TW202411347A - Fluoropolyether group-containing polymer composition, coating agent, article, and method for modifying surface of article - Google Patents

Abstract

This fluoropolyether group-containing polymer composition, which contains, in a specific ratio, (I) a polymer of a specific structure having a fluorooxyalkyl group at one end and a reactive functional group at the other end and (II) a polymer of a specific structure having a fluorooxyalkylene group in a molecule and reactive functional groups at both ends, and not having a polar group, can form a cured coating film having excellent water repellency and oil repellency and wear durability, as well as slip suppression as a result of a high coefficient of friction.

Description

Polymer composition, coating and article containing fluoropolyether group, and surface modification method of article

The present invention relates to a composition of a fluoropolyether group-containing polymer (a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule), more specifically, to a fluoropolyether group-containing polymer composition capable of forming a cured film having excellent water-repellency and oil-repellency, wear durability, and slip inhibition, a coating containing the composition, and an article having a layer formed of a cured product of the coating, and further to a surface modification method of an article comprising the steps of applying the coating and curing the coating to form a layer.

In recent years, the display of mobile phones has been accelerating the trend toward touch panels. However, since the touch panel has an exposed screen, it is more likely to come into direct contact with fingers or cheeks, and dirt such as sebum may easily adhere to it, which may become a problem. Therefore, in order to improve the appearance and visibility, the demand for technology that makes it difficult for fingerprints to adhere to the display surface or technology that makes it easy to wipe off dirt has increased year by year, and it is hoped that materials that can meet these requirements will be developed. Recently, not only the display surface but also the frame has the problem of dirt such as sebum easily adhering to it, and it is hoped that a water-repellent and oil-repellent layer will be provided on both the display and the frame. However, although the conventional water-repellent and oil-repellent layers have high water-repellency and oil-repellency and excellent dirt wiping performance, there is a problem that the anti-fouling performance deteriorates during use.

Generally, compounds containing fluoropolyether groups have very low surface free energy, so they have water-repellent and oil-repellent properties, drug resistance, lubricity, mold release, and antifouling properties. Taking advantage of their properties, they are widely used in industry as water-repellent and oil-repellent antifouling agents for paper and fiber, lubricants for magnetic recording media, oil-repellent agents for precision machinery, mold release agents, cosmetics, protective films, etc. However, this property also means non-adhesion and non-stickiness to other substrates. Even if they can be applied to the surface of the substrate, it is still difficult to make the film adhere tightly.

On the other hand, silane coupling agents are well known as agents for bonding organic compounds to the surface of substrates such as glass or cloth, and are widely used as coating agents for various substrate surfaces. Silane coupling agents have an organic functional group and a reactive silane group (generally a hydrolyzable silane group such as an alkoxysilane group) in one molecule. The hydrolyzable silane group undergoes a self-condensation reaction with water in the air to form a film. The film is chemically and physically bonded to the surface of glass or metal, etc., to form a durable and strong film.

Therefore, a composition is disclosed that is easy to adhere to the surface of a substrate and forms a film having water-repellent and oil-repellent properties, chemical resistance, lubricity, mold release, antifouling properties, etc. on the surface of the substrate by introducing a fluoropolyether group-containing polymer having a hydrolyzable silyl group into a fluoropolyether group-containing compound (Patent Documents 1 to 6: JP-A-2008-534696, JP-A-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, JP-A-2015-199906).

The hardened film (antifouling coating film layer) on the surface of a glass substrate treated with a composition containing a fluoropolyether-containing polymer having a hydrolyzable silyl group introduced into a fluoropolyether-containing compound has excellent wear durability against steel wool and high sliding properties. In addition to the antifouling coating film layer on the surface of a touch panel display, the feel of the touch panel when in use (good sliding, smooth touch) is also important. Good feel is related to a low friction coefficient (Patent Document 6: Japanese Patent Publication No. 2015-199906)

On the other hand, there are also cases where the friction coefficient is too low and inappropriate on the surface of the frame of a portable electronic device terminal. That is, if the friction coefficient is low, the possibility of the terminal falling or vibrating during use becomes higher. Therefore, it is very important to maintain antifouling performance and durability while controlling the friction coefficient for the application of antifouling coating film layers in various applications represented by portable electronic device terminals (Patent Document 7: Japanese Patent Publication No. 2019-131808).

However, when the friction coefficient of the antifouling coating film layer is controlled to be relatively high, the wear durability is insufficient. [Prior art literature] [Patent literature]

[Patent Document 1] Japanese Patent Publication No. 2008-534696 [Patent Document 2] Japanese Patent Publication No. 2008-537557 [Patent Document 3] Japanese Patent Publication No. 2012-072272 [Patent Document 4] Japanese Patent Publication No. 2012-157856 [Patent Document 5] Japanese Patent Publication No. 2013-136833 [Patent Document 6] Japanese Patent Publication No. 2015-199906 [Patent Document 7] Japanese Patent Publication No. 2019-131808

[Problems to be solved by the invention]

The present invention has been made in view of the above circumstances, and its purpose is to provide a polymer composition containing a fluoropolyether group that can form a hardened film having excellent water-repellency and oil-repellency, wear durability and a high friction coefficient, a coating containing the composition, and an article having a layer formed by a hardened product of the coating, and further a surface modification method of the article comprising the steps of applying the coating and hardening it to form a layer.

As a result of intensive studies to achieve the above-mentioned purpose, the inventors of the present invention have found that, among the above-mentioned fluoropolyether group-containing polymer compositions, a fluoropolyether group-containing polymer composition (particularly a coating containing the composition) obtained by combining two specific fluoropolyether group-containing polymers described below in a specific ratio and using the polymers and/or their partial (hydrolyzed) condensates can form a hardened film having excellent water- and oil-repellency, wear durability, and slip-inhibiting properties due to a high friction coefficient, thereby completing the present invention.

Therefore, the present invention provides the following fluoropolyether-containing polymer composition, coating, article, and method for modifying the surface of an article. [1] A fluoropolyether-containing polymer composition comprising (I) a fluoropolyether-containing polymer represented by the following general formula (1) and/or a partial (hydrolyzed) condensate thereof, (wherein, Rf1 is a fluoroalkyl group having repeating units of -(C ₃ F ₆ O) _b - (repeating units of C ₃ F ₆ O are branched structures, b is an integer of 2 to 200), J is a single bond or a carbonyl group, Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom, L is independently a single bond or a divalent heteroatom, M is independently a divalent hydrocarbon group which may contain a silicon atom and/or a siloxane bond, X is independently a hydroxyl group or a hydrolyzable group, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is independently an integer of 1 to 3 for each unit bonded to a silicon atom, and a is 2 or 3), and (II) a polymer containing a fluoropolyether group represented by the following general formula (2) and/or a partial (hydrolyzed) condensate thereof, (wherein, Rf2 is a straight-chain _{fluorooxyalkylene} group having no branches and containing a unit represented by -( _CcF2cO )-( _CcF2cO unit is a straight-chain structure, c is an integer of 1 to 6), and W _is independently a monovalent group having a silyl group containing a hydroxyl group or a hydrolyzable silyl group at the end and having no polar group) The content of component (I) in the total of component (I) and component (II) is 65 to 95% by weight. [2] The fluoropolyether group-containing polymer composition of [1], wherein component (II) is represented by the following general formula (3): (wherein, Rf2 is a straight-chain _{fluorooxyalkylene group without branches and including a unit represented by -(CcF2cO)-(CcF2cO unit is a} straight-chain structure, c is an integer of 1 to 6), R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each unit bonded to a silicon atom, Y is independently a 2 to 6-valent hydrocarbon group which may have a silicon atom and/or a siloxane bond, and m is independently an integer of 1 to 5). [3] A polymer composition containing a fluoropolyether group as described in [1] or [2], wherein Rf1 of the aforementioned formula (1) is a fluorooxyalkylene group represented by the following general formula (4), (wherein A is a fluorine atom, a hydrogen atom or a fluoroalkyl group having a terminal _-CF3 group, and b1 is an integer from 1 to 200). [4] A polymer composition containing a fluoropolyether group as described in any one of [1] to [3], wherein in the aforementioned formula (1), X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms and a halogen group. [5] A polymer composition containing a fluoropolyether group as described in any one of [1] to [4], wherein the polymer represented by formula (1) is selected from the polymers represented by the following formulas: (wherein b1' is an integer between 1 and 199). [6] A fluoropolyether group-containing polymer composition as described in any one of [1] to [5], wherein Rf2 is represented by the following formula (5): (wherein, d is an integer of 0 to 5 for each unit independently, p, q, r, s, t, u are integers of 0 to 200 respectively, p+q+r+s+t+u=10 to 250, and the units are in the form of a straight chain, and the repeated units in the brackets marked with p, q, r, s, t, u may be randomly linked.) [7] A polymer composition containing a fluoropolyether group as described in any one of [1] to [6], wherein the aforementioned Rf2 is selected from a polymer represented by the following formula: (wherein, p', q', r', s', t', u' are integers of 1 to 200, the total of p', q', r', s', t', u' is 10 to 250, each of these units is in the form of a straight chain, and each of the repeated units indicated in the brackets labeled p', q', r', s', t', u' may be randomly bonded, and d' is independently an integer of 0 to 5 in each unit, and each of these units is in the form of a straight chain.) [8] A fluoropolyether group-containing polymer composition as described in any one of [2] to [7], wherein in the aforementioned formula (3), X is independently a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group. [9] The fluoropolyether group-containing polymer composition according to any one of [2] to [8], wherein the polymer represented by the above formula (3) is selected from polymers represented by the following formulas: (wherein p1 and q1 are integers ranging from 1 to 199 respectively, and the sum of p1 and q1 is 10 to 200.) [10] A coating comprising a polymer composition containing a fluoropolyether group as described in any one of [1] to [9]. [11] An article having a layer formed by a cured product of the coating as described in [10]. [12] An article, wherein the coefficient of dynamic friction of the surface of the article as described in [11] is 0.13 or more under the following measurement conditions, and the number of abrasion durability is 5,000 or more under the following test conditions. [Measurement conditions of dynamic friction coefficient] Determined by the method according to ASTM D1894 Load: 100 gf Stroke: 100 mm Tensile speed: 500 mm/min Contact area: 1× ³ cm2 Friction material: Non-woven fabric (BEMCOT (produced by Asahi Kasei Corporation)) Test environment conditions: 25°C, relative humidity 50% [Abrasion durability test conditions] Evaluation of the abrasion durability of steel wool using a reciprocating abrasion tester Friction material: Steel wool #0000 (Bonstar) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocating times per minute Test environment: 25°C, relative humidity 50% The water contact angle of the friction wear part is measured every 2,500 times of friction reciprocating times, and the number of reciprocating times of wear that maintains a water contact angle of more than 100 degrees is set as the wear durability number. [13] A surface modification method for an article, which comprises the steps of applying a coating agent containing a polymer composition containing a fluoropolyether group as described in any one of [1] to [9] to the entire or a part of the surface of the article by a dry method or a wet method and hardening it to form a layer. [Effect of the invention]

According to the polymer composition containing a fluoropolyether group of the present invention, a hardened film having excellent water-repellency and oil-repellency and showing high wear durability despite a high coefficient of friction can be provided. Thus, articles (such as portable electronic device terminals, etc.) having a layer formed by a hardened product of the composition of the present invention (especially a coating containing the composition) have excellent water-repellency and oil-repellency, wear durability, and high slip suppression.

In the present invention, the so-called "partial (hydrolysis) condensate" refers to a partial condensate or a partially hydrolyzed condensate.

The fluoropolyether group-containing polymer composition of the present invention contains two specific fluoropolyether group-containing polymers in a specific ratio, wherein one of the fluoropolyether group-containing polymers (I) is a polymer having a fluorooxyalkyl group in the molecule and a reactive functional group at one end of the polymer, and the other (II) is a polymer having a fluorooxyalkylene group in the molecule and reactive functional groups at both ends of the polymer.

In the fluoropolyether group-containing polymer composition of the present invention, the polymer having a fluorooxyalkyl group in the molecule and a reactive functional group at one end of the polymer as component (I) is a fluoropolyether group-containing polymer represented by the following general formula (1) and/or its partial (hydrolyzed) condensate. (wherein, Rf1 is a fluorooxyalkyl group having repeating units of -(C ₃ F ₆ O) _b - (repeating unit C ₃ F ₆ O is a branched structure, b is an integer of 2 to 200), J is a single bond or a carbonyl group, Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom, L is independently a single bond or a divalent heteroatom (preferably an oxygen atom in an ether bond), M is independently a divalent hydrocarbon group which may contain a silicon atom and/or a siloxane bond, X is independently a hydroxyl group or a hydrolyzable group, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is independently an integer of 1 to 3 for each unit bonded to a silicon atom, and a is 2 or 3).

In the fluoropolyether group-containing polymer composition of the present invention, the polymer having a fluorooxyalkylene group in the molecule and reactive functional groups at both ends of the polymer as component (II) is a fluoropolyether group-containing polymer represented by the following general formula (2) and/or its partial (hydrolyzed) condensate. (In the formula, Rf2 is a linear fluorooxyalkylene group having no branches and containing a unit represented by -(C _c F _2c O)-(C _c F _2c O unit is a linear structure, c is an integer of 1 to 6), and W is independently a monovalent group having a silyl group containing a hydroxyl group or a hydrolyzable silyl group at the terminal and having no polar group).

In the fluoropolyether-containing polymer composition of the present invention, the content of component (I) in the total of component (I) and component (II) is 65-95% by mass, preferably 65-90% by mass, and more preferably 65-85% by mass. If the content of component (I) in the total of component (I) and component (II) is less than 65% by mass, the friction coefficient and wear durability of the hardened film are reduced, and if it is more than 95% by mass, the wear durability of the hardened film is reduced although the friction coefficient is high.

The polymer containing a fluoropolyether group of the above formula (1) is a structure in which a fluorooxyalkyl group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group, and the hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group exists in two or more groups in the molecule. The main chain structure is characterized by a base structure represented by -(C ₃ F ₆ O) _b - (repeating units of C ₃ F ₆ O are branched structures, and b is an integer of 2 to 200) to increase the friction coefficient (not easy to slide).

In the aforementioned formula (1), Rf1 is a fluorooxyalkyl group having as its main structure a group represented by -(C ₃ F ₆ O) _b - (repeating units of C ₃ F ₆ O are branched structures represented by -CF(CF ₃ )CF ₂ О- (i.e., repeating unit structures of hexafluoropropylene oxide through ring opening), b is an integer of 2 to 200, preferably an integer of 3 to 100) (repeating structure of hexafluoropropylene oxide), preferably a fluoroalkoxy group represented by the following general formula (4).

(wherein, A is a fluorine atom, a hydrogen atom or a fluoroalkyl group having a terminal _-CF3 group, and b1 is an integer from 1 to 200).

In the aforementioned formula (4), A is a fluorine atom, a hydrogen atom or a fluoroalkyl group having a _-CF3 group at the end. Examples of the fluoroalkyl group having a _-CF3 group _{at the end} include _{CF3CF2CF2CF2- , CF3CF2CF2-, CF3CF2- , CF3- , CF3ОCF2CFH- , CF3CF2CF2ОCF2CFH- , CF3ОCF2CF2CF2ОCF2CFH- , and CF3ОCF2CF2CF2CF2ОCF2CFH- . Preferably , it is CF3CF2CF2- .}

b1 is an integer of 1 to 200, preferably an integer of 3 to 100, and more preferably an integer of 5 to 50. If b1 is less than the upper limit, the adhesion and curing properties are good and the handling is easy. If b1 is greater than the lower limit, the characteristics of the fluoroalkyl group can be fully exerted, which is preferred.

Specific examples of Rf1 include the following. (Wherein, b1' is an integer between 1 and 199, preferably an integer between 3 and 100).

In the above formula (1), J is a single bond or a carbonyl group (-C(=O)-).

In the above formula (1), Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom. Specific examples of Q other than a single bond include the following. Preferably, the left-side bond is bonded to J, and the right-side bond is bonded to a carbon atom. (wherein, e1 is an integer between 1 and 4, preferably 1 or 2, and e2 is an integer between 1 and 4, preferably 1, 2 or 3).

In the above formula (1), L is independently a single bond or a divalent heteroatom. Examples of the divalent heteroatom include oxygen atom, nitrogen atom, and sulfur atom, and preferably oxygen atom (oxygen atom in ether bond). L is preferably a single bond or an oxygen atom.

In the above formula (1), M is independently a divalent alkyl group which may contain a silicon atom and/or a siloxane bond. Examples of M include alkylene groups having 3 to 10 carbon atoms such as propylene, butylene, and hexamethylene, alkylene groups having 3 to 10 carbon atoms (e.g., alkylene groups and arylene groups having 8 to 16 carbon atoms) including arylene groups having 6 to 8 carbon atoms such as phenyl, divalent groups in which alkylene groups having 3 to 10 carbon atoms are mutually bonded via a silylene alkylene structure or a silylene arylene structure, and linear divalent organic polysilicon groups having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms. The divalent group of an alkylene group having 2 to 10 carbon atoms is bonded to the bonding bond of the oxane residue, preferably an alkylene group having 3 to 10 carbon atoms, an alkylene group having 3 to 10 carbon atoms containing a phenylene group, a divalent group of alkylene groups having 3 to 10 carbon atoms bonded to each other via a silylene alkylene structure or a silylene aryl structure, a divalent group of an alkylene group having 2 to 10 carbon atoms is bonded to the bonding bond of the divalent organic siloxane residue, and more preferably an alkylene group having 3 to 6 carbon atoms, a divalent group of alkylene groups having 3 to 10 carbon atoms bonded to each other via a silylene alkylene structure or a silylene aryl structure.

Here, examples of the silylene alkyl structure and the silylene aryl structure include the following. (In the formula, ^R1 is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, or an aryl group having 6 to 10 carbon atoms, such as phenyl, and ^R1 may be the same or different. ^R2 is an alkyl group having 1 to 6 carbon atoms, such as methylene, ethyl, propyl (trimethylene, methylethyl), or an aryl group having 6 to 10 carbon atoms, such as phenyl).

Furthermore, examples of the linear divalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, include the following. (wherein, ^R1 is the same as above, and g is an integer from 1 to 9, preferably an integer from 1 to 4).

As M, for example, a group represented by the following formula: (In the formula, f1 is an integer between 3 and 10, preferably an integer between 3 and 6, f2 is an integer between 1 and 6, preferably an integer between 2 and 4, f3 is an integer between 3 and 10, preferably an integer between 3 and 6, and g is an integer between 1 and 9, preferably an integer between 1 and 4).

As specific examples of M, for example, the following groups are exemplified. In addition, it is preferred that the left-side bond is bonded to L, and the right-side bond is bonded to a silicon atom.

In the above formula (1), X is independently a hydroxyl group or a hydrolyzable group, specifically, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, an alkoxyalkoxy group having 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, an acyloxy group having 1 to 10 carbon atoms such as acetyloxy, an alkenyloxy group having 2 to 10 carbon atoms such as isopropenyloxy, a halogen group such as chlorine, bromine, iodine, etc. Among them, methoxy, ethoxy, isopropenyloxy, and chloro are preferred. Moreover, R is independently an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc., or a phenyl group, among which methyl is preferred. n is an integer of 1 to 3 for each unit independently bonded to the silicon atom, preferably 2 or 3, and more preferably 3 from the perspective of reactivity and adhesion to the substrate.

In the above formula (1), _-SiXn (R) _3-n is preferably a trialkoxysilyl group such as trimethoxysilyl, triethoxysilyl, tripropoxysilyl, tri(isopropoxy)silyl, tributoxysilyl, tri(isobutoxy)silyl, tri(sec-butoxy)silyl, or tri(tert-butoxy)silyl.

In the aforementioned formula (1), a is 2 or 3. In the aforementioned formula (1), among the 2 or 3 Ls in one molecule, it is preferred that all of them are single bonds, or that 1 L is an oxygen atom and the other 1 or 2 Ls are single bonds. In particular, when a is 2, it is preferred that one of the 2 Ls in one molecule is an oxygen atom and the other L is a single bond. When a is 3, it is preferred that all of the 3 Ls in one molecule are single bonds.

Examples of the fluoropolyether group-containing polymer represented by the above formula (1) include the following. (Wherein, b1' is an integer between 1 and 199). (Wherein, b1' is an integer between 1 and 199). (Wherein, b1' is an integer between 1 and 199). (Wherein, b1' is an integer between 1 and 199). (Wherein, b1' is an integer between 1 and 199). (Wherein, b1' is an integer between 1 and 199). (Wherein, b1' is an integer between 1 and 199). (Wherein, b1' is an integer between 1 and 199). (Wherein, b1' is an integer between 1 and 199). (Wherein, b1' is an integer between 1 and 199).

The fluoropolyether group-containing polymer represented by the above formula (1) is preferably one represented by the following formula. (Wherein, b1' is an integer between 1 and 199).

The polymer containing a fluoropolyether group of the above formula (2) has a structure in which a fluoroalkylene group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group having no polar group. The hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group is present at both ends in one or more groups, and a total of two or more groups are present in the molecule. In addition to the hydrolyzable silyl group or the hydroxyl group-containing silyl group, there is no polar group in the molecule, specifically, no carbonyl group, -NH- group, amide group or hydroxyl group, resulting in a simpler bonding pattern.

In the above formula (2), Rf2 includes a unit represented by the formula: -(C _c F _2c O)-(C _c F _2c O unit is a linear structure, c is an integer of 1 to 6) and a linear fluorooxyalkylene group without branches. By using a linear fluorooxyalkylene group without branches, high wear durability of the cured film can be obtained.

The fluorooxyalkylene group as Rf2 is preferably represented by the following formula (5). (In the formula, d is an integer between 0 and 5 in each unit independently, p, q, r, s, t, and u are integers between 0 and 200 respectively, and p+q+r+s+t+u=integers between 10 and 250. These units are in the form of a direct link. The repeated units shown in the brackets with p, q, r, s, t, and u can be randomly linked).

In the above formula (5), d is an integer of 0 to 5 in each unit independently, preferably an integer of 0 to 2, and more preferably 1 or 2. Moreover, p, q, r, s, t, and u are integers of 0 to 200, respectively, preferably p is an integer of 10 to 150, q is an integer of 10 to 150, r is an integer of 0 to 20, s is an integer of 0 to 20, t is an integer of 0 to 20, and u is an integer of 0 to 20. p+q+r+s+t+u is an integer of 10 to 250, preferably an integer of 20 to 150. If p+q+r+s+t+u is less than the above upper limit, the adhesion between the substrate and the hardened film or the reactivity during synthesis is good. If it is greater than the above lower limit, the water-repellent and oil-repellent properties or wear durability of the hardened film are excellent. These units are in the form of direct links. In addition, the repeated units in brackets with p, q, r, s, t, and u can be randomly linked.

Examples of the fluorooxyalkylene group as Rf2 include those shown in the following structures. (In the formula, p', q', r', s', t' and u' are integers of 1 to 200 respectively, and the sum of p', q', r', s', t' and u' is 10 to 250, and these units are in the form of a straight chain. The repeated units shown in the brackets with p', q', r', s', t' and u' may be randomly linked. In addition, d is an integer of 0 to 5 independently in each unit, and these units are in the form of a straight chain).

As Rf2, the following can be preferably used. (In the formula, p" and q" are integers from 1 to 199 respectively, and the sum of p"+q" is an integer from 10 to 200. The arrangement of the repeating units (CF ₂ CF ₂ O) and (CF ₂ O) in the formula is random).

In the above formula (2), W is independently a monovalent group having a hydroxyl-containing silyl group or a hydrolyzable silyl group at the terminal and having no polar group. Preferably, it is a monovalent group consisting of a hydroxyl-containing silyl group or a hydrolyzable silyl group at the terminal and a linking group having no polar group (carbonyl group, -NH- group, amide group or hydroxyl group, etc.) linking the silyl group to an O group (ether bond oxygen atom). Examples of such W include groups represented by the following formulas (6a) to (6e). (wherein, X, R, and n are the same as above, D is a divalent organic group having 1 to 20 carbon atoms which may be substituted by fluorine, v1 is an integer of 2 to 6, v2 is independently an integer of 2 to 10, and g1 is an integer of 1 to 9).

In the above formulae (6a) to (6e), D is a divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, which may be substituted by fluorine, preferably 1 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, which may be substituted by fluorine, and examples of the divalent alkyl group include methylene, ethyl, propyl (trimethylene, methylethyl), butyl (tetramethylene, methylpropyl), hexamethylene, octamethylene, etc. alkyl, aryl such as phenyl, or a combination of two or more of these groups (alkyl‧aryl), etc., or a group in which a part or all of the hydrogen atoms of these groups are substituted by fluorine atoms. Preferred examples of D include ethyl, propyl, butyl, hexamethylene, phenyl, etc.

In the above formulas (6a) to (6e), v1 is an integer from 2 to 6, preferably an integer from 2 to 4, v2 is an integer from 2 to 10, preferably an integer from 3 to 6, and g1 is an integer from 1 to 9, preferably an integer from 1 to 4.

Specific examples of these W include those shown below.

The fluoropolyether group-containing polymer of the above formula (2) is more preferably one represented by the following formula (3). (wherein, Rf2, R, X, and n are the same as above, Y is independently a 2-6 valent alkyl group which may have a silicon atom and/or a siloxane bond, and m is independently an integer of 1 to 5).

In the above formula (3), Y is independently a 2-6-valent, preferably a 2-4-valent, and more preferably a 2-valent alkyl group, and may have a silicon atom and/or a siloxane bond. Since the molecule does not contain a polar group, a coating film with excellent water-repellency and oil-repellency can be imparted.

Specific examples of Y include alkylene groups having 3 to 10 carbon atoms such as propylene, butylene, and hexamethylene, alkylene groups having 2 to 10 carbon atoms (e.g., alkylene groups and arylene groups having 8 to 16 carbon atoms) including arylene groups having 6 to 8 carbon atoms such as phenylene, divalent groups in which alkylene groups having 2 to 10 carbon atoms are mutually bonded via a silylene alkylene structure or a silylene arylene structure, and 2 to 6 valent organic polysiloxane residues having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, and The 2-6 valent groups of alkylene groups having 2-10 carbon atoms are preferably alkylene groups having 3-10 carbon atoms, alkylene groups having 2-10 carbon atoms including phenylene groups, alkylene groups having 2-10 carbon atoms bonded to each other via a silylene alkylene structure or a silylene aryl structure, and 2-4 valent organic polysiloxane residues having 2-10 silicon atoms in a straight chain or branched or cyclic form bonded to alkylene groups having 2-10 carbon atoms, and alkylene groups having 3-6 carbon atoms are more preferred.

Here, the silylene alkyl structure and the silylene aryl structure may be the same as those exemplified in M of formula (1).

Furthermore, the linear, branched or cyclic 2-6 valent organopolysiloxane residue having 2-10, preferably 2-5, silicon atoms can be exemplified by the following. (wherein, ^R1 is the same as above, g1 is an integer of 1 to 9, preferably an integer of 1 to 4, h is an integer of 2 to 6, preferably an integer of 2 to 4, j is an integer of 0 to 8, preferably 0 or 1, h+j is an integer of 3 to 10, preferably an integer of 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3).

As Y, a group represented by the following formula is exemplified. (In the formula, v1, v2, and g1 are the same as above, v is an integer between 3 and 10, preferably an integer between 3 and 6, and v0 is an integer between 2 and 10, preferably an integer between 3 and 6).

Specific examples of Y include the following groups.

m is independently an integer of 1 to 5. If it is less than 1, the adhesion to the substrate is reduced. If it is 6 or more, the terminal alkoxy group is too high and has an adverse effect on the performance. Therefore, it is preferably an integer of 1 to 3, and particularly preferably 1.

Examples of the fluoropolyether group-containing polymer represented by the above formula (3) include those represented by the following formula.

(In the formula, p1 and q1 are integers ranging from 1 to 199 respectively, and the total of p1 and q1 is 10 to 200).

The present invention provides a coating comprising a fluoropolyether group-containing polymer composition, wherein the polymer composition is composed of a fluoropolyether group-containing polymer represented by the aforementioned formula (1), a fluoropolyether group-containing polymer represented by the aforementioned formula (2), and particularly a fluoropolyether group-containing polymer represented by the aforementioned formula (3) at a specific ratio. The coating may comprise a partial (hydrolyzed) condensate obtained by condensing a hydroxyl group of the fluoropolyether group-containing polymer represented by the aforementioned formula (1) and the aforementioned formula (2), or a hydroxyl group of the terminal hydrolyzable group of the fluoropolyether group-containing polymer partially hydrolyzed in advance by a known method.

Hydrolysis and condensation catalysts such as organic tin compounds (dimethoxydibutyltin, dibutyltin dilaurate, etc.), organic titanium compounds (tetrabutyl titanium, etc.), organic acids (acetic acid, methanesulfonic acid, fluorinated carboxylic acids, etc.), and inorganic acids (hydrochloric acid, sulfuric acid, etc.) may also be added to the coating as needed. Among them, acetic acid, tetrabutyl titanium, dibutyltin dilaurate, fluorinated carboxylic acids, etc. are particularly preferred. The amount of hydrolysis and condensation catalyst added is the amount of catalyst, which is usually 0.01 to 5 parts by mass, especially 0.1 to 1 part by mass, relative to 100 parts by mass of the polymer composition containing the fluoropolyether group.

The coating may contain an appropriate solvent. Examples of such solvents include fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorinated aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorinated ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorinated alkylamine solvents (perfluorotributylamine, perfluorotriphenylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are desirable in terms of solubility, wettability, etc., and particularly preferred are 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether.

The above solvents may be mixed with two or more thereof, preferably to uniformly dissolve the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate. The optimum concentration of the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and partial (hydrolyzed) condensate thereof) dissolved in the solvent varies depending on the treatment method, and may be an amount that can be easily weighed. However, in direct coating, it is preferably 0.01 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and partial (hydrolyzed) condensate thereof). In evaporation treatment, it is preferably 1 to 100 parts by mass, and particularly preferably 3 to 30 parts by mass, based on 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and partial (hydrolyzed) condensate thereof).

The coating of the present invention can be applied to the substrate by known methods such as brush coating, dipping, spraying, and evaporation treatment. The heating method during the evaporation treatment can be either a resistance heating method or an electron beam heating method, and is not particularly limited. The curing temperature also varies with the curing method, but when it is directly coated (brush coating, dipping, spraying, etc.), it is preferably 25~200°C, especially 25~80°C for 30 minutes to 36 hours, especially 1~24 hours. In addition, when applied by evaporation treatment, it is expected to be 20~200°C, especially 25~80°C for 30 minutes to 36 hours, especially 30 minutes to 24 hours. Furthermore, it can also be cured under humidity. The thickness of the cured film is appropriately selected according to the type of substrate, but is generally 0.1~100nm, especially 1~20nm. Moreover, for example, when spraying, it is diluted in a fluorine-based solvent with water added in advance and hydrolyzed, that is, Si-OH is generated, and then spraying is performed, and the curing after coating is fast. In addition, the film thickness can be measured by means such as spectroscopic reflectivity measurement method, X-ray reflectivity measurement method, spectroscopic ellipse measurement method, fluorescent X-ray measurement method, etc.

The substrate treated with the coating of the present invention is not particularly limited, and can be various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc. The coating of the present invention can impart water and oil repellency and steel wool abrasion resistance to the aforementioned substrates. In particular, it can be preferably used as a coating for glass or film treated with _SiO2 .

Examples of articles treated with the coating of the present invention include automotive satellite navigation, mobile phones, smart phones, digital cameras, digital cameras, PDAs, portable audio and video displays, car stereos, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, gastroscopes and other medical devices, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films and other optical articles. In addition, from the perspective of preventing slippage, the frames of mobile phones, smart phones, PCs and the like can also be treated. The coating of the present invention can prevent fingerprints and sebum from adhering to the aforementioned articles, thereby imparting scratch prevention properties (wear resistance), and can therefore be used as a water-repellent and oil-repellent layer for mobile phones, smart phones, PC housings, and the like.

Furthermore, the coating of the present invention can also be used as an antifouling coating for sanitary products such as bathtubs and washbasins, an antifouling coating for window glass or tempered glass of cars, trains, airplanes, etc., an antifouling coating for headlight covers, etc., a water-repellent and oil-repellent coating for exterior wall building materials, an oil-repellent coating for kitchen building materials, an antifouling and anti-sticker and graffiti coating for telephone booths, a coating for preventing fingerprints from being attached to artworks, a coating for preventing fingerprints from being attached to optical discs and DVDs, a mold release agent or coating additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, a tape, a film, etc., as a water-repellent and oil-repellent. Furthermore, based on the viewpoint of being non-slip, it is also useful for anti-fouling coating of building materials, especially floor materials or wall materials.

According to the present invention, the surface of an article can be modified by applying the coating agent containing a polymer composition containing a fluoropolyether group of the present invention to the whole or part of the article by a dry method (evaporation treatment) or a wet method (brush coating, dipping, spraying, etc.), and hardening it to form a layer.

In an article having a layer formed of a cured product of the coating of the present invention, the coefficient of dynamic friction of the surface of the article is preferably 0.13 or more, more preferably 0.18 or more under the measurement conditions described below. When the coefficient of dynamic friction is less than 0.13, the surface of the cured film is too slippery, so the retention and fixation of the coated article may be insufficient. In the present invention, in order to make the coefficient of dynamic friction of the surface of the article above the above value, it can be achieved by setting the polymer containing a fluoropolyether group represented by the above formula (1) in the coating containing a fluoropolyether group-containing polymer composition of the present invention to 65 mass % or more. [Dynamic friction coefficient measurement conditions] Measured by the method based on ASTM D1894 Load: 100gf Stroke: 100mm Tensile speed: 500mm/min Contact area: 1× ^3cm2 Friction material: Non-woven fabric (BEMCOT (manufactured by Asahi Kasei Corporation)) Test environment conditions: 25℃, relative humidity 50%

In an article having a layer formed by the cured product of the coating of the present invention, the number of times the surface of the article is subjected to wear under the test conditions described below is preferably 5,000 times or more, and more preferably 7,500 times or more. In the present invention, in order to make the surface of the article subjected to wear more than the above value, the amount of the polymer containing a fluoropolyether group represented by the above formula (2) in the coating of the present invention containing a polymer composition containing a fluoropolyether group is set to 10% by mass or more. [Wear durability test conditions] Evaluation of steel wool wear durability using a reciprocating wear tester Friction material: steel wool #0000 (Bonstar) Load: 1kgf Reciprocating distance: 40mm Reciprocating speed: 60 reciprocating times per minute Test environment conditions: 25℃, relative humidity 50% The water contact angle of the friction wear part is measured every 2,500 reciprocating times, and the number of reciprocating times that maintain a water contact angle of more than 100 degrees is set as the wear durability number. [Example]

The present invention is described in more detail below by way of examples and comparative examples, but the present invention is not limited to the following examples. In the following formula, the film thickness is a value measured by a spectroscopic ellipse measurement method using a spectroscopic ellipse.

[Examples 1 to 54, Comparative Examples 1 to 39] Preparation of coatings and formation of cured films A polymer containing a fluoropolyether group having a structure represented by the following formulae (A), (B), and (C) is used as component (I). and a fluoropolyether group-containing polymer having a structure represented by the following formulae (D), (E), (F), (G), (H), and (I) as component (II), The polymer composition containing fluoropolyether groups was obtained by mixing in the ratios shown in Tables 1, 2, and 3. The polymer composition was dissolved in Novec 7200 (3M, ethyl perfluorobutyl ether) at a concentration of 20 mass % to prepare a coating. 6 μl of each coating was vacuum-deposited on glass (Corning Gorilla) with 10 nm SiO ₂ treated on the top surface (treatment conditions: pressure: 3.0×10 ^-3 Pa, heating temperature: 500°C), placed in an environment of 80°C and 80% relative humidity for 30 minutes, and then cured for more than 12 hours in an environment of 25°C and 50% relative humidity to form a cured film with a film thickness of 13 nm.

[Evaluation of initial water repellency] For the glass with the hardened film formed as above, the contact angle (water repellency) of the hardened film to water was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2μl, temperature: 25°C, relative humidity: 50%). The results (initial water contact angle) are shown in Tables 1, 2, and 3. In the initial stage, both the embodiment and the comparative example showed good water repellency of more than 110°.

[Evaluation of Sliding Property] The dynamic friction coefficient of the glass with the hardened coating formed thereon was evaluated for sliding property by the method shown below. According to ASTM D1894, the dynamic friction coefficient of the glass with the hardened coating formed thereon for nonwoven fabric was measured under the conditions of a load of 100 gf and a tensile speed of 500 mm/min using a surface property tester TYPE: 14FW (manufactured by Shinto Scientific Co., Ltd.). As evaluation indexes, a dynamic friction coefficient of 0.23 or more was evaluated as ◎ (excellent), 0.18 or more and less than 0.23 was evaluated as ○ (good), 0.13 or more and less than 0.18 was evaluated as △ (acceptable), and less than 0.13 was evaluated as × (unacceptable), and the results are shown in Tables 1, 2, and 3. The test environment was 25°C and the relative humidity was 50%. Sliding load: 100gf Stroke: 100mm Contact area: 1× ^3cm2 Friction material: Non-woven fabric (BEMCOT (manufactured by Asahi Kasei Corporation))

[Evaluation of wear resistance] Evaluation of steel wool wear durability For the substrate with the antifouling coating film layer (hardened film) obtained above, a reciprocating wear tester (model 40, manufactured by Shinto Scientific Co., Ltd.) was used to conduct the test under the following conditions. Friction material: steel wool #0000 (Bonstar) Load: 1kgf Reciprocating distance: 40mm Reciprocating speed: 60 reciprocating times per minute Total friction reciprocating times: 10,000 times The water contact angle of the friction and wear part was measured every 2,500 reciprocating times. The number of reciprocating abrasions with a water contact angle of more than 100° is set as the steel wool abrasion durability times. The steel wool abrasion durability times of more than 10,000 times are evaluated as ◎ (excellent), more than 7,500 times but less than 10,000 times are evaluated as ○ (good), more than 5,000 times but less than 7,500 times are evaluated as △ (acceptable), and less than 5,000 times are evaluated as × (unacceptable), and are shown in Tables 1, 2, and 3. The test environment conditions are 25℃ and relative humidity 50%.

When the fluoropolyether-containing polymer of component (I) is used alone, the dynamic friction coefficient is good, but the wear resistance is insufficient. When a fluoropolyether-containing polymer having a fluorooxyalkylene group in the molecule, reactive functional groups at both ends of the polymer, and no polar group is used in addition to the fluoropolyether-containing polymer of component (I) in the proportion shown in the examples, the dynamic friction coefficient and wear resistance are good. It is seen that if the mixing ratio of component (II) relative to component (I) becomes higher, the dynamic friction coefficient and wear resistance tend to decrease.

Claims (13)

A fluoropolyether group-containing polymer composition comprising (I) a fluoropolyether group-containing polymer represented by the following general formula (1) and/or a partial (hydrolyzed) condensate thereof, (wherein, Rf1 is a fluoroalkyl group having repeating units of -(C ₃ F ₆ O) _b - (repeating units of C ₃ F ₆ O are branched structures, b is an integer of 2 to 200), J is a single bond or a carbonyl group, Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom, L is independently a single bond or a divalent heteroatom, M is independently a divalent hydrocarbon group which may contain a silicon atom and/or a siloxane bond, X is independently a hydroxyl group or a hydrolyzable group, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is independently an integer of 1 to 3 for each unit bonded to a silicon atom, and a is 2 or 3), and (II) a polymer containing a fluoropolyether group represented by the following general formula (2) and/or a partial (hydrolyzed) condensate thereof, (wherein, Rf2 is a straight-chain fluorooxyalkylene group having no branches and a unit represented by -(C _c F _2c 0)-(C _c F _2c 0 unit is a straight-chain structure, c is an integer of 1 to 6), and W is independently a monovalent group having a silyl group containing a hydroxyl group or a hydrolyzable silyl group at the end and having no polar group) The content of component (I) in the total of component (I) and component (II) is 65 to 95% by mass. The polymer composition containing a fluoropolyether group as claimed in claim 1, wherein the component (II) is represented by the following general formula (3): (wherein, Rf2 is a straight-chain fluorooxyalkylene group without branches, which includes a unit represented by -(C _c F _2c O)-(C _c F _2c O unit is a straight-chain structure, c is an integer of 1 to 6), R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is independently an integer of 1 to 3 for each unit bonded to a silicon atom, Y is independently a 2 to 6-valent hydrocarbon group which may have a silicon atom and/or a siloxane bond, and m is independently an integer of 1 to 5). The polymer composition containing a fluoropolyether group as claimed in claim 1, wherein Rf1 of the aforementioned formula (1) is a fluorooxyalkyl group represented by the following general formula (4), (wherein, A is a fluorine atom, a hydrogen atom or a fluoroalkyl group having a terminal _-CF3 group, and b1 is an integer from 1 to 200). The fluoropolyether group-containing polymer composition of claim 1, wherein in the aforementioned formula (1), X is independently selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group. The polymer composition containing a fluoropolyether group as claimed in claim 1, wherein the polymer represented by formula (1) is selected from polymers represented by the following formulas: (Wherein, b1' is an integer between 1 and 199). The polymer composition containing a fluoropolyether group as claimed in claim 1, wherein Rf2 of the aforementioned formula (2) is represented by the following formula (5), (Wherein, d is an integer ranging from 0 to 5 for each unit independently, p, q, r, s, t, and u are integers ranging from 0 to 200 respectively, and p+q+r+s+t+u=10 to 250. These units are in the form of a straight link, and the repeated units shown in the brackets marked with p, q, r, s, t, and u can be randomly linked). The polymer composition containing a fluoropolyether group as claimed in claim 1, wherein Rf2 of the aforementioned formula (2) is selected from polymers represented by the following formula: (wherein, p', q', r', s', t', u' are integers ranging from 1 to 200 respectively, the sum of p', q', r', s', t', u' is 10 to 250, these units are in the form of a straight chain, and the repeated units indicated in the brackets marked with p', q', r', s', t', u' may be randomly linked, d' is an integer ranging from 0 to 5 independently for each unit, these units are in the form of a straight chain). The fluoropolyether group-containing polymer composition of claim 2, wherein in the aforementioned formula (3), X is independently selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group. The polymer composition containing a fluoropolyether group as claimed in claim 2, wherein the polymer represented by the aforementioned formula (3) is selected from polymers represented by the following formulas: (In the formula, p1 and q1 are integers ranging from 1 to 199 respectively, and the total of p1 and q1 is 10 to 200). A coating agent comprising the polymer composition containing a fluoropolyether group as claimed in any one of claims 1 to 9. An article having a layer formed of a cured product of the coating according to claim 10. An article, wherein the coefficient of dynamic friction of the surface of the article as claimed in claim 11 is 0.13 or more under the following measurement conditions, and the number of wear durability times is 5,000 or more under the following test conditions. [Measurement conditions of dynamic friction coefficient] Determined by the method according to ASTM D1894 Load: 100gf Stroke: 100mm Tensile speed: 500mm/min Contact area: 1× ^3cm2 Friction material: Non-woven fabric (BEMCOT (produced by Asahi Kasei Corporation)) Test environment conditions: 25℃, relative humidity 50% [Wear durability test conditions] Evaluation of the wear durability of steel wool using a reciprocating wear tester Friction material: Steel wool #0000 (Bonstar) Load: 1kgf Reciprocating distance: 40mm Reciprocating speed: 60 reciprocating times per minute Test environment: 25℃, relative humidity 50% Friction reciprocating times The water contact angle of the friction and wear part is measured every 2,500 times. The number of reciprocating times when the water contact angle is kept above 100 degrees is set as the wear endurance times. A method for modifying the surface of an article, comprising the steps of applying a coating agent comprising a polymer composition containing a fluoropolyether group as described in any one of claims 1 to 9 to the entire or a part of the surface of the article by a dry method or a wet method and curing the coating agent to form a layer.