JP6365328B2 - Fluorine-containing coating agent and article treated with the coating agent - Google Patents

Description

  The present invention relates to a coating agent containing a silane having a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer, and an article treated with the coating agent.

  In recent years, the touch panel of the screen including the display of the mobile phone has been accelerated. However, many touch panels have a bare screen, and there are many occasions where fingers, cheeks, etc. are in direct contact, and dirt such as sebum is likely to be attached. Therefore, there is an increasing demand for technology that makes it difficult to attach fingerprints to the surface of a display and technology that makes it easy to remove dirt in order to improve the appearance and visibility. Conventional water and oil repellents have high water and oil repellency and can form a film having excellent dirt wiping properties, but have the disadvantage that the durability performance varies greatly from film to film. Moreover, since the processing agents are aggregated, it was difficult to obtain a smooth film. For this reason, development of treatment agents and treatment methods that can stably form high-performance films has been awaited.

  In general, a perfluorooxyalkylene group-containing compound has a very small surface free energy, and thus has water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties and the like. Utilizing its properties, it is widely used industrially for water and oil repellent and antifouling agents such as paper and fiber, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, the property means that it is non-adhesive and non-adhesive to other substrates at the same time, and even if it can be applied to the surface of the substrate, it was difficult to make the film adhere to it. .

  On the other hand, silane coupling agents are well known as those for bonding a substrate surface such as glass or cloth and an organic compound, and are widely used as coating agents for various substrate surfaces. The silane coupling agent has an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group forms a film by causing a self-condensation reaction with moisture in the air. The coating becomes a strong coating having durability by the alkoxysilyl group being hydrolyzed by moisture in the air and chemically and physically bonded to the surface of glass or metal.

（式中、Ｒｆは２価の直鎖型パーフルオロオキシアルキレン基、Ｒは炭素数１〜４のアルキル基又はフェニル基、Ｘは加水分解性基、ｎは０〜２、ｍは１〜５の整数、ａは２又は３である。） Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-238777) proposes a fluorooxyalkylene group-containing silane represented by the following formula as an alkoxysilyl group bonded to the terminal of a fluorooxyalkylene group. The glass or antireflection film treated with the fluorooxyalkylene group-containing silane has excellent dirt wiping properties, but the end groups are bonded to the base material, resulting in insufficient surface lubricity, slipperiness and scratch resistance. Is not enough.

(In the formula, Rf is a divalent linear perfluorooxyalkylene group, R is an alkyl group having 1 to 4 carbon atoms or phenyl group, X is a hydrolyzable group, n is 0 to 2, and m is 1 to 5) , A is 2 or 3.)

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2013-136833) includes mixing a non-functional fluorooxyalkylene group-containing polymer having an average molecular weight larger than that of a fluorooxyalkylene group-containing silane with a fluorooxyalkylene group-containing silane, It is disclosed that the unevenness of the coating surface can be suppressed to several nm when applied by vacuum deposition. In the vapor deposition coating, a layer containing a large amount of fluorooxyalkylene group-containing polymer-modified silane is formed on the substrate side, and a non-functional fluorooxyalkylene group-containing polymer having a higher molecular weight is formed on the surface side. A layer is formed. Even if aggregation occurs in the fluorooxyalkylene group-containing polymer layer, the outermost non-functional fluorooxyalkylene group-containing polymer layer fills the unevenness, so that the haze hardly increases. However, when the composition is diluted in a fluorine-based solvent and subjected to surface treatment by spray coating or Dip coating, the compatibility between the fluorooxyalkylene group-containing silane and the non-functional fluorooxyalkylene group-containing polymer is a problem. And haze may increase. Thus, it has been found that even with the same composition, the degree of increase in haze varies depending on the coating method.

  In Patent Document 3 (Japanese Patent Application Laid-Open No. 2014-015609), one or more perfluoropolyether group-containing silane compounds having a hydrolyzable silyl group defined in a specific molecular weight range are water-repellent. It is disclosed that oil repellency, antifouling properties, and friction durability can be imparted to a substrate. However, the haze problem has not been solved.

  Therefore, development of a treatment agent and a treatment method capable of forming a high-performance film that can stably suppress an increase in haze even under different treatment conditions has been awaited.

JP 2003-238777 A JP 2013-136833 A JP 2014-015609 A

  The present invention has been made in view of the above circumstances, and is a water- and oil-repellent film that does not impair the visibility of a substrate even when the film thickness is thicker than about 10 nm, which is a normal film thickness, particularly 15 nm or more. It is an object of the present invention to provide a fluorine-containing coating agent that can be stably formed and an article coated with the coating agent.

As a result of intensive studies to solve the above problems, the present inventors have found that both ends of the fluorine-containing coating agent containing a polymer having a hydrolyzable group at one end and a fluorooxyalkylene structure in the main chain. The haze can be reduced and the wear durability is excellent by applying to the base material a treatment agent having a hydrolyzable group and a polymer having a fluorooxyalkylene structure in the main chain added thereto. I found out.
That is, (A) a silane having a hydrolyzable group at one end modified with a fluorooxyalkylene group-containing polymer and / or a partially hydrolyzed condensate thereof, and (B) both modified with a fluorooxyalkylene group-containing polymer. Fluorine-containing coating agent comprising a silane having a hydrolyzable group at the terminal and / or a partial hydrolysis-condensation product thereof, wherein the mixing mass ratio of the component (A) to the component (B) is 20:80 to 60:40 And when the film thickness of the cured film of the coating agent is 20 nm, the haze measured by the method described in JIS K7136 is 0.5 or less, and the water contact angle after 2,000 reciprocating wears is 100 ° or more. The wear-resistant fluorine-containing coating agent can stably form a water- and oil-repellent film with excellent wear durability without deteriorating the visibility of the substrate even when the film thickness is increased. Heading, the present invention has been accomplished.

［上記式（４）及び（６）において、Ｒ ¹ は炭素数１〜６のアルキル基又はフェニル基であり、Ｘは加水分解性基であり、ａは２又は３である。Ｒｆは−Ｃ _g Ｆ _2g Ｏ−（式中、ｇは単位毎に独立に１〜６の整数である。）で表される繰り返し単位を１０〜２００個有する２価の（ポリ）フルオロオキシアルキレン基であり、Ａはフッ素原子、水素原子、又は末端が−ＣＦ ₃ 基、−ＣＦ ₂ Ｈ基もしくは−ＣＦＨ ₂ 基である１価のフッ素含有基である。Ｑは単結合、又は酸素原子、窒素原子もしくはケイ素原子を有してもよい、非置換もしくは置換の、炭素数２〜１２の２価の有機基であり、Ｑ’は炭素原子であり、Ｂは水素原子、炭素数１〜４のアルキル基、ヒドロキシル基、又はハロゲン原子である。ｎは２であり、ｍは１である。ｆ’は０〜１０の整数である。］
〔２〕
Ｒｆが−（ＣＦ₂）_d−（ＯＣＦ₂）_p（ＯＣＦ₂ＣＦ₂）_q（ＯＣＦ₂ＣＦ₂ＣＦ₂）_r（ＯＣＦ₂ＣＦ₂ＣＦ₂ＣＦ₂）_s（ＯＣＦ（ＣＦ₃）ＣＦ₂）_t−Ｏ−（ＣＦ₂）_d−（ｄは互いに独立に０〜５の整数であり、ｐ、ｑ、ｒ、ｓ及びｔは互いに独立に０〜２００の整数であり、かつ、ｐ＋ｑ＋ｒ＋ｓ＋ｔは１０〜２００の整数であり、括弧内に示される各単位はランダムに結合されていてよい。）である〔１〕に記載の含フッ素コーティング剤。
〔３〕
更に、下記一般式（７）で表される（ポリ）フルオロオキシアルキレン基含有ポリマーを含有する〔１〕又は〔２〕に記載の含フッ素コーティング剤。
Ａ-Ｒｆ−Ａ （７）
（式中、Ｒｆは−Ｃ_gＦ_2gＯ−（式中、ｇは単位毎に独立に１〜６の整数である。）で表される繰り返し単位を１０〜２００個有する２価の（ポリ）フルオロオキシアルキレン基であり、Ａはフッ素原子、水素原子、又は末端が−ＣＦ₃基、−ＣＦ₂Ｈ基もしくは−ＣＦＨ₂基である１価のフッ素含有基である。）
〔４〕
更に、溶剤を含む〔１〕〜〔３〕のいずれかに記載の含フッ素コーティング剤。
〔５〕
〔１〕〜〔４〕のいずれかに記載の含フッ素コーティング剤の硬化被膜。
〔６〕
〔５〕に記載の硬化被膜を有する物品。
〔７〕
〔５〕に記載の硬化被膜で被覆されたタッチパネル。
〔８〕
〔５〕に記載の硬化被膜で被覆された、反射防止処理された物品。
〔９〕
〔５〕に記載の硬化被膜で被覆された強化ガラス。 Accordingly, the present invention provides a fluorine-containing coating agent and an article treated with the coating agent.
[1]
(A) a silane having a hydrolyzable group at one end and / or a partially hydrolyzed condensate thereof modified with a fluorooxyalkylene group-containing polymer represented by the following general formula (4), and (B) the following general formula ( 6) A silane having a hydrolyzable group at both ends and / or a partially hydrolyzed condensate thereof modified with the fluorooxyalkylene group-containing polymer shown in 6), and a mixture of the component (A) and the component (B) A fluorine-containing coating agent having a mass ratio of 50:50 to 60:40, wherein the haze measured by the method described in JIS K7136 is 0.5 or less when the thickness of the cured film of the coating agent is 20 nm. A fluorine-containing coating agent characterized by having a wear durability with a water contact angle of 100 ° or more after 2,000 reciprocating wears.

[In the above formulas (4) and (6), R ¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3. Rf (wherein, g is an integer of 1 to 6 independently for each unit.) Is -C _g F _2g O- expressed repeating units of 10 to 200 pieces organic bivalent be in (poly) fluorooxyalkylene A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, a —CF ₂ H group, or a —CFH ₂ group. Q is a single bond or an unsubstituted or substituted divalent organic group having 2 to 12 carbon atoms which may have an oxygen atom, a nitrogen atom or a silicon atom, Q ′ is a carbon atom, B Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. n is 2 and m is 1. f ′ is an integer of 0 to 10. ]
[ 2 ]
Rf is _{- (CF 2) d - (} OCF 2) p (OCF 2 CF 2) q (OCF 2 CF 2 CF 2) r (OCF 2 CF 2 CF 2 CF 2) s (OCF (CF 3) CF 2) _{t -O- (CF 2) d -} (d are independently integers of 0 to 5 with each other, p, q, r, s and t are independently an integer of 0 to 200 to each other, and, p + q + r + s + t is 10 It is an integer of -200, Each unit shown in a parenthesis may be couple | bonded at random.) The fluorine-containing coating agent as described in [ 1 ].
[ 3 ]
Furthermore, the fluorine-containing coating agent as described in [1] or [2] containing the (poly) fluoro oxyalkylene group containing polymer represented by following General formula (7).
A-Rf-A (7)
(Wherein, Rf is -C _g F _2g O- (wherein, g is an integer of 1 to 6 independently for each unit.) Divalent (poly to 10 to 200 pieces have a repeating unit represented by the ) A fluorooxyalkylene group, and A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, a —CF ₂ H group, or a —CFH ₂ group.
[ 4 ]
Furthermore, the fluorine-containing coating agent in any one of [1]-[ 3 ] containing a solvent.
[ 5 ]
A cured film of the fluorine-containing coating agent according to any one of [1] to [ 4 ].
[ 6 ]
[ 5 ] An article having the cured coating according to [ 5 ].
[ 7 ]
[ 5 ] A touch panel coated with the cured coating according to [ 5 ].
[ 8 ]
[ 5 ] An antireflective article coated with the cured coating according to [ 5 ].
[ 9 ]
[ 5 ] A tempered glass coated with the cured film described in [ 5 ].

  The cured film formed by wet-coating the fluorine-containing coating agent of the present invention on a substrate can maintain a low haze surface even when the cured film is thick, and is excellent in wear durability. Therefore, the fluorine-containing coating agent of the present invention can impart low haze and wear durability performance to various articles by wet treatment.

It is a figure which shows the relationship between the film thickness and haze of the cured film of Example 1, Reference Example 1, and Comparative Examples 1, 2, 5, and 6 of the present invention. It is a figure which shows the relationship between the film thickness of the cured film of the reference example 2 of this invention, and the comparative examples 3 and 4, and haze. It is a figure which shows the relationship of (A) component content in the cured film of Example 1, Reference example 1, and Comparative Examples 1, 2, 5, and 6 of this invention, and the haze at the film thickness of 20 nm. It is a figure which shows the relationship of (A) component content in the cured film of the reference example 2 of this invention, and the comparative examples 3 and 4, and the haze at the time of a film thickness of 20 nm.

The fluorine-containing coating agent of the present invention comprises a silane having a hydrolyzable group at one end and / or a partially hydrolyzed condensate (A) thereof modified with a fluorooxyalkylene group-containing polymer, and a fluorooxyalkylene group-containing polymer. A modified silane having a hydrolyzable group at both ends and / or a partially hydrolyzed condensate (B) thereof, wherein the mixing mass ratio of the component (A) and the component (B) is 20:80 to 60: 40, preferably 25:75 to 55:45, particularly preferably 30:70 to 50:50. Within this range, the haze value of the cured coating can be kept low and the wear durability can be excellent.
In addition, it is preferable that (B) component has a structure similar to the silane of (A) component except the part which has a hydrolysable group in both terminals.

（式中、Ｒ¹は炭素数１〜６のアルキル基又はフェニル基であり、Ｘは加水分解性基であり、ａは２又は３である。）
で表される加水分解性基を有するものであることが好ましい。 Component (A) The component (A) is a silane having a hydrolyzable group at one end modified with a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate thereof. As the silane, the following formula (1)
-C _g F _2g O- (1)
(In the formula, g is an integer of 1 to 6 independently for each unit.)
Having a fluorooxyalkylene group containing 10 to 200 repeating units represented by formula (2)

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3.)
It is preferable that it has a hydrolysable group represented by these.

Examples of the repeating unit represented by the above formula (1) include the following structures. The fluorooxyalkylene group may be composed of one of the structures shown below, or a combination of two or more. Moreover, these units may be combined at random.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-
-C (CF _{3) 2} O-

  In the group represented by the formula (2), X is a hydrolyzable group which may be different from each other. Examples of the hydrolyzable group include 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 atom. It is done. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the alkoxyalkoxy group include a methoxymethoxy group and a methoxyethoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the alkenyloxy group include an isopropenoxy group. Examples of the halogen atom include a chloro atom, a bromo atom, and an iodo atom. Of these, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro atom are preferable.

In the group represented by the above formula (2), R ¹ is an alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group. Of these, a methyl group is preferred.
a is 2 or 3, and 3 is preferable from the viewpoint of reactivity and adhesion to a substrate.

［上記式（３）において、Ｒ¹、Ｘ、ａは上記の通りであり、Ｒｆは−Ｃ_gＦ_2gＯ−（ｇは上記の通り）で表される繰り返し単位を１０〜２００個有する２価の（ポリ）フルオロオキシアルキレン基であり、Ａはフッ素原子、水素原子、又は末端が−ＣＦ₃基、−ＣＦ₂Ｈ基もしくは−ＣＦＨ₂基である１価のフッ素含有基である。Ｑは単結合、又は酸素原子、窒素原子もしくはケイ素原子を有してもよい、非置換もしくは置換の、炭素数２〜１２の２価の有機基であり、Ｚはシルアルキレン構造もしくはシルフェニレン構造を有していてもよい２〜８価のオルガノシロキサン残基、又は２価のオルガノシルアルキレン残基もしくはオルガノシルフェニレン残基である。ｅは０又は１、ｂは１〜７の整数、αは０又は１、ｃは１〜３の整数であるが、ｅが０のとき、ｂは１、αは０、ｃは１であり、ｅが１のとき、ｂは１〜７の整数、αは０又は１で、αが０のときｃは１であり、αが１のときｃは１〜３の整数である。Ｗは−Ｃ_jＨ_2j−Ｒ⁵ _(3-c)Ｓｉ−又は−Ｃ_jＨ_2j−Ｒ⁵ _(3-c)Ｃ−（式中、ｊは０〜１０の整数であり、ｃは上記の通りであり、Ｒ⁵は炭素数１〜１２のアルキル基である。但し、Ｗが−Ｃ_jＨ_2j−Ｒ⁵ _(3-c)Ｓｉ−で、Ｑ又はＺのＷと連結する末端がケイ素原子の場合、ｊは１〜１０の整数である。）で示される（ｃ＋１）価の基である。ｆは１〜１０の整数である。］

［上記式（４）において、Ｒ¹、Ｘ、ａ、Ｒｆ、Ａ及びＱは上記の通りであり、Ｑ’は炭素原子、又は炭素数２〜１２の３価炭化水素基であり、Ｂは水素原子、炭素数１〜４のアルキル基、ヒドロキシル基、又はハロゲン原子である。ｍは１〜１０の整数、ｋは０又は１、ｎは１〜３の整数であるが、Ｑ’が炭素原子のとき、ｋは０、ｎは２、ｍは１であり、Ｑ’が３価炭化水素基のとき、ｋは０又は１で、ｋが０のときｎは１、ｍは２〜１０の整数であり、ｋが１のときｎは１〜３の整数、ｍは１〜１０の整数である。また、Ｂが水素原子のとき、ｍは２〜１０の整数である。Ｙはフェニレン基、又は（ｎ＋１）価の、Ｒ⁸ _(3-n)Ｓｉ又はＲ⁶ _(3-n)Ｃ〔式中、ｎは上記の通りであり、Ｒ⁸は炭素数１〜１２のアルキル基であり、Ｒ⁶は炭素数１〜１２のアルキル基、ヒドロキシル基又はＲ⁷ ₃ＳｉＯ−（式中、Ｒ⁷は互いに独立に、水素原子、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基又は炭素数１〜１２のアルコキシ基である。）である。〕である。ｆ’は０〜１０の整数である。］ The silane having a hydrolyzable group at one end modified with the fluorooxyalkylene group-containing polymer is at least one selected from compounds represented by the following general formulas (3) and (4). preferable.

[In Formula (3), R ¹ , X, and a are as described above, and Rf has 10 to 200 repeating units represented by —C _g F _2g O— (g is as described above) 2 A valent (poly) fluorooxyalkylene group, and A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, a —CF ₂ H group, or a —CFH ₂ group. Q is a single bond or an unsubstituted or substituted divalent organic group having 2 to 12 carbon atoms which may have an oxygen atom, a nitrogen atom or a silicon atom, and Z is a silalkylene structure or a silphenylene structure Or a divalent organosilalkylene residue or an organosylphenylene residue. e is 0 or 1, b is an integer of 1 to 7, α is 0 or 1, and c is an integer of 1 to 3, but when e is 0, b is 1, α is 0, and c is 1. , E is 1, b is an integer of 1 to 7, α is 0 or 1, c is 1 when α is 0, and c is an integer of 1 to 3 when α is 1. W During _{^{-C j H 2j -R 5 (3}} -c) Si- or _{^{-C j H 2j -R 5 (3}} -c) C- ( wherein, j is an integer of 0, c is the R ⁵ is an alkyl group having 1 to 12 carbon atoms, provided that W is —C _j H _2j —R ⁵ _(3-c) Si—, and the terminal connected to W of Q or Z is In the case of a silicon atom, j is an integer of 1 to 10.) (c + 1) valent group. f is an integer of 1-10. ]

[In the above formula (4), R ¹ , X, a, Rf, A and Q are as described above, Q ′ is a carbon atom or a trivalent hydrocarbon group having 2 to 12 carbon atoms, and B is A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. m is an integer of 1 to 10, k is 0 or 1, and n is an integer of 1 to 3, but when Q ′ is a carbon atom, k is 0, n is 2, m is 1, and Q ′ is When it is a trivalent hydrocarbon group, k is 0 or 1, n is 1 when k is 0, m is an integer of 2 to 10, n is an integer of 1 to 3 when k is 1, m is 1 It is an integer of -10. Moreover, when B is a hydrogen atom, m is an integer of 2-10. Y is a phenylene group, or (n + 1) -valent, R ⁸ _(3-n) Si or R ⁶ _(3-n) C [wherein n is as described above, and R ⁸ has 1 to 12 carbon atoms. An alkyl group, R ⁶ is an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, or R ⁷ ₃ SiO— (wherein R ⁷ are independently of each other a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a carbon number; 6-12 aryl groups or C1-C12 alkoxy groups.). ]. f ′ is an integer of 0 to 10. ]

In the above formulas (3) and (4), R ¹ , X and a are as described in the above formula (2).

In the above formula (3) and (4), Rf is (are g above as) -C _g F _{2 g} O-divalent (poly) fluorooxyalkylene groups 10 to 200 pieces have a repeating unit represented by the There, as the _{Rf, - (CF 2) d} - (OCF 2) p (OCF 2 CF 2) q (OCF 2 CF 2 CF 2) r (OCF 2 CF 2 CF 2 CF 2) s (OCF (CF 3 _{) CF 2) t -O- (CF} 2) d - is preferably.
In the above formula, d is independently an integer of 0 to 5, preferably an integer of 0 to 2, and p, q, r, s and t are independently of each other an integer of 0 to 200, preferably p is It is an integer of 5-100, q is an integer of 5-100, r is an integer of 0-100, s is an integer of 0-50, t is an integer of 0-100. p + q + r + s + t is an integer of 10 to 200, preferably an integer of 20 to 100. Each unit shown in parentheses may be combined randomly.

（式中、ｄ’は上記ｄと同じであり、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’はそれぞれ１以上の整数であり、その上限は上記ｐ、ｑ、ｒ、ｓ、ｔの上限と同じである。） Examples of Rf include those having the following structures.

(Wherein d ′ is the same as d above, p ′, q ′, r ′, s ′, t ′ are each an integer of 1 or more, and the upper limit thereof is p, q, r, s, t above) (It is the same as the upper limit of.)

In the above formulas (3) and (4), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, a —CF ₂ H group, or a —CFH ₂ group.
As A, for example,
-CF ₃
-CF ₂ CF ₃
-CF ₂ CF ₂ CF ₃
-CF ₂ H
-CH ₂ F
Is mentioned.

In the above formulas (3) and (4), Q is a single bond or an unsubstituted or substituted divalent organic group having 2 to 12 carbon atoms which may have an oxygen atom, a nitrogen atom or a silicon atom. is there. The divalent organic group includes a linking group between an Rf group and a Z group, a linking group between an Rf group and a W group, a linking group between an Rf group and a —C _f H _2f — group, or an Rf group and a Q ′ group. And a linking group.

Here, examples of the divalent organic group include an amide bond, an ether bond, an ester bond, a diorganosilylene group such as a dimethylsilylene group, a diethylsilylene group, and a diphenylsilylene group, and —Si [OH] [(CH ₂ ). _w Si (CH ₃ ) ₃ ] — (w is an integer of 2 to 4), an unsubstituted or substituted carbon which may contain one or more structures selected from the group consisting of groups Examples thereof include divalent hydrocarbon groups having 2 to 12, preferably 2 to 8 carbon atoms.

  Divalent hydrocarbon groups include methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene and other alkylene groups, phenylene And arylene groups such as a group. These may be a combination of two or more, or a combination of an alkylene group and an arylene group. Further, a part or all of hydrogen atoms bonded to carbon atoms of these groups may be substituted with halogen atoms such as fluorine atoms.

Q is preferably an unsubstituted or substituted alkylene group having 2 to 4 carbon atoms, or a phenylene group. Furthermore, an amide bond, an ether bond, an ester bond, diorgano silylene group such as dimethylsilylene group, -Si [OH] [(CH 2) w Si (CH 3) 3] - (w is an integer of 2 to 4) A structure having one or two or more structures selected from the group consisting of groups represented by formula (1) and having an unsubstituted or substituted alkylene group having 1 to 4 carbon atoms and / or a phenylene group is preferable.

Examples of such Q include the following groups.

（式中、ｕは０〜４の整数であり、ｖは０〜４の整数であり、ｗは２〜４の整数であり、Ｍｅはメチル基である。）

(In the formula, u is an integer of 0 to 4, v is an integer of 0 to 4, w is an integer of 2 to 4, and Me is a methyl group.)

In the above formula (3), Z is a divalent to octavalent organosiloxane residue which may have a silalkylene structure or a silphenylene structure, or a divalent organosilalkylene residue or an organosylphenylene residue. . The divalent to octavalent organosiloxane residue is a linear or cyclic organo group having 2 to 13 silicon atoms, preferably 2 to 5 silicon atoms, and having a silalkylene structure or a silphenylene structure. A polysiloxane residue is preferred. Here, the silalkylene structure can be represented by Si— (CH ₂ ) _h —Si, and in the above formula, h is preferably an integer of 2 to 6, more preferably an integer of 2 to 4.

  In the organopolysiloxane residue, the monovalent hydrocarbon group bonded to the silicon atom is preferably an alkyl group or phenyl group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of Z include those shown below.

（式中、ｈは２〜６の整数、好ましくは２〜４の整数であり、Ｍｅはメチル基である。）

(In the formula, h is an integer of 2 to 6, preferably an integer of 2 to 4, and Me is a methyl group.)

In the above formula (3), e is 0 or 1, b is an integer of 1 to 7, α is 0 or 1, c is an integer of 1 to 3, but when e is 0, b is 1, α is 0, and c is 1. When e is 1, b is an integer of 1 to 7, α is 0 or 1, c is 1 when α is 0, and c is an integer of 1 to 3 when α is 1. .
Moreover, f is an integer of 1-10, Preferably it is an integer of 2-6.

In the above formula (3), W is ^{_{-C j H 2j -R 5 (3}} -c) Si- or ^{_{-C j H 2j -R 5 (3}} -c) C- at indicated (c + 1) -valent group In the formula, j is an integer of 0 to 10, preferably an integer of 2 to 6, c is as described above, and R ⁵ is an alkyl having 1 to 12 carbons, preferably 1 to 6 carbons. It is a group. However, W is ^{_{-C j H 2j -R 5 (3}} -c) Si- and, when end for coupling with W of Q or Z is a silicon atom, j is an integer of from 1 to 10.
Here, examples of the alkyl group of R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group, and a methyl group, an ethyl group, and a propyl group are preferable.

（式中、ｊは上記の通りであり、Ｍｅはメチル基である。） Examples of W include divalent to tetravalent groups shown below.

(Wherein j is as described above, and Me is a methyl group.)

As W, a group represented by the following structure is particularly preferable.

（式中、ｐ１、ｑ１はｐ１／ｑ１＝０．９、ｐ１＋ｑ１≒４５を満たす数である。）

Examples of the compound represented by the above formula (3) include those shown below.

(In the formula, p1 and q1 are numbers satisfying p1 / q1 = 0.9 and p1 + q1≈45.)

（式中、ｐ１、ｑ１はｐ１／ｑ１＝１．１、ｐ１＋ｑ１≒４５を満たす数である。）

（式中、ｐ１、ｑ１はｐ１／ｑ１＝１．１、ｐ１＋ｑ１≒４５を満たす数である。）

（式中、ｐ１、ｑ１はｐ１／ｑ１＝０．９、ｐ１＋ｑ１≒４５を満たす数である。）

（式中、ｐ１、ｑ１はｐ１／ｑ１＝１．１、ｐ１＋ｑ１≒４５を満たす数である。） As the compound represented by the above formula (3), the following compounds are also suitable.

(Wherein p1 and q1 are numbers satisfying p1 / q1 = 1.1 and p1 + q1≈45)

(Wherein p1 and q1 are numbers satisfying p1 / q1 = 1.1 and p1 + q1≈45)

(In the formula, p1 and q1 are numbers satisfying p1 / q1 = 0.9 and p1 + q1≈45.)

(Wherein p1 and q1 are numbers satisfying p1 / q1 = 1.1 and p1 + q1≈45)

In the above formula (4), Q ′ is a carbon atom or a trivalent hydrocarbon group having 2 to 12 carbon atoms. Examples of the trivalent hydrocarbon group for Q ′ include a methylene group, an ethylene group, a propylene group (trimethylene group, a methylethylene group), a butylene group (tetramethylene group, a methylpropylene group), a hexamethylene group, an octamethylene group, and the like. In which a hydrogen atom bonded to a carbon atom of the alkylene group is removed. Furthermore, a structure in which some or all of the hydrogen atoms bonded to the carbon atom are substituted with a halogen atom such as a fluorine atom may be used.
Q ′ is particularly preferably a carbon atom or a trivalent hydrocarbon group having 2 to 8 carbon atoms, more preferably a carbon atom or a group having the following structure.

  In the above formula (4), B is a hydrogen atom, an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group or a butyl group, a hydroxyl group, or a halogen atom such as a chloro atom, a bromo atom or an iodo atom. It is. B is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group.

In the above formula (4), m is an integer of 1 to 10, k is 0 or 1, n is an integer of 1 to 3, preferably 2 or 3, but when Q ′ is a carbon atom, k is 0, n is 2, and m is 1. When Q ′ is a trivalent hydrocarbon group, k is 0 or 1. In this case, when k is 0, n is 1 and m is an integer of 2 to 10, preferably m is an integer of 2 to 5, and particularly preferably m is 2. When k is 1, n is an integer of 1 to 3, and m is an integer of 1 to 10, preferably m is an integer of 1 to 5, and particularly preferably m is 1 or 2. is there.
Moreover, when B is a hydrogen atom, m is an integer of 2-10.
In said Formula (4), f 'is an integer of 0-10, Preferably it is an integer of 2-6.

In the above formula (4), Y is a phenylene group or a (n + 1) -valent R ⁸ _(3-n) Si or R ⁶ _(3-n) C, in which n is as described above. , R ⁸ is an alkyl group having 1 to 12 carbon atoms, preferably 1 to ⁶ carbon atoms, and R ⁶ is an alkyl group having 1 to 12 carbon atoms, preferably 1 to ⁶ carbon atoms, a hydroxyl group, or R ⁷ _3. SiO— and R ⁷ independently of one another are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

Here, examples of the alkyl group of R ⁶ and R ⁸ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group, and preferably a methyl group, an ethyl group, or a butyl group. is there.
Examples of the alkyl group for R ⁷ include the same groups as those described above for R ⁶ and R ^8. Examples of the aryl group include a phenyl group and a tolyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, Examples thereof include a propoxy group and a butoxy group. R ⁷ is preferably a methoxy group or an ethoxy group.

（式中、Ｍｅはメチル基である。） Examples of (n + 1) -valent R ⁸ _(3-n) Si or R ⁶ _(3-n) C include the following divalent to tetravalent groups.

(In the formula, Me is a methyl group.)

When Y is R ⁸ _(3-n) Si—, Q ′ is preferably a trivalent hydrocarbon group having 2 to 12 carbon atoms, particularly a group represented by the following structure.

（式中、Ｍｅはメチル基である。） Y is particularly preferably a phenylene group or a group represented by the following structure.

(In the formula, Me is a methyl group.)

（式中、ｐ１、ｑ１はｐ１／ｑ１＝０．９、ｐ１＋ｑ１≒４５を満たす数である。）

（式中、ｐ１、ｑ１はｐ１／ｑ１＝１．１、ｐ１＋ｑ１≒４５を満たす数である。）

（式中、ｐ１、ｑ１はｐ１／ｑ１＝１．１、ｐ１＋ｑ１≒４５を満たす数である。）

（式中、ｐ１、ｑ１はｐ１／ｑ１＝１．１、ｐ１＋ｑ１≒４５を満たす数である。）

（式中、ｐ１、ｑ１はｐ１／ｑ１＝１．１、ｐ１＋ｑ１≒４５を満たす数である。）

Examples of the compound represented by the above formula (4) include those shown below.

(In the formula, p1 and q1 are numbers satisfying p1 / q1 = 0.9 and p1 + q1≈45.)

(Wherein p1 and q1 are numbers satisfying p1 / q1 = 1.1 and p1 + q1≈45)

(Wherein p1 and q1 are numbers satisfying p1 / q1 = 1.1 and p1 + q1≈45)

(Wherein p1 and q1 are numbers satisfying p1 / q1 = 1.1 and p1 + q1≈45)

(Wherein p1 and q1 are numbers satisfying p1 / q1 = 1.1 and p1 + q1≈45)

  As the compound represented by the above formula (4), those in which n is 2 or 3 are more preferable.

  In the fluorine-containing coating agent of the present invention, as a component (A), a terminal hydrolyzable group of a silane having a hydrolyzable group at one terminal modified with the fluorooxyalkylene group-containing polymer is prepared in a known method in advance. A partially hydrolyzed condensate obtained by partially hydrolyzing and condensing may be contained.

  In addition, it is preferable that the weight average molecular weight of (A) component is 1,000-20,000, and it is more preferable that it is 2,000-10,000. If the weight average molecular weight is too small, the water / oil repellency and wear durability of the fluoropolyether group may not be exhibited. If the weight average molecular weight is too large, the adhesion to the substrate may be deteriorated. In the present invention, the weight average molecular weight can be measured as a standard polystyrene equivalent value of gel permeation chromatography (GPC) using AK-225 (manufactured by Asahi Glass) as a developing solvent (hereinafter the same).

（式中、Ｒ¹、Ｘ、ａは上記と同じである。）
で表される加水分解性基を有するものであることが好ましい。 Component (B) The component (B) is a silane having a hydrolyzable group at both ends and / or a partially hydrolyzed condensate thereof modified with a fluorooxyalkylene group-containing polymer. As the silane, the following formula (1)
-C _g F _2g O- (1)
(Wherein g is the same as above)
Having a fluorooxyalkylene group containing 10 to 200 repeating units represented by the following formula (2):

(In the formula, R ¹ , X and a are the same as above.)
It is preferable that it has a hydrolysable group represented by these.

［上記式（５）において、Ｒ¹、Ｘ、ａ、Ｒｆ、Ｑ、Ｚ、ｅ、ｂ、α、ｃ、Ｗ及びｆは上記の通りである。］

［上記式（６）において、Ｒ¹、Ｘ、ａ、Ｒｆ、Ｑ、Ｑ’、Ｂ、ｍ、ｋ、ｎ、Ｙ及びｆ’は上記の通りである。］ The silane having a hydrolyzable group at both ends modified with the fluorooxyalkylene group-containing polymer is at least one selected from compounds represented by the following general formulas (5) and (6). preferable.

[In the above formula (5), R ¹ , X, a, Rf, Q, Z, e, b, α, c, W and f are as described above. ]

[In the above formula (6), R ¹ , X, a, Rf, Q, Q ′, B, m, k, n, Y, and f ′ are as described above. ]

In the above formulas (5) and (6), R ¹ , X, a, Rf, Q, Z, e, b, α, c, W, f, Q ′, B, m, k, n, Y and f 'Is as described in the above formulas (2) to (4), and examples thereof are the same as those exemplified above, and each may be the same as or different from the component (A).

（式中、Ｒｆ²は下記式

で示される基である。ｐ２、ｑ２はｐ２／ｑ２＝０．９、ｐ２＋ｑ２≒４５を満たす数である。）

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝０．９、ｐ２＋ｑ２＝２３を満たす数である。）

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝０．９、ｐ２＋ｑ２＝４５を満たす数である。）

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝０．９、ｐ２＋ｑ２＝６０を満たす数である。）

（式中、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒２３を満たす数である。）

（式中、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒４５を満たす数である。）

（式中、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒６０を満たす数である。）

Examples of the compound represented by the above formula (5) include those shown below.

(In the formula, Rf ² represents the following formula:

It is group shown by these. p2 and q2 are numbers satisfying p2 / q2 = 0.9 and p2 + q2≈45. )

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 0.9 and p2 + q2 = 23.)

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 0.9 and p2 + q2 = 45.)

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 0.9 and p2 + q2 = 60.)

(In the formula, p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈23.)

(In the formula, p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈45.)

(Wherein p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈60)

（式中、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒４５を満たす数である。）

（式中、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒２３を満たす数である。）

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝０．９、ｐ２＋ｑ２≒４５を満たす数である。） As the compound represented by the above formula (5), the following compounds are also suitable.

(In the formula, p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈45.)

(In the formula, p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈23.)

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 0.9 and p2 + q2≈45.)

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝０．９、ｐ２＋ｑ２≒４５を満たす数である。）

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒４５を満たす数である。）

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒４５を満たす数である。）

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒４５を満たす数である。）

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒４５を満たす数である。）

（式中、Ｒｆ²は上記と同じであり、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒４５を満たす数である。）

（式中、ｐ２、ｑ２はｐ２／ｑ２＝１．１、ｐ２＋ｑ２≒４５を満たす数である。） Furthermore, what is shown below is mentioned as a compound represented by the said Formula (6).

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 0.9 and p2 + q2≈45.)

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈45.)

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈45.)

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈45.)

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈45.)

(In the formula, Rf ² is the same as above, and p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈45.)

(In the formula, p2 and q2 are numbers satisfying p2 / q2 = 1.1 and p2 + q2≈45.)

  As the compound represented by the above formula (6), those in which n is 2 or 3 are more preferable.

  In the fluorine-containing coating agent of the present invention, as a component (B), terminal hydrolyzable groups of silanes having hydrolyzable groups at both ends modified with the above-mentioned fluorooxyalkylene group-containing polymer are obtained by a known method in advance. A partially hydrolyzed condensate obtained by partially hydrolyzing and condensing may be contained.

  In addition, it is preferable that the weight average molecular weights of (B) component are 1,000-20,000, and it is more preferable that it is 2,000-10,000. If the weight average molecular weight is too small, the water / oil repellency and wear durability of the fluoropolyether group may not be exhibited. If the weight average molecular weight is too large, the adhesion to the substrate may be deteriorated.

(Poly) fluorooxyalkylene group-containing polymer The fluorine-containing coating agent of the present invention further comprises the following general formula (7)
A-Rf-A (7)
(In the formula, Rf and A are as described above.)
(Poly) fluorooxyalkylene group-containing polymer having no hydrolyzable group at any end (hereinafter referred to as non-functional polymer), as long as the characteristics of the present invention are not impaired. Also good.

  In the above formula (7), Rf and A are as described above, and examples are the same as Rf and A exemplified above, and Rf is in the components (A) and (B) described above. Rf may be the same as or different from Rf, and A may be the same as or different from A in the component (A) described above.

（式中、ｐ３、ｑ３、ｒ３、ｔ３は、上記フルオロポリエーテル基含有ポリマーの重量平均分子量が１，０００〜５０，０００となる数である。なお、括弧内に示される各単位はランダムに結合されていてよい。） Examples of the non-functional polymer represented by the formula (7) include the following.

(Wherein p3, q3, r3 and t3 are numbers with which the weight average molecular weight of the fluoropolyether group-containing polymer is 1,000 to 50,000. Each unit shown in parentheses is randomly selected. May be combined.)

  The weight average molecular weight of the non-functional polymer varies depending on the combination of the length of the fluoropolyether chain and the non-fluorine part, but the weight average molecular weight of the functional polymer as the components (A) and (B) is 0.25. ˜4 times is preferable. If the difference between the weight average molecular weight of the non-functional polymer and the weight average molecular weight of the components (A) and (B) is within the above range, it is preferable because they are easily compatible with the components (A) and (B).

  The non-functional polymer may be a commercially available product. For example, those sold under the trade names of FOMBLIN (manufactured by Solvay Solexis), DEMNUM (manufactured by Daikin Industries), and KRYTOX (manufactured by DuPont) are preferable from the viewpoint of availability.

（式中、ｐ３、ｔ３は上記重量平均分子量を満足する数である。なお、括弧内に示される各単位はランダムに結合されていてよい。） More specifically, the following products are listed.
FOMBLIN Y (trade name, product of Solvay Solexis, compound represented by the following formula (8), FOBBLIN Y25 (weight average molecular weight: 3,200), FOMBLIN Y45 (weight average molecular weight: 4,100))

(In the formula, p3 and t3 are numbers satisfying the weight average molecular weight. Each unit shown in parentheses may be bonded at random.)

（式中、ｐ３、ｑ３は上記重量平均分子量を満足する数である。なお、括弧内に示される各単位はランダムに結合されていてよい。） FOMBLIN Z (trade name, manufactured by Solvay Solexis, a compound represented by the following formula (9), FOMBLIN Z03 (weight average molecular weight: 4,000), FOMBLIN Z15 (weight average molecular weight: 8,000), FOMBLIN Z25 (weight average molecular weight) : 9,500))

(In the formula, p3 and q3 are numbers satisfying the weight average molecular weight. In addition, each unit shown in parentheses may be bonded at random.)

（式中、ｒ３は上記重量平均分子量を満足する数である。） DENNUM (trade name, manufactured by Daikin Industries, Ltd., a compound represented by the following formula (10), demnum S20 (weight average molecular weight: 2,700), demnum S65 (weight average molecular weight: 4,500), demnum S100 (weight average molecular weight: 5,600))

(Wherein r3 is a number satisfying the weight average molecular weight)

（式中、ｔ３は上記重量平均分子量を満足する数である。） KRYTOX (trade name, manufactured by DuPont, compound represented by the following formula (11), KRYTOX 143AB (weight average molecular weight: 3,500), KRYTOX 143AX (weight average molecular weight: 4,700), KRYTOX 143AC (weight average molecular weight: 5 , 500), KRYTOX 143AD (weight average molecular weight: 7,000))

(In the formula, t3 is a number satisfying the weight average molecular weight.)

  0.001-10 mass parts is preferable with respect to a total of 100 mass parts of (A) component and (B) component, and, as for the quantity of a nonfunctional polymer, 0.05-2 mass parts is more preferable.

  In addition, other additives can be blended with the fluorine-containing coating agent as necessary within the range not impairing the present invention. Specifically, hydrolysis condensation catalysts such as organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organic titanium compounds (tetra n-butyl titanate, etc.), organic acids (fluorinated carboxylic acids, acetic acid, methane) Sulfonic acid, etc.) and inorganic acids (hydrochloric acid, sulfuric acid, etc.). Of these, fluorine-based carboxylic acid, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly desirable. Although the addition amount is a catalyst amount, it is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass with respect to 100 parts by mass in total of the above component (A) and component (B).

  The fluorine-containing coating agent is preferably applied after being dissolved in a suitable solvent. Such solvents include fluorine-modified aliphatic hydrocarbon solvents (pentafluorobutane, decafluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorocyclohexane, perfluoro-1,3-dimethylcyclohexane, etc. ), Fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, 1,3-trifluoromethylbenzene, etc.), fluorine-modified ether solvents (methyl perfluoropropyl ether, methyl perfluorobutyl ether, Ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbons Solvent (petroleum benzine, mineral spirits, toluene, xylene, etc.), ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ether solvent (tetrahydrofuran, diethyl ether, etc.), ester solvent (ethyl acetate, etc.), alcohol type A solvent (such as isopropyl alcohol) can be exemplified. Among these, a fluorine-modified solvent is desirable from the viewpoint of solubility and wettability, and ethyl perfluorobutyl ether, decafluoropentane, pentafluorobutane, and perfluorohexane are particularly preferable. The said solvent may be used individually by 1 type, or may mix and use 2 or more types.

  The optimum concentration of the components (A) and (B) to be dissolved in the solvent varies depending on the treatment method, but the content of the components (A) and (B) in the fluorine-containing coating agent is 0.01 to 50% by mass, particularly 0. It is preferable that it is the quantity used as 0.03-20 mass%.

  The fluorine-containing coating agent of the present invention can be applied to a substrate by a known method such as a wet coating method (brush coating, dipping, spraying, ink jet), or a vapor deposition method, particularly when applied by a wet coating method. It is more effective.

Moreover, although the curing conditions of the fluorine-containing coating agent vary depending on the coating method, it is room temperature (20 ° C.) to 200 ° C., particularly 25 ° C. to 150 ° C., 30 minutes to 24 hours, particularly 30 minutes to 1 hour. It is desirable to do. As the curing humidity, it is desirable to carry out under humidification in order to promote the reaction.
The thickness of the cured coating is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 3 to 30 nm.

The substrate to be treated with the above-mentioned fluorine-containing coating agent is not particularly limited, and may be made of various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramic, quartz, sapphire, and is repellent to these. Water / oil repellency, chemical resistance, releasability, wear durability, and antifouling properties can be imparted. The surface of the substrate may be subjected to a hard coat treatment or an antireflection treatment. When adhesion is poor, a primer layer is provided with a SiO ₂ layer, a silane coupling agent layer having a hydrolyzable group or SiH group, or vacuum plasma treatment, atmospheric pressure plasma treatment, alkali treatment or acid treatment. The adhesion can be improved by a known method such as the above.

Since the fluorine-containing coating agent of the present invention has a hydrolyzable group, it is preferable to provide a SiO ₂ layer as a primer layer on a substrate and coat the fluorine-containing coating agent thereon. In the case where a hydrolyzable group such as a glass substrate can be in direct contact with the base material, it is not necessary to provide an SiO ₂ layer. The coating method in this case is preferably spray coating, ink jet coating, or Dip coating.

  Articles treated with the fluorine-containing coating agent of the present invention include car navigation, car audio, tablet PC, smartphone, wearable terminal, mobile phone, digital camera, digital video camera, PDA, portable audio player, game machine, various operations Liquid crystal displays, organic EL displays, plasma displays, touch panel displays used for panels, electronic announcements, etc., medical equipment such as eyeglass lenses, camera lenses, lens filters, sunglasses, stomach cameras, photocopiers, protective films, antireflection Examples thereof include optical articles such as films. Since the fluorine-containing coating agent of the present invention can prevent fingerprints and sebum from adhering to the article, and can further provide scratch resistance, the touch panel display, the article treated with antireflection, the repellency of tempered glass, and the like. Useful as a water / oil repellent layer.

The fluorine-containing coating agent of the present invention contains the above components (A) and (B) at a specific ratio, and the fluorine-containing coating agent of the present invention is subjected to glass or SiO ₂ -treated substrate (SiO ₂ is previously deposited or deposited). The antifouling treatment substrate coated with spray coating, ink jet coating, spin coating, dip coating or vacuum deposition coating on the sputtered substrate) is compared with the antifouling treatment article coated only with the component (A). The haze rise is small.

  The fluorine-containing coating agent of the present invention has a haze value measured by the method described in JIS K7136 of 0.5 or less, preferably 0.45 or less, more preferably 0 when the thickness of the cured film of the coating agent is 20 nm. .4 or less. When the haze value exceeds 0.5, a white turbidity phenomenon on the surface of the substrate is confirmed in appearance.

Here, the cured film of the fluorine-containing coating agent can be obtained, for example, by the following method.
[Method for preparing cured film]
(1) The component (A) and the component (B) are dissolved in ethyl perfluorobutyl ether [Novec 7200 (manufactured by 3M)] so as to have a solid content concentration of 20% by mass, and the solid content concentration is further reduced to 0. A fluorine-containing coating agent is prepared by dissolving in 1,1,1,3,3-pentafluorobutane [Solkane 365mfc (manufactured by Solvay)] to 1% by mass.
(2) Chemically tempered glass (manufactured by Corning Co., Ltd.) obtained by subjecting the fluorine-containing coating agent prepared in (1) to plasma treatment (Ar: 10 cc, O ₂ : 100 cc, output: 250 W, time: 20 seconds) within 24 hours after preparation. , Gorilla II) with a spray coating apparatus (manufactured by T & K Co., Ltd., NST-51).
(3) A temperature of 80 ° C., a humidity of 80% RH, and curing for 1 hour to form a cured film to prepare a test specimen.

The film thickness of the obtained cured film can be measured by the following method.
[Measurement method of cured film thickness]
Using the specimen prepared above, the fluorescent X-ray dose of fluorine atoms was quantified with a wavelength-dispersed compact X-ray fluorescence analyzer (manufactured by Rigaku Corporation, ZSX-mini), and coated on a glass plate using a calibration curve The film thickness of the cured film thus obtained is calculated.

The haze value of the obtained cured film having a film thickness of 20 nm can be measured by the following method.
[Method of measuring haze value]
The haze value is calculated | required based on the measuring method of JISK7136: 2000 using the haze meter (Nippon Denshoku Industries Co., Ltd. make, NDH-5000) for the test body prepared above. In addition, the haze value in this invention has shown the value which match | combined the glass substrate and the cured film.

  In order for the haze value to be in the above-described range, in the fluorine-containing coating agent of the present invention, (A) a silane having a hydrolyzable group at one end modified with a fluorooxyalkylene group-containing polymer and / or (B) a partially hydrolyzed condensate, and (B) a silane having a hydrolyzable group at both ends modified with a fluorooxyalkylene group-containing polymer and / or a partially hydrolyzed condensate thereof, This can be achieved by mixing the component B) from 20:80 to 60:40.

The fluorine-containing coating agent of the present invention has wear durability, and the water contact angle after 2,000 reciprocating abrasions of the cured film is 100 ° or more, particularly 101 ° or more. When the water contact angle is less than 100 °, water repellency as a coating film is insufficient, and it cannot be said that the film has excellent wear durability.
The wear durability in the present invention means that the cured coating of the fluorine-containing coating agent is worn 2,000 reciprocating times using a steel wool (counter # 0000) with a friction measuring machine, and the contact angle with water before and after the wear is determined. It can be evaluated by measuring. It can be said that a coating having a small change in contact angle before and after abrasion and a high contact angle after abrasion (that is, a water contact angle of 100 ° or more) is a coating excellent in wear durability.

  Here, the cured film of the fluorine-containing coating agent can be produced by a method similar to the cured film production method described above.

As a specific method for measuring the wear durability, the following method can be used.
[Abrasion durability measurement method]
-Water contact angle measuring method Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle of the cured coating is measured at 25 ° C and humidity 50% RH. The water contact angle is measured 1 second after a 2 μl droplet is deposited on the sample surface.
・ Abrasion and measurement method of cured film The above-mentioned cured film was subjected to an abrasion tester (Tribogear TYPE: 30S (manufactured by Shinto Kagaku Co., Ltd.)) using steel wool (Bonnster commercial steel wool, count # 0000, manufactured by Nippon Steel Wool). )) And 2,000 reciprocating wears, and the contact angle with water after wear is measured in the same manner as described above.
Contact area: 10mm x 10mm
Load: 1kg

  In order for the water contact angle of the cured film to be the value described above, the fluorine-containing coating agent of the present invention has a hydrolyzable group at one end modified with (A) a fluorooxyalkylene group-containing polymer. A silane and / or a partial hydrolysis condensate thereof, and (B) a silane having a hydrolyzable group at both ends modified with a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate thereof (A ) Component and (B) component can be achieved by preparing a fluorine-containing coating agent in a ratio of 20:80 to 60:40.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited by the following Example. In this example, the component (A) and the component (B) were mixed, but the component (A) was synthesized in a state where the component (B) was previously included in the raw material for synthesizing the component (A). May be.

（式中、ｐ１、ｑ１はｐ１／ｑ１＝０．９、ｐ１＋ｑ１≒４５であり、重量平均分子量は４，０００である。） [Example 1 , Reference Examples 1 and 2 , Comparative Examples 1 to 6]
The following compounds 1 and 3 were prepared as the (A) component fluorooxyalkylene group-containing polymer-modified silane, and the following compounds 2 and 4 were prepared as the (B) component fluorooxyalkylene group-containing polymer-modified silane.
[Compound 1]

(In the formula, p1 and q1 are p1 / q1 = 0.9, p1 + q1≈45, and the weight average molecular weight is 4,000.)

（式中、ｐ２、ｑ２はｐ２／ｑ２＝０．９、ｐ２＋ｑ２≒４５であり、重量平均分子量は４，０００である。） [Compound 2]

(Wherein p2 and q2 are p2 / q2 = 0.9, p2 + q2≈45, and the weight average molecular weight is 4,000.)

（式中、ｐ１、ｑ１はｐ１／ｑ１＝０．９、ｐ１＋ｑ１≒４５であり、重量平均分子量は４，０００である。） [Compound 3]

(In the formula, p1 and q1 are p1 / q1 = 0.9, p1 + q1≈45, and the weight average molecular weight is 4,000.)

（式中、ｐ２、ｑ２はｐ２／ｑ２＝０．９、ｐ２＋ｑ２≒４５であり、重量平均分子量は４，０００である。） [Compound 4]

(Wherein p2 and q2 are p2 / q2 = 0.9, p2 + q2≈45, and the weight average molecular weight is 4,000.)

Preparation of fluorine-containing coating agent and formation of cured film The above compounds 1 to 4 were dissolved in ethyl perfluorobutyl ether [Novec 7200 (manufactured by 3M)] at a mixing ratio shown in Table 1 so that the solid content concentration was 20% by mass. After that, a fluorine-containing coating agent is prepared by further dissolving in 1,1,1,3,3-pentafluorobutane (Solkane 365mfc (manufactured by Solvay)) to a solid content concentration of 0.1% by mass. did. Within 24 hours after preparation of the fluorine-containing coating agent, chemically tempered glass (Corning, Gorilla II) was cleaned by plasma treatment (Ar: 10 cc, O ₂ : 100 cc, output: 250 W, time: 20 seconds), The fluorine-containing coating agent was spray-coated with a spray coating apparatus (NST-51, manufactured by T & K Corporation). Then, it hardened at temperature: 80 degreeC and humidity: 80% RH for 1 hour, the cured film was formed, and the test body was produced.

The cured films obtained in Example 1 , Reference Examples 1 and 2 and Comparative Examples 1 to 6 were evaluated by the following methods. All tests were performed at 25 ° C. and humidity 50% RH. The results of Example 1 and Reference Examples 1 and 2 are shown in Tables 2 to 4, and the results of Comparative Examples 1 to 6 are shown in Tables 5 to 10, respectively.

[Evaluation of film thickness]
The film thickness of the cured film produced above was measured using the following apparatus.
Device name: Wavelength dispersive compact fluorescent X-ray analyzer (ZSX-mini (manufactured by Rigaku Corporation))

[Evaluation of haze]
The haze of the test specimen prepared above was measured using the following apparatus according to JIS K7136: 2000.
Device name: Haze meter (NDH-5000 (manufactured by Nippon Denshoku Industries Co., Ltd.))

[Evaluation of water and oil repellency]
Using the test specimen prepared above, the contact angle of the cured film with respect to water (droplet: 2 μl) was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). The water contact angle was measured 1 second after a 2 μl droplet was deposited on the sample surface.

[Evaluation of wear resistance]
Abrasion resistance to steel wool (bonster commercial steel wool, count # 0000, manufactured by Nippon Steel Wool Co., Ltd.) of the hardened coating was measured after 2,000 reciprocating wears using Tribogear TYPE: 30S (Shinto Kagaku Co., Ltd.). The contact angle with water (droplet: 2 μl) was measured.
Contact area: 10mm x 10mm
Load: 1kg

FIG. 1 shows the relationship between the film thickness and haze of the cured film of Example 1, Reference Example 1 and Comparative Examples 1, 2, 5, and 6. FIG. 1 shows the film thickness and haze of the cured film of Reference Example 2 and Comparative Examples 3 and 4. The relationship is shown in FIG.
Further, the first embodiment, the curing in the coating of Reference Example 1 and Comparative Example 1, 2, 5, 6 (A) is a haze upon ingredient content and the film thickness 20nm related to FIG. 3, reference example 2 and comparative FIG. 4 shows the relationship between the content of component (A) in the cured coatings of Examples 3 and 4 and haze when the film thickness is 20 nm.

  From the results of Tables 2 to 10 and FIGS. 1 to 4, since Comparative Examples 1 and 3 did not contain the component (B), the increase in haze was significantly observed as the film thickness increased. In addition, since Comparative Examples 2 and 4 did not contain the component (A), the haze increased with the increase in film thickness, and the wear durability was inferior. In Comparative Example 5, since the mixing mass ratio of the component (A) and the component (B) is larger than the range of the present invention, the amount of the component (A) is larger. Since the mixing mass ratio of the component (A) and the component (B) is larger than the range of the present invention, the amount of the component (B) is larger, so that the haze is increased with the increase of the film thickness and the wear durability is inferior. It was a thing. On the other hand, as for the test body of Examples 1-3 which coated the fluorine-containing coating agent contained by 20: 80-60: 40 of mixing mass ratio of (A) component and (B) component, the raise of haze is suppressed. Furthermore, it was excellent in wear durability. In particular, even when applied to a thick film having a film thickness of 15 nm or more, which is thicker than the usual film thickness of about 10 nm, the increase in haze is suppressed in the examples, and the wear durability is excellent. I understood.

  A silane having a hydrolyzable group at one end and / or a partially hydrolyzed condensate thereof modified with (A) the fluorooxyalkylene group-containing polymer of the present invention, and (B) modified with a fluorooxyalkylene group-containing polymer. Fluorine-containing coating agents containing silanes having hydrolyzable groups at both ends and / or partial hydrolysis condensates thereof in a specific ratio are resistant to wear and low haze without impairing the optical properties and texture of the substrate. A value can be indicated. The fluorine-containing coating agent of the present invention is very effective particularly for applications where visibility is important, such as touch panel displays, antireflection films, and the like, where adhesion of oils and fats is assumed. Since the increase in haze is suppressed in the fluorine-containing coating agent of the present invention, cleaning and wiping work for reducing haze after coating is not necessary.

Claims (9)

(A) a silane having a hydrolyzable group at one end and / or a partially hydrolyzed condensate thereof modified with a fluorooxyalkylene group-containing polymer represented by the following general formula (4), and (B) the following general formula ( 6) A silane having a hydrolyzable group at both ends and / or a partially hydrolyzed condensate thereof modified with the fluorooxyalkylene group-containing polymer shown in 6), and a mixture of the component (A) and the component (B) A fluorine-containing coating agent having a mass ratio of 50:50 to 60:40, wherein the haze measured by the method described in JIS K7136 is 0.5 or less when the thickness of the cured film of the coating agent is 20 nm. A fluorine-containing coating agent characterized by having a wear durability with a water contact angle of 100 ° or more after 2,000 reciprocating wears.

[In the above formulas (4) and (6), R ¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3. Rf (wherein, g is an integer of 1 to 6 independently for each unit.) Is -C _g F _2g O- expressed repeating units of 10 to 200 pieces organic bivalent be in (poly) fluorooxyalkylene A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, a —CF ₂ H group, or a —CFH ₂ group. Q is a single bond or an unsubstituted or substituted divalent organic group having 2 to 12 carbon atoms which may have an oxygen atom, a nitrogen atom or a silicon atom, Q ′ is a carbon atom, B Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. n is 2 and m is 1. f ′ is an integer of 0 to 10. ] Rf is _{- (CF 2) d - (} OCF 2) p (OCF 2 CF 2) q (OCF 2 CF 2 CF 2) r (OCF 2 CF 2 CF 2 CF 2) s (OCF (CF 3) CF 2) _{t -O- (CF 2) d -} (d are independently integers of 0 to 5 with each other, p, q, r, s and t are independently an integer of 0 to 200 to each other, and, p + q + r + s + t is 10 The fluorine-containing coating agent according to claim 1 , which is an integer of ˜200, and each unit shown in parentheses may be bonded at random. Furthermore, the fluorine-containing coating agent of Claim 1 or 2 containing the (poly) fluoro oxyalkylene group containing polymer represented by following General formula (7).
A-Rf-A (7)
(Wherein, Rf is -C _g F _2g O- (wherein, g is an integer of 1 to 6 independently for each unit.) Divalent (poly to 10 to 200 pieces have a repeating unit represented by the ) A fluorooxyalkylene group, and A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, a —CF ₂ H group, or a —CFH ₂ group. Furthermore, the fluorine-containing coating agent of any one of Claims 1-3 containing a solvent. The cured film of the fluorine-containing coating agent of any one of Claims 1-4 . An article having the cured coating according to claim 5 . A touch panel coated with the cured film according to claim 5 . 6. An antireflective article coated with the cured coating according to claim 5 . A tempered glass coated with the cured film according to claim 5 .

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