In addition, the repeating units shown in the parentheses containing p, q, r, s, t, u, v can be combined randomly.

9. The fluorinated ether composition according to claim 1, wherein, The polymer containing a fluorinated polyether group with a silanol group or a hydrolyzable silane group at a single end, represented by formula (1), is selected from at least one of the polymers represented by the following formulas. In the formula, RF 1 RF 2 As above, p1 is an integer from 5 to 440, q1 is an integer from 5 to 250, p1+q1 is an integer from 20 to 450, and the repeating units shown in parentheses with p1 and q1 can be combined randomly.

10. A surface treatment agent comprising a fluorinated ether composition according to any one of claims 1 to 9.

11. Articles surface-treated with the surface treatment agent according to claim 10.

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