JPWO2018066479A1 - Surface treatment agent - Google Patents

Abstract

[Summary] [Problem] An object of the present invention is to provide a surface treatment agent capable of forming a cured coating film quickly and in a simple process and having excellent storage stability. [Solution] The present invention comprises (A) a fluorine-containing organosilicon compound having at least one hydrolyzable group in one molecule, and (B) a compound having a phosphonate ester group in the molecule (A) component ( The article which has the surface treating agent containing the quantity used as 0.001-15 mass parts with respect to a total of 100 mass parts of B) component, and the hardened | cured material of this surface treating agent is provided.

Description

  The present invention relates to a surface treatment agent containing a fluorine-containing organosilicon compound. Specifically, a surface treatment agent that is excellent in storage stability and can be cured at a low temperature in a short time to give a film having excellent water and oil repellency and abrasion resistance, and an article treated with the surface treatment agent About.

  In recent years, the touch panel of the screen including the display of the mobile phone has been accelerated. However, many touch panels are exposed on the screen, and there are many opportunities for direct contact with fingers, cheeks, etc., which makes it easy to get dirt such as sebum. 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.

  Generally, fluorooxyalkylene group-containing compounds are known to have water and oil repellency, chemical resistance, lubricity, releasability, and antifouling properties because their surface free energy is very small. . 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 proofing agents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, since the fluorooxyalkylene group-containing compound is inferior in adhesiveness and adhesion to other substrates, it has been difficult to adhere a film comprising a cured product of the composition containing the compound to the substrate.

  Silane coupling agents are known as additives for bonding organic compounds with substrate surfaces such as glass and cloth, and are widely used as additives contained in coating agents on various substrate surfaces. A silane coupling agent is a compound having an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group causes a self-condensation reaction due to moisture in the air. In a film formed by curing a coating agent, the alkoxysilyl group or a silanol group that is a hydrolyzate thereof is chemically and physically bonded to the surface of glass, metal, or the like to form a strong and durable film. .

（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。）
しかし、該特許文献１に記載の表面処理剤は、室温で１日程度、１００℃程度の加熱で１時間程度の硬化時間が必要であり、生産性に劣るという問題がある。このように、従来の撥水撥油処理剤（表面処理剤）は、良好な撥水撥油性及び汚れ拭取り性を有する膜を形成するこはできるが、硬化性に劣る。そのため、低温・短時間で硬化可能な撥水撥油処理剤（表面処理剤）の開発が要求されている。Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-238777) contains a perfluorooxyalkylene group having a linear perfluorooxyalkylene group represented by the following formula as a compound having a fluorooxyalkylene group and an alkoxysilyl group. Polymer modified silanes are described. By treating the glass surface with a cured product of a surface treatment agent containing the perfluorooxyalkylene group-containing polymer-modified silane, excellent slipperiness, releasability and wear resistance can be imparted to the glass surface.

(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.)
However, the surface treatment agent described in Patent Document 1 requires a curing time of about one day at room temperature and about one hour by heating at about 100 ° C., and has a problem that it is inferior in productivity. As described above, the conventional water / oil repellent treatment agent (surface treatment agent) can form a film having good water / oil repellency and dirt wiping property, but is inferior in curability. Therefore, development of a water and oil repellent treatment agent (surface treatment agent) that can be cured at a low temperature in a short time is required.

Catalysts for promoting curing include organic titanate esters, organic titanium chelate compounds, organic aluminum compounds, organic zirconium compounds, organic tin compounds, metal salts of organic carboxylic acids, amine compounds, and salts thereof, quaternary ammonium salts, alkalis Metal lower fatty acid salts, dialkylhydroxylamines, guanidyl group-containing organosilicon compounds, organic acids, inorganic acids, and the like are known. However, since these catalysts are not dissolved in a fluorine-based solvent or are dissolved very little even if dissolved, the catalyst efficiency is poor. In addition, the metal content may cause deterioration of the characteristics of the cured film.

  In order to solve the above problem, Patent Document 2 (Japanese Patent Application Laid-Open No. 2008-144144) describes a coating agent composition containing perfluoropolyethercarboxylic acid as a curing catalyst soluble in a fluorine-based solvent.

JP 2003-238777 A JP 2008-144144 A

The composition described in Patent Document 2 is cured in a short time to give a cured film excellent in water repellency, oil repellency, and antifouling property, but storability is a problem.
Therefore, an object of the present invention is to provide a surface treatment agent that can quickly form a cured film and is excellent in storage stability by a simple process.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a compound having a phosphonic acid ester group as a curing catalyst for a fluorine-containing organosilicon compound having a hydrolyzable group. .

That is, the present invention
(A) Fluorine-containing organosilicon compound having at least one hydrolyzable group in one molecule, and (B) Compound having a phosphonate ester group in the molecule (A) Component and (B) component in total 100 parts by mass An article having a surface treatment agent in an amount of 0.001 to 15 parts by mass and a cured product of the surface treatment agent is provided.

The surface treatment agent of the present invention cures quickly on the base material and adheres firmly to the base material to form a film having excellent water and oil repellency, slipperiness, releasability and the like.
Moreover, the compound which has a phosphonic acid ester group contained in the surface treating agent of this invention touches the water | moisture content in air, A phosphonic acid ester group hydrolyzes rapidly and becomes phosphonic acid. The phosphonic acid accelerates the hydrolysis of the fluorine-containing organosilicon compound having a hydrolyzable group and cures the surface treatment agent quickly. The phosphonic acid ester can exist stably when not exposed to moisture. Therefore, it is possible to provide a surface treatment agent having excellent storage stability.

[(A) Fluorine-containing organosilicon compound]
The component (A) is a fluorine-containing organosilicon compound having at least one hydrolyzable group in one molecule. The component may be an organosilicon compound having a hydrolyzable group such as a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms and an alkoxyalkoxy group in one molecule and having a fluorine atom. The fluorine-containing organosilicon compound is preferably a compound having a fluorooxyalkylene group. The compound having a fluorooxyalkylene group is a compound having a (poly) fluorooxyalkylene structure in which a plurality of repeating units represented by -C _j F _2j O- are bonded (in the structure, j is 1 or more, preferably 1-6, more preferably an integer of 1-4). In particular, the repeating unit should have 10 to 500, preferably 15 to 200, more preferably 20 to 100, and more preferably 25 to 80.

The repeating unit —C _j F _2j O— may be either a linear type or a branched type. For example, the following units may be mentioned, and two or more of these repeating units may be combined.
—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-
-C _{(CF 3)} 2 O-

前記式中ｄ’は０〜５の整数であり、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’はそれぞれ独立に０〜２００の整数であり、かつ、ｐ’＋ｑ’＋ｒ’＋ｓ’＋ｔ’＝１０〜２００である。The fluorooxyalkylene structure, in _{particular, - (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 - represented by. In the above formula, d is an integer of 0 to 5, p, q, r, s, and t are each independently an integer of 0 to 200, and preferably p + q + r + s + t = 10 to 200. In addition, each unit shown in parentheses may be combined at random. In particular, it can be represented by the following structural formula.

In the above formula, d ′ is an integer of 0 to 5, p ′, q ′, r ′, s ′ and t ′ are each independently an integer of 0 to 200, and p ′ + q ′ + r ′ + s ′. + T ′ = 10 to 200.

The (A) component fluorine-containing organic silicon compound is more preferably a fluorine-containing organic silicon compound represented by any one of the following formulas (1) to (4). These may be used individually by 1 type and may use 2 or more types together.
(A-Rf) _α- ZW _β (1)
_{Rf- (ZW β) 2 (2} )
A-Rf-Q- (Y) _γ B (3)
_{Rf- (Q- (Y) γ B} ) 2 (4)

In the formula (1) and (2), Rf group _{- (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 —, and p, q, r, s, and t are as described above. Each unit shown in parentheses may be combined randomly. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, —CF ₂ H group or —CH ₂ F group, and Z is a single bond, carbon atom, silicon atom, nitrogen It is a divalent to octavalent organic group that may be substituted with an atom or a fluorine atom, the valence of Z in formula (1) is (β + α), and the valence of Z in formula (2) is (β + 1) W is a monovalent organic group having a hydrolyzable group at the terminal. α is an integer of 1 to 7, preferably an integer of 1 to 3. β is an integer of 1 to 7, preferably an integer of 1 to 3.

  In formulas (3) and (4), Rf and A are as described above, Q is a single bond or a divalent organic group, γ is each independently an integer of 1 to 10, and Y is a hydrolysis. B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.

In the above formulas (1) and (3), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a —CF ₃ group, a —CF ₂ H group or a —CH ₂ F group at the terminal. Among these, —CF ₃ group, —CF ₂ CF ₃ group, and —CF ₂ CF ₂ CF ₃ group are preferable.

  In the above formulas (1) and (2), Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a divalent to octavalent organic group that may be substituted with fluorine. The valence of Z in the formula (1) is (β + α), and the valence of Z in the formula (2) is (β + 1). The organic group can be represented by -QM-.

Q is a single bond or a divalent organic group, and is a linking group between the Rf group and the M group. Preferably, it may contain one or more selected from the group consisting of an amide bond, an ether bond, an ester bond, a vinyl bond, or a diorganosilylene group such as a dimethylsilylene group, which is unsubstituted or substituted, A divalent organic group having 2 to 12 carbon atoms. More preferably, it is a divalent hydrocarbon group which may have the bond.

  Examples of the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms represented by Q include, for example, a methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group). Group, a methylpropylene group), an alkylene group such as a hexamethylene group and an octamethylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (such as an alkylene / arylene group). Further, a group in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom such as fluorine may be used. Among these, an unsubstituted or substituted alkylene group having 2 to 4 carbon atoms or a phenylene group is preferable.

（式中、ｆは２〜４の整数であり、ａ、ｂ、ｇは１〜４の整数であり、ｈは１〜５０の整数であり、Ｍｅはメチル基である。）Examples of Q include a group represented by the following structural formula.

(In the formula, f is an integer of 2 to 4, a, b and g are integers of 1 to 4, h is an integer of 1 to 50, and Me is a methyl group.)

M is independently of each other a single bond, a divalent group represented by -R ¹ ₂ C-, a divalent group represented by -R ³ ₂ Si-, a trivalent group represented by -R ¹ C =, A group selected from a trivalent group represented by —R ³ Si═, a tetravalent group represented by —C≡, and a tetravalent group represented by —Si≡, or a divalent to octavalent siloxane residue. is there. In the above, R ¹ is independently of each other, preferably an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, or a silyl ether group represented by R ² ₃ SiO—, and R ² is independently of each other a hydrogen atom, preferably Is an alkyl group having 1 to 3 carbon atoms, an aryl group such as a phenyl group, or an alkoxy group having 1 to 3 carbon atoms. R ³ is independently of each other preferably an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a chloro group. When M is a siloxane residue, it preferably has a chain, branched or cyclic organopolysiloxane structure having 2 to 13 silicon atoms, preferably 2 to 5 silicon atoms. The organopolysiloxane preferably has 1 to 8 carbon atoms, more preferably 1 to 4 alkyl groups such as methyl, ethyl, propyl, and butyl groups, or phenyl groups. In addition, it includes a silalkylene structure or a silphenylene structure in which two silicon atoms are bonded by an alkylene group or a phenylene group, that is, Si— (CH ₂ ) _n —Si or Si— (C ₆ H ₄ ) —Si. Also good. In said formula, n is an integer of 2-6, Preferably it is an integer of 2-4.

（式中、ｉは１〜２０の整数である。）

（式中、Ｍｅはメチル基である。）

（式中、ｆは２〜４の整数であり、ｈは１〜５０の整数であり、Ｍｅはメチル基である。）Examples of such M include those shown in the following structural formula.

(In the formula, i is an integer of 1 to 20.)

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

(In the formula, f is an integer of 2 to 4, h is an integer of 1 to 50, and Me is a methyl group.)

（式中、Ｒは炭素数１〜４のアルキル基また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であり、ｍは０又は１〜１０の整数である）In the above formulas (1) and (2), W is a monovalent organic group having a hydrolyzable group at the terminal, and preferably a group represented by the following formula.

(In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and m is 0 or an integer of 1 to 10)

  X is a carbon such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group or the like, an alkoxy group having 1 to 10 carbon atoms, a methoxymethoxy group, a methoxyethoxy group or the like, an oxyalkoxy group having 2 to 10 carbon atoms, or an acetoxy group. Examples thereof include alkenyloxy groups having 2 to 10 carbon atoms such as acyloxy groups having 1 to 10 carbon atoms and isopropenoxy groups, and halogen groups such as chloro, bromo and iodo groups. Of these, a methoxy group and an ethoxy group are preferable. In said formula, R is a C1-C4 alkyl group or a phenyl group, and especially a methyl group is suitable. a is 2 or 3, and 3 is preferable from the viewpoint of reactivity and adhesion to a substrate. b is an integer of 1 to 7, preferably 1 to 3, and c is an integer of 1 to 5, preferably 1 to 3.

式（７ａ）〜（７ｅ）において、Ｑ、Ｒ、Ｘ、及びａは上記の通りであり、ｍ^１は０〜１０の整数であり、好ましくは２〜８の整数であり、ｍ^２は１〜１０の整数であり、好ましくは２〜８の整数である。ｂは２〜６の整数、好ましくは２〜４の整数であり、ｃは１〜５０の整数、好ましくは１〜１０の整数であり、Ｍｅはメチル基である。In the formula (1) and (2), the structure represented by -zw _beta, include those represented by the following structural formulas.

In the formulas (7a) to (7e), Q, R, X, and a are as described above, m ¹ is an integer of 0 to 10, preferably 2 to 8, and m ² is 1. It is an integer of -10, Preferably it is an integer of 2-8. b is an integer of 2 to 6, preferably an integer of 2 to 4, c is an integer of 1 to 50, preferably an integer of 1 to 10, and Me is a methyl group.

In the above formulas (3) and (4), Q is a divalent organic group, and is a linking group between the Rf group and the Y group. The details of Q are as described above.

式中、Ｒ、Ｘ、ａ、及びｍは上記の通りである。ｐは１〜６の整数、好ましくは１〜３の整数、より好ましくは１または２である。Ｍ’は、３〜８価、好ましくは３〜５価、より好ましくは３価又は４価の、置換又は非置換の炭化水素基であり、該炭化水素基における炭素原子の一部又は全部がケイ素原子に置き換わっていてもよく、また、該炭素原子に結合する水素原子の一部または全部がフッ素原子等のハロゲン原子に置き換わっていてもよい。尚、Ｍ’の価数はｐ＋２である。Ｍ’は好ましくは下記構造式で表される基である。

（上記において、Ｍ^１は２価炭化水素基又はオルガノシリル基であり、Ｍ^２は３価の炭化水素基又はオルガノシリル基であり、Ｒは炭素数１〜６の１価炭化水素基である）In the above formulas (3) and (4), Y is a divalent organic group having a hydrolyzable group independently of each other. A group represented by the following formula is preferred.

In the formula, R, X, a, and m are as described above. p is an integer of 1-6, preferably an integer of 1-3, more preferably 1 or 2. M ′ is a substituted or unsubstituted hydrocarbon group having 3 to 8 valences, preferably 3 to 5 valences, more preferably 3 or 4 valences, and some or all of the carbon atoms in the hydrocarbon groups A silicon atom may be substituted, and a part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom such as a fluorine atom. Note that the valence of M ′ is p + 2. M ′ is preferably a group represented by the following structural formula.

(In the above, M ¹ is a divalent hydrocarbon group or an organosilyl group, M ² is a trivalent hydrocarbon group or an organosilyl group, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms. )

Examples of such Y include groups represented by the following structural formulas.

（式中、Ｘは上記と同じであり、ｊは０〜１０の整数、好ましくは１〜８の整数であり、ｋは２〜１０の整数、好ましくは３〜８の整数である。Ｍｅはメチル基である。）

(In the formula, X is the same as above, j is an integer of 0 to 10, preferably 1 to 8, and k is an integer of 2 to 10, preferably 3 to 8. Me is It is a methyl group.)

  In said formula (3) and (4), (gamma) is an integer of 1-10, Preferably it is an integer of 1-4. B is independently of each other a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a butyl group, or a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of halogen atoms.

（式中、Ｍｅはメチル基であり、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。）Examples of the fluorine-containing organosilicon compounds represented by the above formulas (1) to (4) include compounds represented by the following structural formulas.

(In the formula, Me is a methyl group, and each unit shown in parentheses may be bonded at random.)

  The surface treating agent of the present invention may contain a compound in which a part or all of the hydrolyzable group (X) in the component (A) is hydrolyzed (compound in which X is an OH group). A compound in which part or all of the groups are condensed may be contained.

[Component (B)]
Component (B) is a compound having a phosphonate ester group in the molecule. The phosphonic acid ester group in the present invention is a group represented by -P (O) (OX ') ₂ . X ′ may be a group possessed by a general phosphonate represented by —P (O) (OX ′) ₂ . Preferably, it is an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms, or a group represented by —SiR ₃ . R is a C1-C5 alkyl group or an aryl group mutually independently. More preferably, X ′ is a phenyl group or a trimethylsilyl group.

  From the viewpoint of compatibility with the component (A) described above, the component (B) is preferably a compound having a fluorine atom. Particularly preferred are compounds having a fluorooxyalkylene group. When the component (B) is a compound having no fluorine atom, the surface treatment agent preferably contains a mixture of a fluorinated solvent and a non-fluorinated solvent described later as a solvent. Thereby, the compatibility of (A) component and (B) component can be improved.

The fluorooxyalkylene group refers to the (A) as described in component, -C j _F 2j _O-a repeating unit represented is more binding (poly) fluoro polyoxyalkylene structure. Details are as described for the fluorooxyalkylene group described for the component (A). However, the structures of the fluorooxyalkylene groups contained in the component (A) and the component (B) are independent of each other. The (B) component fluorooxyalkylene group, Rf ′, is preferably — (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 ′} —. In the above, d ′ is an integer of 0 to 5, p ′, q ′, r ′, s ′, and t ′ are each independently an integer of 0 to 200, and p ′ + q ′ + r ′ + s ′. It is preferable that + t ′ = 10 to 200. In addition, each unit shown in parentheses may be combined at random.

The component (B) is preferably a compound represented by the following formula (5) or (6).
A'-Rf'-Z'W '_α' (5)
Rf ′ − (Z′W ′ _{α ′} ) ₂ (6)
In the formula, Rf ′ group is as described above, α ′ is an integer of 1 to 7, A ′ is a fluorine atom, a hydrogen atom, or a terminal is —CF ₃ group, —CF ₂ H group or —CH _2. A monovalent fluorine-containing group which is an F group, Z ′ is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a divalent to octavalent organic group which may be fluorine-substituted, and W ′ is a phosphonic acid at the terminal It is a monovalent organic group having an ester group.

In the above formula (5), A ′ is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, —CF ₂ H group, or —CH ₂ F group, and in particular, —CF _3. Group, —CF ₂ CF ₃ group, and —CF ₂ CF ₂ CF ₃ group are preferred.

  In the above formulas (5) and (6), Z ′ is a single bond, a carbon atom, a silicon atom, a nitrogen atom or a divalent to octavalent organic group which may be substituted with fluorine. The valence of Z ′ is α ′ + 1. The details of Z ′ are as described for the group represented by Z described in the component (A), and the organic group is a group represented by the above-described —QM—. The details are as described in the component (A). However, the component (A) and the component (B) have independent structures.

In the above formulas (5) and (6), W ′ is a monovalent organic group having a phosphonate group at the end, and can be represented by, for example, —Q′—P (O) (OX ′) ₂ . Q ′ is a single bond or a divalent organic group. The divalent organic group is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, which may contain a diorganosilylene group. Moreover, you may have the bivalent organic group chosen from the above-mentioned choice of Q.

式中、Ｘ’は上記の通りであり、ｌ’は０〜２０の整数である。

式中、Ｘ’は上記の通りであり、ｌ’、ｍ’、ｎ’は互いに独立に１〜２０の整数であり、好ましくは各々２又は３である。W ′ is preferably a group represented by the following formula.

In the formula, X ′ is as described above, and l ′ is an integer of 0-20.

In the formula, X ′ is as described above, and l ′, m ′ and n ′ are each independently an integer of 1 to 20, preferably 2 or 3, respectively.

式中、Ｘ’及びQは上記の通りであり、ｍ’及びｎ’は互いに独立に０〜２０の整数であ、好ましくは各々２又は３である。W ′ may be represented by the following formula.

In the formula, X ′ and Q are as described above, and m ′ and n ′ are each independently an integer of 0 to 20, preferably 2 or 3, respectively.

Examples of the compound represented by the above formula (5) or (6) include compounds represented by the following formula.

  In the surface treatment agent of the present invention, the blending amount of the component (B) varies depending on the desired curing time and the molecular weight, but is 0.001 with respect to a total of 100 parts by mass of the component (A) and the component (B). In an amount of 15 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, especially 0.5 to 5 parts by mass. is there. When the amount of the component (B) is less than the lower limit, the effect of the catalyst is hardly exhibited. When the above upper limit is exceeded, the surface properties tend to be adversely affected, for example, the water repellency of the cured coating is lowered. The component (A) and the component (B) may be mixed by a known mixing means, and may be mixed after each is dissolved in the following solvent.

[solvent]
The coating agent composition of the present invention is preferably diluted in advance with a solvent, and as such a solvent, the fluorine group-containing modified silane (A) and the compound (B) having a phosphonic acid ester group are uniformly used. If it is made to melt | dissolve, it will not specifically limit. For example, fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-trifluoromethylbenzene, etc.), fluorine-modified ether solvents (methyl perfluoro) Butyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc., fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.) ) And ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, in terms of solubility and stability, a fluorine-modified solvent is desirable, and in particular, a fluorine-modified ether solvent and a fluorine-modified aromatic hydrocarbon solvent are preferable. The said solvent may be used individually by 1 type, or may mix and use 2 or more types. The solvent is preferably contained so that the total mass% of the component (A) and the component (B) in the composition is 0.01 to 50%, preferably 0.03 to 25%.

The surface treating agent of the present invention is cured by hydrolyzing the phosphonic acid ester group of the component (B) to become phosphonic acid and promoting the hydrolysis reaction of the component (A). In general, phosphonic acid groups (—P (O) (OH) ₂ ) do not react with OH groups in the substrate unless heated for a long time at 100 ° C. or higher. And the reaction between component (B) does not proceed. On the other hand, the component (A) is hydrolyzed even at room temperature and gradually binds to the —OH group of the substrate. Therefore, at room temperature or low temperature, the hydrolysis reaction of component (A) by the catalytic function of component (B) proceeds preferentially and rapidly. Thereby, the cured film excellent in adhesiveness with a base material can be given even if it is low-temperature short-time heating.

[Coating method]
The surface treatment agent can be applied to the substrate by a known method such as a wet coating method (brush coating, dipping, spraying, ink jetting) or a vapor deposition method. The coating conditions and the like may follow a conventionally known method. The surface treatment agent of the present invention is rapidly cured after application and can be cured at room temperature. Furthermore, you may heat at 30-200 degreeC in order to make it harden | cure in a short time. Curing is preferably carried out under humidification in order to enhance the catalytic action in order to promote hydrolysis. The curing time may be appropriately selected. For example, the curing can be performed at 25 ° C. for 40 minutes to 80 minutes, particularly about 60 minutes. Moreover, it can harden | cure in about 30 minutes at 80 degreeC. Humidity should just be adjusted suitably and relative humidity is about 40 to 50%. In addition, since the influence of molecular weight is small in the case of the Ut coating method, the molecular weight is not limited. However, when the surface treatment agent of the present invention is applied by vapor deposition, the components (A) and (B) It is desirable that the number average molecular weight is the same or the component (B) is larger.

  The component (B) preferably has a number average molecular weight that is 0.5 to 5 times the number average molecular weight of the component (A). When the number average molecular weight of the component (B) is significantly smaller than the number average molecular weight of the component (A), a large amount of the component (B) that does not easily react with the substrate at room temperature is deposited at the initial stage of the vacuum deposition process. If it does so, (A) component which is easy to react with a base material will be vapor-deposited at the latter stage of a vapor deposition process, and adhesiveness with a base material may worsen. It is preferable to make the difference in number average molecular weight within the above range because the effects of the present invention can be exhibited without any harmful effects.

  The surface treatment agent of the present invention is applied to a substrate and then cured to form a film. The film thickness of the cured film (fluorine layer) is preferably 50 nm or less, particularly preferably 0.5 to 20 nm, and more preferably 2 to 15 nm.

  The surface treating agent of the present invention imparts water and oil repellency to the substrate surface. The compound having the phosphonic acid ester can enhance the storage stability of the surface treatment agent while having the same curing acceleration effect as that of a conventional curing accelerator, particularly an acid catalyst. In general, an acid catalyst exerts an effect of accelerating curing immediately after mixing with the main agent, but since the curing reaction proceeds during storage, the life of the treatment liquid often becomes a problem. On the other hand, the phosphonic acid ester group exerts the effect of the curing catalyst after reacting with moisture to become a phosphonic acid group, and therefore has little influence on the life of the surface treatment agent.

The substrate to be treated with the surface treatment agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz and the like. The surface treating agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treating agent for SiO ₂ -treated glass, film, and sapphire substrates.

  Articles to be treated with the surface treatment agent of the present invention include car navigation, tablet PC, smartphone, mobile phone, digital camera, digital video camera, PDA, portable audio player, car audio, game device, spectacle lens, camera lens, Examples include optical instruments such as lens filters, sunglasses, gastric cameras, and other medical devices, copying machines, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. The fluorinated surface treatment agent for vapor deposition of the present invention can prevent fingerprints and sebum from adhering to the article, and can further provide scratch resistance. Useful as an oil layer.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

Hereinafter, each component used in Examples and Comparative Examples is as follows. In addition, the number average molecular weight in the following is a value calculated by ¹ H-NMR.

(A) Fluorine-containing organosilicon compound:
(A-1)

（Ｂ−２）

（Ｂ−３）

(B) Phosphonate group-containing compound:
(B-1)

(B-2)

(B-3)

（Ｃ−２）

（Ｃ−３）トリフルオロ酢酸Curing catalyst for comparison:
(C-1)

(C-2)

(C-3) Trifluoroacetic acid

[Examples 1 to 5 and Comparative Examples 1 to 4]
In Preparation Examples 1 to 5 of the surface treatment agent , the above-described component (A-1) and any of the components (B-1) to (B-3) were mixed in the compositions described in Table 1 below. A surface treatment agent was prepared by dissolving in 400 parts by mass of Novec 7200 (manufactured by 3M) so that the concentration of (mixtures 1 to 5) and the mixture (total 100 parts by mass) was 20% by mass. In Comparative Examples 1 to 4, the above-described component (A-1) and any one of the curing catalysts for comparative examples (C-1) to (C-3) were mixed in the compositions described in Table 2 below ( A surface treatment agent was prepared by dissolving in 400 parts by mass of Novec 7200 (manufactured by 3M) so that the concentration of the mixture 6-9) and the mixture (total 100 parts by mass) was 20% by mass.

Formation of cured film by vacuum deposition 5 μL of each of the surface treatment agents prepared above was vacuum-deposited on glass (Corning Gorilla 3) treated with 15 nm of SiO ₂ on the outermost surface under the following conditions, and an atmosphere of 25 ° C. and 50% humidity The test piece in the following evaluation was prepared by curing for 1 hour and forming a film (film thickness: about 10 nm).
[Coating conditions and equipment by vacuum deposition]
・ Measuring device: Small vacuum evaporation system VPC-250F
・ Pressure: 2.0 × 10 ⁻³ Pa to 3.0 × 10 ⁻² Pa
・ Vapor deposition temperature (attainment temperature of boat): 500 ℃
・ Vapor deposition distance: 20mm
・ Processing agent charge: 5mg
・ Deposition amount: 5mg

The cured film in the test specimen was evaluated by the following method.
[Water repellency]
Using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the cured coating with water was measured. The results are listed in Table 3 below.

[Abrasion resistance]
Abrasion resistance to steel wool (# 0000):
Using Tribogear TYPE: 30S (manufactured by Shinto Kagaku Co., Ltd.), the cured coating was subjected to 10,000 round-trip wear under the following conditions, and then the contact angle of the cured coating to water was measured by a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). It measured using. The results are listed in Table 3 below.
Contact area: 1 cm ²
Load: 1kg

[Evaluation of preservability]
The test specimen was stored at 50 ° C. in a sealed container for 1 month. About the test body after a preservation | save, the contact angle with respect to the water of a cured film was measured using the contact angle meter DropMaster (made by Kyowa Interface Science Co., Ltd.). Furthermore, the contact angle with respect to the water of the cured film after implementing the said abrasion resistance test was measured. The results are listed in Table 3 below.

As shown in Table 3, since the surface treating agent of Comparative Example 1 does not contain a catalyst, the curing is slow, and the cured film obtained is inferior in wear resistance because it is not sufficiently cured under low temperature and short time curing conditions. The surface treating agents of Comparative Examples 2 and 3 contain a fluorine-containing compound having phosphonic acid as a curing catalyst. The surface treatment agent cures at a low temperature in a short time to give a cured coating having abrasion resistance. However, the coating obtained by curing after storage at 50 ° C. for one month is inferior in water repellency and further in abrasion resistance. Also inferior. This is presumed that the component (A) was condensed with each other during storage because the surface treatment agent contained phosphonic acid. Comparative Example 4 is a surface treatment agent containing a conventional curing catalyst. The obtained cured film was inferior in water repellency and inferior in abrasion resistance. Since trifluoroacetic acid has a low boiling point, it is presumed that at the time of vacuum deposition, the surface treatment agent was sucked into the pump before adhering to the substrate, and the effect as a catalyst was not sufficiently obtained. Moreover, the surface treating agent of Comparative Example 4 is also inferior in storage stability. It is considered that the component (A) was condensed during storage due to the effect of trifluoroacetic acid during storage.
On the other hand, as shown in Examples 1 to 5 of Table 3, the surface treatment agent of the present invention has excellent wear resistance even under low temperature and short time curing conditions of room temperature (25 ° C., humidity 50%) 1 hour curing. A cured coating can be provided. Furthermore, even after the cured coating is stored at 50 ° C. for one month, excellent wear resistance does not decrease and storage stability is also excellent.

[Examples 6 to 10 and Comparative Examples 5 to 8]
Formation of cured film by spray coating
The mixtures 1 to 9 prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were mixed with 1,1,1,3,3-pentafluorobutane [Solkane 365mfc ( (Solvay)) to prepare a surface treatment agent.
Spray coating the surface treatment agent 1 hour after preparation and the surface treatment agent after storage for 1 week at 50 ° C. on the surface of chemically strengthened glass (Gorilla II, manufactured by Corning) under the following conditions. Spray coating was performed using an apparatus (manufactured by T & K Co., Ltd., NST-51). Then, it hardened | cured for 30 minutes at 80 degreeC and 40% RH, the cured film was formed, and the test body was obtained.
[Plasma treatment conditions]
-Equipment: Plasma dry cleaning equipment PDC210
Gas: _{O 2} gas 80cc, Ar gas 10cc
・ Output: 250W
・ Time: 30 seconds

About the obtained cured film, water repellency, abrasion resistance, and preservability were evaluated by the following method. The results are listed in Table 4.
Evaluation method of water repellency: Evaluation was performed by the same method as the water repellency test described above.
Evaluation of abrasion resistance: The evaluation was performed by the same method as the above-described abrasion resistance test except that the number of reciprocating abrasion was 3,000.
Evaluation of storage stability: Each test specimen was stored in a sealed container at 50 ° C. for 1 week, and then the water repellency and abrasion resistance were evaluated.

As shown in Table 4, since the surface treating agent of Comparative Example 1 did not contain a curing catalyst, a coating film having sufficient abrasion resistance could not be provided under a curing condition at a low temperature of 30 minutes at 80 ° C. The surface treating agents of Comparative Examples 2 to 4 are inferior in storage stability. This is considered that (A) component condensed during storage as above-mentioned.
On the other hand, as shown in Examples 6 to 10 in Table 4, the surface treatment agent of the present invention can give a cured film having excellent abrasion resistance even under low temperature and short time curing conditions of 80 ° C. and 30 minutes. . Furthermore, even after the cured coating is stored at 50 ° C. for one month, excellent wear resistance does not decrease and storage stability is also excellent.

The surface treatment agent of the present invention can provide a cured film having excellent water and oil repellency, excellent adhesion to a substrate, and excellent storage stability by curing at low temperature and short time. Therefore, it can be expected that the surface treating agent of the present invention is widely used industrially. In particular, it is useful as a surface treatment agent for forming water- and oil-repellent films in applications where visibility is important, such as touch panel displays and antireflection films, where oil and fat are expected to be attached, and contributes to improving the productivity of these products. Can be expected to do.

Claims (12)

(A) Fluorine-containing organosilicon compound having at least one hydrolyzable group in one molecule, and (B) Compound having a phosphonate ester group in the molecule (A) Component and (B) component in total 100 parts by mass The surface treating agent which contains the quantity used as 0.001-15 mass parts with respect to. The surface treating agent according to claim 1, wherein the component (B) is a compound having a fluorine atom. The surface treating agent according to claim 2, wherein the component (B) is a compound having a fluorooxyalkylene group. The surface treating agent according to any one of claims 1 to 3, wherein the component (A) is a fluorine-containing organosilicon compound having a fluorooxyalkylene group. The surface treatment according to claim 4, wherein the component (A) is at least one selected from fluorine-containing organosilicon compounds represented by the following general formula (1), (2), (3) or (4). Agent.
(A-Rf) _α- ZW _β (1)
_{Rf- (ZW β) 2 (2} )
A-Rf-Q- (Y) _γ B (3)
_{Rf- (Q- (Y) γ B} ) 2 (4)
[In the above formulas, Rf group, independently of one _{another, - (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 - a is, d is an integer of 0~5, 0~200 p, q, r , s, t each independently And p + q + r + s + t = 10 to 200, each unit shown in parentheses may be bonded at random, and A is, independently of each other, a fluorine atom, a hydrogen atom, or a terminal of —CF ₃ A monovalent fluorine-containing group which is a group, a —CF ₂ H group or a —CH ₂ F group, and Z may be independently substituted with a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a fluorine atom. A divalent to octavalent organic group, W Independently, it is a monovalent organic group having a hydrolyzable group at the terminal, α is an integer of 1 to 7, β is an integer of 1 to 7 independently of each other, and Z in Formula (1) The valence of (β) is (β + α), the valence of Z in formula (2) is (β + 1), Q is independently of each other a single bond or a divalent organic group, and γ is independently of each other. 1 is an integer of 1 to 10, Y is a divalent organic group having a hydrolyzable group independently of each other, and B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, independently of each other. Or a halogen atom]. The surface treating agent according to claim 4 or 5, wherein the component (B) is a compound represented by the following general formula (5) or (6).
A'-Rf'-Z'W '_α' (5)
Rf ′ − (Z′W ′ _{α ′} ) ₂ (6)
[Wherein, Rf ′ groups are independently of each other, — (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' - a and, d 'is an integer of 0~5, p', q ', r', s ′ and t ′ are integers of 0 to 200, and p ′ + q ′ + r ′ + s ′ + t ′ = 10 to 200, and each unit shown in parentheses may be bonded at random, α 'Is independently an integer of 1 to 7, and A' is a fluorine atom, a hydrogen atom, or a -CF ₃ group, a -CF ₂ H group, or a -CH ₂ F group, independently of each other. Is a monovalent fluorine-containing group, and Z ′ is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a 2-8 valent group that may be substituted with fluorine. An organic group, and, W 'is a monovalent organic group having a phosphonic acid ester groups each independently terminated. The phosphonic acid ester group in the component (B) is represented by —P (O) (OX ′) ₂ and X ′ is unsubstituted or substituted, an alkyl group or aryl group having 1 to 5 carbon atoms, or —SiR _3. The surface treatment agent according to any one of claims 1 to 6, wherein the Rs are each independently an alkyl group or an aryl group having 1 to 5 carbon atoms. The surface treating agent according to claim 7, wherein X ′ is a phenyl group or a group represented by —Si (CH ₃ ) ₃ .   The surface treating agent according to any one of claims 1 to 7, wherein the component (B) has a number average molecular weight that is 0.5 to 5 times the number average molecular weight of the component (A). .   An article having a cured product of the surface treatment agent according to any one of claims 1 to 9. Wherein the article, the optical article, a touch panel, an antireflection film, SiO ₂ treated glass, and is selected from the pottery article of claim 10, wherein. A method for forming a cured film on a surface of an article by applying the surface treatment agent according to claim 1 to the surface of the article by vapor deposition and curing.