Fluoropolyether-group-containing polymer composition, surface treatment agent, and article

Abstract

A cured coating film having exceptional water repellency, oil repellency, and wear resistance as well as exceptional chucking properties can be formed by using a surface treatment agent that contains a fluoropolyether-group-containing polymer composition containing: (I) a fluoropolyether-group-containing polymer and / or a partial (hydrolysis) condensate thereof, the fluoropolyether-group-containing polymer having, at the polymer terminals thereof, two or three monovalent organic groups excluding a silanol group or a hydrolyzable silyl group, and having one silanol group or hydrolyzable silyl group; and (II) a fluoropolyether-group-containing polymer and / or a partial (hydrolysis) condensate thereof, the fluoropolyether-group-containing polymer having, at the polymer terminals thereof, at least two silanol groups or hydrolyzable silyl groups, the ratio of the number-average molecular weight of component (I) to the number-average molecular weight of component (II) being (I) / (II) = 1.2 or higher.

Description

Fluoropolyether group-containing polymer composition, surface treatment agent and article

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

[0002] In general, fluoropolyether group-containing compounds have very low surface free energy and therefore have water and oil repellency, chemical resistance, lubricity, release properties, antifouling properties, etc. Utilizing these properties, they are widely used industrially as water and oil repellent and antifouling agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, etc. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and even if they can be applied to the surface of a substrate, it has been difficult to adhere the coating to it.

[0003] On the other hand, silane coupling agents are well known as agents for bonding organic compounds to the surface of substrates such as glass and cloth, and are widely used as coating agents for various substrate surfaces. Silane coupling agents contain an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating. The hydrolyzable silyl group chemically and physically bonds with the surface of various substrates, resulting in a durable, strong coating.

[0004] Thus, compositions have been disclosed that use fluoropolyether group-containing polymers in which a hydrolyzable silyl group has been introduced at one end of a fluoropolyether group-containing compound, thereby forming coatings that easily adhere to the surface of a substrate and have water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, etc. on the surface of the substrate (Patent Documents 1 to 4: JP 2012-072272 A, JP 2012-157856 A, JP 2013-136833 A, JP 2015-199906 A).

[0005] Although lenses and substrates containing cured coatings such as antireflection films that have been surface-treated with a composition containing a fluoropolyether group-containing polymer in which a hydrolyzable silyl group has been introduced into the fluoropolyether group-containing compound have excellent slip properties and releasability, when the substrate is fixed and processed, the slip properties affect the ability to fix the substrate (poor chucking ability), which causes the substrate to slip during processing, making it impossible to process it into the required shape.

[0006] Furthermore, although the problem of substrate fixation can be solved by using a fluoropolyether group-containing polymer in which hydrolyzable silyl groups are introduced at both ends of a fluoropolyether group-containing compound, the polymer does not exhibit sufficient performance in terms of abrasion resistance.

[0007] JP 2012-072272 A JP 2012-157856 A JP 2013-136833 A JP 2015-199906 A JP 2003-238577 A

[0008] The present invention has been made in view of the above circumstances, and aims to provide a composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, which is capable of forming a cured coating that is excellent in water and oil repellency, abrasion resistance, and anti-chucking properties; a surface treatment agent containing the composition; and an article that has been surface-treated with the surface treatment agent.

[0009] As a result of intensive research conducted by the present inventors to achieve the above object, they have found that a cured coating excellent in water and oil repellency, abrasion resistance, and anti-chucking properties can be formed by using a surface treatment agent containing a fluoropolyether group-containing polymer composition comprising: (I) a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, which has two or three monovalent organic groups excluding silanol groups or hydrolyzable silyl groups at the polymer terminal and one silanol group or hydrolyzable silyl group; and (II) a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, which has two or more silanol groups or hydrolyzable silyl groups only at the polymer terminal, wherein the ratio of the number average molecular weight of component (I) to the number average molecular weight of component (II) is (I) / (II) = 1.2 or more, and thus have completed the present invention.

[0010] Accordingly, the present invention provides the following fluoropolyether group-containing polymer composition, surface treatment agent, and article: [1] A fluoropolyether group-containing polymer composition comprising: (I) a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, which has, at the polymer terminal, two or three monovalent organic groups excluding silanol groups or hydrolyzable silyl groups and one silanol group or hydrolyzable silyl group; and (II) a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, which has, at the polymer terminal, two or more silanol groups or hydrolyzable silyl groups only, in which the ratio of the number average molecular weight of component (I) to the number average molecular weight of component (II) is (I) / (II) = 1.2 or more. [2] The fluoropolyether group-containing polymer composition according to [1], wherein the monovalent organic group is a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be fluorine-substituted and which may contain one or more of an oxygen atom, a nitrogen atom, and a silicon atom. [3] The fluoropolyether group-containing polymer composition according to [1] or [2], wherein the ratio of the number average molecular weight of the component (I) to the number average molecular weight of the component (II) is (I) / (II) = 1.2 or more and 5.0 or less. [4] The fluoropolyether group-containing polymer composition according to any one of [1] to [3], wherein the content of the component (I) in the total mass of the components (I) and (II) is 50 mass% or less. [5] The fluoropolyether group-containing polymer composition according to any one of [1] to [3], wherein the component (I) is a fluoropolyether group-containing polymer represented by the following general formula (1): [In the formula, A independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with fluorine and which may contain one or more of an oxygen atom, a nitrogen atom, and a silicon atom; Rf represents a group represented by the following general formula (2): (wherein W is a fluoroalkylene group containing one or more hydrogen atoms; d is independently an integer of 1 to 3 for each unit; p, q, r, s, t, u, and v are each integers of 0 to 450, the total of p, q, r, s, t, u, and v is 20 to 450; and each of these units may be linear or branched. Furthermore, the repeating units shown in parentheses following p, q, r, s, t, u, and v may be bonded randomly), Z is independently a divalent organic group, Q is a tri- or tetravalent group, Y is a divalent organic group, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each silicon atom to which it is bonded, and α is 2 or 3. and (II) is a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, and the component (II) is a polymer represented by the following general formula (3): [In the formula, Rf is a divalent fluoropolyether group represented by the above general formula (2), U is independently a single bond or a trivalent organic group, Z is independently a divalent organic group, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each bonding silicon atom, and m is 1 or 2.] The fluoropolyether group-containing polymer composition according to any one of [1] to [4], which is a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups and / or a partial (hydrolyzed) condensate thereof, represented by the following formula: [In the formula, Rf is a divalent fluoropolyether group represented by the above general formula (2), U is independently a single bond or a trivalent organic group, Z is independently a divalent organic group, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each bonding silicon atom, and m is 1 or 2.] [6] In the above formula (1), Q is represented by the formula =R a A trivalent group represented by C- (R a is an alkyl group having 1 to 3 carbon atoms or a hydroxyl group), =R b A trivalent group represented by Si- (R bis a group selected from an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a chloro group), a trivalent isocyanuric group, a trivalent triazine ring-containing group, a tetravalent group represented by ≡C-, a tetravalent group represented by ≡Si-, and a linear trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms. [7] The fluoropolyether group-containing polymer composition according to [5] or [6], wherein Z in the above formula (1) or (3) is a divalent group in which alkylene groups having 1 to 30 carbon atoms, alkylene groups having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, alkylene groups having 1 to 15 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 1 to 15 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl group, and an amide group, and which may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group. [8] The fluoropolyether group-containing polymer composition according to any one of [5] to [7], wherein in the above formula (1), Y is an alkylene group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom, and an arylene group having 6 to 8 carbon atoms. [9] The fluoropolyether group-containing polymer composition according to any one of [5] to [8], wherein in the above formulas (1) and (3), X is selected from the group consisting of 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 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom.

[10] The fluoropolyether group-containing polymer composition according to any one of [5] to [8], wherein in the above formula (3), U is a single bond or -CR c = (R cThe fluoropolyether group-containing polymer composition according to any one of [5] to [9], wherein the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by formula (1) is a trivalent group represented by -C(=O)N=, a trivalent group represented by -N=, a trivalent isocyanuric group, a trivalent triazine ring-containing group, and a trivalent group which may contain at least one of an alkylene group having 1 to 10 carbon atoms and an oxygen atom, and which is selected from the group consisting of a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms.

[11] The fluoropolyether group-containing polymer composition according to any one of [5] to

[10] , wherein the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by formula (1) is represented by any one of the following formulas: (wherein p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and the sum of p1 and q1 is an integer of 20 to 450. r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and the sum of r2 and r3 is an integer of 20 to 180. The repeating units shown in parentheses with p1 and q1 may be bonded randomly.)

[12] A fluoropolyether group-containing polymer composition according to any one of [5] to

[11] , wherein the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group, represented by formula (3), is represented by any one of the following formulas: (wherein p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and the sum of p1 and q1 is an integer of 20 to 450. r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and the sum of r2 and r3 is an integer of 20 to 180. r4, r5, p2, and q2 are each an integer of 1 or more, and the sum of r4, r5, p2, and q2 is 18 to 400. p3 and q3 are each an integer of 1 or more, and the sum of p3 and q3 is 16 to 400. The repeating units shown in parentheses with p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly.)

[13] A surface treatment agent comprising the fluoropolyether group-containing polymer composition according to any one of [1] to

[12] .

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

[13] .

[15] The article according to

[14] , which is a lens substrate.

[0011] The fluoropolyether group-containing polymer composition of the present invention can provide a cured coating that has excellent water and oil repellency and, in particular, high abrasion resistance to fabrics. As a result, an article having a layer made of a cured product of the composition of the present invention (in particular, a surface treatment agent containing the composition) has water and oil repellency, slipperiness, high abrasion resistance, and also has excellent chucking properties during processing.

[0012] The present invention provides a fluoropolyether group-containing polymer composition capable of forming a cured coating that is excellent in water and oil repellency, slipperiness, abrasion resistance to fabrics, and anti-chucking properties; a surface treatment agent containing the composition; and an article having a layer made of a cured product of the surface treatment agent.

[0013] [Fluoropolyether Group-Containing Polymer Composition] The fluoropolyether group-containing polymer composition of the present invention comprises: (I) a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, which has two or three monovalent organic groups other than silanol groups or hydrolyzable silyl groups and one silanol group or hydrolyzable silyl group at the polymer terminal; and (II) a fluoropolyether group-containing polymer and / or a partial (hydrolyzed) condensate thereof, which has two or more, preferably 2 to 4, silanol groups or hydrolyzable silyl groups only at the polymer terminal, wherein the ratio of the number average molecular weight of component (I) to the number average molecular weight of component (II) is (I) / (II)=1.2 or more.

[0014] In the fluoropolyether group-containing polymer composition of the present invention, the ratio of the number average molecular weight of component (I) to the number average molecular weight of component (II) is (I) / (II) = 1.2 or more, preferably (I) / (II) = 1.2 or more and 5.0 or less, more preferably (I) / (II) = 1.2 or more and 3.0 or less. The smaller the number average molecular weight, the lower the polymer viscosity and the improved mobility of the polymer molecules themselves. Therefore, when polymers of components (I) and (II) with different number average molecular weights are used, component (II), which has a relatively small number average molecular weight, bonds to the substrate surface first, and component (I) fills the voids on the substrate surface, thereby forming a denser surface structure. When the number average molecular weight ratio is below the above upper limit, the above effect of component (II) can be fully exerted. Furthermore, when the number average molecular weight ratio (I) / (II) is less than 1.2, the difference in the mobility of the polymer molecules themselves is small, and the above effect cannot be obtained.

[0015] The number average molecular weight of component (I) is preferably 3,000 to 100,000, and more preferably 4,000 to 30,000. If the number average molecular weight is too small, it may reach the substrate simultaneously with component (II), failing to achieve the above-mentioned effects. If the number average molecular weight is too large, the proportion of silanol groups or hydrolyzable silyl groups relative to the polymer may decrease, resulting in reduced adhesion and reduced abrasion resistance. Furthermore, the number average molecular weight of component (II) is preferably 1,000 to 83,000, and more preferably 2,000 to 25,000. If the number average molecular weight is too small, the proportion of silanol groups or hydrolyzable silyl groups relative to the polymer may increase, resulting in a reduced lubricating effect of the fluoropolyether and reduced abrasion resistance. If the number average molecular weight is too large, it may reach the substrate simultaneously with component (I), failing to achieve the above-mentioned effects. In the present invention, the number average molecular weight is a value measured by gel permeation chromatography (GPC).

[0016] In component (I), the number of monovalent organic groups excluding silanol groups or hydrolyzable silyl groups at the polymer terminals is the same as the number of fluoropolyether groups. If the number of monovalent organic groups is less than 2, the molecular motion of the fluoropolyether groups is hindered, and the slipperiness of the resulting cured coating is reduced. If the number of monovalent organic groups is more than 4, the proportion of hydrolyzable groups in the entire molecule is reduced, and substrate adhesion is reduced. In component (II), by having only silanol groups or hydrolyzable silyl groups at the polymer terminals, a denser surface structure (cured coating) can be formed.

[0017] In the fluoropolyether group-containing polymer composition of the present invention, the monovalent organic groups, excluding two or three silanol groups or hydrolyzable silyl groups, present at the polymer terminals in component (I) are fluorine atoms, hydrogen atoms, or monovalent hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, which may be fluorine-substituted and which may contain one or more of oxygen atoms, nitrogen atoms, and silicon atoms. Examples of monovalent hydrocarbon groups having 1 to 30 carbon atoms, which may be fluorine-substituted and contain one or more of oxygen, nitrogen, and silicon atoms, include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, and octyl, alkenyl groups such as vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, and heptenyl, aryl groups such as phenyl, tolyl, xylyl, and styryl, aralkyl groups such as benzyl, phenylethyl, and phenylpropyl, and groups in which some or all of the hydrogen atoms have been substituted with fluorine atoms, such as trifluoropropyl. The monovalent hydrocarbon group may also contain one or more groups selected from ether groups, carbonyl groups, ester groups, amide groups, and diorganosilylene groups such as dimethylsilylene.

[0018] Examples of the monovalent organic group include the following.

[0019] In the fluoropolyether group-containing polymer composition of the present invention, the fluoropolyether groups in components (I) and (II) are preferably those represented by formula (2) described below.

[0020] In the fluoropolyether group-containing polymer composition of the present invention, examples of the hydrolyzable silyl groups in components (I) and (II) include alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and diethoxymethylsilyl; tri(alkoxyalkoxy)silyl groups such as tri(methoxymethoxy)silyl, tri(methoxyethoxy)silyl, tri(ethoxymethoxy)silyl, and tri(ethoxyethoxy)silyl; triacyloxysilyl groups such as triacetoxysilyl and tripropionoxysilyl; trialkenyloxysilyl groups such as trivinyloxysilyl, triallyloxysilyl, tripropenoxysilyl, and triisopropenoxysilyl; and halogenated silyl groups such as trichlorosilyl, tribromosilyl, and triiodosilyl.

[0021] In the fluoropolyether group-containing polymer composition of the present invention, the fluoropolyether group-containing polymer having two or three monovalent organic groups other than silanol groups or hydrolyzable silyl groups at the polymer terminals of the component (I) and having one silanol group or hydrolyzable silyl group is preferably a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (1): [In the formula, A independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with fluorine and which may contain one or more of an oxygen atom, a nitrogen atom, and a silicon atom; Rf represents a group represented by the following general formula (2): (wherein W is a fluoroalkylene group containing one or more hydrogen atoms; d is independently an integer of 1 to 3 for each unit; p, q, r, s, t, u, and v are each integers of 0 to 450, the sum of p, q, r, s, t, u, and v is 20 to 450; each of these units may be linear or branched; and the repeating units shown in parentheses following p, q, r, s, t, u, and v may be randomly bonded), Z is independently a divalent organic group, Q is a tri- or tetravalent group, Y is a divalent organic group, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each silicon atom to which it is bonded, and α is 2 or 3.)

[0022] In the fluoropolyether group-containing polymer composition of the present invention, the fluoropolyether group-containing polymer having two or more silanol groups or hydrolyzable silyl groups at the polymer terminals of the component (II) is preferably a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the following general formula (3): [In the formula, Rf is a divalent fluoropolyether group represented by the above general formula (2), U is independently a single bond or a trivalent organic group, Z is independently a divalent organic group, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each silicon atom to which it is bonded, and m is 1 or 2.]

[0023] In the above formula (1), A's are independently a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, which may be fluorine-substituted and which may contain one or more of an oxygen atom, a nitrogen atom, and a silicon atom. Examples of monovalent hydrocarbon groups having 1 to 30 carbon atoms, which may be fluorine-substituted and contain one or more of oxygen, nitrogen, and silicon atoms, include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, and octyl, alkenyl groups such as vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, and heptenyl, aryl groups such as phenyl, tolyl, xylyl, and styryl, aralkyl groups such as benzyl, phenylethyl, and phenylpropyl, and groups in which some or all of the hydrogen atoms have been substituted with fluorine atoms, such as trifluoropropyl. The monovalent hydrocarbon group may also contain one or more groups selected from ether groups, carbonyl groups, ester groups, amide groups, and diorganosilylene groups such as dimethylsilylene.

[0024] Examples of A include the following.

[0025] In the above formula (1), Rf is a divalent fluoropolyether group represented by the following general formula (2). (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms; d is independently an integer of 1 to 3 for each unit; p, q, r, s, t, u, and v are each an integer of 0 to 450, the total of p, q, r, s, t, u, and v is 20 to 450; and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.)

[0026] In the above formula (2), W is a fluoroalkylene group containing one or more hydrogen atoms, such as CF, CF, CF, CF, CF 10 , C6F 12and the like, in which one or two fluorine atoms are substituted with hydrogen atoms.

[0027] In the above formula (2), d is independently an integer of 1 to 3 for each unit, preferably 1 or 2. Furthermore, p, q, r, s, t, u, and v are each an integer of 0 to 450, preferably p is an integer of 0 to 440, q is an integer of 0 to 250, r is an integer of 0 to 180, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, and v is an integer of 0 to 100, and the total of p, q, r, s, t, u, and v is 20 to 450, preferably 20 to 200. When the total of p, q, r, s, t, u, and v is smaller than the above upper limit, the adhesion and curability of the resulting cured coating are good, and when it is larger than the above lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable. When r, s, t, u, and v are all 0, p is an integer of 5 to 440, q is an integer of 5 to 250, and the sum of p and q is preferably 20 to 450, particularly 20 to 200.

[0028] In the formula (2), each unit may be linear or branched, and each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.

[0029] The divalent fluoropolyether group (Rf) preferably has a number average molecular weight of 2,000 to 30,000, more preferably 2,000 to 20,000. In the present invention, the number average molecular weight (Mn) can be determined by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent, or 19 It can be calculated by means of F-NMR or the like.

[0030] Specific examples of Rf include the following: (In the formula, p', q', r', s', t', and u' each represent an integer of 1 or greater, the upper limit of which is the same as the upper limit of p, q, r, s, t, and u above, and the sum of p', q', r', s', t', and u' is 20 to 450. r2' and r3' each represent an integer of 1 or greater, and the sum of r2' and r3' is 20 to 180. r4', r5', p1', and q1' each represent an integer of 1 or greater, and the sum of r4', r5', p1', and q1' is 20 to 450. In addition, the repeating units shown in parentheses followed by p', q', r', s', t', u', p1', and q1' may be bonded randomly.)

[0031] In the above formulas (1) and (3), Z is a divalent organic group, and the divalent organic group is selected from the group consisting of an alkylene group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms), a divalent group in which alkylene groups having 1 to 15 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure, or a silarylene structure, a divalent group in which an alkylene group having 1 to 15 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl group, and an amide group, and the divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

[0032] Here, the group bonded to a silicon atom in a diorganosilylene group, a silalkylene structure, a silarylene structure, an organopolysiloxane residue, or the like is preferably 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, or a butyl group, or a phenyl group. Furthermore, the alkylene group in the silalkylene structure is preferably an ethylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as a propylene group (trimethylene group, methylethylene group), or a butylene group (tetramethylene group, methylpropylene group).

[0033] Examples of such Z include the following groups: In the following structures, in the case of formula (1), it is preferable that the left bond is bonded to Rf and the right bond is bonded to Q, and in the case of formula (3), it is preferable that the left bond is bonded to U and the right bond is bonded to the silicon atom. (In the formula, f is an integer of 1 to 4, a, a', and b are each an integer of 1 to 4, b' is an integer of 1 to 8, c is an integer of 1 to 10, and e is an integer of 1 to 9.)

[0034] In the above formula (1), Q is a trivalent or tetravalent group, and the trivalent or tetravalent group is ═R a a trivalent group represented by C-, ═R b Preferred are a trivalent group represented by Si-, a trivalent isocyanuric group, a trivalent triazine ring-containing group, a tetravalent group represented by ≡C-, a tetravalent group represented by ≡Si-, and a linear or branched or cyclic trivalent or tetravalent organopolysiloxane residue having 2 to 10, particularly 2 to 8, silicon atoms, or 3 to 10, particularly 3 to 8, silicon atoms. The organopolysiloxane residue preferably contains a silalkylene structure in which two silicon atoms are bonded via an alkylene group, i.e., Si-(CH2) x -Si (where x is an integer of 2 to 6). a is preferably an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, and R b is preferably an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a chloro group.

[0035] Examples of such Q include the following: In the following structure, it is preferred that the bond on the right side is bonded to Y, and the other bond is bonded to Z.

[0036] In the above formula (1), Y is a divalent organic group, and is preferably an alkylene group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom, and an arylene group having 6 to 8 carbon atoms.

[0037] Examples of such Y include the following groups: In the following structure, it is preferred that the left bond is bonded to Q and the right bond is bonded to the silicon atom. (In the formula, h is an integer of 1 to 20, preferably an integer of 2 to 10; j and k are integers of 1 to 10, preferably an integer of 1 to 5; and the sum of j and k is an integer of 2 to 20, preferably an integer of 2 to 10.)

[0038] In the above formula (3), U is independently a single bond or a trivalent organic group, and is preferably a single bond or a trivalent organic group having 1 to 20 carbon atoms. The trivalent organic group is preferably —CR c = (R c Examples of the organopolysiloxane include a trivalent group represented by -C(=O)N=, a trivalent group represented by -N=, a trivalent isocyanuric group, a trivalent triazine ring-containing group, a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, and a trivalent group in which an alkylene group having 1 to 10 carbon atoms or an oxygen atom is bonded to such a trivalent group. The organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded via an alkylene group having 2 to 6 carbon atoms.

[0039] Examples of U other than a single bond include the following groups: It is preferable that the left bond is bonded to Rf and the other bond is bonded to Z. (In the formula, f is an integer of 1 to 4, and a is an integer of 1 to 4.)

[0040] In the above formulas (1) and (3), X independently represents a hydrolyzable group selected from the group consisting of hydroxyl, alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy, alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy, acyloxy groups having 2 to 10 carbon atoms such as acetoxy and propionoxy, alkenyloxy groups having 2 to 10 carbon atoms such as vinyloxy, allyloxy, propenoxy, and isopropenoxy, and halogen atoms such as chlorine, bromo, and iodo. X is preferably an alkoxy group having 1 to 10 carbon atoms, with methoxy and ethoxy being particularly preferred.

[0041] In the above formulas (1) and (3), R independently represents an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group.

[0042] In the above formulas (1) and (3), n is an integer of 1 to 3, preferably 2 or 3, independently for each silicon atom to be bonded. In the above formula (3), m is 1 or 2.

[0043] The fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by the above formula (1) can be prepared, for example, by the following method: A fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both or one molecular chain terminals is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organosilicon compound having a polysiloxane structure in its molecule and having a SiH group and a silanol group or a hydrolyzable silyl group (such as a halogenated silyl group or an alkoxysilyl group), followed by aging in the presence of a hydrosilylation catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably 70 to 90°C, for 1 to 72 hours, preferably 2 to 36 hours, more preferably 4 to 24 hours. In the case of an organosilicon compound having a polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group, when an organosilicon compound having a halogenated silyl group as the hydrolyzable silyl group is used, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.

[0044] Here, in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), an example of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) at both ends or one end of the molecular chain is the fluoropolyether group-containing polymer represented by the following general formula (4): (In the formula, A and Rf are the same as above, and Z′ is a single bond or a divalent organic group.)

[0045] In the above formula (4), Z' represents a single bond or a divalent organic group, and the divalent organic group is a group selected from the group consisting of an alkylene group having 1 to 28 carbon atoms, preferably 1 to 18 carbon atoms, an alkylene group having 1 to 8 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 16 carbon atoms), a divalent group in which an alkylene group having 1 to 15 carbon atoms is bonded to a diorganosilylene group, a silalkylene structure, or a silarylene structure, a divalent group in which an alkylene group having 1 to 15 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl group, and an amide group, and the divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

[0046] Preferred examples of Z' include the following: It is preferred that the left bond is bonded to Rf and the right bond is bonded to an alkenyl group. (In the formula, f is an integer of 1 to 4, a, a', and b are each an integer of 1 to 4, a" is an integer of 0 to 2, b" is an integer of 0 to 6, c' is an integer of 0 to 8, and e is an integer of 1 to 9.)

[0047] Examples of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) at both or one molecular chain terminal, represented by the above formula (4), include the following. (In the formula, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and the sum of p1 and q1 is an integer of 20 to 450. r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and the sum of r2 and r3 is an integer of 20 to 180. r4, r5, p2, and q2 are each an integer of 1 or more, and the sum of r4, r5, p2, and q2 is 18 to 400. p3 and q3 are each an integer of 1 or more, and the sum of p3 and q3 is 16 to 400. The repeating units shown in parentheses labeled p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly.)

[0048] In preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), the organosilicon compound having a polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group is preferably a compound represented by the following general formulas (5) and (6): [In the formula, R 1 is represented by the following general formula (7): (wherein Y, R, X, and n are the same as above), and R 2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms or —O—Si(CH)—H, h′ is 2 or 3, e′ is an integer of 0 to 4, preferably an integer of 0 to 2, and the sum of h′ and e′ is 2 to 7, preferably 3 or 4.]

[0049] Examples of such organosilicon compounds having a polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group include the following:

[0050] In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), when a fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both or one of the molecular chain ends is reacted with an organosilicon compound having a polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group, the amount of the organosilicon compound used is an amount such that the amount of SiH groups in the organosilicon compound is 0.6 to 1.5 mol, more preferably 0.8 to 1.2 mol, and even more preferably 0.9 to 1.1 mol, per mol of the fluoropolyether group-containing polymer.

[0051] In preparing the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by formula (1), examples of the solvent include fluorine-based solvents, such as hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series) such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, and perfluorosolvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series). The amount of the solvent used is 10 to 500 parts by mass, preferably 50 to 300 parts by mass, and more preferably 150 to 250 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both or one end of the molecular chain.

[0052] In preparing the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by formula (1), examples of hydrosilylation reaction catalysts include the following: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The amount of hydrosilylation reaction catalyst used can be 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (mass), relative to the mass of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both or one end of the molecular chain.

[0053] In addition, when an organosilicon compound having a halogenated silyl group as the hydrolyzable silyl group is used in an organosilicon compound having a polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group. Examples of reagents that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol. The amount used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, per 100 parts by mass of the addition reaction product of a fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both or one end of the molecular chain and an organosilicon compound having a polysiloxane structure in the molecule and having a SiH group and a halogenated silyl group.

[0054] Alternatively, the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) can be prepared by, for example, the following method. A fluoropolyether group-containing polymer having a SiH group at one molecular chain terminal is dissolved in a solvent, such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group (halogenated silyl group, alkoxysilyl group, etc.) in the molecule is mixed. The resulting mixture is aged in the presence of a hydrosilylation catalyst, such as a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably 70 to 90°C, for 1 to 72 hours, preferably 2 to 36 hours, more preferably 4 to 24 hours. After aging, the substituent (halogen atom) on the silyl group may be converted to, for example, a methoxy group.

[0055] Here, in the preparation (alternative method) of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), an example of the fluoropolyether group-containing polymer having a SiH group at one end of the molecular chain is a fluoropolyether group-containing polymer represented by the following general formula (8): (Wherein, A and Rf are the same as above, and Z 1 is a divalent organic group, and Z Si is a group having a SiH group.

[0056] In the above formula (8), Z 1 is a divalent organic group selected from the group consisting of alkylene groups having 1 to 12 carbon atoms, alkylene groups having 1 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms (for example, alkylene-arylene groups having 7 to 18 carbon atoms), carbonyl groups, and amide groups, and the divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, an ester, and a diorganosilylene group such as a dimethylsilylene group.

[0057] Such a Z 1Examples of the groups include the following: In the following structure, the bond on the left is Rf and the bond on the right is Z Si It is preferred to combine with (In the formula, a and b are each an integer of 1 to 4.)

[0058] In the above formula (8), Z Si is a group having a SiH group, and R in the above formula (8) Si Examples of the group include the following groups. (In the formula, f is an integer of 1 to 4, and e is an integer of 1 to 9.)

[0059] Examples of the fluoropolyether group-containing polymer having a SiH group at one molecular chain terminal, represented by the above formula (8), include the following. (In the formula, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and the sum of p1 and q1 is an integer of 20 to 450. r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and the sum of r2 and r3 is an integer of 20 to 180. r4, r5, p2, and q2 are each an integer of 1 or more, and the sum of r4, r5, p2, and q2 is 18 to 400. p3 and q3 are each an integer of 1 or more, and the sum of p3 and q3 is 16 to 400. The repeating units shown in parentheses labeled p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly.)

[0060] In the preparation (alternative method) of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), the organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule is preferably a compound represented by the following general formula (9): (In the formula, Q, R 1 is the same as above, and Z 2 represents a single bond or a divalent organic group; and y is 2 or 3.

[0061] In the above formula (9), Z 2is a single bond or a divalent organic group, and examples of the divalent organic group include alkylene groups having 1 to 8 carbon atoms, and alkylene groups having 1 to 8 carbon atoms including arylene groups having 6 to 8 carbon atoms (for example, alkylene / arylene groups having 7 to 16 carbon atoms), and may contain an oxygen atom.

[0062] Such a Z 2 Examples of the group include the following: In the following structure, it is preferred that the left bond is bonded to an alkenyl group and the right bond is bonded to Q. (In the formula, a″ is an integer of 0 to 2, b′ is an integer of 1 to 8, and b″ is an integer of 0 to 6.)

[0063] Examples of organosilicon compounds having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule represented by the above formula (9) include the following:

[0064] In the preparation (alternative method) of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), when the fluoropolyether group-containing polymer having a SiH group at one molecular chain terminal is reacted with an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule, the amount of the organosilicon compound used is an amount such that the olefin moiety (alkenyl group) in the organosilicon compound is 0.7 to 1.5 mol, more preferably 0.8 to 1.2 mol, and even more preferably 0.9 to 1.1 mol, per 1 mol of SiH groups in the fluoropolyether group-containing polymer.

[0065] In the preparation (alternative method) of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), examples of the solvent include fluorine-based solvents. Examples of fluorine-based solvents include hydrofluoroether (HFE) solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name: Novec series), and perfluorosolvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series). The amount of solvent used is 10 to 500 parts by weight, preferably 50 to 300 parts by weight, and more preferably 150 to 250 parts by weight per 100 parts by weight of the fluoropolyether group-containing polymer having a SiH group at one molecular chain terminal.

[0066] In the preparation (alternative method) of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1), examples of hydrosilylation reaction catalysts include the following: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The amount of hydrosilylation reaction catalyst used can be 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (by mass), relative to the mass of the fluoropolyether group-containing polymer having a SiH group at one molecular chain terminal.

[0067] In addition, when an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule is used, and the hydrolyzable silyl group is an organosilicon compound having a halogenated silyl group, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, such as an alkoxy group such as a methoxy group. Examples of reagents that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, and butanol. The amount used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, per 100 parts by mass of the addition reaction product of a fluoropolyether group-containing polymer having a SiH group at one molecular chain terminal and an organosilicon compound having an olefin moiety (alkenyl group) and a halogenated silyl group in the molecule.

[0068] Examples of the structure of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1) include the following structures. By changing the combination of A, Rf, Z, Q, Y, X, R, and n in the above formula (1), several types of fluoropolyether group-containing polymers having a hydrolyzable silyl group can be obtained. In the following formula, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and the sum of p1 and q1 is an integer of 20 to 450. r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, and r3 is an integer of 1 to 100, and the sum of r2 and r3 is an integer of 20 to 180. The repeating units shown in parentheses after p1 and q1 may be randomly bonded.

[0069]

[0070] The fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by the above formula (3) can be prepared, for example, by the following method: A fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organosilicon compound having a diorganosilylene group or polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group (such as a halogenated silyl group or an alkoxysilyl group), and the resulting mixture is aged in the presence of a hydrosilylation catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably 70 to 90°C, for 1 to 72 hours, preferably 10 to 36 hours, more preferably 20 to 30 hours. In the case of an organosilicon compound having a diorganosilylene group or a polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group, when an organosilicon compound having a halogenated silyl group as the hydrolyzable silyl group is used, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.

[0071] Here, in preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3), an example of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both ends of the molecular chain is the fluoropolyether group-containing polymer represented by the following general formula (10): (wherein Rf, U, and m are the same as above, and Z 3 is a single bond or a divalent organic group.

[0072] In the above formula (10), Z 3is a single bond or a divalent organic group, and the divalent organic group is a group selected from the group consisting of alkylene groups having 1 to 12 carbon atoms, alkylene groups having 1 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms (for example, alkylene-arylene groups having 7 to 18 carbon atoms), carbonyl groups, and amide groups, and the divalent organic group may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, an ester, and a diorganosilylene group such as a dimethylsilylene group.

[0073] Such Z other than a single bond 3 Examples of such groups include the following: In the following structure, it is preferred that the left bond is bonded to U and the right bond is bonded to an alkenyl group. (In the formula, a is an integer of 1 to 4, and a″ is an integer of 0 to 2.)

[0074] Examples of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals, represented by the above formula (10), include the following. (In the formula, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and the sum of p1 and q1 is an integer of 20 to 450. r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and the sum of r2 and r3 is an integer of 20 to 180. r4, r5, p2, and q2 are each an integer of 1 or more, and the sum of r4, r5, p2, and q2 is 18 to 400. p3 and q3 are each an integer of 1 or more, and the sum of p3 and q3 is 16 to 400. The repeating units shown in parentheses labeled p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly.)

[0075] In preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3), the organosilicon compound having a diorganosilylene group or a polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group is preferably a compound represented by the following general formulas (11) to (13): (wherein R, X, n, e, and f are the same as above, and Z 4 is a divalent organic group.

[0076] In the above formulas (11) to (13), Z 4 is a divalent organic group, and examples thereof include alkylene groups having 1 to 8 carbon atoms, and alkylene groups having 1 to 8 carbon atoms including arylene groups having 6 to 8 carbon atoms (for example, alkylene / arylene groups having 7 to 16 carbon atoms), which may contain an oxygen atom.

[0077] Such a Z 4 Examples of such groups include the following: In the following structure, it is preferred that the left bond is bonded to the left silicon atom, and the right bond is bonded to the silicon atom bonded to X. (In the formula, a' is an integer of 1 to 4, and b' is an integer of 1 to 8.)

[0078] Examples of organosilicon compounds having a diorganosilylene group or a polysiloxane structure in the molecule represented by the above formulas (11) to (13) and having a SiH group and a silanol group or a hydrolyzable silyl group include the following:

[0079] In the preparation of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by formula (3), when a fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals is reacted with an organosilicon compound having a diorganosilylene group or polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group, the amount of the organosilicon compound used is an amount such that the amount of SiH groups in the organosilicon compound is 1 to 4 mol, more preferably 1 to 2.5 mol, and even more preferably 1.2 to 1.8 mol, per mol of olefin moieties (alkenyl groups) in the fluoropolyether group-containing polymer.

[0080] In preparing the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups represented by formula (3), examples of the solvent include fluorine-based solvents. Examples of fluorine-based solvents include hydrofluoroether (HFE) solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, product name: Novec series), and perfluorosolvents composed of fully fluorinated compounds (manufactured by 3M, product name: Fluorinert series). The amount of solvent used is 10 to 300 parts by weight, preferably 50 to 150 parts by weight, and more preferably 80 to 120 parts by weight, per 100 parts by weight of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals.

[0081] In preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3), examples of the hydrosilylation reaction catalyst include the following: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The amount of the hydrosilylation reaction catalyst used can be 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, in terms of transition metal (mass), relative to the mass of the fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals.

[0082] In addition, when an organosilicon compound having a diorganosilylene group or polysiloxane structure in the molecule and having a SiH group and a silanol group or a hydrolyzable silyl group is used, and the organosilicon compound has a halogenated silyl group as the hydrolyzable silyl group, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, such as an alkoxy group such as a methoxy group. Examples of reagents that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, and butanol. The amount used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, per 100 parts by mass of the addition reaction product of a fluoropolyether group-containing polymer having olefin moieties (alkenyl groups) at both molecular chain terminals and an organosilicon compound having a diorganosilylene group or polysiloxane structure in the molecule and having a SiH group and a halogenated silyl group.

[0083] Examples of the structure of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (3) include the following structures. By changing the combination of Rf, U, Z, X, R, and n in the above formula (3), several types of fluoropolyether group-containing polymers having a hydrolyzable silyl group can be obtained. In the following formula, p1 is an integer from 5 to 440, q1 is an integer from 5 to 250, and the sum of p1 and q1 is an integer from 20 to 450. r1 is an integer from 20 to 180, r2 is an integer from 1 to 100, and r3 is an integer from 1 to 100, and the sum of r2 and r3 is an integer from 20 to 180. r4, r5, p2, and q2 are each integers of 1 or greater, and the sum of r4, r5, p2, and q2 is 18 to 400. p3 and q3 are each integers of 1 or greater, and the sum of p3 and q3 is 16 to 400. The repeating units indicated in parentheses by p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly.

[0084] The fluoropolyether group-containing polymer composition of the present invention comprises component (I), a fluoropolyether group-containing polymer having two or three monovalent organic groups excluding silanol groups or hydrolyzable silyl groups at the polymer terminal and one silanol group or hydrolyzable silyl group (hereinafter referred to as a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group), preferably a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (1) and / or a partial (hydrolyzed) condensate thereof, and component (II), a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at the polymer terminal. The term "partial (hydrolysis) condensate" refers to a fluoropolyether group-containing polymer having two or more hydrolyzable silyl groups only (hereinafter referred to as a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group), preferably a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by the above formula (3) and / or a partial (hydrolysis) condensate thereof, and may contain unreacted raw materials, reaction intermediates, etc. before introducing terminal silanol groups or terminal hydrolyzable silyl groups of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group of the component (I) or (II). Here, "partial (hydrolysis) condensate" refers to a hydroxyl group of the fluoropolyether group-containing polymer of the component (I) and (II), or a hydroxyl group obtained by partially hydrolyzing the terminal hydrolyzable silyl groups of the fluoropolyether group-containing polymer of the component (I) and (II) by a known method in advance.

[0085] In the fluoropolyether group-containing polymer composition of the present invention, the content of component (I) in the total of components (I) and (II) is preferably 50% by mass or less, more preferably 1 to 50% by mass, and even more preferably 5 to 50% by mass. If the content of component (I) in the total of components (I) and (II) exceeds 50% by mass, the chucking properties of the resulting cured coating may be adversely affected. If the content of component (I) is too low, the abrasion resistance of the resulting cured coating may be reduced.

[0086] In the fluoropolyether group-containing polymer composition of the present invention, the total amount of component (I) and component (II) in the composition is preferably 60 to 100% by mass, more preferably 80 to 100% by mass.

[0087] The fluoropolyether group-containing polymer composition of the present invention may further contain, if necessary, a fluorine-containing compound (non-functional fluoropolyether polymer) represented by the following formula (14) in addition to the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or its partial (hydrolyzed) condensate, which are the above-mentioned components (I) and (II): A"-Rf-A" (14) (wherein Rf is the same as above, and A" independently represents a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group terminated with a -CF3 group, a -CF2H group, or a -CH2F group.)

[0088] In the formula (14), Rf can be exemplified as the same as Rf exemplified in the formula (1), and these Rf may be the same as or different from Rf in the formula (1).

[0089] In the above formula (14), A" independently represents a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group terminally terminated in a -CF3 group, a -CF2H group, or a -CH2F group. Specific examples of the monovalent fluorine-containing group terminally terminated in a -CF3 group, a -CF2CF3 group, a -CF2CF2CF3 group, a -CH2CF(CF3)-OC3F7 group, a -CH2OCF2CFH-OC3F7 group, etc. Among these, a fluorine atom, a -CF3 group, or a -CF2CF3 group is preferred as A".

[0090] Examples of the fluorine-containing compound (non-functional fluoropolyether polymer) represented by formula (14) include the following. (In the formula, p4, q4, and r6 each independently represent an integer of 0 to 450, the sum of p4, q4, and r6 is 20 to 450, and r7 and r8 each represent an integer of 20 to 450. The repeating units shown in parentheses with p4, q4, and r6 may be bonded randomly.)

[0091] The content of the fluorine-containing compound (non-functional fluoropolyether polymer) represented by the above formula (14) may be about 0 to 60 parts by mass, preferably about 0 to 40 parts by mass, and more preferably about 0 to 20 parts by mass, relative to 100 parts by mass of the total of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group, which is the above-mentioned components (I) and (II), and / or its partial (hydrolysis) condensate.

[0092] [Surface Treatment Agent] The present invention further provides a surface treatment agent containing the above-mentioned fluoropolyether group-containing polymer composition as a main component. Here, "containing as a main component (main component)" means that the total content of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group, and / or its partial (hydrolyzed) condensate, of components (I) and (II) in the fluoropolyether group-containing polymer composition, excluding the solvent described below, of the surface treatment agent, is 50 to 100 mass%, preferably 60 to 100 mass%, more preferably 80 to 100 mass%.

[0093] If necessary, a hydrolysis condensation catalyst such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.) may be added to the surface treatment agent. Of these, acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. When a hydrolysis condensation catalyst is incorporated, the amount added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups and / or its partial (hydrolysis) condensate in the fluoropolyether group-containing polymer composition.

[0094] The surface treatment agent may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluorohexane, 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, tetrafluoroethyl trifluoroethyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are desirable in terms of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, tetrafluoroethyl trifluoroethyl ether, and tridecafluorooctane are particularly preferred.

[0095] The above-mentioned solvents may be a mixture of two or more kinds, and it is preferable to dissolve the fluoropolyether group-containing polymer composition uniformly. The optimum concentration of the fluoropolyether group-containing polymer composition dissolved in the solvent varies depending on the treatment method, and may be an amount that is easy to measure, but in the case of direct coating, it is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer composition, and in the case of vapor deposition treatment, it is preferably 1 to 100 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer composition.

[0096] The surface treatment agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition. The heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferably 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, particularly 1 to 18 hours. When applied by vapor deposition, it is desirable to use a temperature in the range of 20 to 200°C for 1 to 18 hours. Furthermore, curing may be performed under humidified conditions. Furthermore, for spray coating, for example, diluting the agent in a fluorine-based solvent to which water has been added in advance, hydrolyzing the agent, i.e., generating Si—OH, and then spray coating the agent results in rapid curing after coating.

[0097] The thickness of the cured coating is determined depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. The thickness can be measured, for example, by an ellipsometer.

[0098] The substrate to be treated with the surface treatment agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, quartz, etc. SiO-treated glass and film are particularly preferred.

[0099] [Articles] Examples of articles to be treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, and other optical articles. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the above-mentioned articles and further impart scratch resistance, and is therefore particularly useful as a water- and oil-repellent layer for lenses, touch panel displays, anti-reflection films, etc.

[0100] The surface treatment agent of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins, an anti-fouling coating for window glass or tempered glass of automobiles, trains, aircraft, etc., and headlamp covers, a water- and oil-repellent coating for exterior wall building materials, an oil-stain-resistant coating for kitchen building materials, an anti-fouling and anti-poster / anti-graffiti coating for telephone booths, a coating for imparting fingerprint resistance to artworks, etc., and an anti-fingerprint coating for compact discs, DVDs, etc. The fluoropolyether group-containing polymer composition of the present invention can also be suitably used as a release agent or paint additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, or a lubricity improver for tapes, films, etc.

[0101] In particular, the surface treatment agent of the present invention can impart to a lens substrate a cured coating that is excellent in water and oil repellency, abrasion resistance, and chucking ability. Chucking ability, as used herein, refers to the degree to which a substrate to be processed is fixed with adhesive tape when processing is performed while the substrate is fixed with the tape. For example, chucking ability is determined based on the adhesive strength (tensile shear adhesive strength) between a lens blocking tape and a lens when the lens is fixed with a lens blocking tape used for edging processing. Chucking ability is said to be good when the adhesive tape can be firmly fixed to a degree that allows the substrate to be processed with high precision.

[0102] The present invention will be explained in more detail below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. 19 The film thickness is a number average value calculated from F-NMR. In the formula below, the repeating units shown in parentheses with p1 and q1 are randomly bonded. Furthermore, the film thickness is a value measured using an ellipsometer.

[0103] Measurement of Number Average Molecular Weight The number average molecular weight of the compounds of the synthesis examples was measured using gel permeation chromatography (GPC) under the following conditions. [Measurement conditions] Developing solvent: hydrochlorofluorocarbon (HCFC)-225 Flow rate: 1 mL / min Detector: evaporative light scattering detector Column: two TSKgel Multipore HXL-M (7.8 mmφ×30 cm) columns manufactured by Tosoh Corporation Column temperature: 35°C Sample injection volume: 100 μL (solution with a concentration of 0.1% by mass)

[0104] Synthesis of fluoropolyether group-containing polymer [Synthesis Example 1] A reaction vessel was charged with a compound represented by the following formula (A): 100 g (2.55 × 10 -2 mol), 200 g of 1,3-bis(trifluoromethyl)benzene, 5.31 g (1.28 × 10) of an organosilicon compound represented by the formula -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 9.46 × 10 -2 g (2.48 x 10 as Pt alone) -6 The mixture was mixed with the above-mentioned components (containing 100 mol) and aged for 4 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 99 g of a liquid product.

[0105] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (C): The number average molecular weight obtained by GPC was 8,500.

[0106] Synthesis Example 2 A reaction vessel was charged with a compound represented by the following formula (D): 100 g (1.54 × 10 -2 mol), 200 g of 1,3-bis(trifluoromethyl)benzene, 2.85 g (7.69 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.70 × 10 -2 g (1.49 x 10 as Pt alone) -6The mixture was mixed with the above-mentioned components (containing 100 mol) and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 101 g of a liquid product.

[0107] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (F): The number average molecular weight obtained by GPC was 13,200.

[0108] Synthesis Example 3 A reaction vessel was charged with a compound represented by the following formula (G): 100 g (2.39 × 10 -2 mol), 200 g of 1,3-bis(trifluoromethyl)benzene, 3.20 g (7.96 × 10 -3 mol), and 8.85 × 10 chloroplatinic acid / vinylsiloxane complex in toluene -2 g (2.32 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 100 g of a liquid product.

[0109] The resulting compound is 1 H-NMR confirmed that the product had a structure represented by the following formula (I): The number average molecular weight obtained by GPC was 14,700.

[0110] Synthesis Example 4 A reaction vessel was charged with a compound represented by the following formula (J): 100 g (2.36 × 10 -2 mol), 200 g of 1,3-bis(trifluoromethyl)benzene, 4.44 g (1.18 × 10 -2 mol), and 8.76 × 10 chloroplatinic acid / vinylsiloxane complex in toluene -2 g (2.29 x 10 as Pt alone) -6 The mixture was mixed with the above-mentioned components (containing 100 mol) and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 98 g of a liquid product.

[0111] The resulting compound is1 H-NMR confirmed that the structure was that of the following formula (L): The number average molecular weight obtained by GPC was 8,200.

[0112] Synthesis Example 5 A reaction vessel was charged with a compound represented by the following formula (M): 100 g (3.53 × 10 -2 mol), 200 g of 1,3-bis(trifluoromethyl)benzene, 7.34 g (1.76 × 10 -2 mol), and 0.131 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (3.43 × 10 as Pt alone) -6 The mixture was mixed with the above-mentioned components (containing 100 mol) and aged for 4 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 102 g of a liquid product.

[0113] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (N): The number average molecular weight obtained by GPC was 5,900.

[0114] Synthesis Example 6 A reaction vessel was charged with a compound represented by the following formula (O): 100 g (4.42 × 10 -2 mol), 200 g of 1,3-bis(trifluoromethyl)benzene, 9.21 g (2.21 × 10 -2 mol), and 0.164 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.30 × 10 as Pt alone) -6 The mixture was mixed with the above-mentioned components (containing 100 mol) and aged for 4 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 103 g of a liquid product.

[0115] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (P): The number average molecular weight obtained by GPC was 4,800.

[0116] Synthesis Example 7 A reaction vessel was charged with a compound represented by the following formula (A): 100 g (2.55 × 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, 21.6 g (7.66 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 9.46 × 10 -2 g (2.48 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 112 g of a liquid product.

[0117] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (R): The number average molecular weight obtained by GPC was 4,600.

[0118] Synthesis Example 8 A reaction vessel was charged with a compound represented by the following formula (S): 100 g (2.34 × 10 -2 mol), 1,3-bis(trifluoromethyl)benzene 100 g, trimethoxysilane 8.56 g (7.01 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 9.40 × 10 -2 g (2.46 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 105 g of a liquid product.

[0119] The resulting compound is 1 H-NMR confirmed that the structure was that of the following formula (T): The number average molecular weight obtained by GPC was 4,200.

[0120] Synthesis Example 9 A reaction vessel was charged with a compound represented by the following formula (U): 100 g (1.53 × 10 -2 mol), 100 g of 1,3-bis(trifluoromethyl)benzene, 25.8 g (9.15 × 10-2 mol), and 5.66 × 10 chloroplatinic acid / vinylsiloxane complex in toluene -2 g (1.48 x 10 as Pt alone) -6 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure and washed to obtain 115 g of a liquid product.

[0121] The resulting compound is 1 H-NMR confirmed that the product had a structure represented by the following formula (V): The number average molecular weight obtained by GPC was 7,700.

[0122] For comparative purposes, the following compounds 1 and 2 were used. [Compound 1] The number average molecular weight obtained by GPC was 4,400. [Compound 2] The number average molecular weight obtained by GPC was 6,700.

[0123] Examples 1 to 20, Comparative Examples 1 to 12 Preparation of Surface Treatment Agents and Formation of Cured Coatings Fluoropolyether group-containing polymers having structures represented by the above compounds (formulas (C), (F), (I), (N), (P), and (X)) as component (I) and fluoropolyether group-containing polymers having structures represented by the above compounds (formulas (R), (T), (V), and (W)) as component (II) were mixed in the proportions shown in Table 1 to obtain fluoropolyether group-containing polymer compositions. The polymer compositions were dissolved in the solvents shown in Table 1 to a concentration of 20% by mass to prepare surface treatment agents. Each surface treatment agent was vacuum-deposited (treatment conditions: pressure: 2.0 × 10) onto an AR-treated plastic lens (size: 80 mmφ) having an SiO layer on the outermost surface. -2 The coating was cured for 12 hours in an atmosphere of 25°C and 50% relative humidity (700°C, 700 Pa).

[0124]

[0125] Solvent a: Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) Solvent b: Novec 7300 (manufactured by 3M, methyl perfluorohexyl ether) Solvent c: Asahiklin AE3000 (manufactured by AGC, tetrafluoroethyl trifluoroethyl ether)

[0126] Evaluation of Water and Oil Repellency [Measurement of Initial Water Repellency] For the lenses having the cured coatings formed thereon, the contact angle of the cured coating with water (water repellency) was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The results (initial water contact angle) are shown in Table 2. Initially, both the Examples and Comparative Examples showed good water repellency.

[0127] Evaluation of Abrasion Resistance The lenses having the cured coatings prepared as described above were rubbed using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.) under the following conditions, and the contact angle of the cured coating with water (water repellency) was measured in the same manner as above to evaluate abrasion resistance. The test environmental conditions were 25°C and a relative humidity of 40%. [Measurement of Fabric Abrasion Resistance] Fabric: Bemcot (manufactured by Asahi Kasei Corporation) Contact area: 1 cm 2 Travel distance (one way): 40 mm Travel speed: 4,800 mm / min Load: 1 kgf / 1 cm 2 Number of abrasion cycles: 30,000 cycles. The water contact angle of the abraded portion was measured every 5,000 cycles using the same method as above. The number of cycles at which a water contact angle of 100° or more was maintained was taken as the nonwoven fabric abrasion durability cycle. A nonwoven fabric abrasion durability cycle of 30,000 cycles was evaluated as ◎ (excellent), 20,000 or more cycles but less than 30,000 cycles as ○ (good), 10,000 or more cycles but less than 20,000 cycles as △ (passable), and less than 10,000 cycles as × (unacceptable). The evaluation results (fabric abrasion durability) are shown in Table 2.

[0128] Evaluation of Slipperiness [Measurement of Dynamic Friction Coefficient] The dynamic friction coefficient of the lenses having the cured coating formed thereon as described above was measured against Bemcot (manufactured by Asahi Kasei Corporation) using a surface property tester 14FW (manufactured by Shinto Scientific Co., Ltd.) under the following conditions. The results (dynamic friction coefficient) are shown in Table 2. Contact area: 10 mm x 30 mm Load: 100 gf

[0129] Evaluation of chucking property Lens blocking tape (LEAP III 1695M manufactured by 3M) was attached to the lens on which the cured coating film prepared above was formed, and the tensile shear adhesive strength was measured. Specifically, the lens on which the cured coating film was formed and the lens blocking tape attached to the lens were pulled so that shear stress was applied to the adhesive surface, and the maximum strength at which the adhesive bond broke was measured. [Measurement of tensile shear adhesive strength] Adhesion area: 2.7 cm 2 Tensile speed: 50 mm / min. If the tensile shear adhesive strength was 40 N or more, it was evaluated as ◯, and if it was less than 40 N, it was evaluated as ×. The results (chuckability) are shown in Table 2.

[0130]

[0131] The surface treatment agents of Examples 1 to 20, which contain fluoropolyether group-containing polymer compositions in which the fluoropolyether group-containing polymers of components (I) and (II) are mixed at a specified number-average molecular weight ratio, are able to achieve both fabric abrasion resistance and chucking properties. On the other hand, the surface treatment agents of Comparative Examples 1 to 4, which contain fluoropolyether group-containing polymer compositions in which the fluoropolyether group-containing polymers of components (I) and (II) are outside the specified number-average molecular weight ratio, and the surface treatment agents of Comparative Examples 5 to 12, which contain fluoropolyether group-containing polymer compositions that do not contain the fluoropolyether group-containing polymer of component (I) or component (II), are unable to achieve both, with either fabric abrasion resistance or chucking properties or both properties being reduced.

Claims

1. A fluoropolyether group-containing polymer composition comprising: (I) a fluoropolyether group-containing polymer and / or its partial (hydrolyzed) condensate, which has two or three monovalent organic groups excluding silanol groups or hydrolyzable silyl groups at the polymer terminal and one silanol group or hydrolyzable silyl group; and (II) a fluoropolyether group-containing polymer and / or its partial (hydrolyzed) condensate, which has two or more silanol groups or hydrolyzable silyl groups only at the polymer terminal, wherein the ratio of the number average molecular weight of component (I) to the number average molecular weight of component (II) is (I) / (II) = 1.2 or more.

2. The fluoropolyether group-containing polymer composition according to claim 1, wherein the monovalent organic group is a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be fluorinated and which may contain one or more of oxygen, nitrogen, and silicon atoms.

3. A fluoropolyether group-containing polymer composition according to claim 1, wherein the ratio of the number average molecular weight of component (I) to the number average molecular weight of component (II) is (I) / (II) = 1.2 or more and 5.0 or less.

4. The fluoropolyether group-containing polymer composition according to claim 1, wherein the content of component (I) in the total mass of components (I) and (II) is 50 mass % or less.

5. The component (I) is represented by the following general formula (1): [In the formula, A independently represents a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be substituted with fluorine and which may contain one or more of an oxygen atom, a nitrogen atom, and a silicon atom; Rf represents a group represented by the following general formula (2): (wherein W is a fluoroalkylene group containing one or more hydrogen atoms; d is independently an integer of 1 to 3 for each unit; p, q, r, s, t, u, and v are each integers of 0 to 450, the total of p, q, r, s, t, u, and v is 20 to 450; and each of these units may be linear or branched. Furthermore, the repeating units shown in parentheses following p, q, r, s, t, u, and v may be bonded randomly), Z is independently a divalent organic group, Q is a tri- or tetravalent group, Y is a divalent organic group, R is independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each silicon atom to which it is bonded, and α is 2 or 3. and (II) is a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and / or a partial (hydrolyzed) condensate thereof, and the component (II) is a polymer represented by the following general formula (3): [wherein Rf is a divalent fluoropolyether group represented by the above general formula (2), U is independently a single bond or a trivalent organic group, Z is independently a divalent organic group, 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 for each bonding silicon atom, and m is 1 or 2.] The fluoropolyether group-containing polymer composition according to claim 1, which is a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups and / or a partial (hydrolyzed) condensate thereof.

6. In the above formula (1), Q is = R a A trivalent group represented by C- (R a is an alkyl group having 1 to 3 carbon atoms or a hydroxyl group), =R b A trivalent group represented by Si- (R b is a group selected from an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a chloro group), a trivalent isocyanuric group, a trivalent triazine ring-containing group, a tetravalent group represented by ≡C-, a tetravalent group represented by ≡Si-, and a linear trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms.

7. The fluoropolyether group-containing polymer composition according to claim 5, wherein in the formulas (1) and (3), Z is a divalent group selected from the group consisting of alkylene groups having 1 to 30 carbon atoms, alkylene groups having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups having 1 to 15 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure or a silarylene structure, a divalent group in which an alkylene group having 1 to 15 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl group, and an amide group, and which may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide, and an ester group.

8. The fluoropolyether group-containing polymer composition according to claim 5, wherein in the above formula (1), Y is an alkylene group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from oxygen atoms, sulfur atoms, and arylene groups having 6 to 8 carbon atoms.

9. The fluoropolyether group-containing polymer composition according to claim 5, wherein in the above formulas (1) and (3), X is selected from the group consisting of 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 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom.

10. In the above formula (3), U is a single bond or -CR c = (R c 6. The fluoropolyether group-containing polymer composition according to claim 5, wherein the fluoropolyether group is a trivalent group selected from the group consisting of a trivalent group represented by -C(=O)N=, a trivalent group represented by -N=, a trivalent isocyanuric group, a trivalent triazine ring-containing group, and a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, and which may contain at least one of an alkylene group having 1 to 10 carbon atoms and an oxygen atom.

11. The fluoropolyether group-containing polymer composition according to claim 5, wherein the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (1) is represented by any one of the following formulas: (In the formula, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and the sum of p1 and q1 is an integer of 20 to 450. r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and the sum of r2 and r3 is an integer of 20 to 180. The repeating units shown in parentheses with p1 and q1 may be bonded randomly.) 12. The fluoropolyether group-containing polymer composition according to claim 5, wherein the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group represented by formula (3) is represented by any one of the following formulas: (In the formula, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, and the sum of p1 and q1 is an integer of 20 to 450. r1 is an integer of 20 to 180, r2 is an integer of 1 to 100, r3 is an integer of 1 to 100, and the sum of r2 and r3 is an integer of 20 to 180. r4, r5, p2, and q2 are each an integer of 1 or more, and the sum of r4, r5, p2, and q2 is 18 to 400. p3 and q3 are each an integer of 1 or more, and the sum of p3 and q3 is 16 to 400. The repeating units shown in parentheses labeled p1 and q1, p2 and q2, and p3 and q3 may be bonded randomly.) 13. A surface treatment agent comprising the fluoropolyether group-containing polymer composition according to any one of claims 1 to 12.

14. An article surface-treated with the surface treatment agent according to claim 13.

15. The article of claim 14 which is a lens substrate.

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