Fluorine-containing composition, surface treatment agent, and article

Abstract

A surface treatment agent comprising a fluorine-containing composition comprising (A) a polymer represented by formula (1) and / or a partial (hydrolyzed) condensate thereof and (B) a polymer represented by formula (2) and / or a partial (hydrolyzed) condensate thereof in a specific ratio is capable of forming a cured coating film having excellent water and oil repellency, excellent wear resistance, excellent sliding properties, excellent chemical resistance, and excellent heat resistance. The fluorine-containing composition comprises (A) a polymer represented by formula (1) and / or a partial (hydrolyzed) condensate thereof, and (B) a polymer represented by formula (2) and / or a partial (hydrolyzed) condensate thereof. [Rf is a group represented by formula (3) (W is a fluoroalkylene group containing H, d is 1-6, p, q, r, s, t, u, and v are 0-450, and the total of p-v is 10-450. ), Rf'is a fluoroalkyl group, and A is a group of formula (4). (B is a single bond or a divalent group, V is a 3-8-valent group, R'is H, OH, an alkyl group, a phenyl group, an oxyalkylene-containing group, an alkoxy group or a halogen, U is a single bond or a divalent group, Z is a single bond or a 3-8-valent group, Y is a divalent group, R is an alkyl group or a phenyl group, X is OH or a hydrolyzable group, n is 1-3, m is 1-7, beta is 1-6, gamma is 0 or 1, and delta is 0-6. )] Rf 'OCF2CF2O-Rf-A (1) Rf' OCF2O-Rf-A (2) # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a fluorine-containing composition comprising a fluoropolyether group-containing polymer (a compound having a monovalent fluorooxyalkylene group-containing polymer residue in the molecule), and more specifically, to a fluorine-containing composition comprising a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, which forms a coating having excellent water and oil repellency, abrasion resistance, sliding properties, chemical resistance, and heat resistance, a surface treatment agent containing the fluorine-containing composition, and an article surface-treated with the surface treatment agent. Background Art

[0002] In recent years, led by mobile phones, the touch panelization of displays is accelerating. However, the touch panel is in a state where the screen is exposed, and there are many opportunities for direct contact with fingers, cheeks, etc., and it is easy to adhere to dirt such as sebum and become a problem. Therefore, in order to improve the appearance and visibility, the requirements of the technology that makes it difficult to adhere to fingerprints on the surface of the display and the technology that easily removes dirt are increased year by year, and it is hoped that the material that can meet these requirements will be developed. In particular, the surface of the touch panel display is easy to adhere to fingerprint dirt, so it is hoped that a water-repellent and oil-repellent layer is provided. However, the water-repellent and oil-repellent properties of the previous water-repellent and oil-repellent layers are high, and the dirt wiping property is excellent, but there is a problem of deterioration of antifouling performance in use.

[0003] Generally, the compound containing fluoropolyether group has water and oil repellency, chemical resistance, lubricity, demoulding property, antifouling property etc. because its surface free energy is very small.Utilize its property, be widely used in the water and oil repellent antifouling agent of paper fiber etc., the lubricant of magnetic recording medium, oil repellent of precision equipment, demoulding agent, cosmetic material, protective film etc. in industry.But its property means non-adhesiveness, non-adhesiveness to other base materials simultaneously, even can be coated on the substrate surface, also be difficult to make its coating close.

[0004] On the other hand, as a substance that allows the surface of a substrate such as glass or cloth to be bonded to an organic compound, silane coupling agents are well known and are widely used as coating agents for the surfaces of various substrates. 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 by causing a self-condensation reaction using moisture in the air. The coating is chemically and physically bonded to the surface of glass, metal, etc. by the hydrolyzable silyl group to form a durable and firm coating.

[0005] Therefore, a composition is disclosed that can form a coating film having water and oil repellency, chemical resistance, lubricity, mold release, antifouling properties, etc. on the surface of a substrate by using a fluoropolyether group-containing polymer in which a hydrolyzable silyl group is introduced into a fluoropolyether group-containing compound (Patent Documents 1 to 6: JP-A-2008-534696, JP-A-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, JP-A-2015-199906).

[0006] Cured films such as lenses and antireflection films surface-treated with a composition comprising a fluoropolyether group-containing polymer having a hydrolyzable silyl group introduced into the fluoropolyether group-containing compound have excellent sliding properties and mold release properties and excellent durability against abrasion by steel wool.

[0007] The use of the composition containing the fluoropolyether group-containing polymer having a hydrolyzable silyl group introduced into the fluoropolyether group-containing compound is expanding, and the development of vehicle-mounted applications such as interior displays is also expanding. When used in vehicle applications, slipperiness as a touch is required, and on the other hand, durability against alkaline cleaning fluids (chemical resistance) and durability under exposure to sunlight and high temperatures (heat resistance) are required.

[0008] In the composition containing the fluoropolyether group-containing polymer in which a hydrolyzable silyl group is introduced into the fluoropolyether group-containing compound, all of the requirements of sliding property, chemical resistance and heat resistance have not been satisfied yet.

[0009] In addition, as prior arts related to the present invention, the following documents can be cited together with the above-mentioned documents.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Application No. 2008-534696

[0013] Patent Document 2: Japanese Patent Application No. 2008-537557

[0014] Patent Document 3: Japanese Patent Application Publication No. 2012-072272

[0015] Patent Document 4: Japanese Patent Application Publication No. 2012-157856

[0016] Patent Document 5: Japanese Patent Application Publication No. 2013-136833

[0017] Patent Document 6: Japanese Patent Application Publication No. 2015-199906

[0018] Patent Document 7: International Publication No. 2017 / 212850 Summary of the invention

[0019] Problems to be solved by the invention

[0020] The present invention has been completed in view of the above-mentioned actual situation, and its object is to provide a fluorine-containing composition comprising a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolysis) condensate thereof, which can form a cured film having excellent water and oil repellency, wear resistance, sliding properties, chemical resistance and heat resistance, a surface treatment agent containing the fluorine-containing composition, and an article surface-treated with the surface treatment agent.

[0021] Means for solving problems

[0022] The present inventors have conducted intensive studies to achieve the above-mentioned purpose and have found that by using a fluorine-containing composition containing a silanol group or a hydrolyzable silyl group-containing polymer and / or its partial (hydrolysis) condensate thereof represented by the general formula (1) described below and a silanol group or a hydrolyzable silyl group-containing polymer and / or its partial (hydrolysis) condensate thereof represented by the general formula (2) described below in a prescribed ratio as a surface treatment agent, the surface treatment agent containing the polymer and / or its partial (hydrolysis) condensate can form a cured film having excellent water and oil repellency and wear resistance, as well as excellent sliding properties, chemical resistance and heat resistance, thereby completing the present invention.

[0023] Therefore, the present invention provides a fluorine-containing composition, a surface treating agent and an article comprising the following fluoropolyether group-containing polymer (a compound having a monovalent fluorooxyalkylene group-containing polymer residue in the molecule).

[0024] [1] A fluorinated composition comprising the following components (A) and (B), wherein the molar ratio (A) / (B) of the components (A) to (B) is 1.2 to 4.0,

[0025] (A) a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (1) and / or a partial (hydrolyzed) condensate thereof

[0026] (B) a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (2) and / or a partial (hydrolyzed) condensate thereof

[0027] [Chemistry 1]

[0028] Rf′OCF2CF2O-Rf-A (1)

[0029] Rf′OCF2O-Rf-A (2)

[0030] [wherein, Rf is a divalent fluorooxyalkylene-containing polymer residue represented by the following general formula (3),

[0031] [Chemistry 2]

[0032]

[0033] (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 independently an integer of 0 to 450, and p+q+r+s+t+u+v=10 to 450. These units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)

[0034] Rf' is a fluoroalkyl group with a -CF3 group at the end,

[0035] A is a monovalent group represented by the following formula (4).

[0036] [Chemistry 3]

[0037]

[0038] (wherein, B is a single bond or a divalent organic group, V is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, R' is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a group having an oxyalkylene group, an alkoxy group having 1 to 4 carbon atoms, or a halogen group, U is independently a single bond or a divalent organic group, Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, and Y is independently a group which may be selected from oxygen atoms R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 on each silicon atom to which it is bonded, m is independently an integer of 1 to 7, β is an integer of 1 to 6, γ is 0 or 1, δ is an integer of 0 to 6, when γ is 0, β is 1, when γ is 1, the sum of β and δ is an integer of 2 to 7. )]

[0039] [2] The fluorinated composition according to [1], further comprising the following component (C) and / or component (D),

[0040] (C) A fluoropolyether group-containing polymer represented by the following general formula (5)

[0041] (D) a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (6) and / or a partial (hydrolyzed) condensate thereof

[0042] [Chemistry 4]

[0043] A′—Rf 1 -A′ (5)

[0044] A-R 1 -A (6)

[0045] [Wherein, Rf 1 is a divalent fluorooxyalkylene-containing polymer residue represented by the following formula (7),

[0046] [Chemistry 5]

[0047]

[0048] (W is a fluoroalkylene group containing one or more hydrogen atoms. d is independently an integer of 1 to 6 in each unit, p, q, r, s, t, u, and v are independently an integer of 0 to 450, and p+q+r+s+t+u+v=10 to 450. These units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)

[0049] A' is a fluorine atom,

[0050] A is independently the same as above.]

[0051] [3] The fluorine-containing composition according to [1], wherein in the formulas (1) and (2), B in the formula (4) is a single bond, an alkylene group having 1 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a diorganosilylene group, a silylene structure or a silylene structure, a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms, and a divalent group which may contain at least any one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, a thioamide and an ester group among carbonyl groups and acylamino groups.

[0052] [4] The fluorine-containing composition according to [1], wherein in the formulas (1) and (2), γ in the formula (4) is 1, and V in the formula (4) is any one selected from a carbon atom, a silicon atom, a nitrogen atom, -C(O-)=, a linear tri- to hexavalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic tri- to hexavalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent isocyanurate group, and a trivalent triazine ring-containing group.

[0053] [5] The fluorine-containing composition according to [1], wherein in the formulas (1) and (2), Y in the formula (4) is a group selected from an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom or a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other or to an arylene group via a diorganosilylene group, a silylalkylene structure or a silylarylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms.

[0054] [6] The fluorine-containing composition according to [1], wherein in the formulas (1) and (2), U in the formula (4) is any one selected from a single bond, an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom and a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a diorganosilylene group, a silylene structure or a silylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms.

[0055] [7] The fluorine-containing composition according to [1], wherein in the formulas (1) and (2), Z in the formula (4) is any one selected from a single bond, a carbon atom, a silicon atom, a nitrogen atom, -C(O-)=, a linear trivalent to hexavalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent to hexavalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent isocyanurate group, and a trivalent triazine ring-containing group.

[0056] [8] The fluorine-containing composition according to [1], wherein in the formulas (1) and (2), X in the formula (4) is a group selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.

[0057] [9] The fluorinated composition according to [1], wherein in the formulae (1) and (2), A is the same.

[0058]

[10] The fluorinated composition according to [1], wherein the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (1) is at least one selected from polymers represented by the following formulas:

[0059] [Chemistry 6]

[0060]

[0061] [Chemistry 7]

[0062] CF3O-CF2CF2O-(CF2O) p1 —(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0063]

[0064] [Chemistry 8]

[0065]

[0066] [Chemistry 9]

[0067]

[0068] [Chemistry 10]

[0069]

[0070] [Chemistry 11]

[0071]

[0072] [Chemistry 12]

[0073] C3F7O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0074]

[0075] C3F7O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3

[0076] [Chemistry 13]

[0077]

[0078] [Chemistry 14]

[0079]

[0080] [Chemistry 15]

[0081]

[0082] [Chemistry 16]

[0083]

[0084] [Chemistry 17]

[0085] CF3O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3

[0086]

[0087] [Chemistry 18]

[0088] CF3O-CF2CF2O-(C3F6O) r1 -CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0089]

[0090] [Chemistry 19]

[0091]

[0092] [Chemistry 20]

[0093] CF3O-CF2CF2O-(C4F8O) s1 -(C2F4O) q1 -CF2CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0094]

[0095] [Chemistry 21]

[0096]

[0097] [Chemistry 22]

[0098]

[0099] [Chemistry 23]

[0100]

[0101] [Chemistry 24]

[0102]

[0103] (In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, but the total of p1', q1', and r1' in each formula is 9 to 199. Each repeating unit shown in the parentheses with p1, q1, r1, s1, p1', and q1' may be randomly bonded, and k is an integer of 1 to 20.)

[0104]

[11] The fluorinated composition according to [1], wherein the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (2) is at least one selected from polymers represented by the following formulas:

[0105] [Chemistry 25]

[0106]

[0107] [Chemistry 26]

[0108] CF3O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2—Si(OCH3)3

[0109]

[0110] [Chemistry 27]

[0111]

[0112] [Chemistry 28]

[0113]

[0114] [Chemistry 29]

[0115]

[0116] [Chemistry 30]

[0117]

[0118] [Chemistry 31]

[0119] C3F7O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0120]

[0121] [Chemistry 32]

[0122]

[0123] [Chemistry 33]

[0124]

[0125] [Chemistry 34]

[0126]

[0127] [Chemistry 35]

[0128]

[0129] [Chemistry 36]

[0130] CF3O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3

[0131]

[0132] [Chemistry 37]

[0133] CF3O-CF2O-(C3F6O) r1 -CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0134]

[0135] [Chemistry 38]

[0136]

[0137] [Chemistry 39]

[0138] CF3O-CF2O-(C4F8O) s1 -(C2F4) q1 -CF2CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0139]

[0140] [Chemistry 40]

[0141]

[0142] [Chemistry 41]

[0143]

[0144] [Chemistry 42]

[0145]

[0146] [Chemistry 43]

[0147]

[0148] (In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, but the total of p1', q1', and r1' in each formula is 9 to 199. Each repeating unit shown in the parentheses with p1, q1, r1, s1, p1', and q1' may be randomly bonded, and k is an integer of 1 to 20.)

[0149]

[12] A surface treating agent comprising the fluorine-containing composition according to any one of [1] to

[11] .

[0150]

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

[12] .

[0151]

[14] The article according to

[13] , which is an optical article.

[0152]

[15] The article according to

[13] , which is a touch panel display.

[0153]

[16] The article according to

[13] , which is an anti-reflection film.

[0154]

[17] The article according to

[13] , wherein the substrate is SiO2 treated glass.

[0155]

[18] The article according to

[13] , wherein the substrate is tempered glass.

[0156]

[19] The article according to

[13] , wherein the substrate is a lens substrate.

[0157]

[20] The article according to

[13] , wherein the substrate is a quartz substrate.

[0158] Effects of the Invention

[0159] According to the present invention, by using a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (1) described later and / or its partial (hydrolysis) condensate and a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (2) described later and / or its partial (hydrolysis) condensate in a prescribed ratio, the main chain is inhibited from being decomposed by chemicals such as alkaline cleaning solutions and heat, thereby an article surface-treated with a surface treatment agent containing a fluorine-containing composition containing the polymer and / or its partial (hydrolysis) condensate has excellent water and oil repellency, wear resistance, sliding properties, chemical resistance and heat resistance. DETAILED DESCRIPTION

[0160] The so-called "about (numerical value)" in this specification is a rounded numerical value (approximate number). When the lower digit of the numerical value represented by it is not "0", it also includes a numerical range until the lower digit is rounded to the numerical value represented by it. For example, "about 3 equivalents" means more than 2.5 equivalents and less than 3.4 equivalents, and "about 0.02 equivalents" means more than 0.015 equivalents and less than 0.024 equivalents. In addition, when the lower digit of the numerical value represented by it is "0", it includes a numerical range until the lower digit is rounded to the numerical value represented by it. For example, "about 80°C" means more than 75°C and less than 84°C.

[0161] The fluorine-containing composition of the present invention is a fluorine-containing composition comprising a fluoropolyether group-containing polymer having a silanol group (a hydroxyl group bonded to a silicon atom) or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, i.e., component (A), and a fluoropolyether group-containing polymer having a silanol group (a hydroxyl group bonded to a silicon atom) or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, i.e., component (B), as a fluoropolyether group-containing polymer having a fluoropolyether group (a monovalent fluorooxyalkylene-containing polymer residue) and a reactive functional group in the molecule, wherein the molar ratio (A) / (B) of the component (A) to the component (B) is 1.2 to 4.0.

[0162] Furthermore, the difference in structure between OCF2CF2ORf of formula (1) and OCF2ORf of formula (2) can be determined by measuring 19 The results were confirmed by F-NMR.

[0163] (A) According to the following general formula (1)

[0164] [Chemistry 44]

[0165] Rf′OCF2CF2O-RF-A (1)

[0166] A fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof,

[0167] (B) According to the following general formula (2)

[0168] [Chemistry 45]

[0169] Rf′OCF2O-Rf-A (2)

[0170] A fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof

[0171] [wherein, Rf is represented by the following general formula (3)

[0172] [Chemistry 46]

[0173]

[0174] (wherein 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 independently an integer of 0 to 450, and p+q+r+s+t+u+v=10 to 450. Each of these units may be linear or branched. In addition, each repeating unit shown in the parentheses with p, q, r, s, t, u, and v may be randomly bonded.) is a divalent polymer residue containing a fluoroalkylene group,

[0175] Rf' is a fluoroalkyl group with a -CF3 group at the end,

[0176] A is represented by the following formula (4):

[0177] [Chemistry 47]

[0178]

[0179] (wherein, B is a single bond or a divalent organic group, V is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, R' is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a group having an oxyalkylene group, an alkoxy group having 1 to 4 carbon atoms, or a halogen group, U is independently a single bond or a divalent organic group, Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, and Y is independently a group which may be selected from oxygen atoms A divalent hydrocarbon group having at least one of a 1-4 carbon atom, a sulfur atom, a silicon atom and a siloxane bond, R independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, X independently represents a hydroxyl group or a hydrolyzable group, n independently represents an integer of 1 to 3 on each silicon atom to which it is bonded, m independently represents an integer of 1 to 7, β represents an integer of 1 to 6, γ represents 0 or 1, and δ represents an integer of 0 to 6. When γ represents 0, β represents 1, and when γ represents 1, the sum of β and δ represents an integer of 2 to 7.

[0180] represents a monovalent group.]

[0181] The present invention uses a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above general formula (1) and / or its partial (hydrolysis) condensate as the (A) component, and a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above general formula (2) and / or its partial (hydrolysis) condensate as the (B) component in a predetermined ratio, thereby suppressing the main chain from being decomposed by chemicals such as alkaline cleaning solutions and heat (divalent fluorooxyalkylene-containing polymer residue Rf), and thus an article surface-treated with a surface treatment agent containing a fluorine-containing composition containing the polymer and / or its partial (hydrolysis) condensate is characterized in that it is excellent in water and oil repellency, wear resistance, sliding properties, chemical resistance and heat resistance.

[0182] In the above formulae (1) and (2), Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (3).

[0183] [Chemistry 48]

[0184]

[0185] (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 independently an integer of 0 to 450, and p+q+r+s+t+u+v=10 to 450. These units may be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)

[0186] In the above formula (3), W is a fluoroalkylene group containing one or more hydrogen atoms, and examples thereof include CF2, C2F4, C3F6, C4F8, C5F 10 、C6F 12 The like; and the like; wherein one or two fluorine atoms in each perfluoroalkylene group are replaced by hydrogen atoms.

[0187] In the above formula (3), d is an integer of 1 to 6, and preferably 1 or 2.

[0188] In addition, p, q, r, s, t, u, and v are each independently an integer of 0 to 450, preferably, p is an integer of 0 to 100, q is an integer of 0 to 100, r is an integer of 0 to 100, 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, and p+q+r+s+t+u+v is 10 to 450, preferably 10 to 200, and more preferably 10 to 100. If p+q+r+s+t+u+v is less than the upper limit value, the adhesion and curing properties are good, and if it is greater than the lower limit value, the characteristics of the fluoropolyether group can be fully exerted, which is preferred.

[0189] In the above formula (3), each unit may be linear or branched. In addition, each repeating unit represented by a parenthesis with p, q, r, s, t, u, or v may be randomly bonded.

[0190] Specifically, the following groups can be exemplified as Rf. In the following structure, the left bonding end is bonded to OCF2O or OCF2CF2O, and the right bonding end is bonded to A.

[0191] [Chemistry 49]

[0192] -(CF2O) p′ CF2-

[0193] -(CF2O) p′ (CF2CF2O) q′ CF2-

[0194] -(CF2O) p′ (CF2CF2CF2CF2O) s′ CF2-

[0195] -(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2-

[0196] -(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2CF2-

[0197]

[0198] -(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2CF2O) s′ CF2-

[0199] -(CF2O)p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ CF2-

[0200] -(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ (CF2CF2CF2CF2CF2O) t′ CF2-

[0201] -(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ (CF2CF2CF2CF2CF2O) t′ (CF2CF2CF2CF2CF2CF2O) u′ CF2-

[0202] [Chemical Formula 50]

[0203]

[0204] [Chemical Formula 51]

[0205] -(CF2CF2O) q′ CF2-

[0206] -(CF2CF2CF2O) r′ CF2CF2-

[0207] -(CF2CF2O) q′ (CF2CF2CF2CF2O) s′ CF2CF2CF2-

[0208]

[0209] -CF2CFHOCH2CF2O(CF2O) p2′ (CF2CF2O) q2′ CF2-

[0210] -CF2CFHOCH2CF2CF2O(CF2CF2CF2O) r4′ CF2CF2-

[0211] -CFHCF2OCH2CF2CF2CF2O(CF2CF2O)q2′ (CF2CF2CF2CF2O) s2′ CF2CF2CF2-

[0212]

[0213] [Chemistry 52]

[0214] -(CF2CF2O) q′ (CF2CF2CF2O) r′ CF2CF2-

[0215]

[0216] (In the formula, p', q', r', s', t', u', r2', and r3' are each independently an integer greater than 1, preferably each independently an integer of 1 to 195, and more preferably each independently an integer of 2 to 100, and the total of p', q', r', s', t', u', r2', and r3' in each formula is 10 to 200. p2', q2', r4', s2', r5', and r6' are each independently Each of the above is an integer greater than 1, preferably an integer of 1 to 197, more preferably an integer of 2 to 100, and the total of p2', q2', r4', s2', r5', and r6' in each formula is 8 to 198. In addition, each repeating unit shown in the brackets with p', q', r', s', t', u', r2', r3', p2', q2', and s2' may be randomly bonded.)

[0217] In the above formulae (1) and (2), Rf' is a fluoroalkyl group having a -CF3 group at the end, preferably a -CF3 group, a -CF2CF3 group, or a -CF2CF2CF3 group.

[0218] In the above formulae (1) and (2), A is a monovalent group represented by the following formula (4). Furthermore, A in the above formulae (1) and (2) may be the same or different, but from the perspective of compatibility between component (A) and component (B), and adhesion to the substrate of the cured film formed by curing the fluorinated composition of the present invention, A is preferably the same.

[0219] [Chemistry 53]

[0220]

[0221] (wherein, B is a single bond or a divalent organic group, V is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, R' is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a group having an oxyalkylene group, an alkoxy group having 1 to 4 carbon atoms, or a halogen group, U is independently a single bond or a divalent organic group, Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, and Y is independently a group which may be selected from oxygen atoms A divalent hydrocarbon group having at least one of a 1-4 carbon atom, a sulfur atom, a silicon atom and a siloxane bond, R independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, X independently represents a hydroxyl group or a hydrolyzable group, n independently represents an integer of 1 to 3 on each silicon atom to which it is bonded, m independently represents an integer of 1 to 7, β represents an integer of 1 to 6, γ represents 0 or 1, and δ represents an integer of 0 to 6. When γ represents 0, β represents 1, and when γ represents 1, the sum of β and δ represents an integer of 2 to 7.

[0222] In the above formula (4), B is a single bond or a divalent organic group, and is a linking group connecting the Rf group to the V group (or the Z group or the Y group). The divalent organic group is preferably a divalent group selected from an alkylene group having 1 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a diorganosilylene group, a silylene structure or a silylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms, a carbonyl group, and an acylamino group, and the divalent organic group may contain at least any one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, a thioamide and an ester group.

[0223] Among them, the group bonded to the silicon atom such as the diorganosilylene group, the silylene structure, the silylene structure and the organopolysiloxane residue is preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc., or a phenyl group. In addition, the alkylene group in the silylene structure is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, a propylene group (trimethylene, methylethylene), a butylene group (tetramethylene, methylpropylene), etc.

[0224] Examples of such B include the following groups in addition to a single bond. In the following structure, the left-side bonding end is bonded to Rf, and the right-side bonding end is bonded to V (or Z or Y).

[0225] [Chemistry 54]

[0226]

[0227] [Chemistry 55]

[0228]

[0229] [Chemistry 56]

[0230]

[0231] [Chemistry 57]

[0232]

[0233] (In the formula, f is an integer of 2 to 4, a, a', and b are each an integer of 1 to 4, c is an integer of 1 to 10, and e is an integer of 1 to 9.)

[0234] In the above formula (4), V is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, preferably a carbon atom, a silicon atom, a nitrogen atom, -C(O-)=, a trivalent to hexavalent organic polysiloxane residue having 2 to 10 silicon atoms, especially 2 to 8 silicon atoms, a straight-chain or branched or cyclic trivalent to hexavalent organic group having 3 to 10 silicon atoms, especially 3 to 8 silicon atoms, a trivalent isocyanurate group, or a trivalent triazine ring-containing group. In addition, the organopolysiloxane residue may contain a silanylene structure in which two silicon atoms are bonded by an alkylene group, i.e., Si-(CH2) x -Si (in the above formula, x is an integer of 2 to 6).

[0235] The organopolysiloxane residue may have an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.

[0236] Examples of such V include the following groups. In the following structure, the left bonding end is bonded to B (or Rf), and the other bonding ends are bonded to U (or Y) or R'.

[0237] [Chemistry 58]

[0238]

[0239] [Chemistry 59]

[0240]

[0241] [Chemistry 60]

[0242]

[0243] [Chemistry 61]

[0244]

[0245] In the above formula (4), R' is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc., a phenyl group, a group having an oxyalkylene group, an alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc., or a halogen group such as fluorine, chlorine, bromine, iodine, etc., preferably a hydrogen atom, a hydroxyl group, a methyl group, or a group having an oxyalkylene group.

[0246] The group having an oxyalkylene group can be represented by -W'(-(LO) k -R”) f’ express.

[0247] Among them, W' is a single bond, an oxygen atom, X' or a divalent or trivalent group which is a combination of X' and an oxygen atom, X' is a divalent or trivalent group containing a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a nitrogen atom, a silicon atom, a siloxane bond, a silylene bond or a silylene bond, and the silicon atom preferably has an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, and may have a hydroxyl group or a hydrolyzable group. In addition, the alkylene group in the silylene bond is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, a propylene group (trimethylene, methylethylene), a butylene group (tetramethylene, methylpropylene), etc.

[0248] L is independently an alkylene group having 1 to 4 carbon atoms, such as methylene, ethylene, propylene, butylene, etc., and the carbon number may be single or mixed. k is an integer of 1 to 20, preferably an integer of 1 to 10. R" is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc., or a phenyl group, among which methyl is preferred. f' is 1 or 2.

[0249] As a group which has an oxyalkylene group, the following groups are mentioned, for example.

[0250] [Chemistry 62]

[0251]

[0252] [Chemistry 63]

[0253]

[0254] [Chemistry 64]

[0255]

[0256] (In the formula, k is the same as above.)

[0257] In the above formula (4), U is independently a single bond or a divalent organic group, and is a connecting group connecting the V group and the Z group. Therefore, when γ is 0 (i.e., there is no V group) and / or the Z group is a single bond, U is preferably a single bond. As the divalent organic group, specifically, it is preferably a group selected from an alkylene group having 1 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a diorganosilylene group, a silylene structure or a silylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the bonding end of a straight-chain organic polysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organic polysiloxane residue having 3 to 10 silicon atoms, and the divalent organic group may contain an oxygen atom or a sulfur atom.

[0258] Among them, as the group bonded to the silicon atom such as the diorganosilylene group, the silylene structure, the silarylene structure and the organopolysiloxane residue, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc., or a phenyl group is preferred. In addition, the alkylene group in the silylene structure is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, a propylene group (trimethylene, methylethylene), a butylene group (tetramethylene, methylpropylene), etc.

[0259] As such U, in addition to a single bond, for example, the following groups can be mentioned. In the following structure, the left bonding end is bonded to V, and the right bonding end is bonded to Z.

[0260] [Chemistry 66]

[0261]

[0262] [Chemistry 67]

[0263]

[0264] [Chemistry 68]

[0265]

[0266] (In the formula, f is an integer of 2 to 4, a and b are each an integer of 1 to 4, c is an integer of 1 to 10, and e is an integer of 1 to 9.)

[0267] In the above formula (4), Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, preferably a single bond, a carbon atom, a silicon atom, a nitrogen atom, -C(O-)=, a linear organopolysiloxane residue having 2 to 10 silicon atoms, especially 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, especially 3 to 8 silicon atoms, a trivalent isocyanurate group, or a trivalent triazine ring-containing group, etc. A trivalent to octavalent organic group. In addition, the organopolysiloxane residue may contain a silanylene structure in which two silicon atoms are bonded by an alkylene group, i.e., Si-(CH2) x -Si (in the above formula, x is an integer of 2 to 6).

[0268] The organopolysiloxane residue may have an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.

[0269] Examples of such Z include the following groups in addition to a single bond. In the following structure, the left bonding end is bonded to U (or B or Rf), and the other bonding ends are bonded to Y.

[0270] [Chemistry 69]

[0271]

[0272] [Chemistry 70]

[0273]

[0274] [Chemistry 71]

[0275]

[0276] [Chemistry 72]

[0277]

[0278] In the above formula (4), Y is independently a divalent hydrocarbon group having preferably 1 to 20 carbon atoms and having at least one selected from an oxygen atom, a sulfur atom, a silicon atom and a siloxane bond, and is a linking group connecting the Z group (or the V group, the B group or the Rf group) to the Si group. The divalent hydrocarbon group is specifically preferably a group selected from an alkylene group having 1 to 10 carbon atoms and containing an oxygen atom or a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other or to an arylene group via a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to a bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms.

[0279] Among them, as the group bonded to the silicon atom such as the diorganosilylene group, the silylene structure, the silarylene structure and the organopolysiloxane residue, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc., or a phenyl group is preferred. In addition, the alkylene group in the silylene structure is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, a propylene group (trimethylene, methylethylene), a butylene group (tetramethylene, methylpropylene), etc.

[0280] Examples of such Y include the following groups: In the following structure, the left-side bonding end is bonded to Z (or V, B, or Rf), and the right-side bonding end is bonded to Si.

[0281] [Chemistry 73]

[0282]

[0283] [Chemistry 74]

[0284]

[0285] [Chemistry 75]

[0286]

[0287] (In the formula, f is an integer of 2 to 4, a and b are each an integer of 1 to 4, b' and c are each an integer of 1 to 10, and e is an integer of 1 to 9.)

[0288] In the above formula (4), R is independently an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc., or a phenyl group, among which methyl is preferred.

[0289] In addition, X is independently a hydroxyl group or a hydrolyzable group, and examples of such X include hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups, alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy groups, acyloxy groups having 1 to 10 carbon atoms such as acetoxy groups, alkenyloxy groups having 2 to 10 carbon atoms such as isopropenyloxy groups, and halogen groups such as chloro, bromo, and iodo groups. Among them, methoxy, ethoxy, isopropenyloxy, and chloro groups are preferred.

[0290] In the above formula (4), β is an integer of 1 to 6, preferably 1 or 2, γ is 0 or 1, and δ is an integer of 0 to 6, preferably 0, 1 or 2. When γ is 0, β is 1, and when γ is 1, the sum of β and δ is an integer satisfying 2 to 7 (i.e., the valence of V - 1).

[0291] In addition, n is independently an integer of 1 to 3, preferably 2 or 3, and m is independently an integer of 1 to 7, preferably an integer of 1 to 4, and more preferably 1 or 3, on each silicon atom to which it is bonded.

[0292] The structure of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1) includes the following structures. By changing the combination of Rf, Rf', and A in the above formula (1) (B, V, R', U, Z, Y, R, X, β, γ, δ, m, and n in the above formula (4)), various fluoropolyether group-containing polymers having a silanol group or a hydrolyzable silyl group can be obtained.

[0293] [Chemistry 76]

[0294]

[0295] [Chemistry 77]

[0296] CF3O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0297]

[0298] [Chemistry 78]

[0299]

[0300] [Chemistry 79]

[0301]

[0302] [Chemistry 80]

[0303]

[0304] [Chemistry 81]

[0305]

[0306] [Chemistry 82]

[0307] C3F7O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0308]

[0309] C3F7O-CF2CF2O-(CF2O) p1-(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3

[0310] [Chemistry 83]

[0311]

[0312] [Chemistry 84]

[0313]

[0314] [Chemistry 85]

[0315]

[0316] [Chemistry 86]

[0317]

[0318] [Chemistry 87]

[0319] CF3O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3

[0320]

[0321] [Chemistry 88]

[0322] CF3O-CF2CF2O-(C3F6O) r1 -CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0323]

[0324] [Chemistry 89]

[0325]

[0326] [Chemistry 90]

[0327] CF3O-CF2CF2O-(C4F8O) s1 -(C2F4O) q1 -CF2CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0328]

[0329] [Chemistry 91]

[0330]

[0331] [Chemistry 92]

[0332]

[0333] [Chemistry 93]

[0334]

[0335] [Chemistry 94]

[0336]

[0337] (In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, preferably each independently an integer of 1 to 199, and more preferably each independently an integer of 2 to 100, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, preferably each independently an integer of 1 to 197, and more preferably each independently an integer of 2 to 100, but the total of p1', q1', and r1' in each formula is 9 to 199. Each repeating unit shown in the parentheses with p1, q1, r1, s1, p1', and q1' may be randomly bonded. k is an integer of 1 to 20.)

[0338] The structure of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (2) includes the following structures. By changing the combination of Rf, Rf', and A in the above formula (2) (B, V, R', U, Z, Y, R, X, β, γ, δ, m, and n in the above formula (4)), various fluoropolyether group-containing polymers having a silanol group or a hydrolyzable silyl group can be obtained.

[0339] [Chemistry 95]

[0340]

[0341] [Chemistry 96]

[0342] CF3O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0343]

[0344] [Chemistry 97]

[0345]

[0346] [Chemistry 98]

[0347]

[0348] [Chemistry 99]

[0349]

[0350] [Chemical 100]

[0351]

[0352] [Chemistry 101]

[0353] C3F7O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0354]

[0355] C3F7O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3

[0356] [Chemistry 102]

[0357]

[0358] [Chemistry 103]

[0359]

[0360] [Chemistry 104]

[0361]

[0362] [Chemistry 105]

[0363]

[0364] [Chemistry 106]

[0365] CF3O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3

[0366]

[0367] [Chemistry 107]

[0368] CF3O-CF2O-(C3F6O) r1-CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0369]

[0370] [Chemistry 108]

[0371]

[0372] [Chemistry 109]

[0373] CF3O-CF2O-(C4F8O) s1 -(C2F4O) q1 -CF2CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3

[0374]

[0375] [Chemistry 110]

[0376]

[0377] [Chemistry 111]

[0378]

[0379] [Chemistry 112]

[0380]

[0381] [Chemistry 113]

[0382]

[0383] (In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, preferably each independently an integer of 1 to 199, and more preferably each independently an integer of 2 to 100, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, preferably each independently an integer of 1 to 197, and more preferably each independently an integer of 2 to 100, but the total of p1', q1', and r1' in each formula is 9 to 199. Each repeating unit shown in the parentheses with p1, q1, r1, s1, p1', and q1' may be randomly bonded. k is an integer of 1 to 20.)

[0384] Examples of a method for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1) or (2) include the following methods.

[0385] A fluoropolyether group-containing polymer having one or more olefin sites at one end of the molecular chain is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organic silicon compound having a SiH group and a silanol group (a hydroxyl group bonded to a silicon atom) or a hydrolyzable silyl group (a silyl group bonded to a halogen atom, an alkoxy group, etc.) in the molecule such as trichlorosilane and trialkoxysilane is mixed, and the mixture is aged at 40 to 120° C., preferably 60 to 100° C., and more preferably about 80° C. for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex. Furthermore, when a halogenated (organic) silicon compound containing a SiH group such as trichlorosilane is used as an organic silicon 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 can then be converted into an alkoxy group such as a methoxy group which is another hydrolyzable group.

[0386] Among them, in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (1) and (2), as the fluoropolyether group-containing polymer having one or more olefin moieties at one molecular chain terminal used in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (1), there can be exemplified a fluoropolyether group-containing polymer having one or more olefin moieties at one molecular chain terminal represented by the following general formula (8), and as the fluoropolyether group-containing polymer having one or more olefin moieties at one molecular chain terminal used in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (2), there can be exemplified a fluoropolyether group-containing polymer having one or more olefin moieties at one molecular chain terminal represented by the following general formula (9).

[0387] [Chemistry 114]

[0388]

[0389] [In the formula, Rf, Rf', B, V, R', U, Z, β, γ, δ, and m are the same as above, and Y' is independently a single bond, or a divalent hydrocarbon group having at least one selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond.]

[0390] In the above formulae (8) and (9), Y' is independently a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms which may have at least one selected from an oxygen atom, a sulfur atom, a silicon atom and a siloxane bond. Specifically, the divalent hydrocarbon group is preferably a group selected from an alkylene group having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which an alkylene group or an arylene group is bonded to a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 to 8 carbon atoms is bonded to a bonding end of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms. Y' is preferably a linear alkylene group having 1 to 6 carbon atoms.

[0391] Examples of the fluoropolyether group-containing polymer represented by the above formula (8) and having one or more olefin moieties at one end of the molecular chain include the following polymers.

[0392] [Chemistry 115]

[0393]

[0394] [Chemistry 116]

[0395] CF3O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH=CH2

[0396]

[0397] [Chemistry 117]

[0398]

[0399] [Chemistry 118]

[0400]

[0401] [Chemistry 119]

[0402]

[0403] [Chemistry 120]

[0404]

[0405] [Chemistry 121]

[0406]

[0407] [Chemistry 122]

[0408]

[0409] [Chemistry 123]

[0410]

[0411] (In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, preferably each independently an integer of 1 to 199, and more preferably each independently an integer of 2 to 100, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, preferably each independently an integer of 1 to 197, and more preferably each independently an integer of 2 to 100, but the total of p1', q1', and r1' in each formula is 9 to 199. Each repeating unit shown in the parentheses with p1, q1, r1, s1, p1', and q1' may be randomly bonded. k is an integer of 1 to 20.)

[0412] Examples of the fluoropolyether group-containing polymer represented by the above formula (9) and having one or more olefin moieties at one end of the molecular chain include the following polymers.

[0413] [Chemistry 124]

[0414]

[0415] [Chemistry 125]

[0416] CF3O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH=CH2

[0417] [Chemistry 126]

[0418]

[0419] [Chemistry 127]

[0420]

[0421] [Chemistry 128]

[0422]

[0423] [Chemistry 129]

[0424]

[0425] [Chemistry 130]

[0426]

[0427] [Chemistry 131]

[0428]

[0429] [Chemistry 132]

[0430]

[0431] (In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, preferably each independently an integer of 1 to 199, and more preferably each independently an integer of 2 to 100, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, preferably each independently an integer of 1 to 197, and more preferably each independently an integer of 2 to 100, but the total of p1', q1', and r1' in each formula is 9 to 199. Each repeating unit shown in the parentheses with p1, q1, r1, s1, p1', and q1' may be randomly bonded. k is an integer of 1 to 20.)

[0432] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) or (2), the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule is preferably a compound represented by the following general formulas (10) to (13).

[0433] [Chemistry 133]

[0434]

[0435] (wherein, R, X, and n are the same as above. 1 are independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 2 is an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 10 carbon atoms, R 3 is a divalent hydrocarbon group having 2 to 8 carbon atoms, h is 1, j' is an integer of 1 to 8, and h+j' is an integer of 2 to 9. In formula (13), each repeating unit shown in the brackets may be randomly bonded.

[0436] Among them, R 1 is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, or an aryl group having 6 to 10 carbon atoms, such as phenyl, 1 Can be the same or different.

[0437] R 2 It is an alkylene group having 1 to 4 carbon atoms such as methylene, ethylene, propylene (trimethylene, methylethylene) or an arylene group having 6 to 10 carbon atoms such as phenylene.

[0438] In addition, as R 3 The divalent hydrocarbon group has 2 to 8 carbon atoms, preferably 2 or 3, and includes alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene, arylene groups such as phenylene, or a combination of two or more of these groups (alkylene-arylene, etc.), among which ethylene and trimethylene are preferred.

[0439] Examples of such organic silicon compounds having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule include the following compounds: trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenyloxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, or the following silane or siloxane compounds, and (partial) hydrolyzates thereof.

[0440] [Chemistry 134]

[0441]

[0442] [Chemistry 135]

[0443]

[0444] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (1) or (2), when the fluoropolyether group-containing polymer having one or more olefin moieties at one molecular chain end is reacted with the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule can be used in an amount of 1 to 4 equivalents, more preferably 1.5 to 4 equivalents, based on 1 equivalent of the olefin moieties of the fluoropolyether group-containing polymer having one or more olefin moieties at one molecular chain end.

[0445] In the preparation of the polymer containing a fluoropolyether group having a silanol group or a hydrolyzable silyl group represented by formula (1) or (2), as a solvent, for example, a fluorine-based solvent can be cited. As the fluorine-based solvent, hydrofluoroether (HFE)-based solvents such as 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 (manufactured by 3M, trade name: Novec series), and perfluoro-based solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series) can be cited.

[0446] The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably 50 to 100 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer having one or more olefin moieties at one end of the molecular chain.

[0447] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) or (2), the following catalysts can be cited as the catalyst for the hydrosilylation reaction. Examples thereof include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes, acetylenic alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and tris(triphenylphosphine)rhodium chloride. Platinum compounds such as vinyl siloxane coordination compounds are preferred.

[0448] The amount of the hydrosilylation reaction catalyst used is 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal (mass) relative to the mass of the fluoropolyether group-containing polymer having one or more olefin moieties at one molecular chain end.

[0449] Furthermore, when a halogenated (organic) silicon compound containing a SiH group such as trichlorosilane is used as an organic silicon 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 can be converted into an alkoxy group such as a methoxy group as another hydrolyzable group. As reagents that can be used when converting the substituent (halogen atom) on the silyl group into another hydrolyzable group, for example, alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol can be listed.

[0450] The amount used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and further preferably about 65 parts by mass, based on 100 parts by mass of the addition reaction product of a fluoropolyether group-containing polymer having one or more olefin sites at one end of the molecular chain and a SiH group-containing halogenated (organic) silicon compound.

[0451] For example, using the following formula

[0452] [Chemistry 136]

[0453]

[0454] (In the formula, p1, q1, and the total of p1 and q1 are the same as above. In addition, each repeating unit shown in the parentheses with p1 and q1 may be randomly bonded.)

[0455] When a fluoropolyether group-containing polymer having one or more olefin sites at one end of the molecular chain represented by formula (8) is used and trimethoxysilane is used as an organic silicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, a compound represented by the following formula is obtained.

[0456] [Chemistry 137]

[0457]

[0458] (In the formula, p1, q1, and the total of p1 and q1 are the same as above. In addition, each repeating unit shown in the parentheses with p1 and q1 may be randomly bonded.)

[0459] For example, using the following formula

[0460] [Chemistry 138]

[0461]

[0462] (In the formula, p1, q1, and the total of p1 and q1 are the same as above. In addition, each repeating unit shown in the parentheses with p1 and q1 may be randomly bonded.)

[0463] When a fluoropolyether group-containing polymer having one or more olefin sites at one end of the molecular chain represented by formula (9) is used, and trimethoxysilane is used as an organic silicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, a compound represented by the following formula is obtained.

[0464] [Chemistry 139]

[0465]

[0466] (In the formula, p1, q1, and the total of p1 and q1 are the same as above. In addition, each repeating unit shown in the parentheses with p1 and q1 may be randomly bonded.)

[0467] As another method for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1) or (2), for example, the following method can be mentioned.

[0468] A fluoropolyether group-containing polymer having one or more SiH groups at one end of the molecular chain, for example, a fluoropolyether group-containing polymer having three SiH groups at one end of the molecular chain and an organosilicon compound having an olefin moiety and a silanol group or a hydrolyzable silyl group in the molecule are used as raw materials, dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and aged at 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex. Two different organosilicon compounds having an olefin moiety and a silanol group or a hydrolyzable silyl group in the molecule may be used. In this case, compounds having different Y moieties in formula (1) may be produced by stepwise addition.

[0469] Among them, in another method for preparing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) or (2), as a fluoropolyether group-containing polymer having one or more SiH groups at one end of the molecular chain used in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), for example, the following polymers can be listed.

[0470] [Chemistry 140]

[0471]

[0472] [Chemistry 141]

[0473]

[0474] (In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, preferably each independently an integer of 1 to 199, and more preferably each independently an integer of 2 to 100, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, preferably each independently an integer of 1 to 197, and more preferably each independently an integer of 2 to 100, but the total of p1', q1', and r1' in each formula is 9 to 199. The repeating units shown in the parentheses with p1, q1, r1, s1, p1', and q1' may be randomly bonded.)

[0475] In another method for preparing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) or (2), the fluoropolyether group-containing polymer having one or more SiH groups at one end of the molecular chain used in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (2) includes, for example, the following polymers.

[0476] [Chemistry 142]

[0477]

[0478] [Chemistry 143]

[0479]

[0480] (In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, preferably each independently an integer of 1 to 199, and more preferably each independently an integer of 2 to 100, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, preferably each independently an integer of 1 to 197, and more preferably each independently an integer of 2 to 100, but the total of p1', q1', and r1' in each formula is 9 to 199. The repeating units shown in the parentheses with p1, q1, r1, s1, p1', and q1' may be randomly bonded.)

[0481] In another method for preparing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) or (2), the organic silicon compound having an olefin portion and a silanol group or a hydrolyzable silyl group in the molecule to be reacted with the fluoropolyether group-containing polymer having one or more SiH groups at one end of the molecular chain is preferably a compound represented by the following general formula (14).

[0482] [Chemistry 144]

[0483]

[0484] (In the formula, R, X, and n are the same as above. Y" is a single bond, or a divalent hydrocarbon group which may have at least one selected from an oxygen atom, a sulfur atom, a silicon atom, and a siloxane bond.)

[0485] In the above formula (14), Y" is a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms which may have at least one selected from an oxygen atom, a sulfur atom, a silicon atom and a siloxane bond. Specifically, the divalent hydrocarbon group is preferably a group selected from an alkylene group having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, an alkylene group bonded to a diorganosilylene group, a silylene structure or a silylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms. Y" is preferably a single bond or a linear alkylene group having 1 to 6 carbon atoms.

[0486] Examples of such organosilicon compounds having an olefin moiety and a silanol group or a hydrolyzable silyl group in the molecule include the following compounds: vinyl trimethoxysilane, allyl trimethoxysilane, hexenyl trimethoxysilane, octenyl trimethoxysilane, vinyl triethoxysilane, allyl triethoxysilane, hexenyl triethoxysilane, octenyl triethoxysilane, vinyl triisopropoxysilane, allyl triisopropoxysilane, vinyl tributoxysilane, allyl tributoxysilane, vinyl triacetoxysilane, allyl triacetoxysilane, vinyl trichlorosilane, vinyl tribromosilane, vinyl triiodosilane, the following silane or siloxane compounds, and (partial) hydrolyzates thereof.

[0487] [Chemistry 145]

[0488]

[0489] The organic silicon compound having an olefin portion and a silanol group or a hydrolyzable silyl group in the molecule can be used in an amount of 1 to 4 equivalents, more preferably 1.5 to 2.5 equivalents, and even more preferably about 2 equivalents, relative to 1 equivalent of SiH groups in the fluoropolyether group-containing polymer having one or more SiH groups at one end of the molecular chain.

[0490] As the hydrosilylation reaction catalyst used in the other method for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (1) or (2), there can be exemplified the same hydrosilylation reaction catalyst as exemplified in the above-mentioned production method, and the amount thereof blended is 0.1 to 100 ppm, more preferably 0.3 to 50 ppm, in terms of transition metal (mass), relative to the mass of the fluoropolyether group-containing polymer having one or more SiH groups at one end of the molecular chain.

[0491] As the solvent used in the other method of the method for producing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (1) or (2), the same solvents as those exemplified in the above-mentioned production method can be exemplified, and the blending amount thereof can be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, relative to 100 parts by mass of the fluoropolyether group-containing polymer having one or more SiH groups at one end of the molecular chain.

[0492] The fluorine-containing composition of the present invention comprises the above-mentioned silanol group or hydrolyzable silyl group-containing polymer and / or its partial (hydrolysis) condensate represented by the formula (1), i.e., component (A), and the above-mentioned silanol group or hydrolyzable silyl group-containing polymer and / or its partial (hydrolysis) condensate represented by the formula (2), i.e., component (B).

[0493] Here, the "partial (hydrolysis) condensate" is a product obtained by partially condensing the hydroxyl groups of the fluoropolyether group-containing polymer having a silanol group represented by the general formula (1) or (2), or the hydroxyl groups of the fluoropolyether group-containing polymer having a hydrolyzable silyl group represented by the general formula (1) or (2) which have been partially hydrolyzed in advance by a known method.

[0494] In the fluorine-containing composition of the present invention, the molar ratio (A) / (B) of the component (A) to the component (B) is 1.2 to 4.0, preferably 1.2 to 3.2, and more preferably 1.2 to 2.5. If (A) / (B) is less than 1.2, the chemical resistance and heat resistance of the cured film formed by curing the fluorine-containing composition of the present invention are reduced, and the durability of each is not taken into account. If (A) / (B) exceeds 4.0, the sliding property of the cured film is reduced. However, in the case of containing the component (C) described later, sometimes even if (A) / (B) exceeds 4.0, the sliding property is maintained, but the chemical resistance and heat resistance are reduced, and the durability of each is not taken into account.

[0495] The fluorine-containing composition of the present invention may further contain, as the component (C), a fluoropolyether group-containing polymer represented by the following general formula (5).

[0496] [Chemistry 146]

[0497] A′-Rf 1 -A′ (5)

[0498] [Wherein, Rf 1 is a divalent fluorooxyalkylene-containing polymer residue represented by the following formula (7),

[0499] [Chemistry 147]

[0500]

[0501] (W is the same as above. d is the same as above independently in each unit, p, q, r, s, t, u, v, p+q+r+s+t+u+v are the same as above, and each of these units may be linear or branched. In addition, each repeating unit shown in the parentheses with p, q, r, s, t, u, v may be randomly bonded.)

[0502] A' is a fluorine atom.]

[0503] In the above formula (5), Rf 1 It is a divalent fluorooxyalkylene group-containing polymer residue represented by formula (7).

[0504] In the above formula (7), W, d, p, q, r, s, t, u, v, p+q+r+s+t+u+v are the same as those described above, and each of these units may be linear or branched. In addition, each repeating unit shown in the brackets with p, q, r, s, t, u, v may be randomly bonded.

[0505] As Rf 1 Specifically, the following groups can be exemplified.

[0506] [Chemistry 148]

[0507] -CF2O(CF2O) p CF2-

[0508] -CF2O(CF2O) p′ (CF2CF2O) q′ CF2-

[0509] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ CF2-

[0510] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2CF2O) s′ CF2-

[0511] -CF2O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ CF2-

[0512] -CF2O(CF2O)p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ (CF2CF2CF2CF2O) s′ (CF2CF2CF2CF2CF2O) t′ (CF2CF2CF2CF2CF2CF2O) u′ CF2-

[0513] -CF2CF2O(CF2CF2CF2O) r′ CF2CF2-

[0514]

[0515] [Chemistry 149]

[0516]

[0517] -C2F4O(CF2O) p′ (CF2CF2O) q′ C2F4-

[0518] -C2F4O(CF2O) p′ (CF2CF2O) q′ (CF2CF2CF2O) r′ C2F4-

[0519] (In the formula, p', q', r', s', t', and u' are each independently an integer greater than 1, preferably each independently an integer of 1 to 195, more preferably each independently an integer of 2 to 100, and the total of p', q', r', s', t', and u' in each formula is 10 to 200. R7' and R8' are each independently an integer greater than 1, preferably each independently an integer of 1 to 199, more preferably each independently an integer of 2 to 100, and the total of R7' and R8' is 9 to 199. In addition, each repeating unit shown in the parentheses with p', q', r', s', t', and u' may be randomly bonded.)

[0520] Examples of the fluoropolyether group-containing polymer represented by formula (5) include the following polymers.

[0521] [Chemistry 150]

[0522] CF3O-(CF2O) p1 -(C2F4O) q1 -CF3

[0523] (In the formula, p1, q1, and the total of p1 and q1 are the same as above. In addition, each repeating unit shown in the parentheses with p1 and q1 may be randomly bonded.)

[0524] When the component (C) is mixed, its content is preferably 0.1 to 500 parts by mass, more preferably 1 to 100 parts by mass, and further preferably 5 to 50 parts by mass relative to 100 parts by mass of the total of the components (A) and (B). If it exceeds 500 parts by mass, the durability (wear resistance) of the cured film formed by curing the fluorine-containing composition of the present invention may be reduced.

[0525] The fluorine-containing composition of the present invention may further contain, as the component (D), a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (6) and / or a partial (hydrolysis) condensate thereof.

[0526] [Chemistry 151]

[0527] A-R 1 -A (6)

[0528] (Where Rf 1 , A is the same as above.)

[0529] In the above formula (6), Rf 1 The polymer residue containing a divalent fluorooxyalkylene group represented by the above formula (7) can be exemplified by the following: 1 The same groups as exemplified in .

[0530] A is a monovalent group represented by the above formula (4), and examples thereof include the same groups as those exemplified for A in the above formulas (1) and (2). The A at both ends may be the same or different, and may be the same or different from A in the formulas (1) and (2).

[0531] Examples of the fluoropolyether group-containing polymer represented by formula (6) include the following polymers.

[0532] [Chemistry 152]

[0533]

[0534] [Chemistry 153]

[0535]

[0536] [Chemistry 154]

[0537]

[0538] (In the formula, p1, q1, and the total of p1 and q1 are the same as above. In addition, each repeating unit shown in the parentheses with p1 and q1 may be randomly bonded.)

[0539] When the component (D) is mixed, its content is preferably 0.1 to 500 parts by mass, more preferably 1 to 100 parts by mass, and further preferably 5 to 50 parts by mass, relative to 100 parts by mass of the total of the components (A) and (B). If it exceeds 500 parts by mass, the sliding property of the surface of the cured film formed by curing the fluorine-containing composition of the present invention may be reduced.

[0540] The fluorine-containing composition of the present invention may further contain unreacted raw materials and reaction intermediates obtained during the synthesis of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1) or (2).

[0541] The fluorine-containing composition of the present invention can be obtained by uniformly mixing the above-mentioned components (A) and (B), the components (C) and (D) used as necessary, and the above-mentioned other components by a conventional method.

[0542] Among them, the total amount of components (A) and (B) in the fluorine-containing composition (i.e., the content of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the general formula (1) or (2) and / or its partial (hydrolysis) condensate) is preferably 50 to 100 mass %, more preferably 60 to 100 mass %, and even more preferably 80 to 100 mass %.

[0543] The present invention also provides a surface treating agent comprising the above-mentioned fluorine-containing composition.

[0544] In the surface treatment agent, a hydrolysis condensation catalyst may be added as needed, such as an organic tin compound (dimethoxydibutyltin, dibutyltin dilaurate, etc.), an organic titanium compound (tetra-n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), and an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly preferred.

[0545] The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, based on 100 parts by mass of the fluorine-containing composition (particularly the total of the above components (A), (B) and (D)).

[0546] The surface treatment agent may contain an appropriate solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, tridecafluorooctane, 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, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferred 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.

[0547] The above solvents may be mixed with two or more thereof, preferably to uniformly dissolve the fluorine-containing composition. The optimum concentration of the fluorine-containing composition dissolved in the solvent varies depending on the treatment method, and any amount that can be easily weighed may be used. In the case of direct coating, the fluorine-containing composition (especially the total of the above-mentioned (A) to (D) components) is preferably 0.01 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total of the solvent and the fluorine-containing composition (especially the total of the solvent and the above-mentioned (A) to (D) components). In the case of vapor deposition treatment, the fluorine-containing composition (especially the total of the above-mentioned (A) to (D) components) is preferably 0.01 to 40 parts by mass, and particularly preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the total of the solvent and the fluorine-containing composition (especially the total of the solvent and the above-mentioned (A) to (D) components).

[0548] The surface treatment agent of the present invention can be applied to the substrate by known methods such as brush coating, dipping, spraying, and evaporation treatment. The heating method during the evaporation treatment may be a resistance heating method or an electron beam heating method, and is not particularly limited. In addition, the curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferably carried out at 25 to 200°C, especially at 25 to 150°C for 30 minutes to 36 hours, especially 1 to 24 hours. In addition, in the case of applying by evaporation treatment, it is preferably carried out in the range of 20 to 200°C for 1 to 24 hours. In addition, it can be cured under humidification. The film thickness of the cured film is appropriately selected according to the type of substrate, usually 0.1 to 100nm, especially 1 to 20nm. In addition, the film thickness can be measured by means such as spectral reflectivity measurement, X-ray reflectivity measurement, spectroscopic ellipsometry measurement, fluorescent X-ray measurement, etc. In addition, for example, in the case of spray coating, if the material is diluted in a fluorine-based solvent to which water has been added in advance and hydrolyzed, that is, Si-OH is generated before spray coating, curing after coating is rapid.

[0549] There is no particular restriction on the substrate treated with the surface treatment agent of the present invention, and the substrate can be a substrate of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc. The surface treatment agent of the present invention can impart water and oil repellency to the above-mentioned substrate. In particular, it can be suitable for use as a surface treatment agent for SiO2 treated glass (SiO2 treated glass), tempered glass, lens substrate, and quartz substrate film.

[0550] As articles treated with the surface treatment agent of the present invention, medical instruments such as car navigation, mobile phones, smart phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch screen displays, protective films, anti-reflection films and other optical articles can be listed. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the articles, and can further impart scratch resistance, so it can be particularly used as a water-repellent and oil-repellent layer of a touch panel display, an anti-reflection film, etc.

[0551] In addition, the surface treatment agent of the present invention can also be used as an antifouling paint for sanitary products such as bathtubs and washstands, an antifouling paint for window glass or tempered glass of automobiles, trains, aircraft, etc., an antifouling paint for headlight covers, etc., a water-repellent and oil-repellent paint for exterior building materials, an anti-oil paint for kitchen building materials, an antifouling and anti-sticker / anti-graffiti paint for telephone boxes, a paint that imparts fingerprint adhesion prevention properties to artworks, etc., a fingerprint adhesion prevention paint for CDs, DVDs, etc., a mold release agent or paint additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, and a lubricity enhancer for tapes, films, etc.

[0552] Example

[0553] The present invention is described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. 19 The number average value calculated by F-NMR. In the following formula, each repeating unit shown in the brackets with p1 and q1, p1' and q1' is randomly bonded. In the following examples, wt% represents mass%. Furthermore, the film thickness is a value measured by spectroscopic ellipsometry using a spectroscopic ellipsometry instrument.

[0554] As the component (A), the following compounds were used.

[0555] [Chemistry 155]

[0556]

[0557] [Chemistry 156]

[0558]

[0559] [Chemistry 157]

[0560]

[0561] [Chemistry 158]

[0562]

[0563] [Chemistry 159]

[0564]

[0565] [Chemistry 160]

[0566]

[0567] [Chemistry 161]

[0568]

[0569] [Chemistry 162]

[0570]

[0571] [Chemistry 163]

[0572]

[0573] [Chemistry 164]

[0574]

[0575] [Chemistry 165]

[0576]

[0577] [Chemistry 166]

[0578]

[0579] [Chemistry 167]

[0580]

[0581] [Chemistry 168]

[0582]

[0583] [Chemistry 169]

[0584]

[0585] [Chemistry 170]

[0586]

[0587] [Chemistry 171]

[0588]

[0589] [Chemistry 172]

[0590]

[0591] [Chemistry 173]

[0592]

[0593] As the component (B), the following compounds were used.

[0594] [Chemistry 174]

[0595]

[0596] [Chemistry 175]

[0597]

[0598] [Chemistry 176]

[0599]

[0600] [Chemistry 177]

[0601]

[0602] [Chemistry 178]

[0603]

[0604] [Chemistry 179]

[0605]

[0606] [Chemistry 180]

[0607]

[0608] [Chemistry 181]

[0609]

[0610] [Chemistry 182]

[0611]

[0612] [Chemistry 183]

[0613]

[0614] [Chemistry 184]

[0615]

[0616] [Chemistry 185]

[0617]

[0618] [Chemistry 186]

[0619]

[0620] [Chemistry 187]

[0621]

[0622] [Chemistry 188]

[0623]

[0624] [Chemistry 189]

[0625]

[0626] [Chemistry 190]

[0627]

[0628] [Chemistry 191]

[0629]

[0630] [Chemistry 192]

[0631]

[0632] As the component (C), the following compounds were used.

[0633] [Chemistry 193]

[0634]

[0635] [Chemistry 194]

[0636]

[0637] As the component (D), the following compounds were used.

[0638] [Chemistry 195]

[0639]

[0640] [Chemistry 196]

[0641]

[0642] [Chemistry 197]

[0643]

[0644] For dilution, the following solvents were used.

[0645] Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether),

[0646] Novec 7300 (manufactured by 3M, methyl perfluorohexyl ether),

[0647] ASAHIKLIN AC-6000 (made by AGC, tridecafluorooctane),

[0648] ASAHIKLIN AE-3000 (manufactured by AGC Corporation, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether),

[0649] Opteon SF10 (manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd., methyl perfluoroheptenyl ether)

[0650] [Examples 1 to 7, Comparative Examples 1 to 7]

[0651] The mixture (fluorinated composition) of the above-mentioned components (A) to (D) was diluted with a diluting solvent so as to be 20 wt% (mass%) in terms of solid content (i.e., the total mass of the components (A) to (D)), thereby preparing a surface treatment agent. The mixture (fluorinated composition) of the above-mentioned components (A) to (D) was prepared in the composition ratio shown in Table 1 (wherein the mixing ratio of the component (A) to the component (B) is a molar ratio).

[0652] [Table 1]

[0653]

[0654] [Examples 8 to 14, Comparative Examples 8 to 12]

[0655] The mixture (fluorinated composition) of the above-mentioned components (A) to (D) was diluted with a diluting solvent so as to be 0.1 wt% (mass%) in terms of solid content (i.e., the total mass of the components (A) to (D)), thereby preparing a surface treatment agent. The mixture (fluorinated composition) of the above-mentioned components (A) to (D) was prepared in the composition ratio shown in Table 2 (wherein the mixing ratio of the component (A) to the component (B) is a molar ratio).

[0656] [Table 2]

[0657]

[0658] [Examples 15 to 20, Comparative Examples 13 to 17]

[0659] The mixture (fluorinated composition) of the above-mentioned components (A) to (D) was diluted with a diluting solvent so as to be 20 wt% (mass%) in terms of solid content (i.e., the total mass of the components (A) to (D)), thereby preparing a surface treatment agent. The mixture (fluorinated composition) of the above-mentioned components (A) to (D) was prepared in the composition ratio shown in Table 3 (wherein the mixing ratio of the component (A) to the component (B) is a molar ratio).

[0660] [Table 3]

[0661]

[0662] [Examples 21 to 39, Comparative Examples 18 to 22]

[0663] The mixture (fluorine-containing composition) of the above-mentioned components (A) and (B) was diluted with a diluting solvent so as to be 20 wt% (mass%) in terms of solid content (i.e., the total mass of the components (A) and (B)) to prepare a surface treatment agent. The mixture (fluorine-containing composition) of the above-mentioned components (A) and (B) was prepared at the composition ratio (molar ratio) shown in Table 4.

[0664] [Table 4]

[0665] Solvents (A) (B) (A) / (B) molar ratio Embodiment 21 AE3000 A-2 B-2 2.0 Embodiment 22 Novec7200 A-3 B-3 2.1 Embodiment 23 Novec7300 A-4 B-4 1.8 Embodiment 24 AE3000 A-6 B-6 2.0 Embodiment 25 Novec7200 A-7 B-7 1.9 Embodiment 26 Opteon SF10 A-8 B-8 2.0 Embodiment 27 Novec7300 A-9 B-9 2.2 Embodiment 28 Novec7200 A-11 B-11 1.5 Embodiment 29 Opteon SF10 A-12 B-12 2.0 Embodiment 30 AE3000 A-13 B-13 2.1 Embodiment 31 Novec7200 A-14 B-14 2.7 Embodiment 32 Novec7200 A-15 B-15 1.9 Embodiment 33 Opteon SF10 A-16 B-16 3.0 Embodiment 34 Novec7200 A-17 B-17 3.5 Embodiment 35 Novec7300 A-18 B-18 2.0 Embodiment 36 Novec7200 A-19 B-19 1.9 Embodiment 37 Novec7200 A-1 B-11 2.6 Embodiment 38 Novec7200 A-3 B-14 1.6 Embodiment 39 Novec7300 A-9 B-16 2.1 Comparative Example 18 AE3000 A-2 B-2 1.1 Comparative Example 19 Novec7200 A-7 B-7 1.0 Comparative Example 20 Novec7300 A-9 B-9 1.1 Comparative Example 21 Novec7200 A-14 B-14 4.2 Comparative Example 22 AE3000 A-1 B-11 1.1

[0666] Curing film of form

[0667] The surface treatment agents prepared in Examples 1 to 39 and Comparative Examples 1 to 22 were used to produce cured films. Each surface treatment agent was vacuum deposited on glass (Gorilla manufactured by Corning Incorporated) that had been coated with SiO2 to a thickness of 10 nm on the outermost surface (treatment conditions were pressure: 2.0×10 -2 Pa, heating temperature: 700° C.), and cured for 12 hours in an atmosphere of 25° C. and a relative humidity of 50% to form a cured film with a film thickness of 10 nm.

[0668] Evaluation of water and oil repellency

[0669] [Evaluation of initial water and oil repellency]

[0670] The contact angles (water and oil repellency) of the cured film formed on the glass prepared above to pure water (droplet: 2 μl) and oleic acid (droplet: 7 μl) were measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (temperature: 25°C, relative humidity: 40%). The results are shown in Tables 5 to 8.

[0671] In the initial stage, both Examples and Comparative Examples showed good water repellency.

[0672] [Evaluation criteria for water and oil repellency]

[0673] Water contact angle 110° or more and oleic acid contact angle 70° or more: A

[0674] Water contact angle less than 110° or oleic acid contact angle less than 70°: B

[0675] Evaluation of sliding properties

[0676] The dynamic friction coefficient of the glass having the cured film formed thereon was measured under the following conditions to evaluate the sliding property. The test environment conditions were 25° C. and a relative humidity of 40%. The results are shown in Tables 5 to 8.

[0677] [Determination of dynamic friction coefficient]

[0678] Friction material: BEMCOT

[0679] Contact area: 3cm 2

[0680] Moving distance (one way): 10mm

[0681] Moving speed: 500mm / min

[0682] Load: 100gf / 3cm 2

[0683] Number of tests: 5 (calculate the average value of 5 glasses)

[0684] Average value 0.02~0.03:A

[0685] Average value greater than 0.03: B

[0686] Evaluation of wear resistance

[0687] The glass having the cured coating formed thereon was tested for abrasion resistance by measuring the contact angle (water repellency) of the cured coating after rubbing under the following conditions in the same manner as above using a friction tester (manufactured by Shinto Scientific Co., Ltd.). The test environment conditions were 25°C and the relative humidity was 40%. The results are shown in Tables 5 to 8.

[0688] [Steel wool wear conditions]

[0689] Steel wool: Bonster#0000

[0690] Contact area: 1cm 2

[0691] Moving distance (one way): 40mm

[0692] Moving speed: 4800mm / min

[0693] Load: 1kgf / 6mmφ

[0694] Wear times: 3000 times

[0695] [Abrasion resistance evaluation criteria]

[0696] Water contact angle after 3000 wear times

[0697] Above 110°: A

[0698] Less than 110°: B

[0699] Evaluation of chemical resistance

[0700] The glass having the cured coating formed thereon was immersed in an alkaline solution under the following conditions and then subjected to a steel wool abrasion test under the conditions described in the above [Steel wool abrasion conditions]. The test environment conditions were 25° C. and a relative humidity of 40%. The results are shown in Tables 5 to 8.

[0701] [Chemical immersion conditions]

[0702] Alkali: Sodium hydroxide

[0703] Concentration: 0.4wt%

[0704] Temperature: 55℃

[0705] Time: 4 hours

[0706] [Chemical resistance evaluation criteria]

[0707] Water contact angle after 3000 wear times

[0708] Above 110°: A

[0709] Less than 110°: B

[0710] Evaluation of heat resistance

[0711] The glass having the cured coating formed thereon was heated under the following conditions and then subjected to a steel wool abrasion test under the conditions described in the above [Steel wool abrasion conditions]. The test environment conditions were 25° C. and a relative humidity of 40%. The results (water contact angle after abrasion) are shown in Tables 5 to 8.

[0712] [Heating conditions]

[0713] Temperature: 200℃

[0714] Time: 30 minutes

[0715] [Heat resistance evaluation criteria]

[0716] Water contact angle after 3000 wear times

[0717] Above 110°: A

[0718] Less than 110°: B

[0719] The surface treatment agents of Examples 1 to 39 and Comparative Examples 1, 3, 5, 7, 8, 10, 12, 13, 15, 17, 18 to 20 and 22 were excellent in water and oil repellency, sliding properties and initial wear durability. On the other hand, Comparative Examples 2, 9, 14 to 17 and 21, in which the molar ratio of (A) / (B) was greater than 4.0, and Comparative Examples 6 and 11, in which only the component (A) was present, exhibited water and oil repellency and initial wear durability, but were inferior in at least one of sliding properties, chemical resistance and heat resistance. In addition, in Comparative Examples 1, 3 to 5, 8, 10, 13, 18 to 20, 22, and Comparative Examples 7 and 12, in which the molar ratio of (A) / (B) is less than 1.2, and only the component (B) is contained, as described above, Comparative Examples 1, 3, 5, 7, 8, 10, 12, 13, 18 to 20, 22 are excellent in water and oil repellency, sliding properties, and initial wear durability, but chemical resistance and heat resistance are not achieved at the same time, and Comparative Example 4 is inferior in sliding properties and chemical resistance. In contrast, Examples 1 to 39 are excellent in water and oil repellency, sliding properties, and initial wear durability, and chemical resistance and heat resistance are achieved at the same time.

[0720] [Table 5]

[0721] Water and oil repellency Sliding Wear resistance Chemical resistance Heat resistance Example 1 A A A A A Example 2 A A A A A Example 3 A A A A A Example 4 A A A A A Example 5 A A A A A Example 6 A A A A A Example 7 A A A A A Comparative Example 1 A A A A B Comparative Example 2 A B A A A Comparative Example 3 A A A B B Comparative Example 4 A B A B A Comparative Example 5 A A A B B Comparative Example 6 A B A A A Comparative Example 7 A A A B B

[0722] [Table 6]

[0723] Water and oil repellency Sliding Wear resistance Chemical resistance Heat resistance Example 8 A A A A A Example 9 A A A A A Example 10 A A A A A Embodiment 11 A A A A A Example 12 A A A A A Embodiment 13 A A A A A Embodiment 14 A A A A A Comparative Example 8 A A A A B Comparative Example 9 A B A A A Comparative Example 10 A A A B B Comparative Example 11 A B A A A Comparative Example 12 A A A B B

[0724] [Table 7]

[0725] Water and oil repellency Sliding Wear resistance Chemical resistance Heat resistance Embodiment 15 A A A A A Example 16 A A A A A Embodiment 17 A A A A A Embodiment 18 A A A A A Embodiment 19 A A A A A Embodiment 20 A A A A A Comparative Example 13 A A A A B Comparative Example 14 A B A A A Comparative Example 15 A A A A B Comparative Example 16 A B A B A Comparative Example 17 A A A B B

[0726] [Table 8]

[0727] Water and oil repellency Sliding Wear resistance Chemical resistance Heat resistance Embodiment 21 A A A A A Embodiment 22 A A A A A Embodiment 23 A A A A A Embodiment 24 A A A A A Embodiment 25 A A A A A Embodiment 26 A A A A A Embodiment 27 A A A A A Embodiment 28 A A A A A Embodiment 29 A A A A A Embodiment 30 A A A A A Embodiment 31 A A A A A Embodiment 32 A A A A A Embodiment 33 A A A A A Embodiment 34 A A A A A Embodiment 35 A A A A A Embodiment 36 A A A A A Embodiment 37 A A A A A Embodiment 38 A A A A A Embodiment 39 A A A A A Comparative Example 18 A A A B B Comparative Example 19 A A A B B Comparative Example 20 A A A B B Comparative Example 21 A B A A A Comparative Example 22 A A A B B

Claims

1. A fluorine-containing composition comprising the following components (A) and (B), wherein the molar ratio (A) / (B) of the components (A) to (B) is 1.2 to 4.0, (A) a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (1) and / or a partial (hydrolyzed) condensate thereof (B) a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (2) and / or a partial (hydrolyzed) condensate thereof [Chemistry 1] Rf'OCF2CF2O-Rf-A (1) Rf'OCF2O-Rf-A (2) In the formula, Rf is a divalent fluorooxyalkylene-containing polymer residue represented by the following general formula (3): [Chemistry 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 independently an integer of 0 to 450, and p+q+r+s+t+u+v=10 to 450. These units may be linear or branched. In addition, the repeating units shown in the parentheses with p, q, r, s, t, u, and v may be randomly bonded. Rf' is a fluoroalkyl group with a -CF3 group at the end, A is a monovalent group represented by the following formula (4), [Chemistry 3] In the formula, B is a single bond or a divalent organic group, V is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, R' is independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a group having an oxyalkylene group, an alkoxy group having 1 to 4 carbon atoms, or a halogen group, U is independently a single bond or a divalent organic group, Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, or a trivalent to octavalent organic group, and Y is independently a group which may have an oxygen atom selected from wherein the present invention is a divalent hydrocarbon group having at least one of a 1-4 carbon atom, a sulfur atom, a silicon atom and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 on each silicon atom to which it is bonded, m is independently an integer of 1 to 7, β is an integer of 1 to 6, γ is 0 or 1, and δ is an integer of 0 to 6, when γ is 0, β is 1, and when γ is 1, the total of β and δ is an integer of 2 to 7.

2. The fluorine-containing composition according to claim 1, further comprising the following component (C) and / or component (D), (C) A fluoropolyether group-containing polymer represented by the following general formula (5) (D) a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (6) and / or a partial (hydrolyzed) condensate thereof [Chemistry 4] A'-Rf 1 -A' (5) A-Rf 1 -A (6) In the formula, Rf 1 is a divalent fluorooxyalkylene-containing polymer residue represented by the following formula (7), [Chemistry 5] In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is independently an integer of 1 to 6 in each unit, p, q, r, s, t, u, and v are each independently an integer of 0 to 450, and p+q+r+s+t+u+v=10 to 450. These units may be linear or branched. In addition, the repeating units shown in the parentheses with p, q, r, s, t, u, and v may be randomly bonded. A' is a fluorine atom, A is independently the same as above.

3. The fluorine-containing composition according to claim 1, wherein In the formulas (1) and (2), B in the formula (4) is a single bond, a divalent group selected from an alkylene group having 1 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, an alkylene group bonded to each other via a diorganosilylene group, a silylene structure or a silylene structure, a divalent group having an alkylene group having 1 to 10 carbon atoms bonded to the bonding end of a straight-chain or branched or cyclic organic polysiloxane residue having 2 to 10 silicon atoms, and a carbonyl group and an acylamino group which may contain at least any one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, a thioamide and an ester group.

4. The fluorine-containing composition according to claim 1, wherein In the formulas (1) and (2), γ in the formula (4) is 1, and V in the formula (4) is any one selected from a carbon atom, a silicon atom, a nitrogen atom, -C(O-)=, a linear 3-6-valent organic polysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic 3-10 silicon atoms, a trivalent isocyanurate group, and a trivalent group containing a triazine ring.

5. The fluorine-containing composition according to claim 1, wherein In the formulae (1) and (2), Y in the formula (4) is a group selected from an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom or a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other or to an arylene group via a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms.

6. The fluorine-containing composition according to claim 1, wherein In the formulae (1) and (2), U in the formula (4) is any one selected from a single bond, an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom and a sulfur atom, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a diorganosilylene group, a silylene structure or a silylene structure, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms.

7. The fluorine-containing composition according to claim 1, wherein In the formulas (1) and (2), Z in the formula (4) is any one selected from a single bond, a carbon atom, a silicon atom, a nitrogen atom, -C(O-)=, a linear trivalent to hexavalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent to hexavalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent isocyanurate group, and a trivalent group containing a triazine ring.

8. The fluorine-containing composition according to claim 1, wherein In the above formulae (1) and (2), X in formula (4) is a group selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.

9. The fluorine-containing composition according to claim 1, wherein In the above formulae (1) and (2), A is the same.

10. The fluorine-containing composition according to claim 1, wherein The fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (1) is at least one selected from polymers represented by the following formulas: [Chemistry 6] [Chemistry 7] CF3O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3 [Chemistry 8] [Chemistry 9] [Chemistry 10] [Chemistry 11] [Chemistry 12] C3F7O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3 C3F7O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3 [Chemistry 13] [Chemistry 14] [Chemistry 15] [Chemistry 16] [Chemistry 17] CF3O-CF2CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3 [Chemistry 18] CF3O-CF2CF2O-(C3F6O) r1 -CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3 [Chemistry 19] [Chemistry 20] CF3O-CF2CF2O-(C4F8O) s1 -(C2F4O) q1 -CF2CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3 [Chemistry 21] [Chemistry 22] [Chemistry 24] In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, but the total of p1', q1', and r1' in each formula is 9 to 199. The repeating units shown in brackets with p1, q1, r1, s1, p1', and q1' may be randomly bonded, and k is an integer from 1 to 20.

11. The fluorine-containing composition according to claim 1, wherein The fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the formula (2) is at least one selected from polymers represented by the following formulas: [Chemistry 25] [Chemistry 26] CF3O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3 [Chemistry 27] [Chemistry 28] [Chemistry 29] [Chemistry 30] [Chemistry 31] C3F7O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-O-CH2CH2CH2-Si(OCH3)3 C3F7O-CF2O-(CF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3 [Chemistry 32] [Chemistry 33] [Chemistry 34] [Chemistry 35] [Chemistry 36] CF3O-CF2O-(OF2O) p1 -(C2F4O) q1 -CF2-CH2-CH2CH2CH2-Si(OCH3)3 [Chemistry 37] CF3O-CF2O-(C3F6O) r1 -CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3 [Chemistry 38] [Chemistry 39] CF3O-CF2O-(C4F8O) s1 -(C2F4O) q1 -CF2CF2CF2-CH2-O-CH2CH2CH2-Si(OCH3)3 [Chemistry 40] [Chemistry 41] [Chemistry 42] [Chemistry 43] In the formula, p1, q1, r1, and s1 are each independently an integer greater than 1, but the total of p1, q1, r1, and s1 in each formula is 10 to 200. In addition, p1', q1', and r1' are each independently an integer greater than 1, but the total of p1', q1', and r1' in each formula is 9 to 199. The repeating units shown in brackets with p1, q1, r1, s1, p1', and q1' may be randomly bonded, and k is an integer from 1 to 20.

12. A surface treating agent comprising the fluorine-containing composition according to any one of claims 1 to 11.

13. An article surface-treated with the surface treating agent according to claim 12.

14. The article according to claim 13, which is an optical article.

15. The article of claim 13 which is a touch panel display. The article according to claim 13 , which is an anti-reflection film.

17. The article of claim 13, wherein: The substrate is SiO2 treated glass.

18. The article of claim 13, wherein: The base material is tempered glass.

19. The article of claim 13, wherein: The substrate is a lens substrate.

20. The article of claim 13, wherein: The substrate is a quartz substrate.

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