Polymer composition containing fluoropolyether group, surface treatment agent, and article

Abstract

By using a surface treatment agent containing a fluorine-containing polyether group-containing polymer composition including the following, a cured film that is excellent in water / oil repellency, abrasion resistance, and gripping property can be formed. The fluorine-containing polyether group-containing polymer composition includes: (I) a fluorine-containing polyether group-containing polymer having 2 or 3 monovalent organic groups other than silanol groups or hydrolyzable silyl groups at the polymer terminal, and / or a partial (hydrolytic) condensate thereof, and having 1 silanol group or hydrolyzable silyl group, and (II) a fluorine-containing polyether group-containing polymer having only 2 or more silanol groups or hydrolyzable silyl groups at the polymer terminal, and / or a partial (hydrolytic) condensate thereof, wherein the ratio of the number average molecular weight of the (I) component to the number average molecular weight of the (II) component is (I) / (II) = 1.2 or more.

Description

Technical Field

[0001] This invention relates to polymer compositions containing fluorinated polyether groups (compositions of compounds having fluorooxyalkyl or fluorooxyalkylene groups in the molecule), and more specifically, to polymer compositions containing fluorinated polyether groups having silanol groups or hydrolyzable silane groups and / or their partial (hydrolyzed) condensates of polymers capable of forming a water- and oil-repellent, abrasion-resistant film, and surface treatment agents containing the compositions, and articles surface-treated with the surface treatment agents. Background Technology

[0002] Generally, compounds containing fluorinated polyether groups possess water and oil repellency, chemical resistance, lubricity, mold release properties, and antifouling properties due to their very low surface free energy. Utilizing these properties, they are widely used industrially as water and oil repellents and antifouling agents for paper and fibers, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, and protective films. However, this property also implies non-adhesion and non-adhesion to other substrates; even if coating can be applied to the substrate surface, it is difficult to achieve a tight seal.

[0003] On the other hand, silane coupling agents are well-known as substances that bond organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as coating agents for various substrate surfaces. Each silane coupling agent contains an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as alkoxysilyl). The hydrolyzable silyl group undergoes a self-condensation reaction using moisture in the air, forming a coating film. This coating film becomes a durable and robust film through chemical and physical bonding between the hydrolyzable silyl group and the surface of various substrates.

[0004] Therefore, a composition is disclosed in which a polymer containing a fluorinated polyether group, in which a hydrolyzable silyl group is introduced at one end of a compound containing a fluorinated polyether group, can easily adhere to the surface of a substrate and form a coating on the surface of the substrate that has water and oil repellency, chemical resistance, lubricity, mold release properties, and antifouling properties (Patent Documents 1-4: Japanese Patent Application Publication No. 2012-072272, Japanese Patent Application Publication No. 2012-157856, Japanese Patent Application Publication No. 2013-136833, Japanese Patent Application Publication No. 2015-199906).

[0005] Substrates containing cured films, such as lenses and antireflective films, that have undergone surface treatment with a composition containing a fluorinated polyether polymer incorporating hydrolyzable silyl groups in a fluorinated polyether compound exhibit excellent sliding and release properties. However, during substrate fixing and processing, the sliding properties become unreliable, making it difficult to secure the substrate (poor clamping properties). Consequently, the substrate shifts during processing, resulting in problems where it cannot be processed into the desired shape.

[0006] In addition, by using a polymer containing fluorinated polyether groups with hydrolyzable silyl groups introduced at both ends of the compound containing fluorinated polyether groups, the above-mentioned problem of substrate fixation can be solved, but the performance cannot be fully utilized in terms of wear durability.

[0007] It should be noted that, as prior art related to this invention, the following documents are listed together with the above-mentioned documents.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2012-072272

[0011] Patent Document 2: Japanese Patent Application Publication No. 2012-157856

[0012] Patent Document 3: Japanese Patent Application Publication No. 2013-136833

[0013] Patent Document 4: Japanese Patent Application Publication No. 2015-199906

[0014] Patent Document 5: Japanese Patent Application Publication No. 2003-238577 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] The present invention was made in view of the above-mentioned actual situation, and aims to provide a composition comprising a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group and / or a portion thereof (hydrolyzed) condensate, capable of forming a cured film with excellent water and oil repellency, abrasion resistance and excellent retention, a surface treatment agent comprising the composition, and articles surface-treated with the surface treatment agent.

[0017] Technical solutions for solving the problem

[0018] In order to solve the above problems, the inventors conducted in-depth research and found that by using a surface treatment agent containing a polymer composition with a fluorinated polyether group, a cured film with excellent water and oil repellency, wear resistance and excellent retention can be formed, thus completing the present invention. The polymer composition containing the fluorinated polyether group includes: (I) a polymer containing a fluorinated polyether group having 2 or 3 monovalent organic groups other than silanol groups or hydrolyzable silyl groups at the polymer end and / or a partial (hydrolyzed) condensate thereof having 1 silanol group or hydrolyzable silyl group at the polymer end; and (II) a polymer containing a fluorinated polyether group having only 2 or more silanol groups or hydrolyzable silyl groups at the polymer end and / or a partial (hydrolyzed) condensate thereof, wherein the number average molecular weight ratio of component (I) to component (II) is (I) / (II) = 1.2 or more.

[0019] Therefore, the present invention provides polymer compositions, surface treatment agents and articles containing fluorinated polyether groups.

[0020] [1]

[0021] A polymer composition containing a fluorinated polyether group, comprising:

[0022] (I) Polymers containing fluorinated polyether groups, having two or three monovalent organic groups other than silanol or hydrolyzable silyl groups at the polymer ends, and / or their partial (hydrolyzable) condensates, and

[0023] (II) Polymers containing fluorinated polyether groups and / or their partial (hydrolyzed) condensates having only two or more silanol groups or hydrolyzable silane groups at the polymer ends.

[0024] Among them, the ratio of the number average molecular weight of component (I) to that of component (II) is greater than 1.2 (I) / (II).

[0025] [2]

[0026] According to the polymer composition containing fluorinated polyether groups as described in [1], wherein the monovalent organic group is a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group that can be substituted with fluorine and may contain one or more of oxygen atoms, nitrogen atoms and silicon atoms, having a carbon number of 1 to 30.

[0027] [3]

[0028] According to [1] or [2], the number average molecular weight of component (I) to component (II) is (I) / (II) = 1.2 or more and 5.0 or less.

[0029] [4]

[0030] The polymer composition containing a fluorinated polyether group according to any one of [1] to [3], wherein the content of component (I) in the total mass of component (I) and component (II) is 50% by mass or less.

[0031] [5]

[0032] According to any one of [1] to [4], a polymer composition containing a fluorinated polyether group, wherein (I) component is a polymer containing a fluorinated polyether group having a silanol group or a hydrolytic silyl group and / or a portion thereof (hydrolytic) condensate of the polymer represented by the following general formula (1).

[0033] [Chemistry 1]

[0034]

[0035] [In the formula, A is independently a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group containing one or more of oxygen atoms, nitrogen atoms and silicon atoms with a carbon number of 1 to 30, Rf is a divalent fluorinated polyether group represented by the following general formula (2), Z is independently a divalent organic group, Q is a trivalent or tetravalent group, Y is a divalent organic group, R is independently an alkyl or phenyl group with a carbon number of 1 to 4, X is independently a hydroxyl or hydrolyzable group, n is independently an integer of 1 to 3 for each bonded silicon atom, and α is 2 or 3.]

[0036] [Chemistry 2]

[0037]

[0038] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer from 1 to 3 for each unit independently, p, q, r, s, t, u, and v are each an integer from 0 to 450, and the sum of p, q, r, s, t, u, and v is 20 to 450. These units can be linear or branched. Furthermore, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be randomly bonded.)

[0039] (II) The components are polymers containing fluorinated polyether groups having silanol groups or hydrolytic silyl groups and / or their partial (hydrolytic) condensates represented by the following general formula (3).

[0040] [Chemistry 3]

[0041]

[0042] [In the formula, Rf is a divalent fluorinated polyether group represented by the above general formula (2), U is an independent single bond or trivalent organic group, Z is an independent divalent organic group, R is an independent alkyl or phenyl group with 1 to 4 carbon atoms, X is an independent hydroxyl or hydrolyzable group, n is an independent integer of 1 to 3 for each bonded silicon atom, and m is 1 or 2.]

[0043] [6]

[0044] According to the polymer composition containing a fluorinated polyether group as described in [5], wherein, in the above formula (1), Q is a group selected from the following: by =R a C- represents a trivalent group (R) a (alkyl or hydroxyl groups having 1 to 3 carbon atoms), by =R b Si- represents a trivalent group (R) b It can be an alkyl group with 1 to 3 carbon atoms, an alkenyl group with 2 or 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms or a chloro group, a trivalent isocyanuric acid group, a trivalent group containing a triazine ring, a tetravalent group represented by ≡C-, a tetravalent group represented by ≡Si-, and a straight-chain or branched or cyclic trivalent or tetravalent organopolysiloxane residue with 2 to 10 silicon atoms.

[0045] [7]

[0046] According to [5] or [6], the polymer composition containing a fluorinated polyether group, wherein in the above formula (1) and (3), Z is a divalent group selected from alkylene groups having 1 to 30 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing 6 to 8 carbon atoms, alkylene groups having 1 to 15 carbon atoms connected to each other by a diorganosilyl group, a silaneylene structure or a silaneylene structure, and a divalent group having alkylene groups having 1 to 15 carbon atoms bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms, a carbonyl group, and an amide group that may contain at least one of an oxygen atom, a sulfur atom, a secondary amine, a tertiary amine, a ketone, an amide group, and an ester group.

[0047] [8]

[0048] According to any one of [5] to [7], the polymer composition containing a fluorinated polyether group, 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 aryl groups having 6 to 8 carbon atoms.

[0049] [9]

[0050] According to any one of [5] to [8], the polymer composition containing a fluorinated polyether group, wherein in the above formulas (1) and (3), X is selected from hydroxyl, alkoxy group with 1 to 10 carbon atoms, alkoxy group with 2 to 10 carbon atoms, acyloxy group with 2 to 10 carbon atoms, olefinic group with 2 to 10 carbon atoms, and halogen atom.

[0051]

[10]

[0052] According to any one of [5] to [9], the polymer composition containing a fluorinated polyether group, wherein in the above formula (3), U is a single bond or selected from -CR c =(R c The trivalent group (represented by hydrogen atom, hydroxyl group or alkyl group having 1 to 3 carbon atoms), the trivalent group represented by -C(=O)N=, the trivalent group represented by -N=, the trivalent isocyanuric acid group, the trivalent group containing a triazine ring, and the trivalent organopolysiloxane residue having 2 to 10 silicon atoms in a straight chain or 3 to 10 silicon atoms in a branched or cyclic form, may contain at least one of an alkylene group having 1 to 10 carbon atoms and an oxygen atom.

[0053]

[11]

[0054] The polymer composition containing a fluorinated polyether group according to any one of [5] to

[10] , wherein the polymer containing a fluorinated polyether group having a silanol group or a hydrolytic silyl group represented by formula (1) is represented by any one of the following formulas.

[0055] [Chemistry 4]

[0056]

[0057] [Chemistry 5]

[0058]

[0059] [Chemistry 6]

[0060]

[0061] [Chemistry 7]

[0062]

[0063] [Chemistry 8]

[0064]

[0065] [Chemistry 9]

[0066]

[0067] [Chemistry 10]

[0068]

[0069] [Chemistry 11]

[0070]

[0071] [Chemistry 12]

[0072]

[0073] [Chemistry 13]

[0074]

[0075] [Chemistry 14]

[0076]

[0077] (In the 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, r3 is an integer from 1 to 100, and the sum of r2 and r3 is an integer from 20 to 180. The repeating units shown in parentheses with p1 and q1 can be bonded randomly.)

[0078]

[12]

[0079] The polymer composition containing a fluorinated polyether group according to any one of [5] to

[11] , wherein the polymer containing a fluorinated polyether group having a silanol group or a hydrolytic silyl group represented by formula (3) is represented by any one of the following formulas.

[0080] [Chemistry 15]

[0081]

[0082] [Chemistry 16]

[0083]

[0084] [Chemistry 17]

[0085]

[0086] [Chemistry 18]

[0087]

[0088] [Chemistry 19]

[0089]

[0090] [Chemistry 20]

[0091]

[0092] [Chemistry 21]

[0093]

[0094] [Chemistry 22]

[0095]

[0096] [Chemistry 23]

[0097]

[0098] [Chemistry 24]

[0099]

[0100] [Chemistry 25]

[0101]

[0102] [Chemistry 26]

[0103]

[0104] [Chemistry 27]

[0105]

[0106] [Chemistry 28]

[0107]

[0108] [Chemistry 29]

[0109]

[0110] [Chemistry 30]

[0111]

[0112] [Chemistry 31]

[0113]

[0114] [Chemistry 32]

[0115]

[0116] [Chemistry 33]

[0117]

[0118] [Chemistry 34]

[0119]

[0120] [Chemistry 35]

[0121]

[0122] [Chemistry 36]

[0123]

[0124] [Chemistry 37]

[0125]

[0126] [Chemistry 38]

[0127]

[0128] [Chemistry 39]

[0129]

[0130] [Chemistry 40]

[0131]

[0132] [Chemistry 41]

[0133]

[0134] [Chemistry 42]

[0135]

[0136] [Chemistry 43]

[0137]

[0138] [Chemistry 44]

[0139]

[0140] [Chemistry 45]

[0141]

[0142] [Chemistry 46]

[0143]

[0144] (In the 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, 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 greater than or equal to 1, and the sum of r4, r5, p2, and q2 is 18 to 400. p3 and q3 are each integers greater than or equal to 1, 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 can be bonded randomly.)

[0145]

[13]

[0146] A surface treatment agent comprising a polymer composition containing a fluorinated polyether group according to any one of [1] to

[12] .

[0147]

[14]

[0148] Articles that have been surface treated with the surface treatment agent according to

[13] .

[0149]

[15]

[0150] The article described in

[14] is a lens substrate.

[0151] The effects of the invention

[0152] The fluorinated polyether-based polymer composition of the present invention can form a cured film with excellent water and oil repellency, particularly exhibiting high abrasion durability for fabrics. Articles having a layer composed of a cured product of the composition of the present invention (especially a surface treatment agent containing the composition) have water and oil repellency, slip resistance and high abrasion durability, and thus excellent clamping properties during processing. Detailed Implementation

[0153] The present invention provides a fluorinated polyether-based polymer composition capable of forming a cured film with excellent water and oil repellency, slip resistance, abrasion resistance to fabric, and clamping properties, a surface treatment agent comprising the composition, and an article having a layer composed of a cured product of the surface treatment agent.

[0154] [Polymer compositions containing fluorinated polyether groups]

[0155] The polymer composition containing fluorinated polyether groups of the present invention comprises:

[0156] (I) Polymers containing fluorinated polyether groups, having two or three monovalent organic groups other than silanol or hydrolyzable silyl groups at the polymer ends, and / or their partial (hydrolyzable) condensates, and

[0157] (II) Polymers containing fluorinated polyether groups and / or their partial (hydrolyzed) condensates having only two or more, preferably two to four, silanol groups or hydrolyzable silane groups at the polymer ends.

[0158] Among them, the ratio of the number average molecular weight of component (I) to that of component (II) is greater than 1.2 (I) / (II).

[0159] In the fluorinated polyether-based polymer composition of the present invention, the ratio of the number-average molecular weight of component (I) to that of component (II) is (I) / (II) = 1.2 or more, preferably (I) / (II) = 1.2 or more and 5.0 or less, and more preferably (I) / (II) = 1.2 or more and 3.0 or less. Since a smaller number-average molecular weight results in lower polymer viscosity and higher molecular mobility, when using polymers with different number-average molecular weights (I) and (II), component (II), with a relatively smaller number-average molecular weight, bonds to the substrate surface first, while 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 aforementioned upper limit, the aforementioned effects of component (II) can be fully realized. Furthermore, when the number-average molecular weight ratio (I) / (II) is less than 1.2, the difference in molecular mobility among polymer molecules becomes smaller, and therefore the aforementioned effects cannot be obtained.

[0160] The number average molecular weight of component (I) is preferably 3,000 to 100,000, more preferably 4,000 to 30,000. If the number average molecular weight is too small, it may sometimes reach the substrate at the same time as component (II), and the above-mentioned effect cannot be obtained. If it is too large, the proportion of silanol groups or hydrolyzable silane groups relative to the polymer will be relatively reduced, the adhesion will be reduced, and thus the wear durability may be reduced.

[0161] Furthermore, the number average molecular weight of component (II) is preferably 1,000 to 83,000, more preferably 2,000 to 25,000. If the number average molecular weight is too small, the proportion of silanol groups or hydrolyzable silane groups relative to the polymer will increase, the lubrication effect of the fluorinated polyether will decrease, and sometimes the wear durability will decrease. If the number average molecular weight is too large, it may reach the substrate at the same time as component (I), and the above-mentioned effects cannot be obtained.

[0162] It should be noted that in this invention, the number-average molecular weight is a value determined by gel permeation chromatography (GPC).

[0163] In component (I), the number of monovalent organic groups (excluding silanol groups or hydrolyzable silyl groups) at the polymer ends is the same as the number of fluorinated polyether groups. If there are fewer than two monovalent organic groups, the molecular movement of the fluorinated polyether groups is hindered, resulting in reduced slippage of the cured film. If there are more than four monovalent organic groups, the proportion of hydrolyzable groups in the overall molecule decreases, leading to reduced substrate adhesion.

[0164] In component (II), by setting the polymer ends only to silanol groups or hydrolyzable silyl groups, a denser surface structure (cured film) can be formed.

[0165] In the fluorinated polyether-based polymer composition of the present invention, the monovalent organic groups other than silanol groups or hydrolyzable silyl groups that have 2 or 3 at the polymer end in component (I) are fluorine atoms, hydrogen atoms, or monovalent hydrocarbon groups that can be substituted with fluorine and may contain one or more of oxygen atoms, nitrogen atoms, and silicon atoms, with a carbon number of 1 to 30, preferably 1 to 12. As a monovalent hydrocarbon group that can be replaced by fluorine and may contain one or more of oxygen, nitrogen, and silicon atoms with 1 to 30 carbon atoms, examples 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; and aralkyl groups such as benzyl, phenethyl, and phenylpropyl. These groups are formed by replacing some or all of the hydrogen atoms with fluorine atoms, such as trifluoropropyl. Furthermore, the monovalent hydrocarbon group may contain one or more groups selected from ether, carbonyl, ester, amide, and dimethylmethylenesilyl groups, etc., of the diorganomethylenesilyl group.

[0166] Examples of monovalent organic groups include the groups shown below.

[0167] [Chemistry 47]

[0168]

[0169] In the polymer composition containing fluorinated polyether groups of the present invention, the fluorinated polyether groups in components (I) and (II) are preferably groups represented by formula (2) as described later.

[0170] Furthermore, in the fluorinated polyether-containing polymer composition of the present invention, the hydrolyzable silyl groups in components (I) and (II) can be exemplified by, for example, alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and diethoxymethylsilyl; tri(methoxymethoxy)silyl, tri(methoxyethoxy)silyl, tri(ethoxymethoxy)silyl, tri(ethoxyethoxy)silyl, tri(alkoxyalkoxy)silyl, triacetyloxysilyl, tripropionyloxysilyl, triacyloxysilyl, triethoxysilyl, triallyloxysilyl, triallyloxysilyl, tripropenyloxysilyl, triisopropenyloxysilyl, and trienyloxysilyl; and halogenated silyl groups such as trichlorosilyl, tribromosilyl, and triiodosilyl.

[0171] In the fluorinated polyether-containing polymer composition of the present invention, the polymer containing the fluorinated polyether group, which is component (I), has 2 or 3 monovalent organic groups other than silanol groups or hydrolyzable silyl groups at the polymer end, or has 1 silanol group or hydrolyzable silyl group, preferably is a polymer containing the fluorinated polyether group with silanol groups or hydrolyzable silyl groups represented by the following general formula (1).

[0172] [Chemistry 48]

[0173]

[0174] [In the formula, A is independently a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group containing one or more of oxygen atoms, nitrogen atoms and silicon atoms with a carbon number of 1 to 30, Rf is a divalent fluorinated polyether group represented by the following general formula (2), Z is independently a divalent organic group, Q is a trivalent or tetravalent group, Y is a divalent organic group, R is independently an alkyl or phenyl group with a carbon number of 1 to 4, X is independently a hydroxyl or hydrolyzable group, n is independently an integer of 1 to 3 for each bonded silicon atom, and α is 2 or 3.]

[0175] [Chemistry 49]

[0176]

[0177] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer from 1 to 3 for each unit independently, and p, q, r, s, t, u, and v are each integer from 0 to 450, with the sum of p, q, r, s, t, u, and v being 20 to 450. These units can be linear or branched. Furthermore, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be randomly bonded.)

[0178] Furthermore, in the fluorinated polyether-containing polymer composition of the present invention, the fluorinated polyether-containing polymer having only two or more silanol groups or hydrolyzable silyl groups at the polymer end as component (II) is preferably a fluorinated polyether-containing polymer having silanol groups or hydrolyzable silyl groups represented by the following general formula (3).

[0179] [Transformation 50]

[0180]

[0181] [In the formula, Rf is a divalent fluorinated polyether group represented by the above general formula (2), U is an independent single bond or trivalent organic group, Z is an independent divalent organic group, R is an independent alkyl or phenyl group with 1 to 4 carbon atoms, X is an independent hydroxyl or hydrolyzable group, n is an independent integer of 1 to 3 for each bonded silicon atom, and m is 1 or 2.]

[0182] In formula (1) above, A is independently a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group containing one or more of oxygen atoms, nitrogen atoms, and silicon atoms, with a carbon number of 1 to 30, preferably 1 to 12. Examples of monovalent hydrocarbon groups containing one or more of oxygen atoms, nitrogen atoms, and silicon atoms, with a carbon number of 1 to 30, that can be substituted with fluorine 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; and aralkyl groups such as benzyl, phenethyl, and phenylpropyl. These groups are formed by replacing some or all of the hydrogen atoms of these groups with fluorine atoms, such as trifluoropropyl. In addition, the monovalent hydrocarbon group may contain one or more groups selected from ether, carbonyl, ester, amide, dimethylmethylenesilyl, and other diorganomethylenesilyl groups.

[0183] As A, the following groups can be exemplified.

[0184] [Chemistry 51]

[0185]

[0186] In the above formula (1), Rf is a divalent fluorinated polyether group represented by the following general formula (2).

[0187] [Chemistry 52]

[0188]

[0189] (In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer from 1 to 3 for each unit independently, and p, q, r, s, t, u, and v are each integer from 0 to 450, with the sum of p, q, r, s, t, u, and v being 20 to 450. These units can be linear or branched. Furthermore, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be randomly bonded.)

[0190] In the above formula (2), W is a fluoroalkylene group containing one or more hydrogen atoms, for example, exemplified by CF2, C2F4, C3F6, C4F8, C5F4, etc. 10 C6F 12 In various perfluoroalkyl groups, one or two fluorine atoms are replaced by hydrogen atoms, etc.

[0191] In the above formula (2), d is an integer from 1 to 3 for each unit, preferably 1 or 2.

[0192] Furthermore, p, q, r, s, t, u, and v are each integers from 0 to 450. Preferably, p is an integer from 0 to 440, q is an integer from 0 to 250, r is an integer from 0 to 180, s is an integer from 0 to 100, t is an integer from 0 to 100, u is an integer from 0 to 100, and v is an integer from 0 to 100. The total of p, q, r, s, t, u, and v is 20 to 450, preferably 20 to 200. If the total of p, q, r, s, t, u, and v is less than the upper limit mentioned above, the resulting cured film has good adhesion and curing properties. If it is greater than the lower limit mentioned above, the characteristics of the fluoropolyether group can be fully utilized, which is therefore preferred.

[0193] It should be noted that when r, s, t, u, and v are all 0, it is preferable that p is an integer from 5 to 440, q is an integer from 5 to 250, and the sum of p and q is 20 to 450, especially preferably 20 to 200.

[0194] In equation (2) above, each unit can be either a straight chain or a branched chain. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, v can be bonded randomly.

[0195] It should be noted that the number average molecular weight of the divalent fluorinated polyether group (Rf) is preferably 2,000 to 30,000, more preferably 2,000 to 20,000. In this invention, the number average molecular weight (Mn) can be analyzed by gel permeation chromatography (GPC) using a fluorinated solvent as the elution solvent. 19 Calculated using methods such as F-NMR.

[0196] Specifically, Rf can be exemplified by the following groups.

[0197] [Chemistry 53]

[0198]

[0199] [Chemistry 54]

[0200]

[0201] [Chemistry 55]

[0202]

[0203] (In the formula, p', q', r', s', t', and u' are each integers greater than or equal to 1, with the same upper limit as the upper limit of p, q, r, s, t, and u mentioned above. The sum of these p', q', r', s', t', and u' is 20 to 450. r2' and r3' are each integers greater than or equal to 1, and the sum of r2' and r3' is 20 to 180. r4', r5', p1', and q1' are each integers greater than or equal to 1, and the sum of r4', r5', p1', and q1' is 20 to 450. In addition, the repeating units shown in parentheses containing p', q', r', s', t', u', p1', and q1' can be bonded randomly.)

[0204] In formulas (1) and (3) above, Z is a divalent organic group. The divalent organic group is selected from alkylene groups with 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, alkylene groups with 1 to 10 carbon atoms containing 6 to 8 carbon atoms (e.g., alkylene-arylene groups with 7 to 18 carbon atoms), divalent groups with 1 to 15 carbon atoms bonded to each other by a diorganosilyl group, a silaneylene structure or a silaneylene structure, and divalent groups with alkylene groups having 1 to 15 carbon atoms bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue with 2 to 10 silicon atoms, a carbonyl group, and an amide group. The divalent organic group may contain at least one of oxygen atoms, sulfur atoms, secondary amines, tertiary amines, ketones, amides and ester groups.

[0205] Here, the group bonded to the silicon atom of the diorganosilyl group, silanediyl group, silanediyl group, and organopolysiloxane residue is preferably an alkyl group such as methyl, ethyl, propyl, or butyl, or a phenyl group, having 1 to 8 carbon atoms, preferably 1 to 4. Furthermore, the alkyl group in the silanediyl group is preferably an ethyl group, propylene group (trimethylene, methyl ethylene), or butyl group (tetramethylene, methyl propyleneene), having 2 to 6 carbon atoms, preferably 2 to 4.

[0206] For example, the following groups can be listed as such Z. It should be noted that in the following structures, in the case of formula (1), it is preferred that the left bonding end is bonded to Rf and the right bonding end is bonded to Q, and in the case of formula (3), it is preferred that the left bonding end is bonded to U and the right bonding end is bonded to silicon atoms.

[0207] [Chemistry 56]

[0208]

[0209] [Chemistry 57]

[0210]

[0211] [Chem.58]

[0212]

[0213] [Chemistry 59]

[0214]

[0215] [Transformation 60]

[0216]

[0217] [Chemistry 61]

[0218]

[0219] [Chemistry 62]

[0220]

[0221] [Chemistry 63]

[0222]

[0223] (In the formula, f is an integer from 1 to 4, a, a', and b are each integers from 1 to 4, b' is an integer from 1 to 8, c is an integer from 1 to 10, and e is an integer from 1 to 9.)

[0224] In the above formula (1), Q is a trivalent or tetravalent group, and preferably, it is composed of =R a C- represents a trivalent group, and is represented by =R bThe term "Si-" refers to trivalent groups, trivalent isocyanuric acid groups, trivalent groups containing triazine rings, tetravalent groups represented by ≡C-, tetravalent groups represented by ≡Si-, and trivalent or tetravalent organopolysiloxane residues with 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, in a straight-chain form, or branched or cyclic form with 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms. Furthermore, these organopolysiloxane residues may contain a silaneide structure formed by two silicon atoms bonded together by an alkylene group, i.e., Si-(CH2). x -Si (where x is an integer from 2 to 6 in the above formula).

[0225] Additionally, in the above, R a Preferably, it is an alkyl or hydroxyl group having 1 to 3 carbon atoms, R b Preferably, it is an alkyl group with 1 to 3 carbon atoms, an alkenyl group with 2 or 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, or a chlorinyl group.

[0226] Examples of such a Q group include the groups shown below. It should be noted that in the following structures, the right-hand bonding end is preferably bonded to Y, and the other bonding ends are bonded to Z.

[0227] [Chemistry 64]

[0228]

[0229] [Chemistry 65]

[0230]

[0231] [Chemistry 66]

[0232]

[0233] [Chemistry 67]

[0234]

[0235] In the above formula (1), Y is a divalent organic group, preferably an alkylene group with 1 to 20 carbon atoms, which may contain one or more atoms or groups selected from oxygen atoms, sulfur atoms and aryl groups with 6 to 8 carbon atoms.

[0236] Examples of such Y groups include the following groups. It should be noted that in the following structures, it is preferable that the left-hand bonding end is bonded to Q, and the right-hand bonding end is bonded to a silicon atom.

[0237] [Chemistry 68]

[0238]

[0239] (In the formula, h is an integer from 1 to 20, preferably an integer from 2 to 10; j and k are integers from 1 to 10, preferably integers from 1 to 5; and the sum of j and k is an integer from 2 to 20, preferably an integer from 2 to 10.)

[0240] In the above formula (3), U is independently a single bond or a trivalent organic group, preferably a single bond or a trivalent organic group with 1 to 20 carbon atoms. As such a trivalent organic group, -CR can be used as an example. c =(R c The organopolysiloxane residues may contain trivalent groups (represented by hydrogen atoms, hydroxyl groups, or alkyl groups with 1 to 3 carbon atoms), trivalent groups represented by -C(=O)N=, trivalent groups represented by -N=, trivalent isocyanuric acid groups, trivalent groups containing triazine rings, and straight-chain or branched-chain or cyclic trivalent organopolysiloxane residues with 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, wherein alkylene groups with 1 to 10 carbon atoms and trivalent oxygen atoms are bonded to these trivalent groups. Furthermore, the organopolysiloxane residues may contain a silanealkylene structure formed by two silicon atoms bonded together by alkylene groups with 2 to 6 carbon atoms.

[0241] Other than such a single bond, U can be represented by, for example, the following groups. It should be noted that the left-hand bonding end is preferably bonded to Rf, and the other bonding ends are bonded to Z.

[0242] [Chemistry 69]

[0243]

[0244] [Chemistry 70]

[0245]

[0246] [Chemistry 71]

[0247]

[0248] (In the formula, f is an integer from 1 to 4, and a is an integer from 1 to 4.)

[0249] In formulas (1) and (3) above, X is independently a hydroxyl group, or a hydrolyzable group selected from alkoxy groups with 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy groups with 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups with 2 to 10 carbon atoms, such as acetoxy and propionyloxy; alkenyloxy groups with 2 to 10 carbon atoms, such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups such as chlorine, bromine, and iodo. As X, an alkoxy group with 1 to 10 carbon atoms is preferred, and methoxy and ethoxy are particularly preferred.

[0250] In the above formulas (1) and (3), R is independently an alkyl or phenyl group with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl.

[0251] In equations (1) and (3) above, n is an integer from 1 to 3 for each bonded silicon atom, preferably 2 or 3.

[0252] In the above formula (3), m is 1 or 2.

[0253] As a method for preparing a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silane group, represented by the above formula (1), the following methods can be listed as an example.

[0254] A polymer containing fluorinated polyether groups with olefinic sites (alkenyl groups) at both ends or one end of the molecular chain is dissolved in a solvent, such as a fluorinated solvent like 1,3-bis(trifluoromethyl)benzene. For example, it is mixed with an organosilicon compound having a polysiloxane structure, having SiH groups and silanol groups or hydrolyzable silyl groups (halosilyl or alkoxysilyl, etc.), and aged at a temperature of 40-120°C, preferably 60-100°C, more preferably 70-90°C, for 1-72 hours, preferably 2-36 hours, more preferably 4-24 hours, in the presence of a toluene solution of a hydrosilylation catalyst, such as a chloroplatinic acid / vinylsiloxane complex. It should be noted that, in the case of organosilicon compounds having a polysiloxane structure in the molecule, having a SiH group and a silanol group or a hydrolyzable silyl group, when using organosilicon compounds having a halosilyl group as a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can then be converted into alkoxy groups such as methoxy groups, which are other hydrolyzable groups.

[0255] In the preparation of a fluorinated polyether group having a silanol group or a hydrolyzable silyl group represented by formula (1), a polymer containing a fluorinated polyether group having an olefinic site (alkenyl group) at both ends or one end of the molecular chain can be exemplified as a polymer containing a fluorinated polyether group represented by the following general formula (4).

[0256] [Chemistry 72]

[0257]

[0258] (In the formula, A and Rf are the same as above, and Z' is a single bond or a divalent organic group.)

[0259] In the above formula (4), Z' is a single bond or a divalent organic group. The divalent organic group is selected from alkylene groups with 1 to 28 carbon atoms, preferably 1 to 18 carbon atoms, alkylene groups with 1 to 8 carbon atoms containing 6 to 8 carbon atoms (e.g., alkylene-arylene groups with 7 to 16 carbon atoms), divalent groups with alkylene groups with 1 to 15 carbon atoms bonded to diorganosilylene, silaneylene or silaneylene structures, and divalent groups with alkylene groups with 1 to 15 carbon atoms bonded to the bonding ends of straight-chain or branched or cyclic organopolysiloxane residues with 2 to 10 silicon atoms, carbonyl groups, and amide groups. The divalent organic group may contain at least one of oxygen atoms, sulfur atoms, secondary amines, tertiary amines, ketones, amides and ester groups.

[0260] As Z', it is preferable to exemplify the group shown below. It should be noted that the left bonding end is preferably bonded to Rf and the right bonding end is preferably bonded to an alkenyl group.

[0261] [Chemistry 73]

[0262]

[0263] [Chemistry 74]

[0264]

[0265] [Chemistry 75]

[0266]

[0267] [Chemistry 76]

[0268]

[0269] [Chemistry 77]

[0270]

[0271] [Chemistry 78]

[0272]

[0273] [Chemistry 79]

[0274]

[0275] [Chemistry 80]

[0276]

[0277] (In the formula, f is an integer from 1 to 4, a, a', and b are each integers from 1 to 4, a'' is an integer from 0 to 2, b'' is an integer from 0 to 6, c' is an integer from 0 to 8, and e is an integer from 1 to 9.)

[0278] As a polymer containing a fluorinated polyether group that has an olefinic site (alkenyl group) at both ends or one end of the molecular chain, as represented by the above formula (4), the following polymers can be listed as examples.

[0279] [Chemistry 81]

[0280]

[0281] [Chemistry 82]

[0282]

[0283] [Chemistry 83]

[0284]

[0285] [Chemistry 84]

[0286]

[0287] [Chemistry 85]

[0288]

[0289] (In the 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, 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 greater than or equal to 1, and the sum of r4 and r5 with p2 and q2 is 18 to 400. p3 and q3 are each integers greater than or equal to 1, and the sum of p3 and q3 is 16 to 400. The repeating units shown in parentheses for p1 and q1, p2 and q2, and p3 and q3 can be bonded randomly.)

[0290] In the preparation of a fluorinated polyether group having a silanol group or a hydrolyzable silyl group, represented by formula (1), the organosilicon compound having a polysiloxane structure in the molecule, 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).

[0291] [Chemistry 86]

[0292]

[0293] [Chemistry 87]

[0294]

[0295] [In the formula, R] 1 For groups represented by the following general formula (7),

[0296] [Chemistry 88]

[0297]

[0298] (In the formula, Y, R, X, and n are the same as above.)

[0299] R 2 It is a monovalent hydrocarbon group with 1 to 4 carbon atoms or -O-Si(CH3)2-H, h' is 2 or 3, e' is an integer from 0 to 4, preferably an integer from 0 to 2, and the sum of h' and e' is 2 to 7, preferably 3 or 4.

[0300] Examples of such organosilicon compounds that have a polysiloxane structure in the molecule, and that have SiH groups and silanol groups or hydrolyzable silyl groups, include the following compounds.

[0301] [Chemistry 89]

[0302]

[0303] [Chemistry 90]

[0304]

[0305] [Chemistry 91]

[0306]

[0307] [Chemistry 92]

[0308]

[0309] In the preparation of a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group, as represented by formula (1), when the polymer containing a fluorinated polyether group having an olefinic site (alkenyl group) at both ends or one end of the molecular chain reacts with an organosilicon compound having a polysiloxane structure in the molecule, having a SiH group and a silanol group or a hydrolyzable silyl group, the amount of the organosilicon compound used is such that, relative to 1 mol of the polymer containing the fluorinated polyether group, the SiH group 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.

[0310] In the preparation of polymers containing fluorinated polyether groups having silanol groups or hydrolyzable silane groups as represented by formula (1), fluorinated solvents can be listed as examples. Examples of fluorinated solvents include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), and perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc.

[0311] Regarding the amount of solvent used, 10 to 500 parts by mass, preferably 50 to 300 parts by mass, and more preferably 150 to 250 parts by mass, can be used relative to 100 parts by mass of a polymer containing fluoropolyether groups that has olefin sites (alkenyl groups) at both ends or one end of the molecular chain.

[0312] In the preparation of polymers containing fluorinated polyether groups having silanol or hydrolyzable silane groups, as represented by formula (1), the following catalysts can be listed as catalysts for the hydrosilylation reaction: Platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, alkynols, etc., and platinum group metal catalysts such as tetra(triphenylphosphine)palladium and tri(triphenylphosphine)rhodium chloride. Platinum group compounds such as vinylsiloxane coordination compounds are preferred.

[0313] Regarding the amount of catalyst used in the hydrosilylation reaction, it can be set to an amount of 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, relative to the mass of the polymer containing fluorinated polyether groups having olefin sites (alkenyl groups) at both ends or one end of the molecular chain, expressed in transition metal conversion (mass).

[0314] It should be noted that, in the case of organosilicon compounds having a polysiloxane structure in the molecule, having a SiH group and a silanol group or a hydrolyzable silyl group, when using an organosilicon compound having a halosilyl group as a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can then be converted into other hydrolyzable groups such as alkoxy or methoxy groups. As reagents that can be used to convert the substituent (halogen atom) on the silyl group into other hydrolyzable groups, examples include alcohols with 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.

[0315] In terms of the amount used, 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, can be used relative to 100 parts by mass of the addition reaction product of a polymer containing a fluorinated polyether group having an olefinic site (alkenyl group) at both ends or one end of the molecular chain and an organosilicon compound having a polysiloxane structure, a SiH group and a halosilyl group in the molecule.

[0316] In addition, as another method for preparing a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silyl group represented by the above formula (1), the following method can be listed as an example.

[0317] A polymer containing a fluorinated polyether group with a SiH group at a single end of the molecular chain is dissolved in a solvent, such as a fluorinated solvent like 1,3-bis(trifluoromethyl)benzene. This is mixed with an organosilicon compound having an olefinic site (alkenyl group) and a silanol group or a hydrolyzable silyl group (halosilyl or alkoxysilyl, etc.). The mixture is then aged at 40–120°C, preferably 60–100°C, more preferably 70–90°C, for 1–72 hours, preferably 2–36 hours, more preferably 4–24 hours, in the presence of a toluene solution of a hydrosilylation catalyst, such as a chloroplatinic acid / vinylsiloxane complex. It should be noted that after aging, the substituents (halogen atoms) on the silyl group can be converted to, for example, methoxy groups.

[0318] In the preparation of a fluorinated polyether group having a silanol group or a hydrolyzable silyl group represented by formula (1) (another method), a polymer containing a fluorinated polyether group having a SiH group at a single end of the molecular chain can be exemplified as a polymer containing a fluorinated polyether group represented by the following general formula (8).

[0319] [Chemistry 93]

[0320]

[0321] (In the formula, A and Rf are the same as above, Z) 1 Z is a divalent organic group. Si (A group containing a SiH group.)

[0322] In the above equation (8), Z 1 The divalent organic group is selected from 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 (e.g., alkylene-arylene groups having 7 to 18 carbon atoms), carbonyl groups, and amide groups. The divalent organic group may contain at least one of the following: oxygen atom, sulfur atom, secondary amine, tertiary amine, ketone, amide, ester, and dimethylmethylenesilyl group.

[0323] As such Z1 Examples of such groups include the following. It should be noted that in the following structures, the left-hand bonding end is preferably bonded to Rf, and the right-hand bonding end to Z. Si Bonding.

[0324] [Chemistry 94]

[0325]

[0326] (In the formula, a and b are integers from 1 to 4.)

[0327] In the above equation (8), Z Si The group having the SiH group is used as R in the above formula (8). Si For example, the following groups can be listed.

[0328] [Chem. 95]

[0329]

[0330] (In the formula, f is an integer from 1 to 4, and e is an integer from 1 to 9.)

[0331] As a polymer containing a fluorinated polyether group with a SiH group at a single end of the molecular chain, as represented by the above formula (8), the following substances can be listed as examples.

[0332] [Chemistry 96]

[0333]

[0334] [Chemistry 97]

[0335]

[0336] [Chem. 98]

[0337]

[0338] [Chemistry 99]

[0339]

[0340] (In the 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, 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 greater than or equal to 1, and the sum of r4 and r5 with p2 and q2 is 18 to 400. p3 and q3 are each integers greater than or equal to 1, and the sum of p3 and q3 is 16 to 400. The repeating units shown in parentheses for p1 and q1, p2 and q2, and p3 and q3 can be bonded randomly.)

[0341] In the preparation of a fluorinated polyether group containing a silanol group or a hydrolyzable silyl group represented by formula (1) (another method), as an organosilicon compound having an olefinic site (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule, a compound represented by the following general formula (9) is preferred.

[0342] [Chemistry 100]

[0343]

[0344] (In the formula, Q and R) 1 Similar to the above, Z 2 It is a single-bonded or divalent organic group. y is 2 or 3.

[0345] In the above equation (9), Z 2 It is a single bond or a divalent organic group. Examples of divalent organic groups include alkylene groups with 1 to 8 carbon atoms, alkylene groups with 1 to 8 carbon atoms that contain arylene groups with 6 to 8 carbon atoms (e.g., alkylene-arylene groups with 7 to 16 carbon atoms), and may contain oxygen atoms.

[0346] As such Z 2 Examples of such groups include the following. It should be noted that in the following structures, the left-hand bonding end is preferably bonded to an alkenyl group, and the right-hand bonding end is preferably bonded to a Q group.

[0347] [Chemistry 101]

[0348]

[0349] (In the formula, a'' is an integer from 0 to 2, b' is an integer from 1 to 8, and b'' is an integer from 0 to 6.)

[0350] As an organosilicon compound represented by the above formula (9) having an olefinic site (alkenyl) and a silanol group or a hydrolyzable silyl group in the molecule, the following compounds can be listed as examples.

[0351] [Chemistry 102]

[0352]

[0353] [Chemistry 103]

[0354]

[0355] [Chemistry 104]

[0356]

[0357] [Chemistry 105]

[0358]

[0359] [Chemistry 106]

[0360]

[0361] [Chemistry 107]

[0362]

[0363] In the preparation of a fluorinated polyether group having a silanol group or a hydrolyzable silyl group represented by formula (1) (another method), the amount of the organosilicon compound used when reacting the polymer having a SiH group at a single end of the molecular chain with an organosilicon compound having an olefinic site (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule is such that, relative to 1 mol of SiH group in the polymer containing the fluorinated polyether group, the olefinic site (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.

[0364] In the preparation of a fluorinated polyether group containing a silanol group or a hydrolyzable silane group, represented by formula (1) (another method), fluorinated solvents can be listed as solvents, for example. Examples of fluorinated solvents include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), and perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc.

[0365] Regarding the amount of solvent used, 10 to 500 parts by mass can be used relative to 100 parts by mass of a polymer containing a fluorinated polyether group having a SiH group at a single end of the molecular chain, preferably 50 to 300 parts by mass, and more preferably 150 to 250 parts by mass.

[0366] In the preparation (another method) of a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silane group, as represented by formula (1), the following catalysts can be listed as catalysts for the hydrosilylation reaction: Platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, alkynols, etc., and platinum group metal catalysts such as tetra(triphenylphosphine)palladium and tri(triphenylphosphine)rhodium chloride. Platinum group compounds such as vinylsiloxane coordination compounds are preferred.

[0367] Regarding the amount of catalyst used in the hydrosilylation reaction, it can be set to 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, relative to the mass of the polymer containing fluorinated polyether groups having SiH groups at a single end of the molecular chain, expressed in transition metal conversion (mass).

[0368] It should be noted that, in the case of organosilicon compounds having an olefinic site (alkenyl group) and a silanol group or a hydrolyzable silyl group in the molecule, when using an organosilicon compound having a halosilyl group as a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can then be converted into other hydrolyzable groups such as alkoxy or methoxy groups. As reagents that can be used to convert the substituent (halogen atom) on the silyl group into other hydrolyzable groups, examples include alcohols with 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.

[0369] In terms of the amount used, 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, can be used relative to 100 parts by mass of the addition reaction product of a polymer containing a fluorinated polyether group having a SiH group at a single end of the molecular chain and an organosilicon compound having an olefinic site (alkenyl group) and a halosilyl group in the molecule.

[0370] As for the structure of a polymer containing a fluorinated polyether group with a silanol group or a hydrolyzable silyl group, represented by the above formula (1), the following structures can be listed. By changing the combination of A, Rf, Z, Q, Y, X, R, and n in the above formula (1), various polymers containing a fluorinated polyether group with a hydrolyzable silyl group can be obtained. It should be noted that in the following formulas, 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, r3 is an integer from 1 to 100, and the sum of r2 and r3 is an integer from 20 to 180. The repeating units shown in parentheses with p1 and q1 can be randomly bonded.

[0371] [Chemistry 108]

[0372]

[0373] [Chemistry 109]

[0374]

[0375] [Chemical 110]

[0376]

[0377] [Chemistry 111]

[0378]

[0379] [Chemistry 112]

[0380]

[0381] [Chemistry 113]

[0382]

[0383] [Chemistry 114]

[0384]

[0385] [Chemistry 115]

[0386]

[0387] [Chemistry 116]

[0388]

[0389] [Chemistry 117]

[0390]

[0391] [Chemistry 118]

[0392]

[0393] As a method for preparing a polymer containing a fluorinated polyether group having a silanol group or a hydrolyzable silane group, represented by the above formula (3), the following methods can be listed as an example.

[0394] A polymer containing fluorinated polyether groups with olefinic sites (alkenyl groups) at both ends of the molecular chain is dissolved in a solvent, such as a fluorinated solvent like 1,3-bis(trifluoromethyl)benzene. For example, it is mixed with an organosilicon compound having a diorganomymethylene silane and / or polysiloxane structure, having SiH groups and silanol groups or hydrolyzable silanes (halosilanes or alkoxysilanes, etc.), and aged at a temperature of 40-120°C, preferably 60-100°C, more preferably 70-90°C, for 1-72 hours, preferably 10-36 hours, more preferably 20-30 hours, in the presence of a toluene solution of a hydrosilylation catalyst, such as a chloroplatinic acid / vinylsiloxane complex. It should be noted that, in the case of organosilicon compounds having a diorganomymethylene silyl and / or polysiloxane structure in the molecule, having a SiH group and a silanol group or a hydrolyzable silyl group, when using organosilicon compounds having a halosilyl group as a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can then be converted into alkoxy groups such as methoxy groups as other hydrolyzable groups.

[0395] In the preparation of a fluorinated polyether group having a silanol group or a hydrolyzable silyl group as represented by formula (3), a polymer containing a fluorinated polyether group having an olefinic site (alkenyl group) at both ends of the molecular chain can be exemplified as a polymer containing a fluorinated polyether group represented by the following general formula (10).

[0396] [Chemistry 119]

[0397]

[0398] (In the formula, Rf, U, and m are the same as above, Z) 3 It is an organic group that is either single-bonded or divalent.

[0399] In the above equation (10), Z 3 It is a single bond or a divalent organic group. As a divalent organic group, it is a group selected from alkylene with 1 to 12 carbon atoms, alkylene with 1 to 10 carbon atoms including arylene with 6 to 8 carbon atoms (e.g., alkylene-arylene with 7 to 18 carbon atoms), carbonyl and amide. The divalent organic group may contain at least one of the following: oxygen atom, sulfur atom, secondary amine, tertiary amine, ketone, amide, ester and dimethylmethylenesilyl.

[0400] Z, in addition to such a single key 3 Examples of such groups include the following. It should be noted that in the following structures, the left-hand bonding end is preferably bonded to U, and the right-hand bonding end is preferably bonded to an alkenyl group.

[0401] [Chemistry 120]

[0402]

[0403] (In the formula, a is an integer from 1 to 4, and a'' is an integer from 0 to 2.)

[0404] As a polymer containing fluorinated polyether groups that has olefin sites (alkenyl groups) at both ends of the molecular chain, as represented by the above formula (10), the following polymers can be listed as examples.

[0405] [Chemistry 121]

[0406]

[0407] [Chemistry 122]

[0408]

[0409] [Chemistry 123]

[0410]

[0411] [Chemistry 124]

[0412]

[0413] [Chemistry 125]

[0414]

[0415] [Chemistry 126]

[0416]

[0417] [Chemistry 127]

[0418]

[0419] [Chemistry 128]

[0420]

[0421] (In the 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, 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 greater than or equal to 1, and the sum of r4 and r5 with p2 and q2 is 18 to 400. p3 and q3 are each integers greater than or equal to 1, and the sum of p3 and q3 is 16 to 400. The repeating units shown in parentheses for p1 and q1, p2 and q2, and p3 and q3 can be bonded randomly.)

[0422] In the preparation of a fluorinated polyether group having a silanol group or a hydrolyzable silyl group, represented by formula (3), the organosilicon compound having a diorganomymethylene silyl and / or polysiloxane structure in the molecule, 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).

[0423] [Chemistry 129]

[0424]

[0425] (In the formula, R, X, n, e, and f are the same as above, and Z...) 4 (It is a divalent organic group.)

[0426] In the above equations (11) to (13), Z 4 It is a divalent organic group, and examples include alkylene groups with 1 to 8 carbon atoms, alkylene groups with 1 to 8 carbon atoms that contain arylene groups with 6 to 8 carbon atoms (e.g., alkylene-arylene groups with 7 to 16 carbon atoms), and may contain oxygen atoms.

[0427] As such Z 4 Examples of such groups include the following. It should be noted that in the following structures, preferably the left-side bonding end is bonded to the left-side silicon atom, and the right-side bonding end is bonded to the silicon atom bonded to X.

[0428] [Chemistry 130]

[0429]

[0430] (In the formula, a' is an integer from 1 to 4, and b' is an integer from 1 to 8.)

[0431] As organosilicon compounds represented by the above formulas (11) to (13) that have a diorganomymethylene silyl and / or polysiloxane structure in the molecule, and have SiH groups and silanol groups or hydrolyzable silyl groups, the following compounds can be listed as examples.

[0432] [Chemistry 131]

[0433]

[0434] [Chemistry 132]

[0435]

[0436] [Chemistry 133]

[0437]

[0438] In the preparation of a fluorinated polyether group having a silanol group or a hydrolyzable silyl group as represented by formula (3), when the polymer containing a fluorinated polyether group having an olefinic site (alkenyl group) at both ends of the molecular chain reacts with an organosilicon compound having a diorganomymethylene silyl group and / or a polysiloxane structure, having a SiH group and a silanol group or a hydrolyzable silyl group, the amount of the organosilicon compound used is such that, relative to 1 mol of the olefinic site (alkenyl group) in the polymer containing the fluorinated polyether group, the SiH group 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.

[0439] In the preparation of polymers containing fluorinated polyether groups having silanol groups or hydrolyzable silane groups as represented by formula (3), fluorinated solvents can be listed as solvents, for example. Examples of fluorinated solvents include 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), and perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc.

[0440] Regarding the amount of solvent used, 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably 80 to 120 parts by mass, can be used relative to 100 parts by mass of a polymer containing fluorinated polyether groups that has olefin sites (alkenyl groups) at both ends of the molecular chain.

[0441] In the preparation of polymers containing fluorinated polyether groups having silanol or hydrolyzable silane groups, as represented by formula (3), the following catalysts can be listed as catalysts for the hydrosilylation reaction: Platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, alkynols, etc., and platinum group metal catalysts such as tetra(triphenylphosphine)palladium and tri(triphenylphosphine)rhodium chloride. Platinum group compounds such as vinylsiloxane coordination compounds are preferred.

[0442] Regarding the amount of catalyst used in the hydrosilylation reaction, it can be set to an amount of 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, relative to the mass of the polymer containing fluorinated polyether groups having olefin sites (alkenyl groups) at both ends of the molecular chain, expressed in transition metal conversion (mass).

[0443] It should be noted that, in the case of organosilicon compounds having a diorganomysilayl and / or polysiloxane structure in the molecule, having a SiH group and a silanol group or a hydrolyzable silyl group, when using an organosilicon compound having a halosilyl group as a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group can then be converted into other hydrolyzable groups such as alkoxy or methoxy. As reagents that can be used when converting the substituent (halogen atom) on the silyl group into other hydrolyzable groups, examples include alcohols with 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, and butanol.

[0444] In terms of the amount used, 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, are used relative to 100 parts by mass of the addition reaction product of a polymer containing a fluorinated polyether group having an olefinic site (alkenyl group) at both ends of the molecular chain and an organosilicon compound having a diorganomymethylene silane and / or a polysiloxane structure, having a SiH group and a halosilyl group.

[0445] As for the structure of the polymer containing fluorinated polyether groups with silanol groups or hydrolyzable silyl groups represented by the above formula (3), the following structures can be listed. By changing the combination of Rf, U, Z, X, R, and n in the above formula (3), a variety of polymers containing fluorinated polyether groups with hydrolyzable silyl groups can be obtained. It should be noted that in the following formulas, 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, 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 more, and the sum of r4 and r5 with p2 and q2 is 18 to 400. p3 and q3 are each integers of 1 or more, and the sum of p3 and q3 is 16 to 400. The repeating units shown in parentheses, p1 and q1, p2 and q2, p3 and q3, can be bonded randomly.

[0446] [Chemistry 134]

[0447]

[0448] [Chemistry 135]

[0449]

[0450] [Chemistry 136]

[0451]

[0452] [Chemistry 137]

[0453]

[0454] [Chemistry 138]

[0455]

[0456] [Chemistry 139]

[0457]

[0458] [Chemistry 140]

[0459]

[0460] [Chemistry 141]

[0461]

[0462] [Chemistry 142]

[0463]

[0464] [Chemistry 143]

[0465]

[0466] [Chemistry 144]

[0467]

[0468] [Chemistry 145]

[0469]

[0470] [Chemistry 146]

[0471]

[0472] [Chemistry 147]

[0473]

[0474] [Chemistry 148]

[0475]

[0476] [Chemistry 149]

[0477]

[0478] [Chemistry 150]

[0479]

[0480] [Chemistry 151]

[0481]

[0482] [Chemistry 152]

[0483]

[0484] [Chemistry 153]

[0485]

[0486] [Chemistry 154]

[0487]

[0488] [Chemistry 155]

[0489]

[0490] [Chemistry 156]

[0491]

[0492] [Chemistry 157]

[0493]

[0494] [Chemistry 158]

[0495]

[0496] [Chemistry 159]

[0497]

[0498] [Chemistry 160]

[0499]

[0500] [Chemistry 161]

[0501]

[0502] [Chemistry 162]

[0503]

[0504] [Chemistry 163]

[0505]

[0506] [Chemistry 164]

[0507]

[0508] [Chemistry 165]

[0509]

[0510] The fluorinated polyether polymer composition of the present invention comprises, as component (I), a polymer containing a fluorinated polyether group having 2 or 3 monovalent organic groups other than silanol or hydrolyzable silyl groups at the polymer end (hereinafter referred to as a polymer containing a fluorinated polyether group having 1 silanol or hydrolyzable silyl group), preferably a polymer containing a fluorinated polyether group having 1 silanol or hydrolyzable silyl group represented by the above formula (1), and / or a partial (hydrolyzed) condensate thereof; and, as component (II), a polymer containing a fluorinated polyether group having 2 or 3 monovalent organic groups other than silanol or hydrolyzable silyl groups at the polymer end. The polymer containing a fluorinated polyether group with only two or more silanol groups or hydrolyzable silyl groups at the end (hereinafter referred to as a fluorinated polyether group containing a silanol group or hydrolyzable silyl group), preferably a fluorinated polyether group containing a silanol group or hydrolyzable silyl group represented by the above formula (3) and / or a portion thereof (hydrolyzed) condensate, may also contain unreacted raw materials, reaction intermediates, etc. before the terminal silanol group or terminal hydrolyzable silyl group of the polymer containing a fluorinated polyether group containing a silanol group or hydrolyzable silyl group into which these (I) and (II) components are introduced.

[0511] Among them, "partial (hydrolyzed) condensate" refers to a substance obtained by partially condensing the hydroxyl groups of the polymer containing fluorinated polyether groups in components (I) and (II), or the hydroxyl groups of the terminal hydrolyzable silyl groups of the polymer containing fluorinated polyether groups in components (I) and (II) in advance by partially hydrolyzing them using a known method.

[0512] Furthermore, in the fluorinated polyether-based polymer composition of the present invention, the content of component (I) in the total of component (I) and component (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 component (I) and component (II) exceeds 50% by mass, it may sometimes adversely affect the clamping properties of the obtained cured film. In addition, if the content of component (I) is too low, the wear durability of the obtained cured film may sometimes be reduced.

[0513] It should be noted that in the fluorinated polyether-based 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.

[0514] In the fluorinated polyether polymer composition of the present invention, in addition to the fluorinated polyether polymers with silanol groups or hydrolytic silyl groups and / or their partial (hydrolytic) condensates having silanol groups or hydrolytic silyl groups as components (I) and (II) as described above, a fluorinated compound (non-functional fluorinated polyether polymer) represented by the following formula (14) may be included as needed.

[0515] A”-Rf-A” (14)

[0516] (In the formula, Rf is the same as above, and A” is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group terminated with a -CF3 group, a -CF2H group, or a -CH2F group.)

[0517] In the above formula (14), Rf can represent the same group as Rf in the above formula (1). These Rf can be the same as or different from Rf in the above formula (1).

[0518] In the above formula (14), A” is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group terminated with a -CF3 group, a -CF2H group, or a -CH2F group. Specifically, examples of monovalent fluorine-containing groups terminated with a -CF3 group, a -CF2H group, or a -CH2F group include -CF3 group, -CF2CF3 group, -CF2CF2CF3 group, -CH2CF(CF3)-OC3F7 group, and -CH2OCF2CFH-OC3F7 group. Among A”, a fluorine atom, a -CF3 group, or a -CF2CF3 group are preferred.

[0519] The following compounds can be listed as fluorinated compounds (nonfunctional fluorinated polyether polymers) represented by formula (14).

[0520] [Chemistry 166]

[0521]

[0522] (In the formula, p4, q4, and r6 are each independent integers from 0 to 450, and the sum of p4, q4, and r6 is 20 to 450. r7 and r8 are each integers from 20 to 450. The repeating units shown in parentheses with p4, q4, and r6 can be bonded randomly.)

[0523] The content of the fluorinated compound (non-functional fluorinated polyether polymer) represented by the above formula (14) is about 0 to 60 parts by mass, preferably 0 to 40 parts by mass, and more preferably about 0 to 20 parts by mass, relative to the total of 100 parts by mass of the polymers containing fluorinated polyether groups with silanol groups or hydrolyzable silane groups and / or their partial (hydrolyzed) condensates as components (I) and (II).

[0524] [Surface treatment agent]

[0525] The present invention also provides a surface treatment agent containing the above-mentioned polymer composition containing fluorinated polyether groups as the main component.

[0526] Wherein, "containing... as a main component (designated as the main component)" means that the total content of (I) and (II) components of the polymer composition containing fluorinated polyether groups, having silanol groups or hydrolyzable silane groups, and / or a portion thereof (hydrolyzed) condensates, in the total amount of solvents after the removal of the surface treatment agent is 50 to 100% by mass, preferably 60 to 100% by mass, and more preferably 80 to 100% by mass.

[0527] The surface treatment agent may contain hydrolysis-condensation catalysts, such as organotin compounds (dimethoxydibutyltin, dibutyltin dilaurate, etc.), organotitanium compounds (tetrabutyl titanate, etc.), organic acids (acetic acid, methanesulfonic acid, fluorinated carboxylic acids, etc.), and inorganic acids (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetrabutyl titanate, dibutyltin dilaurate, and fluorinated carboxylic acids are particularly preferred.

[0528] The amount added when combined with a hydrolysis condensation catalyst is the catalytic amount, which is typically 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, relative to 100 parts by mass of the fluorinated polyether-containing polymer and / or its partial (hydrolysis) condensate having a silanol group or a hydrolyzable silyl group in the polymer composition containing a fluorinated polyether group.

[0529] The surface treatment agent may contain a suitable solvent. Examples of such solvents include fluorinated aliphatic hydrocarbon solvents (perfluorohexane, perfluoroheptane, perfluorooctane, tridecafluorooctane, etc.), fluorinated aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorinated ether solvents (methyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptene ether, tetrafluoroethyltrifluoroethyl ether, etc.), fluorinated alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum spirits, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, considering solubility and wettability, fluorine-modified solvents are preferred, especially 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, tetrafluoroethyl trifluoroethyl ether, and tridecylfluorooctane.

[0530] Regarding the aforementioned solvents, two or more can be mixed, preferably to uniformly dissolve the polymer composition containing fluorinated polyether groups. It should be noted that the optimal concentration of the polymer composition containing fluorinated polyether groups dissolved in the solvent varies depending on the processing method; any easily weighable amount is acceptable. However, in the case of direct coating, it is preferably 0.01 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass, relative to a total of 100 parts by mass of the solvent and the polymer composition containing fluorinated polyether groups. In the case of vapor deposition, it is preferably 1 to 100 parts by mass, particularly preferably 3 to 30 parts by mass, relative to a total of 100 parts by mass of the solvent and the polymer composition containing fluorinated polyether groups.

[0531] The surface treatment agent of the present invention can be applied to a substrate using known methods such as brushing, dipping, spraying, and vapor deposition. The heating method during vapor deposition can be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferable to perform the process at 25–200°C, particularly 25–150°C, for 30 minutes to 36 hours, particularly 1–18 hours. When applying the agent using vapor deposition, it is preferable to perform the process at 20–200°C for 1–18 hours. Furthermore, it can be cured under humidification. Additionally, for example, in the case of spraying, if the agent is diluted in a fluorinated solvent with pre-added water, hydrolyzed (i.e., sprayed after the formation of Si-OH), the curing after coating is faster.

[0532] The thickness of the cured film can be appropriately determined according to the type of substrate, typically ranging from 0.1 to 100 nm, and particularly from 1 to 20 nm. It should be noted that the film thickness can be measured, for example, using an ellipsometer.

[0533] There are no particular limitations on the substrate treated with the surface treatment agent of the present invention; it can be a substrate of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, and quartz. In particular, glass and films treated with SiO2 are preferred.

[0534] 〔thing〕

[0535] Articles treated with the surface treatment agent of the present invention include, but are not limited to, car navigation systems, mobile phones, smartphones, digital cameras, digital camcorders, PDAs, portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, endoscopes and other medical devices, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective 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, thereby imparting scratch resistance, and is therefore particularly suitable as a water- and oil-repellent layer for lenses, touch panel displays, anti-reflective films, etc.

[0536] In addition, the surface treatment agent of the present invention can also be used as a stain-resistant coating for sanitary products such as bathtubs and washbasins, a stain-resistant coating for window glass or tempered glass of automobiles, trams, aircraft, etc., a stain-resistant coating for headlight covers, a water- and oil-repellent coating for exterior wall building materials, an oil-resistant coating for kitchen building materials, a stain-resistant and sticker / graffiti-resistant coating for telephone booths, a fingerprint-resistant coating for artworks, and a fingerprint-resistant coating for CDs, DVDs, etc.

[0537] It should be noted that the polymer compositions containing fluorinated polyether groups of the present invention are also suitable for use as mold release agents or coating additives, resin modifiers, flow modifiers or dispersant modifiers for inorganic fillers, and lubrication improvers for tapes, films, etc.

[0538] In particular, the surface treatment agent of the present invention can impart a cured film to the lens substrate with excellent water and oil repellency, wear resistance, and clamping properties.

[0539] The clamping performance mentioned here refers to the degree to which the substrate is fixed when it is being processed, with the substrate being secured by adhesive tape. For example, it can be judged by the strength of the bond between the lens stop tape and the lens when the lens is fixed by the lens stop tape used for grinding (tensile shear bond strength). Good clamping performance is defined as the ability to firmly fix the substrate to a degree that allows for accurate processing through the bonding of adhesive tape to the substrate.

[0540] [Example]

[0541] The following examples, embodiments, and comparative examples illustrate the invention in more detail, but the invention is not limited to the examples described below. It should be noted that the number of repetitions of each fluorooxyalkylene unit in the divalent fluoropolyether group is determined by using… 19 The number mean calculated by F-NMR. Furthermore, in the following formula, the repeating units shown within parentheses containing p1 and q1 are randomly bonded. The film thickness is then a value measured using an ellipsometer.

[0542] Number-average molecular weight determination

[0543] Regarding the molecular weight of the compounds in the synthetic examples, the number-average molecular weight was determined using gel permeation chromatography (GPC) under the following conditions.

[0544] [Measurement Conditions]

[0545] Elution solvent: Hydrochlorofluorocarbon (HCFC)-225

[0546] Flow rate: 1 mL / min

[0547] Detector: Evaporative Light Scattering Detector

[0548] Chromatographic column: Two TSKgel Multipore HXL-M (7.8 mm) columns manufactured by Tosoh Corporation were used. (×30 cm)

[0549] Column temperature: 35℃

[0550] Sample injection volume: 100 μL (0.1% by mass solution)

[0551] Synthesis of polymers containing fluorinated polyether groups

[0552] [Synthesis example 1]

[0553] In a reaction vessel, 100 g (2.55 × 10⁻⁶) of the compound represented by the following formula (A) are added. -2 mol)

[0554] [Chemistry 167]

[0555]

[0556] 200 g of 1,3-bis(trifluoromethyl)benzene, 5.31 g of an organosilicon compound represented by the following formula (B) (1.28 × 10⁻⁶ g / g) -2 mol)

[0557] [Chemistry 168]

[0558]

[0559] And a toluene solution of chloroplatinic acid / vinylsiloxane complex 9.46 × 10 -2 g (containing 2.48 × 10 g of elemental Pt) -6 The mixture (mol) was aged at 80°C for 4 hours. Subsequently, the solvent and unreacted substances were removed by vacuum distillation and the mixture was washed to obtain 99 g of liquid product.

[0560] Regarding the compounds obtained, through 1 H-NMR confirmed the structure as represented by the following formula (C). The number-average molecular weight obtained by GPC was 8,500.

[0561] [Chemistry 169]

[0562]

[0563] [Synthesis example 2]

[0564] In a reaction vessel, 100 g (1.54 × 10⁻⁶) of the compound represented by the following formula (D) are added. -2 mol)

[0565] [Chemistry 170]

[0566]

[0567] 200 g of 1,3-bis(trifluoromethyl)benzene, 2.85 g (7.69 × 10⁻⁶) of an organosilicon compound represented by the following formula (E). -3 mol)

[0568] [Chemistry 171]

[0569]

[0570] And a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.70 × 10 -2 g (containing 1.49 × 10⁻⁶ Pt elements) -6 The mixture (mol) was aged at 80°C for 24 hours. Subsequently, the solvent and unreacted substances were removed by vacuum distillation and the mixture was washed to obtain 101 g of liquid product.

[0571] Regarding the compounds obtained, through 1 H-NMR confirmed the structure as represented by the following formula (F). The number-average molecular weight obtained by GPC was 13,200.

[0572] [Chemistry 172]

[0573]

[0574] [Synthesis example 3]

[0575] In a reaction vessel, 100 g (2.39 × 10⁻⁶) of the compound represented by the following formula (G) are added. -2 mol)

[0576] [Chemistry 173]

[0577]

[0578] 200 g of 1,3-bis(trifluoromethyl)benzene, 3.20 g (7.96 × 10⁻⁶) of an organosilicon compound represented by the following formula (H). -3 mol)

[0579] [Chemistry 174]

[0580]

[0581] And a toluene solution of chloroplatinic acid / vinylsiloxane complex 8.85 × 10 -2 g (containing 2.32 × 10 g of Pt) -6 The mixture (mol) was aged at 80°C for 24 hours. Subsequently, the solvent and unreacted substances were removed by vacuum distillation and the mixture was washed to obtain 100 g of liquid product.

[0582] Regarding the compounds obtained, through 1 H-NMR confirmed the structure as represented by the following formula (I). The number-average molecular weight obtained by GPC was 14,700.

[0583] [Chemistry 175]

[0584]

[0585] [Synthesis Example 4]

[0586] In a reaction vessel, 100 g (2.36 × 10⁻⁶) of the compound represented by the following formula (J) are added. -2 mol)

[0587] [Chemistry 176]

[0588]

[0589] 200 g of 1,3-bis(trifluoromethyl)benzene, 4.44 g of an organosilicon compound represented by the following formula (K) (1.18 × 10⁻⁶ g / g) -2 mol)

[0590] [Chemistry 177]

[0591]

[0592] And a toluene solution of chloroplatinic acid / vinylsiloxane complex 8.76 × 10 -2 g (containing 2.29 × 10⁻⁶ Pt elements) -6 The mixture (mol) was aged at 80°C for 24 hours. Subsequently, the solvent and unreacted substances were removed by vacuum distillation and the mixture was washed to obtain 98 g of liquid product.

[0593] Regarding the compounds obtained, through 1 H-NMR confirmed the structure as represented by the following formula (L). The number-average molecular weight obtained by GPC was 8,200.

[0594] [Chemistry 178]

[0595]

[0596] [Synthesis example 5]

[0597] In a reaction vessel, 100 g (3.53 × 10⁻⁶) of the compound represented by the following formula (M) are added. -2 mol)

[0598] [Chemistry 179]

[0599]

[0600] 200 g of 1,3-bis(trifluoromethyl)benzene, 7.34 g of an organosilicon compound represented by the following formula (B) (1.76 × 10⁻⁶ g / g) -2 mol)

[0601] [Chemistry 180]

[0602]

[0603] And 0.131 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 3.43 × 10⁻⁶ Pt as elemental Pt). -6 The mixture (mol) was aged at 80°C for 4 hours. Subsequently, the solvent and unreacted substances were removed by vacuum distillation and the mixture was washed to obtain 102 g of liquid product.

[0604] Regarding the compounds obtained, through 1 H-NMR confirmed the structure as represented by the following formula (N). The number-average molecular weight obtained by GPC was 5,900.

[0605] [Chemistry 181]

[0606]

[0607] [Synthesis example 6]

[0608] In a reaction vessel, 100 g (4.42 × 10⁻⁶) of the compound represented by the following formula (O) are added. -2 mol)

[0609] [Chemistry 182]

[0610]

[0611] 200 g of 1,3-bis(trifluoromethyl)benzene, 9.21 g of an organosilicon compound represented by the following formula (B) (2.21 × 10⁻⁶ g / g) -2 mol)

[0612] [Chemistry 183]

[0613]

[0614] And 0.164 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 4.30 × 10⁻⁶ Pt as elemental Pt). -6 The mixture (mol) was aged at 80°C for 4 hours. Subsequently, the solvent and unreacted substances were removed by vacuum distillation and the mixture was washed to obtain 103 g of liquid product.

[0615] Regarding the compounds obtained, through 1H-NMR confirmed the structure as represented by the following formula (P). The number-average molecular weight obtained by GPC was 4,800.

[0616] [Chemistry 184]

[0617]

[0618] [Synthesis Example 7]

[0619] In a reaction vessel, 100 g (2.55 × 10⁻⁶) of the compound represented by the following formula (A) are added. -2 mol)

[0620] [Chemistry 185]

[0621]

[0622] 100 g of 1,3-bis(trifluoromethyl)benzene, 21.6 g (7.66 × 10⁻⁶) of an organosilicon compound represented by the following formula (Q). -2 mol)

[0623] [Chemistry 186]

[0624]

[0625] And a toluene solution of chloroplatinic acid / vinylsiloxane complex 9.46 × 10 -2 g (containing 2.48 × 10 g of elemental Pt) -6 The mixture (mol) was aged at 80°C for 24 hours. Subsequently, the solvent and unreacted substances were removed by vacuum distillation and the mixture was washed to obtain 112 g of liquid product.

[0626] Regarding the compounds obtained, through 1 H-NMR confirmed the structure as represented by the following formula (R). The number-average molecular weight obtained by GPC was 4,600.

[0627] [Chemistry 187]

[0628]

[0629] [Synthesis example 8]

[0630] In a reaction vessel, 100 g (2.34 × 10⁻⁶) of the compound represented by the following formula (S) are added. -2 mol)

[0631] [Chem.188]

[0632]

[0633] 1,3-Bis(trifluoromethyl)benzene 100 g, trimethoxysilane 8.56 g (7.01×10⁻⁶) -2 9.40 × 10⁻⁶ mol) and a toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (containing 2.46 × 10 g of elemental Pt) -6 The mixture (mol) was aged at 80°C for 24 hours. Subsequently, the solvent and unreacted substances were removed by vacuum distillation and the mixture was washed to obtain 105 g of liquid product.

[0634] Regarding the compounds obtained, through 1 H-NMR confirmed the structure as represented by the following formula (T). The number-average molecular weight obtained by GPC was 4,200.

[0635] [Chemistry 189]

[0636]

[0637] [Synthesis Example 9]

[0638] In a reaction vessel, 100 g (1.53 × 10⁻⁶) of the compound represented by the following formula (U) are added. -2 mol)

[0639] [Chemistry 190]

[0640]

[0641] 100 g of 1,3-bis(trifluoromethyl)benzene, 25.8 g of an organosilicon compound represented by the following formula (Q) (9.15 × 10⁻⁶ g / g) -2 mol)

[0642] [Chemistry 191]

[0643]

[0644] And a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.66 × 10 -2 g (containing 1.48 × 10⁻⁶ Pt elements) -6 The mixture (mol) was aged at 80°C for 24 hours. Subsequently, the solvent and unreacted substances were removed by vacuum distillation and the mixture was washed to obtain 115 g of liquid product.

[0645] Regarding the compounds obtained, through 1 H-NMR confirmed the structure as represented by the following formula (V). The number-average molecular weight obtained by GPC was 7,700.

[0646] [Chemistry 192]

[0647]

[0648] For comparative purposes, compounds 1 and 2 were used.

[0649] [Compound 1]

[0650] [Chemistry 193]

[0651]

[0652] The number-average molecular weight obtained using GPC was 4,400.

[0653] [Compound 2]

[0654] [Chemistry 194]

[0655]

[0656] The number-average molecular weight obtained using GPC was 6,700.

[0657] [Examples 1-20, Comparative Examples 1-12]

[0658] Preparation of surface treatment agent and formation of cured film

[0659] A polymer containing fluorinated polyether groups, comprising (I) and having the structure represented by the above-mentioned compounds (formulas (C), (F), (I), (N), (P), (X)), and comprising (II) and having the structure represented by the above-mentioned compounds (formulas (R), (T), (V), (W))), was mixed in the proportions shown in Table 1 to obtain a polymer composition containing fluorinated polyether groups. This polymer composition was dissolved in the solvents listed in Table 1 at a concentration of 20% by mass to prepare a surface treatment agent. An AR-treated plastic lens (size: 80 mm) with a SiO2 layer on its outermost surface was then prepared. The surface treatment agents were vacuum vapor deposited (treatment conditions: pressure: 2.0 × 10⁻⁶). -2 The film is cured for 12 hours at 25°C and 50% relative humidity (Pa, heating temperature: 700°C) to form a 10 nm thick cured film.

[0660] [Table 1]

[0661]

[0662] Solvent a: Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether)

[0663] Solvent b: Novec 7300 (manufactured by 3M, methyl perfluorohexyl ether)

[0664] Solvent c: Asahiklin AE3000 (manufactured by AGC, tetrafluoroethyl trifluoroethyl ether)

[0665] Evaluation of water and oil repellency

[0666] [Determination of initial water repellency]

[0667] For the lenses with the cured coating formed as described above, the contact angle (hydrophobicity) of the cured coating to water was measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The results (initial water contact angle) are shown in Table 2.

[0668] In the initial stages, both the examples and comparative examples showed good water repellency.

[0669] Evaluation of wear resistance

[0670] For the lenses with the cured coating formed as described above, the contact angle (water repellency) of the cured coating to water after rubbing under the following conditions was measured using a friction tester (manufactured by Shin-To Science Co., Ltd.) in the same manner as above, as an evaluation of abrasion resistance. The test environment conditions were 25°C and 40% relative humidity.

[0671] [Determination of Fabric Abrasion Resistance]

[0672] Fabric: Bemcot (manufactured by Asahi Kasei Corporation)

[0673] Contact area: 1 cm²

[0674] Travel distance (one way): 40 mm

[0675] Movement speed: 4,800 mm / min

[0676] Load: 1 kgf / 1cm²

[0677] Number of friction cycles: 30,000

[0678] For every 5,000 rubbing cycles, the water contact angle of the friction-wearing portion was measured using the same method as described above. The number of rubbing cycles maintaining a water contact angle of 100° or higher was defined as the wear durability of the nonwoven fabric. A wear durability of 30,000 cycles was rated ◎ (Excellent), 20,000 to 30,000 cycles was rated ○ (Good), 10,000 to 20,000 cycles was rated △ (Acceptable), and less than 10,000 cycles was rated × (Unacceptable). The evaluation results (fabric wear durability) are shown in Table 2.

[0679] Evaluation of sliding performance

[0680] [Determination of the coefficient of kinetic friction]

[0681] For the lenses with cured coatings produced above, the coefficient of kinetic friction against Bemcot (manufactured by Asahi Kasei Corporation) was measured using a surface testing machine 14FW (manufactured by Shinto Science Co., Ltd.) under the following conditions. The results (coefficient of kinetic friction) are shown in Table 2.

[0682] Contact area: 10 mm × 30 mm

[0683] Load: 100 gf

[0684] Evaluation of clamping

[0685] Lens stop tape (manufactured by 3M: LEAP III1695M) with a cured coating was attached to the lens prepared above, and the tensile shear bond strength was measured. Specifically, the lens with the cured coating and the lens stop tape attached to the lens were stretched to apply shear stress to their bonding surface, and the maximum strength at which the bond joint breaks was measured.

[0686] [Tensile Shear Bond Strength Test]

[0687] Bonding area: 2.7cm² 2

[0688] Stretching speed: 50mm / minute

[0689] If the tensile shear bond strength is above 40 N, the rating is ○; if it is below 40 N, the rating is ×. The results (clamping properties) are shown in Table 2.

[0690] [Table 2]

[0691]

[0692] The surface treatment agents of Examples 1-20, which are polymer compositions containing fluorinated polyether groups containing components (I) and (II) mixed at a specified number-average molecular weight ratio, can achieve a balance between fabric abrasion durability and holding properties. On the other hand, the surface treatment agents of Comparative Examples 1-4, which are polymer compositions containing fluorinated polyether groups containing components (I) and (II) at a specified number-average molecular weight ratio, and the surface treatment agents of Comparative Examples 5-12, which are polymer compositions containing fluorinated polyether groups containing components (I) or (II), reduce one or both of the characteristics of fabric abrasion durability and holding properties, and it is impossible to achieve both simultaneously.

Claims

1. A polymer composition containing a fluorinated polyether group, comprising: (I) Polymers containing fluorinated polyether groups, having two or three monovalent organic groups other than silanol or hydrolyzable silyl groups at the polymer ends, and / or their partial (hydrolyzable) condensates, and (II) Polymers containing fluorinated polyether groups and / or their partial (hydrolyzed) condensates having only two or more silanol groups or hydrolyzable silane groups at the polymer ends. in, The ratio of the number average molecular weight of component (I) to that of component (II) is greater than 1.2 (I) / (II).

2. The polymer composition containing a fluorinated polyether group according to claim 1, wherein, The monovalent organic group is a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group that can be substituted with fluorine and may contain one or more of oxygen, nitrogen and silicon atoms, with a carbon number of 1 to 30.

3. The polymer composition containing a fluorinated polyether group according to claim 1, wherein, The ratio of the number average molecular weight of component (I) to that of component (II) is greater than 1.2 and less than 5.

0.

4. The polymer composition containing a fluorinated polyether group according to claim 1, wherein, The content of component (I) in the total mass of component (I) and component (II) is less than 50% by mass.

5. The polymer composition containing a fluorinated polyether group according to claim 1, wherein, (I) The components are polymers containing fluorinated polyether groups having silanol groups or hydrolyzable silyl groups, represented by the following general formula (1), and / or their partial (hydrolyzed) condensates. [Chemistry 1] In the formula, A is independently a fluorine atom, a hydrogen atom, or a monovalent hydrocarbon group containing one or more of oxygen, nitrogen, and silicon atoms with 1 to 30 carbon atoms; Rf is a divalent fluorinated polyether group represented by the following general formula (2); Z is independently a divalent organic group; Q is a trivalent or tetravalent group; Y is a divalent organic group; R is independently an alkyl or phenyl group with 1 to 4 carbon atoms; X is independently a hydroxyl or hydrolyzable group; n is independently an integer of 1 to 3 for each bonded silicon atom; and α is 2 or 3. [Chemistry 2] In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms, d is an integer from 1 to 3 for each unit independently, p, q, r, s, t, u, and v are each integer from 0 to 450, and the sum of p, q, r, s, t, u, and v is 20 to 450. These units can be linear or branched. In addition, the repeating units shown in parentheses with p, q, r, s, t, u, and v can be randomly bonded. (II) The components are polymers containing fluorinated polyether groups having silanol groups or hydrolyzable silane groups, represented by the following general formula (3), and / or their partial (hydrolyzed) condensates. [Chemistry 3] In the formula, Rf is a divalent fluorinated polyether group represented by the above general formula (2), U is an independent single bond or trivalent organic group, Z is an independent divalent organic group, R is an independent alkyl or phenyl group with 1 to 4 carbon atoms, X is an independent hydroxyl or hydrolyzable group, n is an independent integer of 1 to 3 for each bonded silicon atom, and m is 1 or 2.

6. The polymer composition containing a fluorinated polyether group according to claim 5, wherein, In equation (1) above, Q is a basis selected from the following: where R a =R is an alkyl or hydroxyl group having 1 to 3 carbon atoms. a C- represents a trivalent group, where R... b =R is 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. b The following are trivalent groups represented by Si-: trivalent isocyanuric acid group, trivalent triazine ring-containing group, tetravalent group represented by ≡C-, tetravalent group represented by ≡Si-, and trivalent or tetravalent organopolysiloxane residues with 2 to 10 silicon atoms in a straight chain or with 3 to 10 silicon atoms in a branched chain or cyclic structure.

7. The polymer composition containing a fluorinated polyether group according to claim 5, wherein, In the above formulas (1) and (3), Z is a divalent group selected from alkylene groups with 1 to 30 carbon atoms, alkylene groups with 1 to 10 carbon atoms containing arylene groups with 6 to 8 carbon atoms, alkylene groups with 1 to 15 carbon atoms connected by a diorganosilyl group, a silaneylene structure or a silaneylene structure, and a divalent group with alkylene groups with 1 to 15 carbon atoms bonded to the bonding end of a linear or branched or cyclic organopolysiloxane residue with 2 to 10 silicon atoms, a carbonyl group, and an amide group, which may contain at least one of oxygen atoms, sulfur atoms, secondary amines, tertiary amines, ketones, amides and ester groups.

8. The polymer composition containing a fluorinated polyether group 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 aryl groups having 6 to 8 carbon atoms.

9. The polymer composition containing a fluorinated polyether group according to claim 5, wherein, In the above formulas (1) and (3), X is selected from hydroxyl, alkoxy with 1 to 10 carbon atoms, alkoxy with 2 to 10 carbon atoms, acyloxy with 2 to 10 carbon atoms, olefinic oxygen with 2 to 10 carbon atoms, and halogen atoms.

10. The polymer composition containing a fluorinated polyether group according to claim 5, wherein, In the above formula (3), U is a single bond, or is selected from R. c -CR is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. c The trivalent group represented by =, the trivalent group represented by -C(=O)N=, the trivalent group represented by -N=, the trivalent isocyanuric acid group, the trivalent group containing a triazine ring, and the trivalent organopolysiloxane residues of 2 to 10 silicon atoms in a straight chain or in a branched or cyclic manner in a chain with 3 to 10 silicon atoms, which may contain at least one of an alkylene group with 1 to 10 carbon atoms and an oxygen atom.

11. The polymer composition containing a fluorinated polyether group according to claim 5, wherein, The polymer containing fluorinated polyether groups with silanol groups or hydrolyzable silane groups, represented by formula (1), is represented by any one of the following formulas. [Chemistry 4] [Chemistry 5] [Chemistry 6] [Chemistry 7] [Chemistry 8] [Chemistry 9] [Chemistry 10] [Chemistry 11] [Chemistry 12] [Chemistry 13] [Chemistry 14] In the formula, p1 is an integer from 5 to 440, q1 is an integer from 5 to 250, 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, r3 is an integer from 1 to 100, the sum of r2 and r3 is an integer from 20 to 180, and the repeating units shown in the parentheses with p1 and q1 can be bonded randomly.

12. The polymer composition containing a fluorinated polyether group according to claim 5, wherein, The polymer containing fluorinated polyether groups with silanol groups or hydrolyzable silane groups, represented by formula (3), is represented by any one of the following formulas. [Chemistry 15] [Chemistry 16] [Chemistry 17] [Chemistry 18] [Chemistry 19] [Chemistry 20] [Chemistry 21] [Chemistry 22] [Chemistry 23] [Chemistry 24] [Chemistry 25] [Chemistry 26] [Chemistry 27] [Chemistry 28] [Chemistry 29] [Chemistry 30] [Chemistry 31] [Chemistry 32] [Chemistry 33] [Chemistry 34] [Chemistry 35] [Chemistry 36] [Chemistry 37] [Chemistry 38] [Chemistry 39] [Chemistry 40] [Chemistry 41] [Chemistry 42] [Chemistry 43] [Chemistry 44] [Chemistry 45] [Chemistry 46] In the formula, p1 is an integer from 5 to 440, q1 is an integer from 5 to 250, 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, r3 is an integer from 1 to 100, the sum of r2 and r3 is an integer from 20 to 180, r4, r5, p2, and q2 are each integers greater than or equal to 1, the sum of r4, r5, p2, and q2 is 18 to 400, p3 and q3 are each integers greater than or equal to 1, the sum of p3 and q3 is 16 to 400, and the repeating units shown in parentheses with p1 and q1, p2 and q2, and p3 and q3 can be bonded randomly.

13. A surface treatment agent comprising a polymer composition containing a fluorinated polyether group according to any one of claims 1 to 12.

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

15. The article according to claim 14, wherein it is a lens substrate.

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